Dibenzothiophene hydrodesulfurization performance over hierarchically porous NiMoS(Si,Zr)/Al2O3 catalysts
The effects of the synthesis method, dopant nature, and porosity on the dibenzothiophene hydrodesulfurization performance of hierarchically porous NiMoS(Si,Zr)/Al2O3 catalysts were studied. Si and Zr incorporation was carried out using grafting (G) and sol-gel (SG) methods. The catalysts were charac...
- Autores:
-
Puello Polo, Esneyder
Checca Huaman, Noemi-Raquel
Toloza, Carlos A. T.
Santolalla Vargas, Carlos E.
Díaz, Yraida
Fals, Jayson
Mendoza, Cesar D.
Stand, Neileth
Márquez, Edgar
Albis Arrieta, Alberto R.
Garcia Macedo, Jorge A.
Méndez, Franklin J.
- Tipo de recurso:
- Article of investigation
- Fecha de publicación:
- 2024
- Institución:
- Corporación Universidad de la Costa
- Repositorio:
- REDICUC - Repositorio CUC
- Idioma:
- eng
- OAI Identifier:
- oai:repositorio.cuc.edu.co:11323/13566
- Acceso en línea:
- https://hdl.handle.net/11323/13566
https://repositorio.cuc.edu.co/
- Palabra clave:
- Hydrodesulfurization
NiMoS(Si,Zr)/Al2O3
Catalysts
- Rights
- openAccess
- License
- Atribución-NoComercial-SinDerivadas 4.0 Internacional (CC BY-NC-ND 4.0)
| id |
RCUC2_8dd0d59f04943f9e7a74d99a42bb0657 |
|---|---|
| oai_identifier_str |
oai:repositorio.cuc.edu.co:11323/13566 |
| network_acronym_str |
RCUC2 |
| network_name_str |
REDICUC - Repositorio CUC |
| repository_id_str |
|
| dc.title.eng.fl_str_mv |
Dibenzothiophene hydrodesulfurization performance over hierarchically porous NiMoS(Si,Zr)/Al2O3 catalysts |
| title |
Dibenzothiophene hydrodesulfurization performance over hierarchically porous NiMoS(Si,Zr)/Al2O3 catalysts |
| spellingShingle |
Dibenzothiophene hydrodesulfurization performance over hierarchically porous NiMoS(Si,Zr)/Al2O3 catalysts Hydrodesulfurization NiMoS(Si,Zr)/Al2O3 Catalysts |
| title_short |
Dibenzothiophene hydrodesulfurization performance over hierarchically porous NiMoS(Si,Zr)/Al2O3 catalysts |
| title_full |
Dibenzothiophene hydrodesulfurization performance over hierarchically porous NiMoS(Si,Zr)/Al2O3 catalysts |
| title_fullStr |
Dibenzothiophene hydrodesulfurization performance over hierarchically porous NiMoS(Si,Zr)/Al2O3 catalysts |
| title_full_unstemmed |
Dibenzothiophene hydrodesulfurization performance over hierarchically porous NiMoS(Si,Zr)/Al2O3 catalysts |
| title_sort |
Dibenzothiophene hydrodesulfurization performance over hierarchically porous NiMoS(Si,Zr)/Al2O3 catalysts |
| dc.creator.fl_str_mv |
Puello Polo, Esneyder Checca Huaman, Noemi-Raquel Toloza, Carlos A. T. Santolalla Vargas, Carlos E. Díaz, Yraida Fals, Jayson Mendoza, Cesar D. Stand, Neileth Márquez, Edgar Albis Arrieta, Alberto R. Garcia Macedo, Jorge A. Méndez, Franklin J. |
| dc.contributor.author.none.fl_str_mv |
Puello Polo, Esneyder Checca Huaman, Noemi-Raquel Toloza, Carlos A. T. Santolalla Vargas, Carlos E. Díaz, Yraida Fals, Jayson Mendoza, Cesar D. Stand, Neileth Márquez, Edgar Albis Arrieta, Alberto R. Garcia Macedo, Jorge A. Méndez, Franklin J. |
| dc.subject.proposal.eng.fl_str_mv |
Hydrodesulfurization NiMoS(Si,Zr)/Al2O3 Catalysts |
| topic |
Hydrodesulfurization NiMoS(Si,Zr)/Al2O3 Catalysts |
| description |
The effects of the synthesis method, dopant nature, and porosity on the dibenzothiophene hydrodesulfurization performance of hierarchically porous NiMoS(Si,Zr)/Al2O3 catalysts were studied. Si and Zr incorporation was carried out using grafting (G) and sol-gel (SG) methods. The catalysts were characterized using scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), N2 physisorption, Hg intrusion porosimetry (MIP), X-ray diffraction, hydrogen temperature-programmed reduction (H2-TPR), pyridine-adsorbed Fourier transform infrared spectroscopy (Py-FTIR), high-resolution transmission electron microscopy (HRTEM), and X-ray photoelectron spectroscopy and then correlated with the kinetic parameters. The experimental results showed that Si- and Zr-modified catalysts promoted different degrees of activity and selectivity. The NMS/A-Zr(G) catalyst displayed the highest HDS activity, followed by NMS/A-Zr(SG), NMS/A, NMS/A-Si(G), and NMS/A-Si(SG) in descending order. The presence of Si and Zr in the catalysts and their incorporation methods were identified as the main reasons for this trend. More active catalysts exhibited an increased total acidity. Furthermore, Lewis sites were positively related to kDDS (CUS sites), while Brönsted sites were related to kHYD (BRIM sites). These modifications were found to enhance various characteristics of the catalysts, such as larger edge sites, Mo and NiMo coordination, and large pores. © 2024 The Authors. Published by American Chemical Society. |
| publishDate |
2024 |
| dc.date.accessioned.none.fl_str_mv |
2024-10-28T12:04:18Z |
| dc.date.available.none.fl_str_mv |
2024-10-28T12:04:18Z |
| dc.date.issued.none.fl_str_mv |
2024-04-30 |
| dc.type.none.fl_str_mv |
Artículo de revista |
| dc.type.coar.none.fl_str_mv |
http://purl.org/coar/resource_type/c_2df8fbb1 |
| dc.type.content.none.fl_str_mv |
Text |
| dc.type.driver.none.fl_str_mv |
info:eu-repo/semantics/article |
| dc.type.redcol.none.fl_str_mv |
http://purl.org/redcol/resource_type/ART |
| dc.type.version.none.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
| dc.type.coarversion.none.fl_str_mv |
http://purl.org/coar/version/c_970fb48d4fbd8a85 |
| format |
http://purl.org/coar/resource_type/c_2df8fbb1 |
| status_str |
publishedVersion |
| dc.identifier.citation.none.fl_str_mv |
Esneyder Puello-Polo, Noemi-Raquel Checca-Huaman, Carlos A. T. Toloza, Carlos E. Santolalla-Vargas, Yraida Díaz, Jayson Fals, Cesar D. Mendoza, Neileth Stand, Edgar Márquez, Alberto R. Albis Arrieta, Jorge A. Garcia-Macedo, and Franklin J. Méndez Industrial & Engineering Chemistry Research 2024 63 (19), 8553-8565 DOI: 10.1021/acs.iecr.3c03242 |
| dc.identifier.issn.none.fl_str_mv |
0888-5885 |
| dc.identifier.uri.none.fl_str_mv |
https://hdl.handle.net/11323/13566 |
| dc.identifier.doi.none.fl_str_mv |
10.1021/acs.iecr.3c03242 |
| dc.identifier.eissn.none.fl_str_mv |
1520-5045 |
| dc.identifier.reponame.none.fl_str_mv |
REDICUC - Repositorio CUC |
| dc.identifier.repourl.none.fl_str_mv |
https://repositorio.cuc.edu.co/ |
| identifier_str_mv |
Esneyder Puello-Polo, Noemi-Raquel Checca-Huaman, Carlos A. T. Toloza, Carlos E. Santolalla-Vargas, Yraida Díaz, Jayson Fals, Cesar D. Mendoza, Neileth Stand, Edgar Márquez, Alberto R. Albis Arrieta, Jorge A. Garcia-Macedo, and Franklin J. Méndez Industrial & Engineering Chemistry Research 2024 63 (19), 8553-8565 DOI: 10.1021/acs.iecr.3c03242 0888-5885 10.1021/acs.iecr.3c03242 1520-5045 REDICUC - Repositorio CUC |
| url |
https://hdl.handle.net/11323/13566 https://repositorio.cuc.edu.co/ |
| dc.language.iso.none.fl_str_mv |
eng |
| language |
eng |
| dc.relation.ispartofjournal.none.fl_str_mv |
Industrial & Engineering Chemistry Research |
| dc.relation.references.none.fl_str_mv |
