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    The influence of cobalt in bimetallic Ni-Co catalyst supported on H_Beta for phenol hydrodeoxygenation.

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    The influence of cobalt in bimetallic Ni-Co catalyst supported on H_Beta for phenol hydrodeoxygenation.

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    © All Rights Reserved
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    4 views5 pages

    2014 Chemistry Today Huynh

    Uploaded by

    Thuan Huynh Minh
    The influence of cobalt in bimetallic Ni-Co catalyst supported on H_Beta for phenol hydrodeoxygenation.

    Copyright:

    © All Rights Reserved
    Download as PDF or read online from Scribd
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    CATALYSIS THUAN MINH HUYNH'2*, UDO ARMBRUSTER’ IN MINH QUOC PHAN [DUC ANH NGUYEN, ANDREAS MARTIN’ *Conesponding author |. Lebonz rst for Catan ot ne Universy of Rostock, ‘Alber-Einstal-Strade 270, 518059, Rostock 2. Vietnam Petolaum Intute, 173 Trung Kinn, Yen Hos, ou Giey. Hanoi Vietnam en eens The influence of cobalt in bimetallic Ni-Co catalyst supported on H-Beta for phenol hydrodeoxygenation KEYWORDS: Suppotted N-Co bimetalic catalyst, N-Co alloy, H-Beta, Phenol, Hydrodeoxygenaion. AST ACT eee eee ene eae oaassecoe Raceube se descent sate Cotas for his process chatenging up to now dus fo high ke formation and deactivation. hs paper, wa deserbe anew [Eimetalic cotalys! using nor-sulied, non-noblo metals for E20 of phenol as model compound for biol. The resuts show thatthe ‘combination of rickeland cobalt sypoorted on zeolte Beta fet] to form a bimetalic cola nol only increased aot but oko ‘changed the prouet dibution toward sotursted nycrooar npared to monometalie NfBeta ond Co/seta carob, Mercover, Na bimatalic catalyst stectively avoised cote formation Ine formation of N-Co olay in Ne-Ca/Bata corals fea 10 Teduced paricie ze: and hence increaied tne dperson of active ses on NkCovBeta and inally improved catabie perlorance. Notobly, 36% selectivity fo hydrocarbon of 97% phenol convention were achieved on IORNTORC/Beta catohst ct 250°C within Sh INTRODUCTION (HOS) catalsts (Co-MO/ALO,, NEMO/ALO4) (8, 4] and ue to the shortage of fost uel ang environmental concern, he search for alternative and renewable energy resources has otracted attention all over the world, Of he Interesting resources sok, wine, biomass, geothermal and £0 on, Bomoss ®orGed as an obundon! sustainable souce for production of carbon based fuel Thus, the convenion of Bomoss to renewable laud ek nas received ‘considerable interes! for pary replacing convertionaltues There ore several patnways 9 convert Biomass to lquid fuels in which biomass fast pyroliss ana subsequent ypgrading of resulting Bc-lls a promising one, The conversion af biomass to bio-ollvia fat pyro increases volumetric and energy ‘density and therefore reduces tne ransnoration cos) However tne dieet ure of bo-ol far eomoustion engine! turbine has some implications because of dierent properties of bio-ll compared with conventional fos ls ‘Mote than 200 compaundsin biol ove known, having vorious types of Knetonal groups with soecite chemi. Furthermore, woter alo oceaunts for 15-30 0% (I) Theretor, upgrading of bio-ol is necessory fo moe it suiloble for luther use. Among the availble uogresing strategies, cotati nycrodeoxygenation 00) s considered os interesting new technology (2) The development of suitable catals's for ths process is ccnalenging up *o now ave "o high coke formation and rapid deactivation ot hycrethermal conti. Many researchers have apples conventional nyarodesuluteation hydrotreating catalys! based on supparied noble metal Pa or Ru} (5, 6. However, he fst clas of catchals snowes low activity and poly deactivation due fo aching of sulphur during reaction, ond phase changes in support at hycrothermal condlion caused by kage waler conten’ in bio-l, Me Inter clos of cotalys's presented