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. 72014年7月Joural of Fuel Chemistry and TechnologyJul. 2014文章编号: 0253-2409( 2014 )07 -0865-05Effect of support oncatalytic performance for metathesis of butene to propeneHUA De-run!2, CHEN Sheng-liz, ZHOU ZhengCHEN Ai-cheng2, LIU Hong-bo'，HUANG Qing', LU Xin-ning'( 1. Gannan Normal University, Chemical Institute of Chemical Indlustry, Ganzhou 341000， China ;2. China Uniersity of Petroleum, State Key of Heavy oil Processing, Beijing 102249, China;3. Natural Gas Treating Plant , Sinopec Zhongyuan Oilfield Branch, Puyang 457001, China)Abstract: The catalysts with SBA-15， MCM-48， SiO2, and MTS-9 as supports were synthesized with 8% WO3, and theircatalytic performance for metathesis of butene to propene were carried out. The conversion of butene is 30% ~ 37% on the catalystswith SBA-15，MCM-48，and SiO2 as supports， and that of butene is 37% ~ 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 best.Keywords : propene ; metathesis; support; WO,CLC number: 0643.3 Document code: AOlefin metathesis is a catalytically inducedattracted the most attention.Compared withreaction wherein olefins undergo bond reorganization ,conventional catalystsupported molybdenum andresulting in a redistribution of alkylidene moieties.rhenium，catalystssupportedtungstenwereOlefin metathesis was first reported by Eleuterio inthoroughly investigated for a long timedue to1963(2]，which has been regarded as an importantconsiderable. resistance to poison. But there werereaction for the conversion of low value olefin intofew reports on an effect of support on metathesis ofdemanded olefinic substratesl1,3 ~6The reactionbutene to propone 4.513.2010 .pathways of olefin metathesis can be illustrated asThe highlight of the paper was to investigate theshowed in Figure 1.effect of support on the activity of catalysts formetathesis of butene to propene. Four supports withRCHECHR,RCHR.CHdifferent pore sizes and architectures had beenemployed in this study: conventional SiO2，SBA-15of hexagonal structure, cubic MCM-48 with three-R.CH#CHR,R.CH .dimensional intersecting channels, MTS-9 containingtitanium. The effect of support on catalyst activityFigure 1 Reaction of olefin metathesisand selectivity was investigated.The catalytic activity was found to dependparticularly on the content of active component，1 Experimentalthe state of activecomponentactivation1.1 Synthesis of supportsconditions[lpreparation conditiosl1,2]and theMCM-48 was hydrothermally synthesized fromproperties of the support. As concerns support ，an assembly of surfactant micelle ( CTAB ) withsupport often affected the dispersity and properties ofsilicate precursors in alkali media as described in thesupported metal oxide， which resulted in catalystsliteratureexhibiting different catalytic activity. MoreoverMesoporous SBA-15 was synthesized in stronglyreducibility of catalyst was dependent on support-8acidic media [221.So support was important to metathesis catalyst.MTS-9 was hydrothermally synthesized fromMesoporous materials have a unique characteristic ,assembly of triblock polymers ( P12) with preformedand are candidates for support. Mesoporous silica-titanosilicate precursors in strongly acidic media ( pHbased catalysts exhibited higher activity， which wasvalue<1) by a two-step procedure. First, precursorsattributed to the better dispersion of the active phasecontaining titanosilicate ( TS-1 ) nanoclusters wereon the mesoporous support surfacel4-17. Theprepared4. Second, the preformed precursors weresupported tungsten oxide catalysts had a high potentialassembled with triblockcopolymers in a strong acidfor practical applications in metathesisl.li andmedium (pH value< 1). The synthesis procedure for866燃料化学学报第42卷MTS-9 was reported in detail in literature 25] .used as the excitation source. The spectrum resolution1.2 Preparation of catalystswas estimated to be 4.0 cmAll catalysts werepreparedby the wet1.4 Test of catalystsimpregnation method. The WO3 to support ratio ( inCatalytic propertiesof all catalysts wereweight) of catalyst was 8. 0%，The impregnatedevaluated by the metathesis of butene. The metathesisproducts were dried at 80 C for 12 h, and then thewas carried out in a down flow fixed bed stainlesscatalysts were thermally treated at 550 C for 4 h.steel microreactor ( 10 mm i. d. ). C4 stream was1.3Characterization of catalyststreated through BASF adsorbents Selexsorb CD andX-ray powder diffraction patterns of the catalystsCOS for the removal of oxygenated organicwererecorded on a BrukerD8ADVACEcompounds and other trace contaminants， which candiffractometer，using Cu Ko ( 0. 