Wu, J.; Jia, Y.; Cheng, M.; Xia, X. A complex network perspective on embodiment of air pollutants from global oil refining industry. Sci. Total Environ. 2022, 824, No. 153740. Babich, I. V.; Moulijn, J. A. Science and technology of novel processes for deep desulfurization of oil refinery streams: A review. Fuel 2003, 82, 607−631. Im, E.; Seo, H. J.; Kim, D. I.; Hyun, D. C.; Moon, G. D. Bimodally-porous alumina with tunable mesopore and macropore for efficient organic adsorbents. Chem. Eng. J. 2021, 416, No. 129147. Absi-Halabi, M.; Stanislaus, A.; Al-Mughni, T.; Khan, S.; Qamra, A. Hydroprocessing of vacuum residues: Relation between catalyst activity, deactivation and pore size distribution. Fuel 1995, 74, 1211− 1215. Clauset, A.; Moore, C.; Newman, M. E. J. Hierarchical structure and the prediction of missing links in networks. Nature 2008, 453, 98−101. Parlett, C. M. A.; Wilson, K.; Lee, A. F. Hierarchical porous materials: Catalytic applications. Chem. Soc. Rev. 2013, 42, 3876− 3893. Schwieger, W.; Machoke, A. G.; Weissenberger, T.; Inayat, A.; Selvam, T.; Klumpp, M.; Inayat, A. Hierarchy concepts: Classification and preparation strategies for zeolite containing materials with hierarchical porosity. Chem. Soc. Rev. 2016, 45, 3353−3376. Zhang, D.; Liu, W.-Q.; Liu, Y.-A.; Etim, U. J.; Liu, X.-M.; Yan, Z.-F. Pore confinement effect of MoO3/Al2O3 catalyst for deep hydrodesulfurization. Chem. Eng. J. 2017, 330, 706−717. Zhang, D.; Xue, L.; Xu, Y.; Song, L.; Liu, X. Adsorption of 4,6- dimethyldibenzothiophene and collidine over MoO3/γ-Al2O3 catalysts with different pore structures. J. Colloid Interface Sci. 2017, 493, 218− 227. Huang, Y.; Zhou, Z.; Qi, Y.; Li, X.; Cheng, Z.; Yuan, W. Hierarchically macro-/mesoporous structured Co-Mo-Ni/γ-Al2O3 catalyst for the hydrodesulfurization of thiophene. Chem. Eng. J. 2011, 172, 444−451. Liu, X.; Li, X.; Yan, Z. Facile route to prepare bimodal mesoporous γ-Al2O3 as support for highly active CoMo-based hydrodesulfurization catalyst. Appl. Catal., B 2012, 121−122, 50−56. Yang, L.; Peng, C.; Fang, X.; Cheng, Z.; Zhou, Z. Hierarchically macro-mesoporous Ni-Mo/Al2O3 catalysts for hydrodesulfurization of dibenzothiophene. Catal. Commun. 2019, 121, 68−72. Shafiq, I.; Shafique, S.; Akhter, P.; Yang, W.; Hussain, M. Recent developments in alumina supported hydrodesulfurization catalysts for the production of sulfur-free refinery products: A technical review. Catal. Rev. Sci. Eng. 2022, 64, 1−86. Zhang, D.; Duan, A.; Zhao, Z.; Wan, G.; Gao, Z.; Jiang, G.; Chi, K.; Chuang, K. H. Preparation, characterization and hydrotreating performances of ZrO2-Al2O3-supported NiMo catalysts. Catal. Today 2010, 149, 62−68. Jabbarnezhad, P.; Haghighi, M.; Taghavinezhad, P. Sonochemical synthesis of NiMo/Al2O3-ZrO2 nanocatalyst: Effect of sonication and zirconia loading on catalytic properties and performance in hydrodesulfurization reaction. Fuel Process. Technol. 2014, 126, 392− 401. Díaz-García, L.; Santes, V.; Viveros-García, T.; SánchezTrujillo, A.; Ramírez-Salgado, J.; Ornelas, C.; Rodríguez-Castellón, E. Electronic binding of sulfur sites into Al2O3-ZrO2 supports for NiMoS configuration and their application for hydrodesulfurization. Catal. Today 2017, 282, 230−239. Chavez-Esquivel, G.; García-Martínez, J. C.; de los Reyes, J. A.; Suárez-Toriello, V. A.; Vera-Ramírez, M. A.; Huerta, L. The influence of Al2O3 content on Al2O3-ZrO2 composite-textural structural and morphological studies. Mater. Res. Express 2019, 6, No. 105201. Gutiérrez, O. Y.; Klimova, T. E. Effect of the support on the high activity of the (Ni)Mo/ZrO2-SBA-15 catalyst in the simultaneous hydrodesulfurization of DBT and 4,6-DMDBT. J. Catal. 2011, 281, 50−62. Garg, S.; Soni, K.; Kumaran, G. M.; Kumar, M.; Gupta, J. K.; Sharma, L. D.; Dhar, G. M. Effect of Zr-SBA-15 support on catalytic functionalities of Mo, CoMo. NiMo hydrotreating catalysts. Catal. Today 2008, 130, 302−308. da Silva Neto, A. V.; Leite, E. R.; da Silva, V. T.; Zotin, J. L.; Urquieta-González, E. A. NiMoS HDS catalysts: The effect of the Ti and Zr incorporation into the silica support and of the catalyst preparation methodology on the orientation and activity of the formed MoS2 slabs. Appl. Catal., A 2016, 528, 74−85. International Center for Diffraction Data. X’pert HighScore Plus software v.3.0 PANalytical; PDF-2 database, Almelo, Netherlands. Kasztelan, S.; Toulhoat, H.; Grimblot, J.; Bonnelle, J. P. A geometrical model of the active phase of hydrotreating catalysts. Appl. Catal. 1984, 13, 127−159. Hensen, E. J. M.; Kooyman, P. J.; van der Meer, Y.; van der Kraan, A. M.; de Beer, V. H. J.; van Veen, J. A. R.; van Santen, R. A. The relation between morphology and hydrotreating activity for supported MoS2 particles. J. Catal. 2001, 199, 224−235. Li, M.; Li, H.; Jiang, F.; Chu, Y.; Nie, H. The relation between morphology of (Co)MoS2 phases and selective hydrodesulfurization for CoMo catalysts. Catal. Today 2010, 149, 35−39. Ishutenko, D.; Nikulshin, P.; Pimerzin, A. Relation between composition and morphology of K(Co)MoS active phase species and their performances in hydrotreating of model FCC gasoline. Catal. Today 2016, 271, 16−27. Nikulshin, P.; Ishutenko, D.; Anashkin, Y.; Mozhaev, A.; Pimerzin, A. Selective hydrotreating of FCC gasoline over KCoMoP/ Al2O3 catalysts prepared with H3PMo12O40: Effect of metal loading. Fuel 2016, 182, 632−639. Thommes, M.; Kaneko, K.; Neimark-Alexander, V.; OlivierJames, P.; Rodriguez-Reinoso, F.; Rouquerol, J.; Sing-Kenneth, S. W. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure Appl. Chem. 2015, 87, 1051−1069. Rouquerol, J.; Baron, G.; Denoyel, R.; Giesche, H.; Groen, J.; Klobes, P.; Levitz, P.; Neimark, A. V.; Rigby, S.; Skudas, R.; Sing, K.; Thommes, M.; Unger, K. Liquid intrusion and alternative methods for the characterization of macroporous materials (IUPAC Technical Report). Pure Appl. Chem. 2011, 84, 107−136. Vradman, L.; Landau, M. V.; Kantorovich, D.; Koltypin, Y.; Gedanken, A. Evaluation of metal oxide phase assembling mode inside the nanotubular pores of mesostructured silica. Microporous Mesoporous Mater. 2005, 79, 307−318. Semeykina, V. S.; Parkhomchuk, E. V.; Polukhin, A. V.; Parunin, P. D.; Lysikov, A. I.; Ayupov, A. B.; Cherepanova, S. V.; Kanazhevskiy, V. V.; Kaichev, V. V.; Glazneva, T. S.; Zvereva, V. V. CoMoNi catalyst texture and surface properties in heavy oil processing. Part I: Hierarchical macro/mesoporous alumina support. Ind. Eng. Chem. Res. 2016, 55, 3535−3545. Cychosz, K. A.; Guillet-Nicolas, R.; García-Martínez, J.; Thommes, M. Recent advances in the textural characterization of hierarchically structured nanoporous materials. Chem. Soc. Rev. 2017, 46, 389−414. Al-Dalama, K.; Stanislaus, A. Temperature programmed reduction of SiO2-Al2O3 supported Ni, Mo and NiMo catalysts prepared with EDTA. Thermochim. Acta 2011, 520, 67−74. Brito, J. L.; Laine, J.; Pratt, K. C. Temperature-programmed reduction of Ni-Mo oxides. J. Mater. Sci. 1989, 24, 425−431. Zavoianu, ̌ R.; Dias, C. R.; Soares, A. P. V.; Portela, M. F. Oxidative dehydrogenation of i-butane over nanostructured silicasupported NiMoO4 catalysts with low content of active phase. Appl. Catal. A 2006, 298, 40−49. Barzetti, T.; Selli, E.; Moscotti, D.; Forni, L. Pyridine and ammonia as probes for FTIR analysis of solid acid catalysts. J. Chem. Soc., Faraday Trans. 