Deactivation and regeneration of catalyst for cyclohexanone ammoximation in ceramic membrane reactor

doi:10.11949/j.issn.0438-1157.20161772

Abstract

Abstract:

The deactivation mechanism of TS-1 used in the organic solvent-free cyclohexanone ammoximation based on ceramic membrane reactor was investigated. The framework structure, crystal parameters, specific surface area and pore volume and the major composition of organic, of fresh and deactivated TS-1 zeolites were examined by XRD, FT-IR, N₂ adsorption, TGA/DSC and GC-MS techniques. The results have shown that the dissolution of silicon has taken place in the reaction system, but the topological structure and crystal volume of deactivated TS-1 zeolite remained almost the same to the fresh one. The catalyst deactivation was mainly due to the adsorption of cyclohexanone, cyclohexanone oxime and by-product on the surface and channel of TS-1 zeolite, and because of this, the specific surface area of TS-1 catalysts decreased by 52.6% and the pore volume decreased by 41.6%. The catalyst activity can be recovered by air calcination at 600℃ for 3 h.

Key words: cyclohexanone oxime, TS-1 zeolites, ammoximation, membrane reactor, deactivation, regeneration, catalyst

摘要：

基于陶瓷膜反应器开发出无有机溶剂的环己酮氨肟化新工艺，探讨TS-1催化剂失活机制。采用XRD及Rietveld全谱拟合、FT-IR、N₂吸附-脱附、TGA/DSC、GC-MS等手段对TS-1分子筛的骨架结构、晶胞参数、比表面积和有机物种类进行了表征分析。结果表明，无有机溶剂的环己酮氨肟化反应过程中，存在硅流失的现象，但TS-1骨架完整，晶胞参数未明显变化；环己酮、环己酮肟及反应副产物等吸附在TS-1催化剂的表面及孔道内，使比表面积下降52.6%、孔体积减少了41.6%，是造成TS-1失活的主要原因，空气氛围中于600℃煅烧3 h，可以恢复催化剂的活性。

关键词: 环己酮肟, TS-1分子筛, 氨肟化, 膜反应器, 失活, 再生, 催化剂

CLC Number:

TQ032.4

JIN Dongyang, ZHANG Feng, CHEN Rizhi, ZHONG Zhaoxiang, XING Weihong. Deactivation and regeneration of catalyst for cyclohexanone ammoximation in ceramic membrane reactor[J]. CIESC Journal, 2017, 68(5): 1874-1881.

晋东洋, 张峰, 陈日志, 仲兆祥, 邢卫红. 陶瓷膜反应器中环己酮氨肟化的催化剂失活机制与再生[J]. 化工学报, 2017, 68(5): 1874-1881.