154 06 nm )cause catalyst deactivation. Before introduction of C4radiation in the 20 range of 10° ~ 60° with a scanningstream into the reactor, the catalyst was pretreated inrate of 1(° )/ min. N, adsorption-desorption isothermssitu with a mixture flow of N2 and H2 for 30 min atat -196 C were recorded with a Micromeritics ASAP420 C. Weight hour space velocity ( WHSV) of the2010 automatic sorption analyzer. The BET surfacemetathesis reaction was 6. 4 h~ '，All products wereareas were calculated from the desorption isotherms inanalyzed using a gas chromatograph equipped with athe relative pressure range of p/p。= 0.01 ~1.0. UV-flame ionization detector ( FID) and a 50 m PONARaman spectra were obtained on a HR800 UV- Ramancapillary column.The reaction pathways werespectrograph( Horiba Jobin YvonCompany ,illustrated in Figure 2 in detail.France). The 244.0 nm line from a He-Cd laser isCH,CH=CHCH,' y-cross-metathesis+ CH,CH=CH+CH,CH=CHCH,CH,self-metathesisisomerization十CH_=CH.+CH,CH.CH=CHCH,CH,一2CH,CH=CHCHCH,CH=CH2CH,CH,CH=CH,Figure 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% WO3/SiO2 wasFigure 3 shows the effect of support onlowest and 8% WO,/SBA-15 and 8% WO,/MCM-48metathesis of butene to propene. After 10 h，thepossessed the same activity.performance of catalysts reached stability.The selectivity of propene is shown in Figure 4.5560。57。50，54影514昌48-三35百42Fg 30剪39F8 25362001022:3010 15 20Time t/Time t/hFigure 3 Effect of supports on the conversion of buteneFigure 4 Effect of supports on the selectivity of propenereaction conditions: 1=320 C, p=0. 8 MPa, WHSV=6.4 h-lreaction conditions: 1=320 C, p=0.8 MPa, WHSV=6.4 h"■: 8% WO,/MTS-9;●: 8% WO3/ SBA-15;■:8% WO/MTS9;●: 8% WO,/SBA-15;gce. wo86燃料化学学报第42卷the bulk WO3，which is assigned to the symmetriccompared withother catalysts， 8% WO,/ SiO,bending and stretching vibration of W-0O11.28] ,possessing a lower activity is not surprising.respectively.As showed in Figure 6，tungsten species weredominant on 8% WO,/MTS-9 and 8% WO;/SBA-15 ,so their activities were higher than that of others. On8%WO,/MCM-4870610878% WO3/SBA-15 catalyst, surface polytungstens wereprevailing. For 8% WO,/MTS-9，isolated surface8%WO,/SiO,tungstens are prevailing, and the metathesis activity ofisolated surface species is greater than that of surface「8%WO/SBA-15poly species-29, thus the activity of 8% WO3/MTS-9is higher than that of 8% WO:/SBA-15.8%WO/MTS-23 ConclusionsFour supports SiO2， SBA-15， MCM-48 and200400 600 800 1000 1200 1400MTS-9 were synthesized， and the correspondingRaman shift o/cm 1catalysts were synthesized. Effect of supports onFigure 6 Raman spectra of the catalystsmetathesis of butene was investigated. Results showedAs the relationship between the concentration ofthat support only affects the conversion of butene andW species and the intensity of corresponding peaks ishad no effect on the selectivity to propene. For allcatalysts，8% WO,/MTS-9catalyst exhibited theknown and the intensity of bands is proportional tohighest activity, and conversion of butene was 41% .concentration of W species， qualitative conclusionsThe activity of 8% WO3/ SiO, was lowest， andcanbe drawn from the spectra.8% WO3/SiO,conversion of butene was 30%.According to thepossesses much more the bulk WO3， which is incharacterization of catalysts, which was attributed toaccordance with XRD. Based on literaturesl0.11.1the acidic numbers of catalysts and the distribution ofthe active species is surface W species.Thus ,tungstens on the surface of support.References[1] LIPPARD s J, GRUBBS R H. The olefin metahesis reaction[M]. Wiley, 1978.] ELEUTERIO H S. Polymerization of cyclic olefins: Us, 3074918[ P].1963-01-22.[3] VAN SCHALKWYK C, VOSL0O HC M, BOTHA J M. An investigation into the activity of the in situ ruthenium( II). Choride catalyticsystem for the metathesis of 1-octene[J]. 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Mesoprous molecular sieves as supports for metathesis catalysts[ J]，Metathesis Chem, 2007, 243: 151-166.载体对烯烃歧化制丙烯的影响华德润2，陈胜利”,周政33, 陈爱诚”，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341000;2.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SiO2(SBA-15、MCM- 48和SiO2)和TiO2-SiO2(MTS-9)介孔分子筛为载体负载8% WO,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.MCM-48和SiO,为载体时,催化剂的T烯转化率在30%~37%;以MTS-9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MTS-9具有更好的分散能力,表面活性物种数量最多,催化剂WO3/ MTS-9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: 0643.3文 献标识码: A