载体对烯烃歧化制丙烯的影响

第42卷第7期燃料化学学报Vol 42 No. 7014年7月Journal of Fuel Chemistry and TechnologyJul.2014文章编号:0253-2409(2014)070865-05Effect of support oncatalytic performance for metathesis of butene to propeneHUA De-run''-. Chen Sheng-Ii-. ZHOU-chenng, LIU Hong-bo, HUANG QingXin-ning(1. Gannan Normal University, Chemical Institute of Chemical Industry, Ganzhou 341000, China2. China University of Petroleum, State Key of Heavy Oil Processing, Beiying 102249, Chi3. Natural Gas Treating Plant, Sinopec Zhongyuan Oilfield Branch, Puyang 457001, ChinaAbstract: The catalysts with SBA-15, MCM-48, SiO,, and MTS-9 as supports were synthesized with 8% WO,, and theircatalytic performance for metathesis of butene to propene were carried out. The conversion of butene is 30%0-37% on the catalystswith SBA-15, MCM-48, and Sio, as supports, and that of butene is 37%0-42% on WO,/MTS 9 catalyst. The catalystcharacterization results show that the catalytic activities depend on the acidic numbers of catalysts prepared and the distribution oftungstens on the supports used. As a result, the performance of 8% WO,/MTS-9 catalyst for the titled reaction is bestKeywords: propene; metathesis; support; wO3CLC number: 0643. 3 Document code : Arec, Olefin metathesis is a catalytically induced attracted the most attentionComparedtion wherein olefins undergo bond reorganization, conventional catalyst supported molybdenum andresulting in a redistribution of alkylidene moietiesenumcatalysts supported tungstenwereOlefin metathesis was first reported by Eleuterio in thoroughly investigated for a long time due to19632, which has been regarded as an important considerable resistance to poison19.Bureaction for the conversion of low value olefin into few reports on an effect of support on metathesis ofdemanded olefinic substrates.,3-6. The reaction butene to propone 4, 5, Ipathways of olefin metathesis can be illustrated asThe highlight of the paper was to investigate theshowed in Figure 1effect of support on the activity of catalysts forthesis of butene toorts withR, CH: CHRRCHdifferent pore sizes and architectures had beenemployed in this study: conventional SiO,, SBA-15of hexagonal structure cubic mCm-48 with threeR CHECHRR CHR CHdimensional intersecting channels, MTS-9 containingFigure 1 Reaction of olefin metathesistitanium. The effect of support on catalyst activityand selectivity was investigatedThe catalytic activity was found to dependparticularly on the content of active component,8)Eexperimenthe state of active component 9, activation 1.1 Synthesis of supportsprepand theMCM-48 was hydrothermally synthesized fromproperties of the support 4, 5, 13. As concerns support, an assembly of surfactant micelle( CTAB ) withsupport often affected the dispersity and properties of silicate precursors in alkali media as described in thesupported metal oxide, which resulted in catalysts literatureexhibiting different catalytic activity. MoreoverMesoporous SBA-15 was synthesized in stronglyreducibility of catalyst was dependent on supportacidic mediaSo support was important to metathesis catalystMTS-9 was hydrothermally synthesized frorMesoporous materials have a unique characteristic, assembly of triblock polymers( P123)with preformedand are candidates for support. Mesoporous silica- titanosilicate precursors in strongly acidic media(pHbased catalysts exhibited higher activity, which was valud中国煤化工 ure. First, precursorsattributed to the better dispersion of the active phase cont,nanoclustersrfaceThe preplHCNMHsupported tungsten oxide catalysts had a high potential assembled with triblockcopolymers in a strong acidfor practical applications in metathesis 6. I and medium (ph value< 1). The synthesis procedure forReceived date. 2013-11-27: Received in revised form: 2014-03-1Correspondingauthor:CHENSheng-li,E-mail:slchen@cup.edu.cn.866燃料化学学报第42卷All catalysts were prepared by the wet 1.4 Test of catalysts 73MTS-9 was reported in detail in literature 2.used as the excitation sourcespectrum reso1. 