1996, 92, 1401−1407. Reddy, B. M.; Chowdhury, B.; Smirniotis, P. G. An XPS study of the dispersion of MoO3 on TiO2-ZrO2, TiO2-SiO2, TiO2-Al2O3, SiO2-ZrO2, and SiO2-TiO2-ZrO2 mixed oxides. Appl. Catal., A 2001, 211, 19−30. Song, S.; Di, L.; Wu, G.; Dai, W.; Guan, N.; Li, L. Meso-Zr-Albeta zeolite as a robust catalyst for cascade reactions in biomass valorization. Appl. Catal., B 2017, 205, 393−403. Rajagopal, S.; Marzari, J. A.; Miranda, R. Silica-aluminasupported Mo oxide catalysts: Genesis and demise of Bro̷nsted-Lewis acidity. J. Catal. 1995, 151, 192−203. Finocchio, E.; Busca, G.; Rossini, S.; Cornaro, U.; Piccoli, V.; Miglio, R. FT-IR characterization of silicated aluminas, active olefin skeletal isomerization catalysts. Catal. Today 1997, 33, 335−352. Klimova, T.; Peña, L.; Lizama, L.; Salcedo, C.; Gutiérrez, O. Y. Modification of activity and selectivity of NiMo/SBA-15 HDS catalysts by grafting of different metal oxides on the support surface. Ind. Eng. Chem. Res. 2009, 48, 1126−1133. NIST X-ray Photoelectron Spectroscopy Database, NIST Standard Reference Database 20, Version 4.1. Lamkaouane, H.; Ftouhi, H.; Richard-Plouet, M.; Gautier, N.; Stephant, N.; Zazoui, M.; Addou, M.; Cattin, L.; Bernede, ̀ J. C.; Mir, Y.; Louarn, G. Efficient and facile synthetic route of MoO3:MoS2 hybrid thin layer via oxidative reaction of MoS2 nanoflakes. Nanomaterials 2022, 12, 3171. Lin, J.; Ma, C.; Wang, Q.; Xu, Y.; Ma, G.; Wang, J.; Wang, H.; Dong, C.; Zhang, C.; Ding, M. Enhanced low-temperature performance of CO2 methanation over mesoporous Ni/Al2O3-ZrO2 catalysts. Appl. Catal., B 2019, 243, 262−272. Vrinat, M.; Hamon, D.; Breysse, M.; Durand, B.; des Courieres, T. Zirconia- and alumina-supported molybdenum-based catalysts: A comparative study in hydrodesulfurization and hydrogenation reactions. Catal. Today 1994, 20, 273−282. Bataille, F.; Lemberton, J.-L.; Michaud, P.; Pérot, G.; Vrinat, M.; Lemaire, M.; Schulz, E.; Breysse, M.; Kasztelan, S. Alkyldibenzothiophenes hydrodesulfurization-promoter effect, reactivity, and reaction mechanism. J. Catal. 2000, 191, 409−422. Cristol, S.; Paul, J.-F.; Payen, E.; Bougeard, D.; Hutschka, F.; Clémendot, S. DBT derivatives adsorption over molybdenum sulfide catalysts: A theoretical study. J. Catal. 2004, 224, 138−147. Rangarajan, S.; Mavrikakis, M. On the preferred active sites of promoted MoS2 for hydrodesulfurization with minimal organonitrogen inhibition. ACS Catal. 2017, 7, 501−509. Wang, L.; Fang, D.; Wang, Y.; Tian, H.; Liu, J.; Ren, W. Impact of diffusion at the gas/liquid interface on deep hydrodesulfurization of fluid catalytic cracking naphtha. Chem. Eng. J. 2018, 346, 369−375. Wang, T.; Fan, Y.; Wang, X.; Chou, L.; Lin, H. Selectivity enhancement of CoMoS catalysts supported on tri-modal porous Al2O3 for the hydrodesulfurization of fluid catalytic cracking gasoline. Fuel 2015, 157, 171−176. Daage, M.; Chianelli, R. R. Structure-function relations in molybdenum sulfide catalysts: The ″Rim-Edge″ model. J. Catal. 1994, 149, 414−427. Besenbacher, F.; Brorson, M.; Clausen, B. S.; Helveg, S.; Hinnemann, B.; Kibsgaard, J.; Lauritsen, J. V.; Moses, P. G.; No̷rskov, J. K.; Topso̷e, H. Recent STM, DFT and HAADF-STEM studies of sulfide-based hydrotreating catalysts: Insight into mechanistic, structural and particle size effects. Catal. Today 2008, 130, 86−96. |
| dc.relation.citationendpage.none.fl_str_mv |
8565 |
| dc.relation.citationstartpage.none.fl_str_mv |
8553 |
| dc.relation.citationissue.none.fl_str_mv |
19 |
| dc.relation.citationvolume.none.fl_str_mv |
63 |
| dc.rights.eng.fl_str_mv |
© 2024 The Authors. |
| dc.rights.license.none.fl_str_mv |
Atribución-NoComercial-SinDerivadas 4.0 Internacional (CC BY-NC-ND 4.0) |
| dc.rights.uri.none.fl_str_mv |
https://creativecommons.org/licenses/by-nc-nd/4.0/ |
| dc.rights.accessrights.none.fl_str_mv |
info:eu-repo/semantics/openAccess |
| dc.rights.coar.none.fl_str_mv |
http://purl.org/coar/access_right/c_abf2 |
| rights_invalid_str_mv |
Atribución-NoComercial-SinDerivadas 4.0 Internacional (CC BY-NC-ND 4.0) © 2024 The Authors. https://creativecommons.org/licenses/by-nc-nd/4.0/ http://purl.org/coar/access_right/c_abf2 |
| eu_rights_str_mv |
openAccess |
| dc.format.extent.none.fl_str_mv |
13 páginas |
| dc.format.mimetype.none.fl_str_mv |
application/pdf |
| dc.publisher.none.fl_str_mv |
American Chemical Society |
| dc.publisher.place.none.fl_str_mv |
United States |
| publisher.none.fl_str_mv |
American Chemical Society |
| dc.source.none.fl_str_mv |
https://pubs.acs.org/doi/10.1021/acs.iecr.3c03242 |
| institution |
Corporación Universidad de la Costa |
| bitstream.url.fl_str_mv |
https://repositorio.cuc.edu.co/bitstreams/8485d342-7b33-4e22-bd6e-abd38cd3d1f0/download https://repositorio.cuc.edu.co/bitstreams/21706b80-0ca5-42fe-9c8b-80f84700128d/download https://repositorio.cuc.edu.co/bitstreams/b8e039ff-0c96-4dd5-bf46-88f3d9eb8c13/download https://repositorio.cuc.edu.co/bitstreams/f315ca91-eabc-4625-929e-db067f95ea3a/download |
| bitstream.checksum.fl_str_mv |
c3c1a5c25421445ee15d846944a1e09a 73a5432e0b76442b22b026844140d683 f73bb2689bf5c7fedd0db2e02a78e780 5bbdad91cfff94a8ff00276b6b3c76ea |
| bitstream.checksumAlgorithm.fl_str_mv |
MD5 MD5 MD5 MD5 |
| repository.name.fl_str_mv |
Repositorio de la Universidad de la Costa CUC |
| repository.mail.fl_str_mv |
repdigital@cuc.edu.co |
| _version_ |
1828166793851568128 |
| spelling |
Atribución-NoComercial-SinDerivadas 4.0 Internacional (CC BY-NC-ND 4.0)© 2024 The Authors.https://creativecommons.org/licenses/by-nc-nd/4.0/info:eu-repo/semantics/openAccesshttp://purl.org/coar/access_right/c_abf2Puello Polo, EsneyderChecca Huaman, Noemi-RaquelToloza, Carlos A. T.Santolalla Vargas, Carlos E.Díaz, YraidaFals, JaysonMendoza, Cesar D.Stand, NeilethMárquez, EdgarAlbis Arrieta, Alberto R.Garcia Macedo, Jorge A.Méndez, Franklin J.2024-10-28T12:04:18Z2024-10-28T12:04:18Z2024-04-30Esneyder Puello-Polo, Noemi-Raquel Checca-Huaman, Carlos A. T. Toloza, Carlos E. Santolalla-Vargas, Yraida Díaz, Jayson Fals, Cesar D. Mendoza, Neileth Stand, Edgar Márquez, Alberto R. Albis Arrieta, Jorge A. Garcia-Macedo, and Franklin J. Méndez Industrial & Engineering Chemistry Research 2024 63 (19), 8553-8565 DOI: 10.1021/acs.iecr.3c032420888-5885https://hdl.handle.net/11323/1356610.1021/acs.iecr.3c032421520-5045REDICUC - Repositorio CUChttps://repositorio.cuc.edu.co/The effects of the synthesis method, dopant nature, and porosity on the dibenzothiophene hydrodesulfurization performance of hierarchically