Propylene production from 11-butene and ethylene catalytic cracking: Study of the performance of HZSMHZSM-5 zeolites and silicoaluminophosphates SAPO--34 and SAPOSAPO SAPO-18 E. Epelde Epelde*, *, A.G. Gayubo Gayubo,, M. Gamero, A.T. Aguayo, J. Bilbao eva.epelde@ehu.es Departamento de Ingeniería Química, Universidad del País Vasco, Apartado 644, 488 Bilbao, Spain
Propylene: key building block for the production of important petrochemicals RESULTS CONCLUSIONS C-C double bond Adjacent methyl group J.S. Plotkin,Catalysis Today,16 (25) 1 1414 Propylene worlwide demand has been increasing at an annual average of 5.7% and by year 215, demand will grow to 15 million tonnes T. Mokrani and M. Scurrell Scurrell, Catalysis Reviews,, 51 (29),1
CONCLUSIONS RESULTS Sustainability 18% Fluid Catalytic Cracking Steam Cracking Crude Oil Natural Gas Coal Biomass Wastes Refinery Coupled Methanol Hydrocarbons Cracking 7% Methane Oxidative Coupling Paraffins Oxidative Dehydrogenation 2 % On purpose technologies (paraffin dehydrogenation, metathesis) Steam Reforming Gasification Syngas Methanol Dimethil Ether Methanol To Olefins OLEFINS Propylene Intensification 1% Fermentation Bio-Ethanol Bio-Oil PROPYLENE Pyrolisis CO 2 D. Mier et al. Chemical Engineering Journal, 16 (21) 76-769769
Catalytic Processes and Waste Valorization www.ehu.es/cpwv SPLITTER Propylene RESULTS MeOH MTO Paraffins Olefins (C 2=, C 4= ) PROPYLENE INTENSIFICATION Propylene CONCLUSIONS Paraffins
RESULTS C 2 -C 4 olefin interconversion Acid catalysts Mechanism of oligomerization-cracking Shape selectivity of the catalysts significant role in propylene yield and selectivity New catalyst development for C 2 -C 4 olefin catalytic cracking Modification of HZSM-5 by metal incorporation (P, P-La, Ni, K ) by dealumination methods (NaOH, steaming ) Silicoaluminophosphates (SAPO-34, SAPO-18) CONCLUSIONS Aim of this work: Study the role of the properties of the catalyst (acidity and shape selectivity) in the intensification fo propylene production from 1-butene and ethylene transformation Conversion-propylene yield selectivity-stability X. Zhu, S. Liu, Y. Song, L. Xu, Catal. Lett., 13 (25) 21-21 G. Zhao, J. Teng, Z. Xie, W. Jin, W. Jang, Q. Chen, Y. Tang, J. Catal., 248 (27) 29-37 A.T. Aguayo, D. Mier, A.G. Gayubo, M. Gamero, J. Bilbao,Ind. Eng. Chem. Res., 49 (21)
CONCLUSIONS RESULTS Catalyst preparation Zeolite HZSM-5 or SAPOs (25 %) Wet extrusion, dry, calcination (55 ºC, 2h) Bentonite Alumina (3 %) (45 %) HZ-3 (SiO 2 /Al 2 O 3 =3) HZ-8 (SiO 2 /Al 2 O 3 =8) HZ-28 (SiO 2 /Al 2 O 3 =28) SAPO-18 SAPO-34 Confer suitable size and mechanical resistance to the catalytic particles in fixed and fluidized bed reactors A matrix with meso- and macroporous structure is formed reducing deactivation by coke increasing hydrothermal stability A.T. Aguayo, A.G. Gayubo, R. Vivanco, M. Olazar, J. Bilbao, Appl. Catal. A.: Gen. 283 (25) 197
CONCLUSIONS RESULTS Catalyst characterization N 2 adsorption-desorption (77 K) Active phase S BET (m 2 /g) V mesopore (cm 3 /g) V micropore (cm 3 /g) HZ-3 448.15.12 HZ-8 556.11.1 HZ-28 512.1.16 SAPO-18 797.8.28 SAPO-34 611.6.24 Catalyst S BET (m 2 /g) V mesopore (cm 3 /g) V micropore (cm 3 /g) HZ-3 22.53.42 HZ-8 29.48.36 HZ-28 231.38.48 SAPO-18 236.23.72 SAPO-34 215.2.46-1 ) V ads (cm 3 g - 5 4 3 2 1 Catalyst (agglomerated) Active phase.2.4.6.8 1 P/P
CONCLUSIONS RESULTS Catalyst characterization DSC (15 ºC)- TPD of NH 3 (up to 55 ºC) Active Total acidity T peak(ºc) in the TPD phase (mmol NH 3 g -1 ) 1st 2nd peak peak HZ-3 1.7 23 34 HZ-8.46 21 395 HZ-28.15 227 325 SAPO-18.37 243 335 SAPO-34.64 258 348 TPD NH 3 (mmol NH3 3/s g catalyst ).8.6.4.2. HZ-3 HZ-8 1 2 3 4 5 6 T (ºC) These acid properties remain after agglomeration HZ-28