high acivily nd slabily, but ther application i ited due fo high costs ‘Apart rom that, norenoble metalsuoperted carahs's, mostly based on N have been feported (78). Although these cotalyss were ao active, coke depestion wos sil the problem. Recently, some supported bimetalic catalsls such DS N-CU/BALOy NeFefrrALO, were ako ‘ested for HOO of ‘model compounds and eal bio-ol by ether grours 9,10), “hese catalysts sight improved the product properties ‘compared to coresponcing monometalic catals', but the stably of he support should be corsidered. In adatton, HOO of m-cresolas model over cimetalic eatatsls such oF PINE and P.Co on +-ALO wos studied in vapour phase recent [11). was found ou! that the deaxygenation proceeds vo hwo consecutive steps hyarogerstion of ‘he eromatie ring on the Pt metal follower by i) sdenyaration ofthe formed alcohols onthe alumina suppert 11], Another report ey Sun et ol. nicely shows he effect of PosFe/C catalysts for he gas phose HOG of guaiacol used ‘3s model compound (12). Phenclwas found os ‘ntermectale, Ihe prefered reaction pathway she soturation of tne aromatc ring over the precious metal as akeaay stated Is |). The formed intermediates etn rer ve ate cyclohexanone and cyclohexanol react underng opening fe gaseous products (12). summary of catalysts uses for HDO of model compounds orreal biol can be found in recent reviews (2,12) To overcome the above drowbacks of previous calalts, we have developed non-sufided, nomnoble bimetale cola fer blo-oi #00, Zeotte Seta (H-Bela] was ured ot @ supper! because ofishigh hycrothermal stabil, nigh sorplion capactly ang high acidy,\e. number and srenglh of ace ses, A Series of NiCo/h-bete somes were prepared by incipient weiness imoxegnation and ‘charoctereed by ICP. Ne-hyssorption TPR, XRD, and I, To emonsrate ine deoxygenation efciency and te Understand the effect of te Co substivion on bimetalic, Catalysts, phanolwas used as o model compound for biel EXPERIMENTAL SECTION Catalyst preparation The monometalic ond bimetolic catohs's were orepored 'by impregnation. nti study, NNO,), ‘HO (Merek and CoJNOg), $H,0 [FLka) wore used os precursors for Ni and Co, respecively. the aqueous solution with calculated ‘omounis of ihe precuso%s wos impregncied onto H-8e0 [zeccnem AG] Under siting for 16h at oom temperature, After emoving water by rary evaporator Ine resuting sample wos died at 110°C overnight ond finaly calcines in Gir at 550°C for 4h to get the calcined catalysis oro reaction, the calcined catalyst was activated a 450°C for 4 under hydrogen Row of 100 min, Cotalyst characterization The motal conten! of the calcined colals!s was determines by ICP-OES [71545 Vion). Before anchss, tho somple was gested ino solution of & mot aaus regia and 2 ml of hyorofverie ocid and then filed upto 109 mi. The resulting solution was analysed and the ICP Exoer! sothwore war ured for anatysis 'Niragen physiorption measurements were performed on a Micromeritics ASAP 2010 apparatus at -196 C. rior to ‘analy, he calcined catalysts were degassed ot 200° in vocuum ford, The Xeay powder difaction [XRD measuements used for ‘ne phase composition study were caried out by 0 neta tnete citactometer[X'Per Pro fom Panalycal, Almelo, Netherlands) with Cua radiation (k= 1.418 A, a0 Kv, 40.ma) fond aX'Celorator RIMS Detectex. The samples wore scanned inthe 28 ange of £70". Terperalure progrorrmedreduction [TPR] experiments were performed to invesigate the reductbtty of catalyst os well 168 0 delermine the optimum temperature foreduce the rmeioloxide completely. The experiments were cared out in ‘home-made setup equioped with a colorated TCD (GOM-MAC Instuments for ‘equipped with a homemade reaction col with CaF, Windows. The preveduced catalysts were prateated in 5S Hyyle 2 400°C for 10 min. after coong ta room tomperature and evacuation, the pyridine adsorption by ‘means ofa satuator and a cantor gas was performed unl oluration, Then, the reaction cell was evacuoted to remove