porous NiMoS(Si,Zr)/Al2O3 catalysts were studied. Si and Zr incorporation was carried out using grafting (G) and sol-gel (SG) methods. The catalysts were characterized using scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), N2 physisorption, Hg intrusion porosimetry (MIP), X-ray diffraction, hydrogen temperature-programmed reduction (H2-TPR), pyridine-adsorbed Fourier transform infrared spectroscopy (Py-FTIR), high-resolution transmission electron microscopy (HRTEM), and X-ray photoelectron spectroscopy and then correlated with the kinetic parameters. The experimental results showed that Si- and Zr-modified catalysts promoted different degrees of activity and selectivity. The NMS/A-Zr(G) catalyst displayed the highest HDS activity, followed by NMS/A-Zr(SG), NMS/A, NMS/A-Si(G), and NMS/A-Si(SG) in descending order. The presence of Si and Zr in the catalysts and their incorporation methods were identified as the main reasons for this trend. More active catalysts exhibited an increased total acidity. Furthermore, Lewis sites were positively related to kDDS (CUS sites), while Brönsted sites were related to kHYD (BRIM sites). These modifications were found to enhance various characteristics of the catalysts, such as larger edge sites, Mo and NiMo coordination, and large pores. © 2024 The Authors. Published by American Chemical Society.13 páginasapplication/pdfengAmerican Chemical SocietyUnited Stateshttps://pubs.acs.org/doi/10.1021/acs.iecr.3c03242Dibenzothiophene hydrodesulfurization performance over hierarchically porous NiMoS(Si,Zr)/Al2O3 catalystsArtículo de revistahttp://purl.org/coar/resource_type/c_2df8fbb1Textinfo:eu-repo/semantics/articlehttp://purl.org/redcol/resource_type/ARTinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/version/c_970fb48d4fbd8a85Industrial & Engineering Chemistry ResearchWu, J.; Jia, Y.; Cheng, M.; Xia, X. A complex network perspective on embodiment of air pollutants from global oil refining industry. Sci. Total Environ. 2022, 824, No. 153740.Babich, I. V.; Moulijn, J. A. Science and technology of novel processes for deep desulfurization of oil refinery streams: A review. Fuel 2003, 82, 607−631.Im, E.; Seo, H. J.; Kim, D. I.; Hyun, D. C.; Moon, G. D. Bimodally-porous alumina with tunable mesopore and macropore for efficient organic adsorbents. Chem. Eng. J. 2021, 416, No. 129147.Absi-Halabi, M.; Stanislaus, A.; Al-Mughni, T.; Khan, S.; Qamra, A. Hydroprocessing of vacuum residues: Relation between catalyst activity, deactivation and pore size distribution. Fuel 1995, 74, 1211− 1215.Clauset, A.; Moore, C.; Newman, M. E. J. Hierarchical structure and the prediction of missing links in networks. Nature 2008, 453, 98−101.Parlett, C. M. A.; Wilson, K.; Lee, A. F. Hierarchical porous materials: Catalytic applications. Chem. Soc. Rev. 2013, 42, 3876− 3893.Schwieger, W.; Machoke, A. G.; Weissenberger, T.; Inayat, A.; Selvam, T.; Klumpp, M.; Inayat, A. Hierarchy concepts: Classification and preparation strategies for zeolite containing materials with hierarchical porosity. Chem. Soc. Rev. 2016, 45, 3353−3376.Zhang, D.; Liu, W.-Q.; Liu, Y.-A.; Etim, U. J.; Liu, X.-M.; Yan, Z.-F. Pore confinement effect of MoO3/Al2O3 catalyst for deep hydrodesulfurization. Chem. Eng. J. 2017, 330, 706−717.Zhang, D.; Xue, L.; Xu, Y.; Song, L.; Liu, X. Adsorption of 4,6- dimethyldibenzothiophene and collidine over MoO3/γ-Al2O3 catalysts with different pore structures. J. Colloid Interface Sci. 2017, 493, 218− 227.Huang, Y.; Zhou, Z.; Qi, Y.; Li, X.; Cheng, Z.; Yuan, W. Hierarchically macro-/mesoporous structured Co-Mo-Ni/γ-Al2O3 catalyst for the hydrodesulfurization of thiophene. Chem. Eng. J. 2011, 172, 444−451.Liu, X.; Li, X.; Yan, Z. Facile route to prepare bimodal mesoporous γ-Al2O3 as support for highly active CoMo-based hydrodesulfurization catalyst. Appl. Catal., B 2012, 121−122, 50−56.Yang, L.; Peng, C.; Fang, X.; Cheng, Z.; Zhou, Z. Hierarchically macro-mesoporous Ni-Mo/Al2O3 catalysts for hydrodesulfurization of dibenzothiophene. Catal. Commun. 2019, 121, 68−72.Shafiq, I.; Shafique, S.; Akhter, P.; Yang, W.; Hussain, M. Recent developments in alumina supported hydrodesulfurization catalysts for the production of sulfur-free refinery products: A technical review. Catal. Rev. Sci. Eng. 2022, 64, 1−86.Zhang, D.; Duan, A.; Zhao, Z.; Wan, G.; Gao, Z.; Jiang, G.; Chi, K.; Chuang, K. H. Preparation, characterization and hydrotreating performances of ZrO2-Al2O3-supported NiMo catalysts. Catal. Today 2010, 149, 62−68.Jabbarnezhad, P.; Haghighi, M.; Taghavinezhad, P. Sonochemical synthesis of NiMo/Al2O3-ZrO2 nanocatalyst: Effect of sonication and zirconia loading on catalytic properties and performance in hydrodesulfurization reaction. Fuel Process. Technol. 2014, 126, 392− 401.Díaz-García, L.; Santes, V.; Viveros-García, T.; SánchezTrujillo, A.; Ramírez-Salgado, J.; Ornelas, C.; Rodríguez-Castellón, E. Electronic binding of sulfur sites into Al2O3-ZrO2 supports for NiMoS configuration and their application for hydrodesulfurization. Catal. Today 2017, 282, 230−239.Chavez-Esquivel, G.; García-Martínez, J. C.; de los Reyes, J. A.; Suárez-Toriello, V. A.; Vera-Ramírez, M. A.; Huerta, L. The influence of Al2O3 content on Al2O3-ZrO2 composite-textural structural and morphological studies. Mater. Res. Express 2019, 6, No. 105201.Gutiérrez, O. Y.; Klimova, T. E. Effect of the support on the high activity of the (Ni)Mo/ZrO2-SBA-15 catalyst in the simultaneous hydrodesulfurization of DBT and 4,6-DMDBT. J. Catal. 2011, 281, 50−62.Garg, S.; Soni, K.; Kumaran, G. M.; Kumar, M.; Gupta, J. K.; Sharma, L. D.; Dhar, G. M. Effect of Zr-SBA-15 support on catalytic functionalities of Mo, CoMo. NiMo hydrotreating catalysts. Catal. Today 2008, 130, 302−308.da Silva Neto, A. V.; Leite, E. R.; da Silva, V. T.; Zotin, J. L.; Urquieta-González, E. A. NiMoS HDS catalysts: The effect of the Ti and Zr incorporation into the silica support and of the catalyst preparation methodology on the orientation and activity of the formed MoS2 slabs. Appl. Catal., A 2016, 528, 74−85.International Center for Diffraction Data. X’pert HighScore Plus software v.3.0 PANalytical; PDF-2 database, Almelo, Netherlands.Kasztelan, S.; Toulhoat, H.; Grimblot, J.; Bonnelle, J. P. A geometrical model of the active phase of hydrotreating catalysts. Appl. Catal. 1984, 13, 127−159.Hensen, E. J. M.; Kooyman, P. J.; van der Meer, Y.; van der Kraan, A. M.; de Beer, V. H. J.; van Veen, J. A. R.; van Santen, R. A. The relation between morphology and hydrotreating activity for supported MoS2 particles. J. Catal. 