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Volumn 264, Issue , 2015, Pages 359-375

Dual-template synthesis of nanostructured CoAPSO-34 used in methanol to olefins: Effect of template combinations on catalytic performance and coke formation

Author keywords

CoAPSO 34; Deactivation; Dual template; Hydrothermal; MTO

Indexed keywords

COBALT; COKE; CRYSTALLINITY; LIGHT OLEFINS; METHANOL; MIXTURES; MOLAR RATIO; PARTICLE SIZE; PARTICLE SIZE ANALYSIS; SILICON; X RAY DIFFRACTION;

EID: 84916626669     PISSN: 13858947     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.cej.2014.11.102     Document Type: Article
Times cited : (64)

References (57)
  • 1
    • 84865340740 scopus 로고    scopus 로고
    • Effect of oil prices on trade balance: new insights into the cointegration relationship from Pakistan
    • Hassan S.A., Zaman K. Effect of oil prices on trade balance: new insights into the cointegration relationship from Pakistan. Econ. Model. 2012, 29:2125-2143.
    • (2012) Econ. Model. , vol.29 , pp. 2125-2143
    • Hassan, S.A.1    Zaman, K.2
  • 2
    • 84866341118 scopus 로고    scopus 로고
    • System analysis approach for the identification of factors driving crude oil prices
    • Ji Q. System analysis approach for the identification of factors driving crude oil prices. Comput. Ind. Eng. 2012, 63:615-625.
    • (2012) Comput. Ind. Eng. , vol.63 , pp. 615-625
    • Ji, Q.1
  • 3
    • 84864822965 scopus 로고    scopus 로고
    • OPEC news announcements: effects on oil price expectation and volatility
    • Schmidbauer H., Rösch A. OPEC news announcements: effects on oil price expectation and volatility. Energy Econ. 2012, 34:1656-1663.
    • (2012) Energy Econ. , vol.34 , pp. 1656-1663
    • Schmidbauer, H.1    Rösch, A.2
  • 4
    • 84855828488 scopus 로고    scopus 로고
    • The synthesis of SAPO-34 with mixed template and its catalytic performance for methanol to olefins reaction
    • Wang P., Lv A., Hu J., Xu J.a., Lu G. The synthesis of SAPO-34 with mixed template and its catalytic performance for methanol to olefins reaction. Microporous Mesoporous Mater. 2012, 152:178-184.
    • (2012) Microporous Mesoporous Mater. , vol.152 , pp. 178-184
    • Wang, P.1    Lv, A.2    Hu, J.3    Xu, J.4    Lu, G.5
  • 5
    • 38349187666 scopus 로고    scopus 로고
    • Synthesis, characterization and catalytic performance of metal-incorporated SAPO-34 for chloromethane transformation to light olefins
    • Wei Y., Zhang D., Xu L., Chang F., He Y., Meng S., Su B.-L., Liu Z. Synthesis, characterization and catalytic performance of metal-incorporated SAPO-34 for chloromethane transformation to light olefins. Catal. Today 2008, 131:262-269.
    • (2008) Catal. Today , vol.131 , pp. 262-269
    • Wei, Y.1    Zhang, D.2    Xu, L.3    Chang, F.4    He, Y.5    Meng, S.6    Su, B.-L.7    Liu, Z.8
  • 6
    • 84856044449 scopus 로고    scopus 로고
    • The economic value of co-movement between oil price and exchange rate using copula-based GARCH models
    • Wu C.-C., Chung H., Chang Y.-H. The economic value of co-movement between oil price and exchange rate using copula-based GARCH models. Energy Econ. 2012, 34:270-282.
    • (2012) Energy Econ. , vol.34 , pp. 270-282
    • Wu, C.-C.1    Chung, H.2    Chang, Y.-H.3
  • 7
    • 79958291834 scopus 로고    scopus 로고
    • Effect of different TEAOH/DEA combinations on SAPO-34's synthesis and catalytic performance
    • Ye L., Cao F., Ying W., Fang D., Sun Q. Effect of different TEAOH/DEA combinations on SAPO-34's synthesis and catalytic performance. J. Porous Mater. 2011, 18:225-232.
    • (2011) J. Porous Mater. , vol.18 , pp. 225-232
    • Ye, L.1    Cao, F.2    Ying, W.3    Fang, D.4    Sun, Q.5
  • 8
    • 84865150662 scopus 로고    scopus 로고
    • Metathesis of C4 olefin over Mo-based heterogeneous catalysts: a novel route to propene and isopentene
    • Zhang D., Li X., Liu S., Huang S., Zhu X., Chen F., Xie S., Xu L. Metathesis of C4 olefin over Mo-based heterogeneous catalysts: a novel route to propene and isopentene. Appl. Catal. A 2012, 439-440:171-178.