References 31

[1]	DREONI DP, PINELLI D,TRIFIRO F, et al. Ti-silicalite as catalyst for gas-phase ammoximation of cyclohexanone with molecular-oxygen[J]. Catalysis Letters, 1991, 11(3-6): 285-294.
[2]	WU C T, WANG Y Q, MI Z T, et al. Effects of organic solvents on the structure stability of TS-1 for the ammoximation of cyclohexanone[J]. Reaction Kinetics and Catalysis Letters, 2002, 77(1): 73-81.
[3]	KULKOVA N V, KOTOVA V G, KVYATHOVASKAYA M Y, et al. Kinetics of liquid-phase cyclohexanone ammoximation over a titanium silicate[J]. Chemical Eengineering & Technology, 1997, 20(1): 43-46.
[4]	YIP A C K, HU X J. Catalytic activity of clay-based titanium silicalite-1 composite in cyclohexanone ammoximation[J]. Industrial & Engineering Chemistry Research, 2009, 48(18): 8441-8450.
[5]	POZZO L D, FORNASARI G, MONTI T. TS-1 catalytic mechanism in cyclohexanone oxime production[J]. Catalysis Communications, 2002, 3(8): 369-375.
[6]	LZUMI Y, ICHIHASHI H, SHIMAZU Y, et al. Development and industrialization of the vapor-phase Beckmann rearrangement process[J]. Bulletin the Chenical Society of Japan, 2007, 80(7): 1280-1287.
[7]	SOOKNOI T, CHITRANUWATKUL V. Ammoximation of cyclo-hexanone in acetic acid using titanium silicalite-1 catalyst: activity and reaction pathway[J]. Journal of Molecular Catalysis A: Chemical, 2005, 236(1/2): 220-226.
[8]	刘国清, 袁霞, 吴剑, 等. 环己酮肟Beckmann重排反应微观混合的数值模拟[J]. 化工学报, 2011, 62(3): 658-663. LIU G Q, YUAN X, WU J, et al. Numerical simulation of micromixing in Beckmann rearrangement of cyclohexanone oxime[J]. CIESC Journal, 2011, 62(3): 658-663.
[9]	SUN R, XIN F, YANG L B. Modeling of monolithic catalyst washcoated with TS-1 and reactor for continuous cyclohexanone ammoximation reation[J]. Industrial & Engineering Chemistry Research, 2015, 54(7): 2254-2258.
[10]	SONG F, LIU Y M, WU H H, et al. A novel titanosilicate with MWW structure: highly effective liquid-phase ammoximation of cyclohexan-one[J]. Journal of Catalysis, 2006, 237(2): 359-367.
[11]	赵虹, 周继承. TS-1催化环己酮氨氧化反应本征动力学模型[J]. 化工学报, 2004, 55(4): 575-579. ZHAO H, ZHOU J C. Kinetic model of cyclohexanone ammoximation catalized by titanium silicalite-1[J]. Journal of Chemical Industry and Engineering(China), 2004, 55(4) : 575-579.
[12]	邢卫红, 金万勤, 陈日志, 等. 陶瓷膜连续反应器的设计与工程应用[J]. 化工学报, 2010, 61(7): 1666-1673. XING W H, JIN W Q, CHEN R Z, et al. Design and application of continuous ceramic membrane reactor[J]. CIESC Journal, 2010, 61(7): 1666-1673.
[13]	CHEN R Z, MAO H L, ZHANG X R, et al. A dual-membrane airlift reactor for cyclohexanone ammoximation over titanium silicalite-1[J]. Industrial & Engineering Chemistry Research, 2014, 53(15): 6372-6379.
[14]	ZHONG Z X, XING W H, LIU X, et al. Fouling and regeneration of ceramic membranes used in recovering titanum silicalite-1 cataylsts[J]. Journal of Membrane Science, 2007, 301(1/2): 67-75.
[15]	ZHONG Z X, LI D Y, LIU X, et al. The fouling mechanism of ceramic membranes used for recovering TS-1 cataylsts[J]. Chinese Journal of Chemical Eengineering, 2009, 17(1): 53-57.
[16]	MAO H L, CHEN R Z, XING W H, et al. Organic solvent-free process for cyclohexanone ammoximation by a ceramic membrane distributor[J]. Chemical Engineering & Technology, 2016, 39(5): 883-890.
[17]	ZHOU Z X, WANG L, ZHANG X Q, et al. Insights into the key to highly selective synthesis of oxime via ammoximation over titanosilicates[J]. Journal of Catalysis, 2015, 329: 107-118.
[18]	SINCLAIR P E, CATLOW C R A, Quantum chemical study of the mechanism of partial oxidation reactivity in titanosilicate catalysts: active site formation,oxygen transfer, and catalyst deactivation[J]. The Journal of Physical Chemistry B, 1999, 103(7): 1084-1095.
[19]	XIA C J, LIN M, ZHENG A, et al. Irreversible deactivation of hollow TS-1 zeolite caused by the formation of acidic amorphous TiO2-SiO2 nanoparticles in a commercial cyclohexanone ammoximation process[J]. Journal of Catalysis, 2016, 338: 340-348.
[20]	ZHANG X J, WANG Y, YANG L B, et al. Coking deactivation of TS-1 catalyst in cyclohexanone ammoximation[J]. Chinese Journal of Catalysis, 2006, 27(5): 427-432.
[21]	刘银乾, 李永祥, 吴魏, 等. 环己酮氨肟化反应体系中TS-1分子筛失活原因的研究[J]. 石油炼制与化工, 2002, 33(5): 41-45. LIU Y Q, LI Y X, WU W, et al. Study on deactivation behavior of TS-1 molecular sieve in cyclohexanone ammoximation[J]. Petroleum Processing and Petrochenicals, 2002, 33(5): 41-45.
[22]	VAN DER POL A J H P, VAN HOOFF J H C. Parameters affecting the synthesis of titanium silicalite 1[J]. Applied Catalysis A: General, 1992, 92(2): 93-111.
[23]	PAWLAK A, MUCHA A. Thermogravimetric and FTIR studies of chitosan blends[J]. Thermochimica Acta, 2003, 396(1/2): 153-166.
[24]	DRAGO R S, DIAS S C, MCGILVRAY J M, et al. Acidity and hydrophobicity of TS-1[J]. The Journal of Physical Chemistry B, 1998, 102(9): 1508-1514.
[25]	KLAAS J, SCHULZEKLOFF G, JAEGER N I. UV-visible diffuse reflectance spectroscopy of zeolite-hosted mononuclear titanium oxide species[J]. J. Phys. Chem. B, 1997, 101(8): 1305-1311.
[26]	GEOBALDO F, BORDIGA S, ZECCHINA A, et al. DRS UV-VIS and EPR spectroscopy of hydroperoxo and superoxo complexes in titanium silicalite[J]. Catalysis Letters, 1992, 16(1/2): 109-115.
[27]	姜锋, 傅送保, 汤琴. 等. 环己酮肟化工艺中钛硅分子筛流失问题的研究[J]. 化工进展, 2003, 22(10): 1116-1118. JIANG F, FU B S, TANG Q, et al. Research on the loss of Ti-Si molecular sieve in the cyclohexane ammonium-oximation process[J]. Chemical Industry and Engineering Progress, 2003, 22(10): 1116-1118.
[28]	孙斌, 朱丽. 钛硅-1分子筛催化环己酮氨肟化制环己酮肟工艺的研究[J]. 石油炼制与化工, 2001, 32(9): 22-24. SUN B, ZHU L. Study on ammoximation of cyclohexanone to cyclohexanone oxime catalyzed by titanium-silicalite-1 zeolite[J]. Petroleum Processing and Petrochenicals, 2001, 32(9): 22-24.
[29]	YIP A C K, LAM F L Y, HU Y. A heterostructured titanium silicalite-1 catalytic composite for cyclohexan-one ammoximation[J]. Microporous and Mesoporous Materials, 2009, 120(3): 368-374.
[30]	SHI H N, WANG Y Q, WU G Q, et al. Deactivation and regeneration of TS-1/SiO2 catalyst for epoxidation for epoxidation of propylene with hydrogen perdrogen peroxide in a fixed-bed reactor[J]. Chemical Science and Engineering, 2013, 7(2): 202-209.
[31]	孙斌, 吴魏, 王恩泉, 等. 一种含钛催化剂的再生方法: CN03137913.3[P]. 2003-12-7. SUN B, WU W, WANG E Q, et al. A regeneration method of titanium-containing catalyst: CN03137913.3[P]. 2003-12-7.