2001, 199, 224−235.Li, M.; Li, H.; Jiang, F.; Chu, Y.; Nie, H. The relation between morphology of (Co)MoS2 phases and selective hydrodesulfurization for CoMo catalysts. Catal. Today 2010, 149, 35−39.Ishutenko, D.; Nikulshin, P.; Pimerzin, A. Relation between composition and morphology of K(Co)MoS active phase species and their performances in hydrotreating of model FCC gasoline. Catal. Today 2016, 271, 16−27.Nikulshin, P.; Ishutenko, D.; Anashkin, Y.; Mozhaev, A.; Pimerzin, A. Selective hydrotreating of FCC gasoline over KCoMoP/ Al2O3 catalysts prepared with H3PMo12O40: Effect of metal loading. Fuel 2016, 182, 632−639.Thommes, M.; Kaneko, K.; Neimark-Alexander, V.; OlivierJames, P.; Rodriguez-Reinoso, F.; Rouquerol, J.; Sing-Kenneth, S. W. Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution (IUPAC Technical Report). Pure Appl. Chem. 2015, 87, 1051−1069.Rouquerol, J.; Baron, G.; Denoyel, R.; Giesche, H.; Groen, J.; Klobes, P.; Levitz, P.; Neimark, A. V.; Rigby, S.; Skudas, R.; Sing, K.; Thommes, M.; Unger, K. Liquid intrusion and alternative methods for the characterization of macroporous materials (IUPAC Technical Report). Pure Appl. Chem. 2011, 84, 107−136.Vradman, L.; Landau, M. V.; Kantorovich, D.; Koltypin, Y.; Gedanken, A. Evaluation of metal oxide phase assembling mode inside the nanotubular pores of mesostructured silica. Microporous Mesoporous Mater. 2005, 79, 307−318.Semeykina, V. S.; Parkhomchuk, E. V.; Polukhin, A. V.; Parunin, P. D.; Lysikov, A. I.; Ayupov, A. B.; Cherepanova, S. V.; Kanazhevskiy, V. V.; Kaichev, V. V.; Glazneva, T. S.; Zvereva, V. V. CoMoNi catalyst texture and surface properties in heavy oil processing. Part I: Hierarchical macro/mesoporous alumina support. Ind. Eng. Chem. Res. 2016, 55, 3535−3545.Cychosz, K. A.; Guillet-Nicolas, R.; García-Martínez, J.; Thommes, M. Recent advances in the textural characterization of hierarchically structured nanoporous materials. Chem. Soc. Rev. 2017, 46, 389−414.Al-Dalama, K.; Stanislaus, A. Temperature programmed reduction of SiO2-Al2O3 supported Ni, Mo and NiMo catalysts prepared with EDTA. Thermochim. Acta 2011, 520, 67−74.Brito, J. L.; Laine, J.; Pratt, K. C. Temperature-programmed reduction of Ni-Mo oxides. J. Mater. Sci. 1989, 24, 425−431.Zavoianu, ̌ R.; Dias, C. R.; Soares, A. P. V.; Portela, M. F. Oxidative dehydrogenation of i-butane over nanostructured silicasupported NiMoO4 catalysts with low content of active phase. Appl. Catal. A 2006, 298, 40−49.Barzetti, T.; Selli, E.; Moscotti, D.; Forni, L. Pyridine and ammonia as probes for FTIR analysis of solid acid catalysts. J. Chem. Soc., Faraday Trans. 1996, 92, 1401−1407.Reddy, B. M.; Chowdhury, B.; Smirniotis, P. G. An XPS study of the dispersion of MoO3 on TiO2-ZrO2, TiO2-SiO2, TiO2-Al2O3, SiO2-ZrO2, and SiO2-TiO2-ZrO2 mixed oxides. Appl. Catal., A 2001, 211, 19−30.Song, S.; Di, L.; Wu, G.; Dai, W.; Guan, N.; Li, L. Meso-Zr-Albeta zeolite as a robust catalyst for cascade reactions in biomass valorization. Appl. Catal., B 2017, 205, 393−403.Rajagopal, S.; Marzari, J. A.; Miranda, R. Silica-aluminasupported Mo oxide catalysts: Genesis and demise of Bro̷nsted-Lewis acidity. J. Catal. 1995, 151, 192−203.Finocchio, E.; Busca, G.; Rossini, S.; Cornaro, U.; Piccoli, V.; Miglio, R. FT-IR characterization of silicated aluminas, active olefin skeletal isomerization catalysts. Catal. Today 1997, 33, 335−352.Klimova, T.; Peña, L.; Lizama, L.; Salcedo, C.; Gutiérrez, O. Y. Modification of activity and selectivity of NiMo/SBA-15 HDS catalysts by grafting of different metal oxides on the support surface. Ind. Eng. Chem. Res. 2009, 48, 1126−1133.NIST X-ray Photoelectron Spectroscopy Database, NIST Standard Reference Database 20, Version 4.1.Lamkaouane, H.; Ftouhi, H.; Richard-Plouet, M.; Gautier, N.; Stephant, N.; Zazoui, M.; Addou, M.; Cattin, L.; Bernede, ̀ J. C.; Mir, Y.; Louarn, G. Efficient and facile synthetic route of MoO3:MoS2 hybrid thin layer via oxidative reaction of MoS2 nanoflakes. Nanomaterials 2022, 12, 3171.Lin, J.; Ma, C.; Wang, Q.; Xu, Y.; Ma, G.; Wang, J.; Wang, H.; Dong, C.; Zhang, C.; Ding, M. Enhanced low-temperature performance of CO2 methanation over mesoporous Ni/Al2O3-ZrO2 catalysts. Appl. Catal., B 2019, 243, 262−272.Vrinat, M.; Hamon, D.; Breysse, M.; Durand, B.; des Courieres, T. Zirconia- and alumina-supported molybdenum-based catalysts: A comparative study in hydrodesulfurization and hydrogenation reactions. Catal. Today 1994, 20, 273−282.Bataille, F.; Lemberton, J.-L.; Michaud, P.; Pérot, G.; Vrinat, M.; Lemaire, M.; Schulz, E.; Breysse, M.; Kasztelan, S. Alkyldibenzothiophenes hydrodesulfurization-promoter effect, reactivity, and reaction mechanism. J. Catal. 2000, 191, 409−422.Cristol, S.; Paul, J.-F.; Payen, E.; Bougeard, D.; Hutschka, F.; Clémendot, S. DBT derivatives adsorption over molybdenum sulfide catalysts: A theoretical study. J. Catal. 2004, 224, 138−147.Rangarajan, S.; Mavrikakis, M. On the preferred active sites of promoted MoS2 for hydrodesulfurization with minimal organonitrogen inhibition. ACS Catal. 2017, 7, 501−509.Wang, L.; Fang, D.; Wang, Y.; Tian, H.; Liu, J.; Ren, W. Impact of diffusion at the gas/liquid interface on deep hydrodesulfurization of fluid catalytic cracking naphtha. Chem. Eng. J. 2018, 346, 369−375.Wang, T.; Fan, Y.; Wang, X.; Chou, L.; Lin, H. Selectivity enhancement of CoMoS catalysts supported on tri-modal porous Al2O3 for the hydrodesulfurization of fluid catalytic cracking gasoline. Fuel 2015, 157, 171−176.Daage, M.; Chianelli, R. R. Structure-function relations in molybdenum sulfide catalysts: The ″Rim-Edge″ model. J. Catal. 1994, 149, 414−427.Besenbacher, F.; Brorson, M.; Clausen, B. S.; Helveg, S.; Hinnemann, B.; Kibsgaard, J.; Lauritsen, J. V.; Moses, P. G.; No̷rskov, J. K.; Topso̷e, H. Recent STM, DFT and HAADF-STEM studies of sulfide-based hydrotreating catalysts: Insight into mechanistic, structural and particle size effects. Catal. Today 2008, 130, 86−96.856585531963HydrodesulfurizationNiMoS(Si,Zr)/Al2O3CatalystsPublicationORIGINALDibenzothiophene Hydrodesulfurization Performance OverHierarchically Porous.pdfDibenzothiophene Hydrodesulfurization Performance OverHierarchically Porous.pdfapplication/pdf11382937https://repositorio.cuc.edu.co/bitstreams/8485d342-7b33-4e22-bd6e-abd38cd3d1f0/downloadc3c1a5c25421445ee15d846944a1e09aMD51LICENSElicense.txtlicense.txttext/plain; charset=utf-815543https://repositorio.cuc.edu.co/bitstreams/21706b80-0ca5-42fe-9c8b-80f84700128d/download73a5432e0b76442b22b026844140d683MD52TEXTDibenzothiophene Hydrodesulfurization Performance OverHierarchically Porous.pdf.txtDibenzothiophene Hydrodesulfurization Performance OverHierarchically Porous.pdf.txtExtracted texttext/plain88426https://repositorio.cuc.edu.co/bitstreams/b8e039ff-0c96-4dd5-bf46-88f3d9eb8c13/downloadf73bb2689bf5c7fedd0db2e02a78e780MD53THUMBNAILDibenzothiophene Hydrodesulfurization Performance OverHierarchically Porous.pdf.jpgDibenzothiophene Hydrodesulfurization Performance OverHierarchically Porous.pdf.jpgGenerated Thumbnailimage/jpeg18726https://repositorio.cuc.edu.co/bitstreams/f315ca91-eabc-4625-929e-db067f95ea3a/download5bbdad91cfff94a8ff00276b6b3c76eaMD5411323/13566oai:repositorio.cuc.edu.co:11323/135662024-10-29 03:01:55.995https://creativecommons.org/licenses/by-nc-nd/4.0/© 2024 The