2 Preparation of catalystswas estimated to be 4.0impregnation method. The WO, to support ratio( inCatalytic properties ofcatalysts wereweight)of catalyst was 8.0%. The impregnated evaluated by the metathesis of butene. The metathesisproducts were dried at 80C for 12 h, and then the was carried out in a down flow fixed bed stainlesscatalysts were thermally treated at 550 C for 4hsteel microreactd.C4 stream was1. 3 Characterization of catalyststreated through basf adsorbents selexsorb Cd andX-ray powder diffraction patterns of the catalycos for the removal ofwere recorded on a Bruker D8 ADVACe compounds and other trace contaminants, which candiffractometer, using Cu Ka (0. 15406 nm) cause catalyst deactivation. Before introduction of C4radiation in the 20 range of 10-60 with a scanning stream into the reactor, the catalyst was pretreatedrate of 1(o)/min. N, adsorption-desorption isotherms situ with a mixture flow of N, and H, for 30 min atat-196C were recorded with a Micromeritics ASAP 420C. Weight hour space velocity( WHSV of the2010 automatic sorption analyzer. The bet surface metathesis reaction was 6. 4 h. All products wereareas were calculated from the desorption isotherms in analyzed using a gas chromatograph equipped with athe relative pressure range of p/po=0.01-1.0. UV- flame ionization detector FID )and a 50 m PONARaman spectra were obtained on a Hr800 UV-Raman capillary column. The reaction pathways werespectrograph( Horiba Jobin Yvon Company, illustrated in Figure 2 in detailFrance). The 244.0 nm line from a He-Cd laser iscross-metathesisCH CH-CHCICH, CH=CH, +CH, CH=CHCH, CHelf-metathesisCHCH,+CHCH, CH=CHCH, CHcross-metathesis2CH CHECHH CH CHECHCHCHCH=CHFigure 2 Possible reaction pathways of 2-butene2 Results and discussionAmong all catalyst, 8% WO,/MTS-9 exhibited2.1 Test of catalyststhe highest activity. Activity of 8%WO,/SiO,wasFigure 3 shows the effect of support on lowest and 8% wO,/SBA-15 and 8%WO,/MCM-48metathesis of butene to propene. After 10 h, the possessed the same activityperformance of catalysts reached stabilityThe selectivity of propene is shown in Figure 40745书52V凵中国煤化工20230CNMHGFigure 3 Effect of supports on the conversion of buteneFigure 4 Effect of supports on the selectivity of propenereaction conditions: t=320C, p=0. 8 MPa, WHSV=6. 4 h" reaction conditions: (=320C, p=0.8 MPa, WHSV=6.4h"8%WO3MTS-9;·:8%WO3/SBA-15■:8%WO3MTS9;·:8%WO3/SBA-15A:8%WO,/SiO,; V: 8%WO,/MCM-48A:8%WO,/SiO,: V:8% WO,/MCM-48第7期HUA De-run et al Effect of support on catalytic performance for metathesis of butene to propeneThe support had no significant impact on the 8%WO,/MCM-48 <8%WO3/SiO2, suggesting theelectivity of propene, and the selectivity to propene dispersing capacity was different for the differentwas about 45% on all catalysts. In order to illustrate supports and worst on Sio, support. The bulk wopossesses nocharacterized by XRD, N2-adsorption isotherm and activity of 8%WO, /SiO, catalyst was worstUⅤ- RamanTable I shows the surface area, pore size and2. 2 Characterization of catalystspore volume of supports and catalysts. The surfaceFigure 5 shows power XRD patterns of supported area, pore size and pore volume of catalysts are lowerwO, catalysts around 5-80than these of supports, which were attributed toadsorption of the active phase on the surface of thesupports. Pore size of catalyst was larger than thedynamic size of production, and diffusion limitation isabsent, so selectivity to propene is independent ofsupportsTo our knowledge, besides active species, thedistribution of active components and reaction8% WO/SiOconditions, metathesis reaction depends on acidic8% WO/SBA-15numbers of catalyst, so the acidic numbers of%o WO/MCM-48catalysts are determined, and the results were listed inTable 2. The acidic numbers of catalyst are more than1020304050607080that of support, which was attributed to the formationFigure 5 Wide-angle XRD patterns of the catalystsof new acidic sites. The acidic numbers decrease asfollowing