Reactor setup Fixed bed reactor Microactivity (316-L SS,D i = 9 mm) Feed: 35 cm 3 min - 1 of 1-butene or ethylene diluted (1%) in He 5 ºC Mass of catalyst:.55 g t= 5 h RESULTS CONCLUSIONS MS5A PPQ Alumina OV1
CONCLUSIONS RESULTS Evaluation criteria used for catalytic performance Conversion (X): F F X = F Yield of i lump: Y i F i = F Selectivity of i lump: Molar flowrates: F = reactant in the feed F= reactant in the outlet stream F i = i-lump in the product stream F Y i (% %) 7 6 5 4 CH4 C2H4 C3H6 C2-C3 C4H1 C5+ BTX X S = i i F -F. Terms expressed as CH 2 equivalent units, corresponding to zero time on stream 3 2 1 5 1 15 2 25 3 t (min) 1..8.6.4.2 HZ-3 catalyst 5 º C, W/F A =24.5 g catalyst h (mol CH 2 ) -1 X
CONCLUSIONS RESULTS Transformation of 1-butene Effect of SiO 2 /Al 2 O 3 in HZM-5 zeolites Y S i,x i (%) 1 5 4 8 3 6 2 4 1 2 CH4 C2H4 C3H6 C2-C3 C4H1X C5+ BTX YC2H4 YC3H6 4 4 8 12 16 2 2428 28 SiO SiO 2 /Al 2 3 ratio 2 /Al 2 O 3 ratio HZ-28 SiO 2 /Al 2 O 3 ratio Butene conversion C 2 H 4 and C 3 H 6 yield C 2 H 4, C 3 H 6 and C 5+ selectivities Hydrogen transfer reactions (catalyzed by strong acid sites) C 2 -C 4 and BTX selectivities
X, Y i (%) Transformation of 1-butene Shape selectivity catalysts 1 8 6 4 HZ-28 SAPO-18 SAPO-34 S i (%) 1 8 6 4 HZ-28 SAPO-18 SAPO-34 CONCLUSIONS RESULTS 2 X YC3H6 YC2H4 2 C2H4 C3H6 C2-C3 C4H1 C5+ BTX Severity of shape selectivity is higher for SAPOs (steric limitations) SC 3 H 6 SAPO-34 is more active than SAPO-18 HIGHER TOTAL ACIDITY AND ACID STRENGTH OF SAPO-34
CONCLUSIONS RESULTS X Transformation of 1-butene Deactivation by coke 1..8.6.4.2. SAPO-34 (4.7 wt%)> SAPO-18 (3.3 wt%) >HZ-28 (2.7 wt%) HZ-28 SAPO-18 SAPO-34 5 1 15 2 25 3 t (min) cat) -1 Mass variation µg (s g c 6 4 2 HZ-28 SAPO-34 SAPO-18 (537 ºC) 2 4 6 8 t (min) (569 ºC) (563 ºC) 7 6 5 4 3 2 T (ºC)
CONCLUSIONS RESULTS Transformation of ethylene Effect of SiO 2 /Al 2 O 3 in HZM-5 zeolites Y i,x (% %) 1 8 6 4 2 7 6 5 X 4 YC4H8 YC3H6 4 8 12 16 2 24 28 SiO 2 /Al 2 O 3 ratio S i (%) 3 2 1 CH4 C3H6 C4H8 C2-C3 C4H1 C5+ BTX 4 8 12 16 2 24 28 SiO 2 /Al 2 O 3 ratio Ethylene conversion requires low values of SiO 2 /Al 2 O 3 ratio HZ-28 SC 3 H 6, YC 3 H 6
X, Y i (%) Transformation of ethylene Shape selectivity catalysts 1 8 6 4 2 HZ-28 SAPO-18 SAPO-34 S i (% %) 1 8 6 4 2 HZ-28 SAPO-18 SAPO-34 CONCLUSIONS RESULTS X YC3H6 YC4H8 C3H6 C4H8 C2-C3 C4H1 C5+ SAPO-34 and SAPO-18 higher ethylene conversion and propylene yield SAPO-18 suitable for the Steric restrictions in selective SAPOs production SC 3 H 6 of Deactivation rate: SAPO-34>>SAPO-18 propylene BTX
CONCLUSIONS RESULTS CONCLUSIONS The moderation of total acidity and acid strength is an appropriate way to modify HZSM-5 zeolites in order to enhance propylene production SAPO-18 shows higher propylene selectivities using both feeds, although the deactivation by coke is slightly faster than for HZ- 28 catalyst The use of SAPO-34 is conditioned by the fast deactivation by coke Operating conditions may have a great influence; the study should be extended to higher temperatures (up to 55 ºC) and feed composed of ethylene/propylene mixtures
ACKNOWLEDGMENTS This work was carried out with the financial support of the Ministry of Science and Innovation of the Spanish Government (Project CTQ21-191888) and of the Department of Education Universities and Research of the Basque Government (Project GIC7/24-IT-22-7). E. Epelde is grateful for the Ph.D. grant from the Department of Education, University and Research of the Basque country (BFI8.122).
THANK YOU eva.epelde@ehu.es