Authors.open.accesshttps://repositorio.cuc.edu.coRepositorio de la Universidad de la Costa CUCrepdigital@cuc.edu.coPHA+TEEgT0JSQSAoVEFMIFkgQ09NTyBTRSBERUZJTkUgTcOBUyBBREVMQU5URSkgU0UgT1RPUkdBIEJBSk8gTE9TIFRFUk1JTk9TIERFIEVTVEEgTElDRU5DSUEgUMOaQkxJQ0EgREUgQ1JFQVRJVkUgQ09NTU9OUyAo4oCcTFBDQ+KAnSBPIOKAnExJQ0VOQ0lB4oCdKS4gTEEgT0JSQSBFU1TDgSBQUk9URUdJREEgUE9SIERFUkVDSE9TIERFIEFVVE9SIFkvVSBPVFJBUyBMRVlFUyBBUExJQ0FCTEVTLiBRVUVEQSBQUk9ISUJJRE8gQ1VBTFFVSUVSIFVTTyBRVUUgU0UgSEFHQSBERSBMQSBPQlJBIFFVRSBOTyBDVUVOVEUgQ09OIExBIEFVVE9SSVpBQ0nDk04gUEVSVElORU5URSBERSBDT05GT1JNSURBRCBDT04gTE9TIFTDiVJNSU5PUyBERSBFU1RBIExJQ0VOQ0lBIFkgREUgTEEgTEVZIERFIERFUkVDSE8gREUgQVVUT1IuPC9wPgo8cD5NRURJQU5URSBFTCBFSkVSQ0lDSU8gREUgQ1VBTFFVSUVSQSBERSBMT1MgREVSRUNIT1MgUVVFIFNFIE9UT1JHQU4gRU4gRVNUQSBMSUNFTkNJQSwgVVNURUQgQUNFUFRBIFkgQUNVRVJEQSBRVUVEQVIgT0JMSUdBRE8gRU4gTE9TIFRFUk1JTk9TIFFVRSBTRSBTRcORQUxBTiBFTiBFTExBLiBFTCBMSUNFTkNJQU5URSBDT05DRURFIEEgVVNURUQgTE9TIERFUkVDSE9TIENPTlRFTklET1MgRU4gRVNUQSBMSUNFTkNJQSBDT05ESUNJT05BRE9TIEEgTEEgQUNFUFRBQ0nDk04gREUgU1VTIFRFUk1JTk9TIFkgQ09ORElDSU9ORVMuPC9wPgo8b2wgdHlwZT0iMSI+CiAgPGxpPgogICAgRGVmaW5pY2lvbmVzCiAgICA8b2wgdHlwZT1hPgogICAgICA8bGk+T2JyYSBDb2xlY3RpdmEgZXMgdW5hIG9icmEsIHRhbCBjb21vIHVuYSBwdWJsaWNhY2nDs24gcGVyacOzZGljYSwgdW5hIGFudG9sb2fDrWEsIG8gdW5hIGVuY2ljbG9wZWRpYSwgZW4gbGEgcXVlIGxhIG9icmEgZW4gc3UgdG90YWxpZGFkLCBzaW4gbW9kaWZpY2FjacOzbiBhbGd1bmEsIGp1bnRvIGNvbiB1biBncnVwbyBkZSBvdHJhcyBjb250cmlidWNpb25lcyBxdWUgY29uc3RpdHV5ZW4gb2JyYXMgc2VwYXJhZGFzIGUgaW5kZXBlbmRpZW50ZXMgZW4gc8OtIG1pc21hcywgc2UgaW50ZWdyYW4gZW4gdW4gdG9kbyBjb2xlY3Rpdm8uIFVuYSBPYnJhIHF1ZSBjb25zdGl0dXllIHVuYSBvYnJhIGNvbGVjdGl2YSBubyBzZSBjb25zaWRlcmFyw6EgdW5hIE9icmEgRGVyaXZhZGEgKGNvbW8gc2UgZGVmaW5lIGFiYWpvKSBwYXJhIGxvcyBwcm9ww7NzaXRvcyBkZSBlc3RhIGxpY2VuY2lhLiBhcXVlbGxhIHByb2R1Y2lkYSBwb3IgdW4gZ3J1cG8gZGUgYXV0b3JlcywgZW4gcXVlIGxhIE9icmEgc2UgZW5jdWVudHJhIHNpbiBtb2RpZmljYWNpb25lcywganVudG8gY29uIHVuYSBjaWVydGEgY2FudGlkYWQgZGUgb3RyYXMgY29udHJpYnVjaW9uZXMsIHF1ZSBjb25zdGl0dXllbiBlbiBzw60gbWlzbW9zIHRyYWJham9zIHNlcGFyYWRvcyBlIGluZGVwZW5kaWVudGVzLCBxdWUgc29uIGludGVncmFkb3MgYWwgdG9kbyBjb2xlY3Rpdm8sIHRhbGVzIGNvbW8gcHVibGljYWNpb25lcyBwZXJpw7NkaWNhcywgYW50b2xvZ8OtYXMgbyBlbmNpY2xvcGVkaWFzLjwvbGk+CiAgICAgIDxsaT5PYnJhIERlcml2YWRhIHNpZ25pZmljYSB1bmEgb2JyYSBiYXNhZGEgZW4gbGEgb2JyYSBvYmpldG8gZGUgZXN0YSBsaWNlbmNpYSBvIGVuIMOpc3RhIHkgb3RyYXMgb2JyYXMgcHJlZXhpc3RlbnRlcywgdGFsZXMgY29tbyB0cmFkdWNjaW9uZXMsIGFycmVnbG9zIG11c2ljYWxlcywgZHJhbWF0aXphY2lvbmVzLCDigJxmaWNjaW9uYWxpemFjaW9uZXPigJ0sIHZlcnNpb25lcyBwYXJhIGNpbmUsIOKAnGdyYWJhY2lvbmVzIGRlIHNvbmlkb+KAnSwgcmVwcm9kdWNjaW9uZXMgZGUgYXJ0ZSwgcmVzw7ptZW5lcywgY29uZGVuc2FjaW9uZXMsIG8gY3VhbHF1aWVyIG90cmEgZW4gbGEgcXVlIGxhIG9icmEgcHVlZGEgc2VyIHRyYW5zZm9ybWFkYSwgY2FtYmlhZGEgbyBhZGFwdGFkYSwgZXhjZXB0byBhcXVlbGxhcyBxdWUgY29uc3RpdHV5YW4gdW5hIG9icmEgY29sZWN0aXZhLCBsYXMgcXVlIG5vIHNlcsOhbiBjb25zaWRlcmFkYXMgdW5hIG9icmEgZGVyaXZhZGEgcGFyYSBlZmVjdG9zIGRlIGVzdGEgbGljZW5jaWEuIChQYXJhIGV2aXRhciBkdWRhcywgZW4gZWwgY2FzbyBkZSBxdWUgbGEgT2JyYSBzZWEgdW5hIGNvbXBvc2ljacOzbiBtdXNpY2FsIG8gdW5hIGdyYWJhY2nDs24gc29ub3JhLCBwYXJhIGxvcyBlZmVjdG9zIGRlIGVzdGEgTGljZW5jaWEgbGEgc2luY3Jvbml6YWNpw7NuIHRlbXBvcmFsIGRlIGxhIE9icmEgY29uIHVuYSBpbWFnZW4gZW4gbW92aW1pZW50byBzZSBjb25zaWRlcmFyw6EgdW5hIE9icmEgRGVyaXZhZGEgcGFyYSBsb3MgZmluZXMgZGUgZXN0YSBsaWNlbmNpYSkuPC9saT4KICAgICAgPGxpPkxpY2VuY2lhbnRlLCBlcyBlbCBpbmRpdmlkdW8gbyBsYSBlbnRpZGFkIHRpdHVsYXIgZGUgbG9zIGRlcmVjaG9zIGRlIGF1dG9yIHF1ZSBvZnJlY2UgbGEgT2JyYSBlbiBjb25mb3JtaWRhZCBjb24gbGFzIGNvbmRpY2lvbmVzIGRlIGVzdGEgTGljZW5jaWEuPC9saT4KICAgICAgPGxpPkF1dG9yIG9yaWdpbmFsLCBlcyBlbCBpbmRpdmlkdW8gcXVlIGNyZcOzIGxhIE9icmEuPC9saT4KICAgICAgPGxpPk9icmEsIGVzIGFxdWVsbGEgb2JyYSBzdXNjZXB0aWJsZSBkZSBwcm90ZWNjacOzbiBwb3IgZWwgcsOpZ2ltZW4gZGUgRGVyZWNobyBkZSBBdXRvciB5IHF1ZSBlcyBvZnJlY2lkYSBlbiBsb3MgdMOpcm1pbm9zIGRlIGVzdGEgbGljZW5jaWE8L2xpPgogICAgICA8bGk+VXN0ZWQsIGVzIGVsIGluZGl2aWR1byBvIGxhIGVudGlkYWQgcXVlIGVqZXJjaXRhIGxvcyBkZXJlY2hvcyBvdG9yZ2Fkb3MgYWwgYW1wYXJvIGRlIGVzdGEgTGljZW5jaWEgeSBxdWUgY29uIGFudGVyaW9yaWRhZCBubyBoYSB2aW9sYWRvIGxhcyBjb25kaWNpb25lcyBkZSBsYSBtaXNtYSByZXNwZWN0byBhIGxhIE9icmEsIG8gcXVlIGhheWEgb2J0ZW5pZG8gYXV0b3JpemFjacOzbiBleHByZXNhIHBvciBwYXJ0ZSBkZWwgTGljZW5jaWFudGUgcGFyYSBlamVyY2VyIGxvcyBkZXJlY2hvcyBhbCBhbXBhcm8gZGUgZXN0YSBMaWNlbmNpYSBwZXNlIGEgdW5hIHZpb2xhY2nDs24gYW50ZXJpb3IuPC9saT4KICAgIDwvb2w+CiAgPC9saT4KICA8YnIvPgogIDxsaT4KICAgIERlcmVjaG9zIGRlIFVzb3MgSG9ucmFkb3MgeSBleGNlcGNpb25lcyBMZWdhbGVzLgogICAgPHA+TmFkYSBlbiBlc3RhIExpY2VuY2lhIHBvZHLDoSBzZXIgaW50ZXJwcmV0YWRvIGNvbW8gdW5hIGRpc21pbnVjacOzbiwgbGltaXRhY2nDs24gbyByZXN0cmljY2nDs24gZGUgbG9zIGRlcmVjaG9zIGRlcml2YWRvcyBkZWwgdXNvIGhvbnJhZG8geSBvdHJhcyBsaW1pdGFjaW9uZXMgbyBleGNlcGNpb25lcyBhIGxvcyBkZXJlY2hvcyBkZWwgYXV0b3IgYmFqbyBlbCByw6lnaW1lbiBsZWdhbCB2aWdlbnRlIG8gZGVyaXZhZG8gZGUgY3VhbHF1aWVyIG90cmEgbm9ybWEgcXVlIHNlIGxlIGFwbGlxdWUuPC9wPgogIDwvbGk+CiAgPGxpPgogICAgQ29uY2VzacOzbiBkZSBsYSBMaWNlbmNpYS4KICAgIDxwPkJham8gbG9zIHTDqXJtaW5vcyB5IGNvbmRpY2lvbmVzIGRlIGVzdGEgTGljZW5jaWEsIGVsIExpY2VuY2lhbnRlIG90b3JnYSBhIFVzdGVkIHVuYSBsaWNlbmNpYSBtdW5kaWFsLCBsaWJyZSBkZSByZWdhbMOtYXMsIG5vIGV4Y2x1c2l2YSB5IHBlcnBldHVhIChkdXJhbnRlIHRvZG8gZWwgcGVyw61vZG8gZGUgdmlnZW5jaWEgZGUgbG9zIGRlcmVjaG9zIGRlIGF1dG9yKSBwYXJhIGVqZXJjZXIgZXN0b3MgZGVyZWNob3Mgc29icmUgbGEgT2JyYSB0YWwgeSBjb21vIHNlIGluZGljYSBhIGNvbnRpbnVhY2nDs246PC9wPgogICAgPG9sIHR5cGU9ImEiPgogICAgICA8bGk+UmVwcm9kdWNpciBsYSBPYnJhLCBpbmNvcnBvcmFyIGxhIE9icmEgZW4gdW5hIG8gbcOhcyBPYnJhcyBDb2xlY3RpdmFzLCB5IHJlcHJvZHVjaXIgbGEgT2JyYSBpbmNvcnBvcmFkYSBlbiBsYXMgT2JyYXMgQ29sZWN0aXZhcy48L2xpPgogICAgICA8bGk+RGlzdHJpYnVpciBjb3BpYXMgbyBmb25vZ3JhbWFzIGRlIGxhcyBPYnJhcywgZXhoaWJpcmxhcyBww7pibGljYW1lbnRlLCBlamVjdXRhcmxhcyBww7pibGljYW1lbnRlIHkvbyBwb25lcmxhcyBhIGRpc3Bvc2ljacOzbiBww7pibGljYSwgaW5jbHV5w6luZG9sYXMgY29tbyBpbmNvcnBvcmFkYXMgZW4gT2JyYXMgQ29sZWN0aXZhcywgc2Vnw7puIGNvcnJlc3BvbmRhLjwvbGk+CiAgICAgIDxsaT5EaXN0cmlidWlyIGNvcGlhcyBkZSBsYXMgT2JyYXMgRGVyaXZhZGFzIHF1ZSBzZSBnZW5lcmVuLCBleGhpYmlybGFzIHDDumJsaWNhbWVudGUsIGVqZWN1dGFybGFzIHDDumJsaWNhbWVudGUgeS9vIHBvbmVybGFzIGEgZGlzcG9zaWNpw7NuIHDDumJsaWNhLjwvbGk+CiAgICA8L29sPgogICAgPHA+TG9zIGRlcmVjaG9zIG1lbmNpb25hZG9zIGFudGVyaW9ybWVudGUgcHVlZGVuIHNlciBlamVyY2lkb3MgZW4gdG9kb3MgbG9zIG1lZGlvcyB5IGZvcm1hdG9zLCBhY3R1YWxtZW50ZSBjb25vY2lkb3MgbyBxdWUgc2UgaW52ZW50ZW4gZW4gZWwgZnV0dXJvLiBMb3MgZGVyZWNob3MgYW50ZXMgbWVuY2lvbmFkb3MgaW5jbHV5ZW4gZWwgZGVyZWNobyBhIHJlYWxpemFyIGRpY2hhcyBtb2RpZmljYWNpb25lcyBlbiBsYSBtZWRpZGEgcXVlIHNlYW4gdMOpY25pY2FtZW50ZSBuZWNlc2FyaWFzIHBhcmEgZWplcmNlciBsb3MgZGVyZWNob3MgZW4gb3RybyBtZWRpbyBvIGZvcm1hdG9zLCBwZXJvIGRlIG90cmEgbWFuZXJhIHVzdGVkIG5vIGVzdMOhIGF1dG9yaXphZG8gcGFyYSByZWFsaXphciBvYnJhcyBkZXJpdmFkYXMuIFRvZG9zIGxvcyBkZXJlY2hvcyBubyBvdG9yZ2Fkb3MgZXhwcmVzYW1lbnRlIHBvciBlbCBMaWNlbmNpYW50ZSBxdWVkYW4gcG9yIGVzdGUgbWVkaW8gcmVzZXJ2YWRvcywgaW5jbHV5ZW5kbyBwZXJvIHNpbiBsaW1pdGFyc2UgYSBhcXVlbGxvcyBxdWUgc2UgbWVuY2lvbmFuIGVuIGxhcyBzZWNjaW9uZXMgNChkKSB5IDQoZSkuPC9wPgogIDwvbGk+CiAgPGJyLz4KICA8bGk+CiAgICBSZXN0cmljY2lvbmVzLgogICAgPHA+TGEgbGljZW5jaWEgb3RvcmdhZGEgZW4gbGEgYW50ZXJpb3IgU2VjY2nDs24gMyBlc3TDoSBleHByZXNhbWVudGUgc3VqZXRhIHkgbGltaXRhZGEgcG9yIGxhcyBzaWd1aWVudGVzIHJlc3RyaWNjaW9uZXM6PC9wPgogICAgPG9sIHR5cGU9ImEiPgogICAgICA8bGk+VXN0ZWQgcHVlZGUgZGlzdHJpYnVpciwgZXhoaWJpciBww7pibGljYW1lbnRlLCBlamVjdXRhciBww7pibGljYW1lbnRlLCBvIHBvbmVyIGEgZGlzcG9zaWNpw7NuIHDDumJsaWNhIGxhIE9icmEgc8OzbG8gYmFqbyBsYXMgY29uZGljaW9uZXMgZGUgZXN0YSBMaWNlbmNpYSwgeSBVc3RlZCBkZWJlIGluY2x1aXIgdW5hIGNvcGlhIGRlIGVzdGEgbGljZW5jaWEgbyBkZWwgSWRlbnRpZmljYWRvciBVbml2ZXJzYWwgZGUgUmVjdXJzb3MgZGUgbGEgbWlzbWEgY29uIGNhZGEgY29waWEgZGUgbGEgT2JyYSBxdWUgZGlzdHJpYnV5YSwgZXhoaWJhIHDDumJsaWNhbWVudGUsIGVqZWN1dGUgcMO6YmxpY2FtZW50ZSBvIHBvbmdhIGEgZGlzcG9zaWNpw7NuIHDDumJsaWNhLiBObyBlcyBwb3NpYmxlIG9mcmVjZXIgbyBpbXBvbmVyIG5pbmd1bmEgY29uZGljacOzbiBzb2JyZSBsYSBPYnJhIHF1ZSBhbHRlcmUgbyBsaW1pdGUgbGFzIGNvbmRpY2lvbmVzIGRlIGVzdGEgTGljZW5jaWEgbyBlbCBlamVyY2ljaW8gZGUgbG9zIGRlcmVjaG9zIGRlIGxvcyBkZXN0aW5hdGFyaW9zIG90b3JnYWRvcyBlbiBlc3RlIGRvY3VtZW50by4gTm8gZXMgcG9zaWJsZSBzdWJsaWNlbmNpYXIgbGEgT2JyYS4gVXN0ZWQgZGViZSBtYW50ZW5lciBpbnRhY3RvcyB0b2RvcyBsb3MgYXZpc29zIHF1ZSBoYWdhbiByZWZlcmVuY2lhIGEgZXN0YSBMaWNlbmNpYSB5IGEgbGEgY2zDoXVzdWxhIGRlIGxpbWl0YWNpw7NuIGRlIGdhcmFudMOtYXMuIFVzdGVkIG5vIHB1ZWRlIGRpc3RyaWJ1aXIsIGV4aGliaXIgcMO6YmxpY2FtZW50ZSwgZWplY3V0YXIgcMO6YmxpY2FtZW50ZSwgbyBwb25lciBhIGRpc3Bvc2ljacOzbiBww7pibGljYSBsYSBPYnJhIGNvbiBhbGd1bmEgbWVkaWRhIHRlY25vbMOzZ2ljYSBxdWUgY29udHJvbGUgZWwgYWNjZXNvIG8gbGEgdXRpbGl6YWNpw7NuIGRlIGVsbGEgZGUgdW5hIGZvcm1hIHF1ZSBzZWEgaW5jb25zaXN0ZW50ZSBjb24gbGFzIGNvbmRpY2lvbmVzIGRlIGVzdGEgTGljZW5jaWEuIExvIGFudGVyaW9yIHNlIGFwbGljYSBhIGxhIE9icmEgaW5jb3Jwb3JhZGEgYSB1bmEgT2JyYSBDb2xlY3RpdmEsIHBlcm8gZXN0byBubyBleGlnZSBxdWUgbGEgT2JyYSBDb2xlY3RpdmEgYXBhcnRlIGRlIGxhIG9icmEgbWlzbWEgcXVlZGUgc3VqZXRhIGEgbGFzIGNvbmRpY2lvbmVzIGRlIGVzdGEgTGljZW5jaWEuIFNpIFVzdGVkIGNyZWEgdW5hIE9icmEgQ29sZWN0aXZhLCBwcmV2aW8gYXZpc28gZGUgY3VhbHF1aWVyIExpY2VuY2lhbnRlIGRlYmUsIGVuIGxhIG1lZGlkYSBkZSBsbyBwb3NpYmxlLCBlbGltaW5hciBkZSBsYSBPYnJhIENvbGVjdGl2YSBjdWFscXVpZXIgcmVmZXJlbmNpYSBhIGRpY2hvIExpY2VuY2lhbnRlIG8gYWwgQXV0b3IgT3JpZ2luYWwsIHNlZ8O6biBsbyBzb2xpY2l0YWRvIHBvciBlbCBMaWNlbmNpYW50ZSB5IGNvbmZvcm1lIGxvIGV4aWdlIGxhIGNsw6F1c3VsYSA0KGMpLjwvbGk+CiAgICAgIDxsaT5Vc3RlZCBubyBwdWVkZSBlamVyY2VyIG5pbmd1bm8gZGUgbG9zIGRlcmVjaG9zIHF1ZSBsZSBoYW4gc2lkbyBvdG9yZ2Fkb3MgZW4gbGEgU2VjY2nDs24gMyBwcmVjZWRlbnRlIGRlIG1vZG8gcXVlIGVzdMOpbiBwcmluY2lwYWxtZW50ZSBkZXN0aW5hZG9zIG8gZGlyZWN0YW1lbnRlIGRpcmlnaWRvcyBhIGNvbnNlZ3VpciB1biBwcm92ZWNobyBjb21lcmNpYWwgbyB1bmEgY29tcGVuc2FjacOzbiBtb25ldGFyaWEgcHJpdmFkYS4gRWwgaW50ZXJjYW1iaW8gZGUgbGEgT2JyYSBwb3Igb3RyYXMgb2JyYXMgcHJvdGVnaWRhcyBwb3IgZGVyZWNob3MgZGUgYXV0b3IsIHlhIHNlYSBhIHRyYXbDqXMgZGUgdW4gc2lzdGVtYSBwYXJhIGNvbXBhcnRpciBhcmNoaXZvcyBkaWdpdGFsZXMgKGRpZ2l0YWwgZmlsZS1zaGFyaW5nKSBvIGRlIGN1YWxxdWllciBvdHJhIG1hbmVyYSBubyBzZXLDoSBjb25zaWRlcmFkbyBjb21vIGVzdGFyIGRlc3RpbmFkbyBwcmluY2lwYWxtZW50ZSBvIGRpcmlnaWRvIGRpcmVjdGFtZW50ZSBhIGNvbnNlZ3VpciB1biBwcm92ZWNobyBjb21lcmNpYWwgbyB1bmEgY29tcGVuc2FjacOzbiBtb25ldGFyaWEgcHJpdmFkYSwgc2llbXByZSBxdWUgbm8gc2UgcmVhbGljZSB1biBwYWdvIG1lZGlhbnRlIHVuYSBjb21wZW5zYWNpw7NuIG1vbmV0YXJpYSBlbiByZWxhY2nDs24gY29uIGVsIGludGVyY2FtYmlvIGRlIG9icmFzIHByb3RlZ2lkYXMgcG9yIGVsIGRlcmVjaG8gZGUgYXV0b3IuPC9saT4KICAgICAgPGxpPlNpIHVzdGVkIGRpc3RyaWJ1eWUsIGV4aGliZSBww7pibGljYW1lbnRlLCBlamVjdXRhIHDDumJsaWNhbWVudGUgbyBlamVjdXRhIHDDumJsaWNhbWVudGUgZW4gZm9ybWEgZGlnaXRhbCBsYSBPYnJhIG8gY3VhbHF1aWVyIE9icmEgRGVyaXZhZGEgdSBPYnJhIENvbGVjdGl2YSwgVXN0ZWQgZGViZSBtYW50ZW5lciBpbnRhY3RhIHRvZGEgbGEgaW5mb3JtYWNpw7NuIGRlIGRlcmVjaG8gZGUgYXV0b3IgZGUgbGEgT2JyYSB5IHByb3BvcmNpb25hciwgZGUgZm9ybWEgcmF6b25hYmxlIHNlZ8O6biBlbCBtZWRpbyBvIG1hbmVyYSBxdWUgVXN0ZWQgZXN0w6kgdXRpbGl6YW5kbzogKGkpIGVsIG5vbWJyZSBkZWwgQXV0b3IgT3JpZ2luYWwgc2kgZXN0w6EgcHJvdmlzdG8gKG8gc2V1ZMOzbmltbywgc2kgZnVlcmUgYXBsaWNhYmxlKSwgeS9vIChpaSkgZWwgbm9tYnJlIGRlIGxhIHBhcnRlIG8gbGFzIHBhcnRlcyBxdWUgZWwgQXV0b3IgT3JpZ2luYWwgeS9vIGVsIExpY2VuY2lhbnRlIGh1YmllcmVuIGRlc2lnbmFkbyBwYXJhIGxhIGF0cmlidWNpw7NuICh2LmcuLCB1biBpbnN0aXR1dG8gcGF0cm9jaW5hZG9yLCBlZGl0b3JpYWwsIHB1YmxpY2FjacOzbikgZW4gbGEgaW5mb3JtYWNpw7NuIGRlIGxvcyBkZXJlY2hvcyBkZSBhdXRvciBkZWwgTGljZW5jaWFudGUsIHTDqXJtaW5vcyBkZSBzZXJ2aWNpb3MgbyBkZSBvdHJhcyBmb3JtYXMgcmF6b25hYmxlczsgZWwgdMOtdHVsbyBkZSBsYSBPYnJhIHNpIGVzdMOhIHByb3Zpc3RvOyBlbiBsYSBtZWRpZGEgZGUgbG8gcmF6b25hYmxlbWVudGUgZmFjdGlibGUgeSwgc2kgZXN0w6EgcHJvdmlzdG8sIGVsIElkZW50aWZpY2Fkb3IgVW5pZm9ybWUgZGUgUmVjdXJzb3MgKFVuaWZvcm0gUmVzb3VyY2UgSWRlbnRpZmllcikgcXVlIGVsIExpY2VuY2lhbnRlIGVzcGVjaWZpY2EgcGFyYSBzZXIgYXNvY2lhZG8gY29uIGxhIE9icmEsIHNhbHZvIHF1ZSB0YWwgVVJJIG5vIHNlIHJlZmllcmEgYSBsYSBub3RhIHNvYnJlIGxvcyBkZXJlY2hvcyBkZSBhdXRvciBvIGEgbGEgaW5mb3JtYWNpw7NuIHNvYnJlIGVsIGxpY2VuY2lhbWllbnRvIGRlIGxhIE9icmE7IHkgZW4gZWwgY2FzbyBkZSB1bmEgT2JyYSBEZXJpdmFkYSwgYXRyaWJ1aXIgZWwgY3LDqWRpdG8gaWRlbnRpZmljYW5kbyBlbCB1c28gZGUgbGEgT2JyYSBlbiBsYSBPYnJhIERlcml2YWRhICh2LmcuLCAiVHJhZHVjY2nDs24gRnJhbmNlc2EgZGUgbGEgT2JyYSBkZWwgQXV0b3IgT3JpZ2luYWwsIiBvICJHdWnDs24gQ2luZW1hdG9ncsOhZmljbyBiYXNhZG8gZW4gbGEgT2JyYSBvcmlnaW5hbCBkZWwgQXV0b3IgT3JpZ2luYWwiKS4gVGFsIGNyw6lkaXRvIHB1ZWRlIHNlciBpbXBsZW1lbnRhZG8gZGUgY3VhbHF1aWVyIGZvcm1hIHJhem9uYWJsZTsgZW4gZWwgY2Fzbywgc2luIGVtYmFyZ28sIGRlIE9icmFzIERlcml2YWRhcyB1IE9icmFzIENvbGVjdGl2YXMsIHRhbCBjcsOpZGl0byBhcGFyZWNlcsOhLCBjb21vIG3DrW5pbW8sIGRvbmRlIGFwYXJlY2UgZWwgY3LDqWRpdG8gZGUgY3VhbHF1aWVyIG90cm8gYXV0b3IgY29tcGFyYWJsZSB5IGRlIHVuYSBtYW5lcmEsIGFsIG1lbm9zLCB0YW4gZGVzdGFjYWRhIGNvbW8gZWwgY3LDqWRpdG8gZGUgb3RybyBhdXRvciBjb21wYXJhYmxlLjwvbGk+CiAgICAgIDxsaT4KICAgICAgICBQYXJhIGV2aXRhciB0b2RhIGNvbmZ1c2nDs24sIGVsIExpY2VuY2lhbnRlIGFjbGFyYSBxdWUsIGN1YW5kbyBsYSBvYnJhIGVzIHVuYSBjb21wb3NpY2nDs24gbXVzaWNhbDoKICAgICAgICA8b2wgdHlwZT0iaSI+CiAgICAgICAgICA8bGk+UmVnYWzDrWFzIHBvciBpbnRlcnByZXRhY2nDs24geSBlamVjdWNpw7NuIGJham8gbGljZW5jaWFzIGdlbmVyYWxlcy4gRWwgTGljZW5jaWFudGUgc2UgcmVzZXJ2YSBlbCBkZXJlY2hvIGV4Y2x1c2l2byBkZSBhdXRvcml6YXIgbGEgZWplY3VjacOzbiBww7pibGljYSBvIGxhIGVqZWN1Y2nDs24gcMO6YmxpY2EgZGlnaXRhbCBkZSBsYSBvYnJhIHkgZGUgcmVjb2xlY3Rhciwgc2VhIGluZGl2aWR1YWxtZW50ZSBvIGEgdHJhdsOpcyBkZSB1bmEgc29jaWVkYWQgZGUgZ2VzdGnDs24gY29sZWN0aXZhIGRlIGRlcmVjaG9zIGRlIGF1dG9yIHkgZGVyZWNob3MgY29uZXhvcyAocG9yIGVqZW1wbG8sIFNBWUNPKSwgbGFzIHJlZ2Fsw61hcyBwb3IgbGEgZWplY3VjacOzbiBww7pibGljYSBvIHBvciBsYSBlamVjdWNpw7NuIHDDumJsaWNhIGRpZ2l0YWwgZGUgbGEgb2JyYSAocG9yIGVqZW1wbG8gV2ViY2FzdCkgbGljZW5jaWFkYSBiYWpvIGxpY2VuY2lhcyBnZW5lcmFsZXMsIHNpIGxhIGludGVycHJldGFjacOzbiBvIGVqZWN1Y2nDs24gZGUgbGEgb2JyYSBlc3TDoSBwcmltb3JkaWFsbWVudGUgb3JpZW50YWRhIHBvciBvIGRpcmlnaWRhIGEgbGEgb2J0ZW5jacOzbiBkZSB1bmEgdmVudGFqYSBjb21lcmNpYWwgbyB1bmEgY29tcGVuc2FjacOzbiBtb25ldGFyaWEgcHJpdmFkYS48L2xpPgogICAgICAgICAgPGxpPlJlZ2Fsw61hcyBwb3IgRm9ub2dyYW1hcy4gRWwgTGljZW5jaWFudGUgc2UgcmVzZXJ2YSBlbCBkZXJlY2hvIGV4Y2x1c2l2byBkZSByZWNvbGVjdGFyLCBpbmRpdmlkdWFsbWVudGUgbyBhIHRyYXbDqXMgZGUgdW5hIHNvY2llZGFkIGRlIGdlc3Rpw7NuIGNvbGVjdGl2YSBkZSBkZXJlY2hvcyBkZSBhdXRvciB5IGRlcmVjaG9zIGNvbmV4b3MgKHBvciBlamVtcGxvLCBsb3MgY29uc2FncmFkb3MgcG9yIGxhIFNBWUNPKSwgdW5hIGFnZW5jaWEgZGUgZGVyZWNob3MgbXVzaWNhbGVzIG8gYWxnw7puIGFnZW50ZSBkZXNpZ25hZG8sIGxhcyByZWdhbMOtYXMgcG9yIGN1YWxxdWllciBmb25vZ3JhbWEgcXVlIFVzdGVkIGNyZWUgYSBwYXJ0aXIgZGUgbGEgb2JyYSAo4oCcdmVyc2nDs24gY292ZXLigJ0pIHkgZGlzdHJpYnV5YSwgZW4gbG9zIHTDqXJtaW5vcyBkZWwgcsOpZ2ltZW4gZGUgZGVyZWNob3