pBhyssorbed pytaine and tinaly the desorption of pyridine ‘Was fllowed by heating he sample in vacuum up fo 300 °C ‘ond recording sovcita every 50K. ‘The carbon content of spent catalyst wos determines by ‘elemental analiss conieg out using 9 uespace CHAS. ‘analiser [loco instrument, 19), ‘Activity tests Hyaroceoxygenation of phenol was carga out nan ‘stt0clave (Parr Inerumanis, 25 mi volume. Ia ‘yeical ‘experiment, phenol 0.5], 4,0 {10 g), and catalyst (0025 g. ‘5 wR related to phen were laded to tne reactor. After Tushing wih argon to remove air the autoclave was prestuized with Hi 0 SO bar ot room temperature, The stat lime was recorded when the temporatize reached 250°C. ‘oh then sing speed wor se 10680 rpm. Alter coating to room temperature, the product gas wos analysed by gos ‘chromotogronhy {HP $890) onine om autoctave, The Fauld ‘roducts (organic and aqueous phose] were analysed by ‘nother gas chromatograph [Shimaczy I7A), The nernel Sstandaras mesiylene and | 4udloxane were Used for ‘quantfcaion of erganic and aqueous phases, respectively. ‘Conversion and selactviy were colevlated bases on the {olowing eavations: | Conversion = [males of phenol [al] ~moles of phenal {final #moles of pheno ital x 100% 2, Selectivity = males of carbon atoms in each product/total ‘moles of carton atoms in tne products x 100%. ‘The eorbon balances were coleuated trom tne detected ‘reduc in gos and liquid phase and reaches! 90+ 3% inthis ‘work. Missing carbon was estly due to deposi on Ine surface of he catalysis ond some unknown minor peaks in ‘cnromotograns, [RESULTS AND DISCUSSION Characterization of catalysts The metal contents of tne colchned cotalss os measured by ICP-O55 ate Isteain Table |, The catalts nave Deen ‘Senoted as xNyCo/Beta, where x and y are the rounded ‘contents wi) of nel and cobalt, respectively, Nirogen ‘ootorption studies revealed that adsorption capacities ecroased with increasing metalloading comoared lo pporent svepor H-2et0, Ths can be atirbuted to pore Blocking by the metal species (14).In the case of the ‘calatjls wih the some metal content of 20 wt, Ihe adsorbed niogen quantity wos more o ess ‘ho some, thus ine dsctimination of catalyst Colculsion of hydrogen consumption. After | [sagq | BlbSfagIAEL] | performance can be dscussed in terms of pretreatment in Ny ot 400%C for 30min, tne | -eaM#®_ fo sructure, parle se or acy TPR proles were recorded dung neating ‘onitaa [03 [= The XRD onalyses of some preveduced tne sample in SIHG/Ar om S010 650°C and | [aoweta [200 |= catalysis are sown ia Fgure |. The existence 40 min fratnela fre. eae |__| 8 ‘of metalic N and Co was only observed in Pyraine IR was ured to determine acicty properties. The measurements were cared futon @ Bruker Tensor 27 spectrometer © ens cnr tmaoevree fa ‘he 20Ni/Beia and 20Co/Bata catalysts, respectively. A resolved anal of he pattem for TONTOCo/Bete evidenced that ‘ble. Bemental ona a ne solened eatin eed Ss 2 Teta! degree ——+ Flows 1 X80 pattems of he suppor andredicod eatalnh, {ne metalic reactions didnot match he metalic reflections ‘of monometalic N'er Co samples satitactotly. The high resolution pattern in Figure Tp shows that the discussed refecions appeated in between Ine Niond Ce refections Thitindicotes the formation of N=Co alloy inthe IONITOCoF Beta cotats, Furhnermore, ne refections of metalic species in 1ONIGCo/Geta and 20Co/8ota were smoller and broader tnan the retlecton of Niof 20NiBeta catalyst [see Figwe 1b), hence the aspession of metal paricle se in he 20co/Bera fone ION! OCo/Beta catalyst was pose higher than tat in tne 20Ni/8e%o In order to understand tne reductbilty of metal oxaes curing tne reduction stap, TR of given catalysts was measured and ‘ne profes are shown in Figur 2. For each sample a broad reduction 200s | — 10010000 reduced when increasing he motal loadings as abvious for monometalie Ni estas. Thi can bo attributed tothe raplacerant of Ht fom Bansted ster with onic metalspecies (e.g. Nt) which