order: 8%WO,/MTS-98%WO,/SBA-15There was evidence of crystalline tungsten oxide >8%WO3/MCM48>8%WO3/SiO2, and whichin all cases, and the intensity of peaks was different. consists with the order of catalytic activity ofThe intensity of peaks increased in the following catalysts, so the acidic numbers of catalyst affect theorder :8% WO./ MTS-9< 8%wo,/ SBA-15< performance of the catalystTable 1 Texture of supports and catalystsSpecific surface area A/(m"g) Pore volume v/(cm.g") Average pore size d/nmMTS-90.71706.646%O WO,/MTS-90.6880MCM-488%0 WO,/MCM-480.61102.340682.40.95008%WO,/SBA-15632.10.86005.450SiO,435.30.96008.7808%o wO/SiO395.30.87008.660Table 2 Acidic numbers of supports and catalystsAcidic numbers/(mmol.g)Acidic numbers /( mmol.g")MrS-90.188348%WO/MrS-90.3169SBA-1586 WO,/SBA-150.2209MCM-488%0 WO,/MCM-480.2123Sio0.033780 wO/SiO0.0947中国煤化工To further explore the influence of the support on bandthe catalyst structure, Raman's analyses were done surfCNMHGre characteristic of theBands at 1 087 andand illustrated in Figure 6. There are three tungsten 995 cm" correspond to the stretching vibration modespecies on the surface of catalysts in the spectra: of the terminal bond of isolated surface tungsten oxideisolated surface turoxide species, highly species and surface poly tungsten, respectivelydispersed surface poly tungsten and bulk WO3. Raman Raman bands at 706 and 805 cm are characteristic of燃料化学学报第42卷bulk wO,, which is assigned to the symmetric compared with other catalysts, 8% WO,/SiO2bending and stretching vibration of W-o 1.28, possessing a lower activity is not surprisingrespectivelyAs showed in Figure 6, tungsten species weredominant on 8 %o WO/MTS-9 and 8%0 WO/SBA-15so their activities were higher than that of others On10878%WO,MCM-488%WO,/SBA-15 catalyst, surface polytungstens wereprevailing. For 8%WO,/MTS-9, isolated surface8%wo, /Siotungstens are prevailing, and the metathesis activity of金8%WO/SBAisolated surface species is greater than that of surfacepoly species 29, thus the activity of 8%WO,/MTS-9is higher than that of 8 Wo,/SBA-158%WO/MTS-3 ConclusionsFour supports Sio2, SBA-15, MCM-48 and200400600800100012001400MTS-9 were synthesized, and the correspondingRaman shift a/cmcatalysts were synthesized. Effect of supports onFigure 6 Raman spectra of the catalystsmetathesis of butene was investigated. Results showedthatAs the relationship between the concentration ofort only affects thew species and the intensity of corresponding peaks is had no effect on the selectivity to propene. For allknown and the intensity of bands is proportionalcatalysts, 8%WO,/MTS-9 catalyst exhibited theconcentration of w species, qualitative conclusionshighest activity, and conversion of butene was 41%can be drawn from the spectra. 8%WO,/SiOThe activity of 8% WO,/ Sio, was lowest, andpossesses much more the bulk wo, which is in conversion of butene was 30% According to theaccordance with XRD. Based on literatures [6, 11, 131 characterization of catalysts, which was attributed tothe active species is surface w species. thusthe acidic numbers of catalysts and the distribution oftungstens on the surface of supportReferences[1 LIPPARD S J, GRUBBS R H. The olefin metathesis reaction[ M]. Wiley, 1978[2 ELEUTERIO H S. Polymerization of cyclic olefins: US, 3074918[ P.1963-01-22[3 VAN SCHALKWYK C, VOSLOO H C M, BOTHA J M. An investigation into the activity of the in situ ruthenium( Ill). Chloride catalyticsystem for the metathesis of 1-octene[ J]. 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Metathesis Chem, 2007, 243:151-1载体对烯烃歧化制丙烯的影响华德润2,陈胜利2,周政23,陈爱诚2,刘红波!,黄庆,卢新宁(1.赣南师范学院,化学化工学院,江西赣州3410002.中国石油大学(北京)重质油国家重点实验室,北京102249;3,.中原石油天然气处理厂,河南濮阳457001)摘要:以SO2(SBA15、MCM48和SO2)和TO2SO2(MTS9)介孔分子筛为载体负载8%WO3合成钨基催化剂,研究载体对丁烯歧化制丙烯性能的影响以及载体对丁烯转化率和丙烯选择性的影响。以SBA-15、MCM48和SiO,为载体时,催化剂的丁烯转化率在30%~37%;以MTS9为催化剂载体时,丁烯的转化率高达到37%~42%。对所有使用的催化剂进行多种技术表征。结果表明,活性组分在各种载体上的分散度不同,载体MTS9具有更好的分散能力,表面活性物种数量最多,催化剂WO3MTS9的歧化性能最佳。关键词:丙烯;歧化;载体;三氧化钨中图分类号:O643.3文献标识码:A中国煤化工CNMHG