MgZGUgYXV0b3IsIHNpIGxhIGNyZWFjacOzbiBvIGRpc3RyaWJ1Y2nDs24gZGUgZXNhIHZlcnNpw7NuIGNvdmVyIGVzdMOhIHByaW1vcmRpYWxtZW50ZSBkZXN0aW5hZGEgbyBkaXJpZ2lkYSBhIG9idGVuZXIgdW5hIHZlbnRhamEgY29tZXJjaWFsIG8gdW5hIGNvbXBlbnNhY2nDs24gbW9uZXRhcmlhIHByaXZhZGEuPC9saT4KICAgICAgICA8L29sPgogICAgICA8L2xpPgogICAgICA8bGk+R2VzdGnDs24gZGUgRGVyZWNob3MgZGUgQXV0b3Igc29icmUgSW50ZXJwcmV0YWNpb25lcyB5IEVqZWN1Y2lvbmVzIERpZ2l0YWxlcyAoV2ViQ2FzdGluZykuIFBhcmEgZXZpdGFyIHRvZGEgY29uZnVzacOzbiwgZWwgTGljZW5jaWFudGUgYWNsYXJhIHF1ZSwgY3VhbmRvIGxhIG9icmEgc2VhIHVuIGZvbm9ncmFtYSwgZWwgTGljZW5jaWFudGUgc2UgcmVzZXJ2YSBlbCBkZXJlY2hvIGV4Y2x1c2l2byBkZSBhdXRvcml6YXIgbGEgZWplY3VjacOzbiBww7pibGljYSBkaWdpdGFsIGRlIGxhIG9icmEgKHBvciBlamVtcGxvLCB3ZWJjYXN0KSB5IGRlIHJlY29sZWN0YXIsIGluZGl2aWR1YWxtZW50ZSBvIGEgdHJhdsOpcyBkZSB1bmEgc29jaWVkYWQgZGUgZ2VzdGnDs24gY29sZWN0aXZhIGRlIGRlcmVjaG9zIGRlIGF1dG9yIHkgZGVyZWNob3MgY29uZXhvcyAocG9yIGVqZW1wbG8sIEFDSU5QUk8pLCBsYXMgcmVnYWzDrWFzIHBvciBsYSBlamVjdWNpw7NuIHDDumJsaWNhIGRpZ2l0YWwgZGUgbGEgb2JyYSAocG9yIGVqZW1wbG8sIHdlYmNhc3QpLCBzdWpldGEgYSBsYXMgZGlzcG9zaWNpb25lcyBhcGxpY2FibGVzIGRlbCByw6lnaW1lbiBkZSBEZXJlY2hvIGRlIEF1dG9yLCBzaSBlc3RhIGVqZWN1Y2nDs24gcMO6YmxpY2EgZGlnaXRhbCBlc3TDoSBwcmltb3JkaWFsbWVudGUgZGlyaWdpZGEgYSBvYnRlbmVyIHVuYSB2ZW50YWphIGNvbWVyY2lhbCBvIHVuYSBjb21wZW5zYWNpw7NuIG1vbmV0YXJpYSBwcml2YWRhLjwvbGk+CiAgICA8L29sPgogIDwvbGk+CiAgPGJyLz4KICA8bGk+CiAgICBSZXByZXNlbnRhY2lvbmVzLCBHYXJhbnTDrWFzIHkgTGltaXRhY2lvbmVzIGRlIFJlc3BvbnNhYmlsaWRhZC4KICAgIDxwPkEgTUVOT1MgUVVFIExBUyBQQVJURVMgTE8gQUNPUkRBUkFOIERFIE9UUkEgRk9STUEgUE9SIEVTQ1JJVE8sIEVMIExJQ0VOQ0lBTlRFIE9GUkVDRSBMQSBPQlJBIChFTiBFTCBFU1RBRE8gRU4gRUwgUVVFIFNFIEVOQ1VFTlRSQSkg4oCcVEFMIENVQUzigJ0sIFNJTiBCUklOREFSIEdBUkFOVMONQVMgREUgQ0xBU0UgQUxHVU5BIFJFU1BFQ1RPIERFIExBIE9CUkEsIFlBIFNFQSBFWFBSRVNBLCBJTVBMw41DSVRBLCBMRUdBTCBPIENVQUxRVUlFUkEgT1RSQSwgSU5DTFVZRU5ETywgU0lOIExJTUlUQVJTRSBBIEVMTEFTLCBHQVJBTlTDjUFTIERFIFRJVFVMQVJJREFELCBDT01FUkNJQUJJTElEQUQsIEFEQVBUQUJJTElEQUQgTyBBREVDVUFDScOTTiBBIFBST1DDk1NJVE8gREVURVJNSU5BRE8sIEFVU0VOQ0lBIERFIElORlJBQ0NJw5NOLCBERSBBVVNFTkNJQSBERSBERUZFQ1RPUyBMQVRFTlRFUyBPIERFIE9UUk8gVElQTywgTyBMQSBQUkVTRU5DSUEgTyBBVVNFTkNJQSBERSBFUlJPUkVTLCBTRUFOIE8gTk8gREVTQ1VCUklCTEVTIChQVUVEQU4gTyBOTyBTRVIgRVNUT1MgREVTQ1VCSUVSVE9TKS4gQUxHVU5BUyBKVVJJU0RJQ0NJT05FUyBOTyBQRVJNSVRFTiBMQSBFWENMVVNJw5NOIERFIEdBUkFOVMONQVMgSU1QTMONQ0lUQVMsIEVOIENVWU8gQ0FTTyBFU1RBIEVYQ0xVU0nDk04gUFVFREUgTk8gQVBMSUNBUlNFIEEgVVNURUQuPC9wPgogIDwvbGk+CiAgPGJyLz4KICA8bGk+CiAgICBMaW1pdGFjacOzbiBkZSByZXNwb25zYWJpbGlkYWQuCiAgICA8cD5BIE1FTk9TIFFVRSBMTyBFWElKQSBFWFBSRVNBTUVOVEUgTEEgTEVZIEFQTElDQUJMRSwgRUwgTElDRU5DSUFOVEUgTk8gU0VSw4EgUkVTUE9OU0FCTEUgQU5URSBVU1RFRCBQT1IgREHDkU8gQUxHVU5PLCBTRUEgUE9SIFJFU1BPTlNBQklMSURBRCBFWFRSQUNPTlRSQUNUVUFMLCBQUkVDT05UUkFDVFVBTCBPIENPTlRSQUNUVUFMLCBPQkpFVElWQSBPIFNVQkpFVElWQSwgU0UgVFJBVEUgREUgREHDkU9TIE1PUkFMRVMgTyBQQVRSSU1PTklBTEVTLCBESVJFQ1RPUyBPIElORElSRUNUT1MsIFBSRVZJU1RPUyBPIElNUFJFVklTVE9TIFBST0RVQ0lET1MgUE9SIEVMIFVTTyBERSBFU1RBIExJQ0VOQ0lBIE8gREUgTEEgT0JSQSwgQVVOIENVQU5ETyBFTCBMSUNFTkNJQU5URSBIQVlBIFNJRE8gQURWRVJUSURPIERFIExBIFBPU0lCSUxJREFEIERFIERJQ0hPUyBEQcORT1MuIEFMR1VOQVMgTEVZRVMgTk8gUEVSTUlURU4gTEEgRVhDTFVTScOTTiBERSBDSUVSVEEgUkVTUE9OU0FCSUxJREFELCBFTiBDVVlPIENBU08gRVNUQSBFWENMVVNJw5NOIFBVRURFIE5PIEFQTElDQVJTRSBBIFVTVEVELjwvcD4KICA8L2xpPgogIDxici8+CiAgPGxpPgogICAgVMOpcm1pbm8uCiAgICA8b2wgdHlwZT0iYSI+CiAgICAgIDxsaT5Fc3RhIExpY2VuY2lhIHkgbG9zIGRlcmVjaG9zIG90b3JnYWRvcyBlbiB2aXJ0dWQgZGUgZWxsYSB0ZXJtaW5hcsOhbiBhdXRvbcOhdGljYW1lbnRlIHNpIFVzdGVkIGluZnJpbmdlIGFsZ3VuYSBjb25kaWNpw7NuIGVzdGFibGVjaWRhIGVuIGVsbGEuIFNpbiBlbWJhcmdvLCBsb3MgaW5kaXZpZHVvcyBvIGVudGlkYWRlcyBxdWUgaGFuIHJlY2liaWRvIE9icmFzIERlcml2YWRhcyBvIENvbGVjdGl2YXMgZGUgVXN0ZWQgZGUgY29uZm9ybWlkYWQgY29uIGVzdGEgTGljZW5jaWEsIG5vIHZlcsOhbiB0ZXJtaW5hZGFzIHN1cyBsaWNlbmNpYXMsIHNpZW1wcmUgcXVlIGVzdG9zIGluZGl2aWR1b3MgbyBlbnRpZGFkZXMgc2lnYW4gY3VtcGxpZW5kbyDDrW50ZWdyYW1lbnRlIGxhcyBjb25kaWNpb25lcyBkZSBlc3RhcyBsaWNlbmNpYXMuIExhcyBTZWNjaW9uZXMgMSwgMiwgNSwgNiwgNywgeSA4IHN1YnNpc3RpcsOhbiBhIGN1YWxxdWllciB0ZXJtaW5hY2nDs24gZGUgZXN0YSBMaWNlbmNpYS48L2xpPgogICAgICA8bGk+U3VqZXRhIGEgbGFzIGNvbmRpY2lvbmVzIHkgdMOpcm1pbm9zIGFudGVyaW9yZXMsIGxhIGxpY2VuY2lhIG90b3JnYWRhIGFxdcOtIGVzIHBlcnBldHVhIChkdXJhbnRlIGVsIHBlcsOtb2RvIGRlIHZpZ2VuY2lhIGRlIGxvcyBkZXJlY2hvcyBkZSBhdXRvciBkZSBsYSBvYnJhKS4gTm8gb2JzdGFudGUgbG8gYW50ZXJpb3IsIGVsIExpY2VuY2lhbnRlIHNlIHJlc2VydmEgZWwgZGVyZWNobyBhIHB1YmxpY2FyIHkvbyBlc3RyZW5hciBsYSBPYnJhIGJham8gY29uZGljaW9uZXMgZGUgbGljZW5jaWEgZGlmZXJlbnRlcyBvIGEgZGVqYXIgZGUgZGlzdHJpYnVpcmxhIGVuIGxvcyB0w6lybWlub3MgZGUgZXN0YSBMaWNlbmNpYSBlbiBjdWFscXVpZXIgbW9tZW50bzsgZW4gZWwgZW50ZW5kaWRvLCBzaW4gZW1iYXJnbywgcXVlIGVzYSBlbGVjY2nDs24gbm8gc2Vydmlyw6EgcGFyYSByZXZvY2FyIGVzdGEgbGljZW5jaWEgbyBxdWUgZGViYSBzZXIgb3RvcmdhZGEgLCBiYWpvIGxvcyB0w6lybWlub3MgZGUgZXN0YSBsaWNlbmNpYSksIHkgZXN0YSBsaWNlbmNpYSBjb250aW51YXLDoSBlbiBwbGVubyB2aWdvciB5IGVmZWN0byBhIG1lbm9zIHF1ZSBzZWEgdGVybWluYWRhIGNvbW8gc2UgZXhwcmVzYSBhdHLDoXMuIExhIExpY2VuY2lhIHJldm9jYWRhIGNvbnRpbnVhcsOhIHNpZW5kbyBwbGVuYW1lbnRlIHZpZ2VudGUgeSBlZmVjdGl2YSBzaSBubyBzZSBsZSBkYSB0w6lybWlubyBlbiBsYXMgY29uZGljaW9uZXMgaW5kaWNhZGFzIGFudGVyaW9ybWVudGUuPC9saT4KICAgIDwvb2w+CiAgPC9saT4KICA8YnIvPgogIDxsaT4KICAgIFZhcmlvcy4KICAgIDxvbCB0eXBlPSJhIj4KICAgICAgPGxpPkNhZGEgdmV6IHF1ZSBVc3RlZCBkaXN0cmlidXlhIG8gcG9uZ2EgYSBkaXNwb3NpY2nDs24gcMO6YmxpY2EgbGEgT2JyYSBvIHVuYSBPYnJhIENvbGVjdGl2YSwgZWwgTGljZW5jaWFudGUgb2ZyZWNlcsOhIGFsIGRlc3RpbmF0YXJpbyB1bmEgbGljZW5jaWEgZW4gbG9zIG1pc21vcyB0w6lybWlub3MgeSBjb25kaWNpb25lcyBxdWUgbGEgbGljZW5jaWEgb3RvcmdhZGEgYSBVc3RlZCBiYWpvIGVzdGEgTGljZW5jaWEuPC9saT4KICAgICAgPGxpPlNpIGFsZ3VuYSBkaXNwb3NpY2nDs24gZGUgZXN0YSBMaWNlbmNpYSByZXN1bHRhIGludmFsaWRhZGEgbyBubyBleGlnaWJsZSwgc2Vnw7puIGxhIGxlZ2lzbGFjacOzbiB2aWdlbnRlLCBlc3RvIG5vIGFmZWN0YXLDoSBuaSBsYSB2YWxpZGV6IG5pIGxhIGFwbGljYWJpbGlkYWQgZGVsIHJlc3RvIGRlIGNvbmRpY2lvbmVzIGRlIGVzdGEgTGljZW5jaWEgeSwgc2luIGFjY2nDs24gYWRpY2lvbmFsIHBvciBwYXJ0ZSBkZSBsb3Mgc3VqZXRvcyBkZSBlc3RlIGFjdWVyZG8sIGFxdcOpbGxhIHNlIGVudGVuZGVyw6EgcmVmb3JtYWRhIGxvIG3DrW5pbW8gbmVjZXNhcmlvIHBhcmEgaGFjZXIgcXVlIGRpY2hhIGRpc3Bvc2ljacOzbiBzZWEgdsOhbGlkYSB5IGV4aWdpYmxlLjwvbGk+CiAgICAgIDxsaT5OaW5nw7puIHTDqXJtaW5vIG8gZGlzcG9zaWNpw7NuIGRlIGVzdGEgTGljZW5jaWEgc2UgZXN0aW1hcsOhIHJlbnVuY2lhZGEgeSBuaW5ndW5hIHZpb2xhY2nDs24gZGUgZWxsYSBzZXLDoSBjb25zZW50aWRhIGEgbWVub3MgcXVlIGVzYSByZW51bmNpYSBvIGNvbnNlbnRpbWllbnRvIHNlYSBvdG9yZ2FkbyBwb3IgZXNjcml0byB5IGZpcm1hZG8gcG9yIGxhIHBhcnRlIHF1ZSByZW51bmNpZSBvIGNvbnNpZW50YS48L2xpPgogICAgICA8bGk+RXN0YSBMaWNlbmNpYSByZWZsZWphIGVsIGFjdWVyZG8gcGxlbm8gZW50cmUgbGFzIHBhcnRlcyByZXNwZWN0byBhIGxhIE9icmEgYXF1w60gbGljZW5jaWFkYS4gTm8gaGF5IGFycmVnbG9zLCBhY3VlcmRvcyBvIGRlY2xhcmFjaW9uZXMgcmVzcGVjdG8gYSBsYSBPYnJhIHF1ZSBubyBlc3TDqW4gZXNwZWNpZmljYWRvcyBlbiBlc3RlIGRvY3VtZW50by4gRWwgTGljZW5jaWFudGUgbm8gc2UgdmVyw6EgbGltaXRhZG8gcG9yIG5pbmd1bmEgZGlzcG9zaWNpw7NuIGFkaWNpb25hbCBxdWUgcHVlZGEgc3VyZ2lyIGVuIGFsZ3VuYSBjb211bmljYWNpw7NuIGVtYW5hZGEgZGUgVXN0ZWQuIEVzdGEgTGljZW5jaWEgbm8gcHVlZGUgc2VyIG1vZGlmaWNhZGEgc2luIGVsIGNvbnNlbnRpbWllbnRvIG11dHVvIHBvciBlc2NyaXRvIGRlbCBMaWNlbmNpYW50ZSB5IFVzdGVkLjwvbGk+CiAgICA8L29sPgogIDwvbGk+CiAgPGJyLz4KPC9vbD4K |