oct {8 exchangeable cations Furthermore, cl he catalysts with o metalloading of 20wi% showed mote or lest the some total aciaty, However the Bronsted scia concentaton of Nicantoining catalysts was higher than that of Co-containing catalyst, whereos the Lowis acy showed a reverse ftendk Tis observation i yet no full Uundentood. # might be due tothe ferent pore valence sates of Niand Co, Anyway, tne prepared catahyss after reduction possess ¢ combination of Bransiod and predominant Lewis acd ses. ‘Activity tests The eotalvtc performance resus of phen HOO ore sted ln Table 31 wos found thot Ine supper H-Belo wos almost ‘noetive lor his recetion wil les than IS conversion. The monometalic Ni catalyst showed much nigher activ ly ‘han the support and reached 40% and 81% for 1ON/Bet0 ‘and 20Ni/Bera, respectively In the case of monometalic, ‘catalyst 20¢e/86"a, the phenol conversion was less than 7% revealing that Co metalic ses ‘were only Tle active for this reaction. Gn the other sido, the frole worcblined tare wee ct (calmopeatscoeneaneacn | I . hstoton lowe fe So [role reeesning the very 1 / anne | febtedio he cctoatwelgh Ccmeiccroarodvcton rocenes |B] wwocaper | | Ay Kemtne beta cota dang ire scontocmones | f [_aewoa | lNteCof'osnowed noeteg si’ yo reton spe . \ tout acty igh en Reonrondneonery | ovaee | thatotbom moronetate Giteenttercton stengin ctmetot | E PDS cal tome ona 20013 tbocer nine oppor due to i ad cra roocned oR winn2n Gere ocohon cide oie tne | reaction ie, seote ramewor 7 More J Regering he prod! Gib, importantly, the reduction temperature shitted ‘lower temperature in the case of !ONIIOCo/ Beta [dotted curve] compared with monometaie Niand Co eatalsts [sod curves) This demorsirates that tne substution of Co info Note strongly promotes the eduction of N oxides. The acialy ofthe prepored cototss wos measured by monitoring the pyridine edsorotion by means of spectroscony, and the esl are presented in Figure 3 and Table 2. The Branstea ond Lewis acs ste concentations were calculated based on tne malar extinction coatficiont accoraing olteraturs 118) ana the intenstas of he bands fo 1544 en! anc 1448 erin ne spectarecerded a! 10°C (Figure 3) The Srarsted sle gersiy wae fotine prepares calabss. lenge’ owe? TPR profes ofthe propa procure, Howe 9 IRapecta of skated pycine of 150% ‘he overall selectivity toware deonygenctea products (cyclonexane, benzene, cyclonexene) reached 41% 78% and 83% for 20Co/Beta, 1ONY/Beta ana 20Ni/Beta, respectively. Win the lst cotahs, the solectvtias to {cyclohexane ans benzene wore ‘approximately 71 ona S%.In tho case of TONIOCo/BeIa carats! the vera selectivity to deoxygencted prodvels was mote orless the same ‘ot with ZONi/Bela, however Ins catalyst pertormed better than the monemetalic catabsts 20NiBeta ‘and |ONiBera in terms of he seleclviy foward satiated hydrocarbon jeyelohexane]. In other ‘Words, the hyarogenation depth was higher win the bimetare catalyst Regarding the reaction networe, there ars wo possible patnways 10 ein ror ve ae aE ; “amg | ovsen fom aon Fagasrfinge ag | | pctol eer S| ee son elie Herter | seowyaonat rwacgorsien ofthe aromatic ting lolowed! by dehydration for oxygen removal. Ths wos proved in separate tess [not shown here) in our fsb. The latter patnway involves several steps sven as phenol hyorogenation to cyclohexanone (as ako reported in (12) ion is tuner hyarogenate to cyclonexanol Subsequently, cyclohexanol may enydrate to form cyclohexene ond measured by moans of CH analyser. As shownin Figure 4 monometallc Ni catalysis showed cake fermation up to 27 \wiferelated tothe catahst weight Interestingly, 2Co/Bera ‘ord birotalic TONTIOCo/Beta catclyss exhibited lower coke dopestion compared fo manometalic Nicatalsls. Two pposticle explanations fr ths behaviout can be explored. Fit, the formation of N-Co aloy'n 1ONIOCo/Beta catahst reduces monometaic particle see ond possbly reduces the rate of coke formation 20,2). Second, the eonsiserably bbwer Sensted acidly of ION OCo/Bete ane 20Co/Beta ‘catolsts may obo contoute 1 a decrease in coke fermation (22) Anyhow. he substution of NI for Co showed ‘clor postive effect on cateMic performance that not only ‘enhances actviy but cho suppresses coke formation. Sealy be nycrogenatests a —————— cyclohexane. cm emcee | hexane | heme | pentane | hexane | hexanane Farner arotheroxpertment was | H=a—per——po———pat ere ee Corodeu! win no bestpertming | FMB —a aH Cota ohccorseto overs hs = se 8 feocton tie ol he sore conation. | HSHESEaE —t : Tho phon conven cod 97% «he» [ss [sb fond Ine selectivity to deorygenaleg hyoreeatbons achieved 96% Aadltionaly, hwo new products [methyleyclopentone ond bicyclonexane) were observed with small concentrations. he presence of fist product inaoates, tne paralsometzation ofthe carbon skeleton due to ne ovalaole Beanstedstes ofthe support. he latter products formed by condensation of phenol wit intermediate products e.g. cyelonexarol] on acid Sites of support and futher hycrogenation to bicyclohoxcne. This btervation in Ine with previous report 9), To elieate the reasons fr the oulstenaing catalytic perlormance of bimetabe catalyst compared to monometolic cotahss, the sol stole properies of he catalysts wore ‘compared. Ihe 20N/Bet i highly fctive due to nignes' N content fomong al catalysts Substtution ofNi |g fer Co joninactive metal for his reaction) leads lower Nisurfoce fomount. However, is teams 19 = compensated by Co fering highly Gispersed oloys with Nias proved by XRD [Figure 1b]. Asc osu the lotolamount ef active sites is preserved even though the ltalsurlace content ef Nis Fecuced by diution wth Co. The diferen’ zelectvtieg foward cyclohexane as observed with 20NiBeta and TONTOCo/Beta thus might be due to the NACo olloy formation one Ine linked diperson effect ana on the other side due tothe ailerent omoun's of Bansteg ond ews ac Stes iat might afect the adsorption mode of phenolon tne Coals. Further investigation of agsorpton of pherolon the Coals using I technique s necessary to understand ths beervation, [As mentioned above, coke dapastion isa severe problarn in heterogensously catalysed biol upgrading, Therefore, n= cotton content of spent catalysts after? hreaction ime was Shimon tet hhreacson re, Shaye Flour 4 Coke depostin onset cota ater? Jobe Pharot DO on super and prepared cates “yogeton cordon 05 9 phono 10 g,0.002 g cata 90 bora. 247.2 hreacton ns, ‘CONCLUSIONS. In the present study, we reported on an oustanding bimetale catalyst [10Ni10Co/2eta] for panel HOO in ‘aqueous phase. The combination of Nand Cain the bimetalie catahst showed advanced properties that Ccoatly pointed 100 synergic offoct between the two elemen's thei ‘combination no! only increased ‘civ bul abo skronay sified the seleclvly loward saturates hyarocarbon as compared to the ‘analogous monometale somoles Moreover. coke formation on tis Dimetalic catalyst was strongly reduced. The amature of Co into NiBe'a catalyst strongly promotes nickel oxides reduction leacing 12 the formation o# NECe aly with smaller particle see and enhancos the dispersion ef active Nisites on TONiIOCo/Beto. is wath fo hightght hat phoncl conversion was 97% and overa selectiviy to deoxygenated produes reached 96% on 1ONIOGo/eta at 250°C within 5m reaction time. These fndings might provide some valuable sralegies for development of elleciive bio-oil upgrading catch Such tests are now in progres ACKNOWLEDGMENTS The authors wont fo thank MR. Eckstt for N, adsorption suis, Dr M, Scansidar for ¥RO measurements, De. U. Bontrup for pyine-R analysis, Or 4. Hoang for TFR _mecturemen's, Ms. A, Smmula for ICP-CES meosutements i ‘and Ms. A. Leman for CHN anak. Financial uot by 9. AR Ardent SA Khvemova, Ri endetboich, WA, Youle, ‘ne Vietnam O and Gas Group (Perreviainam| and LKAT HU Heetes Appl Coral 817-18, 15-117 (2012 re grotehuly acknowledged. Vo, Sleng. Wong. X He (Uy Y-Uu, X Jang hea long. 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