    • (2012) Appl. Catal. A , pp. 171-178
    • Zhang, D.1    Li, X.2    Liu, S.3    Huang, S.4    Zhu, X.5    Chen, F.6    Xie, S.7    Xu, L.8
  • 9
    • 53949123353 scopus 로고    scopus 로고
    • MgAPSO-34 molecular sieves with various Mg stoichiometries: synthesis, characterization and catalytic behavior in the direct transformation of chloromethane into light olefins
    • Zhang D., Wei Y., Xu L., Chang F., Liu Z., Meng S., Su B.-L., Liu Z. MgAPSO-34 molecular sieves with various Mg stoichiometries: synthesis, characterization and catalytic behavior in the direct transformation of chloromethane into light olefins. Microporous Mesoporous Mater. 2008, 116:684-692.
    • (2008) Microporous Mesoporous Mater. , vol.116 , pp. 684-692
    • Zhang, D.1    Wei, Y.2    Xu, L.3    Chang, F.4    Liu, Z.5    Meng, S.6    Su, B.-L.7    Liu, Z.8
  • 10
    • 79958140903 scopus 로고    scopus 로고
    • Study on the deactivation and regeneration of the ZSM-5 catalyst used in methanol to olefins
    • Zhang J., Zhang H., Yang X., Huang Z., Cao W. Study on the deactivation and regeneration of the ZSM-5 catalyst used in methanol to olefins. J. Nat. Gas Chem. 2011, 20:266-270.
    • (2011) J. Nat. Gas Chem. , vol.20 , pp. 266-270
    • Zhang, J.1    Zhang, H.2    Yang, X.3    Huang, Z.4    Cao, W.5
  • 12
    • 84858618325 scopus 로고    scopus 로고
    • Effect of contributing factors on microwave-assisted hydrothermal synthesis of nanosized SAPO-34 molecular sieves
    • Shalmani F.M., Halladj R., Askari S. Effect of contributing factors on microwave-assisted hydrothermal synthesis of nanosized SAPO-34 molecular sieves. Powder Technol. 2012, 221:395-402.
    • (2012) Powder Technol. , vol.221 , pp. 395-402
    • Shalmani, F.M.1    Halladj, R.2    Askari, S.3
  • 13
    • 84855474056 scopus 로고    scopus 로고
    • Kinetic modeling and optimization of the operating condition of MTO process on SAPO-34 catalyst
    • Taheri Najafabadi A., Fatemi S., Sohrabi M., Salmasi M. Kinetic modeling and optimization of the operating condition of MTO process on SAPO-34 catalyst. J. Ind. Eng. Chem. 2012, 18:29-37.
    • (2012) J. Ind. Eng. Chem. , vol.18 , pp. 29-37
    • Taheri Najafabadi, A.1    Fatemi, S.2    Sohrabi, M.3    Salmasi, M.4
  • 15
    • 9444297011 scopus 로고    scopus 로고
    • Synthesis, characterization, and MTO performance of MeAPSO-34 molecular sieves
    • Elsevier, B. Xinhe, X. Yide (Eds.)
    • Xu L., Liu Z., Du A., Wei Y., Sun Z. Synthesis, characterization, and MTO performance of MeAPSO-34 molecular sieves. Studies in Surface Science and Catalysis 2004, 445-450. Elsevier. B. Xinhe, X. Yide (Eds.).
    • (2004) Studies in Surface Science and Catalysis , pp. 445-450
    • Xu, L.1    Liu, Z.2    Du, A.3    Wei, Y.4    Sun, Z.5
  • 16
    • 84922678588 scopus 로고    scopus 로고
    • Efficient hydrothermal synthesis of nanostructured SAPO-34 using ultrasound energy: physicochemical characterization and catalytic performance toward methanol conversion to light olefins
    • Charghand M., Haghighi M., Saedy S., Aghamohammadi S. Efficient hydrothermal synthesis of nanostructured SAPO-34 using ultrasound energy: physicochemical characterization and catalytic performance toward methanol conversion to light olefins. Adv. Powder Technol. 2014, 25:1728-1736.
    • (2014) Adv. Powder Technol. , vol.25 , pp. 1728-1736
    • Charghand, M.1    Haghighi, M.2    Saedy, S.3    Aghamohammadi, S.4
  • 17
    • 84901374990 scopus 로고    scopus 로고
    • The beneficial use of ultrasound in synthesis of nanostructured Ce-Doped SAPO-34 used in methanol conversion to light olefins
    • Charghand M., Haghighi M., Aghamohammadi S. The beneficial use of ultrasound in synthesis of nanostructured Ce-Doped SAPO-34 used in methanol conversion to light olefins. Ultrason. Sonochem. 2014, 21:1827-1838.
    • (2014) Ultrason. Sonochem. , vol.21 , pp. 1827-1838
    • Charghand, M.1    Haghighi, M.2    Aghamohammadi, S.3
  • 18
    • 85096202523 scopus 로고    scopus 로고
    • Energy, Alternative, renewable and novel feedstocks for producing chemicals, in
    • U.S.D.O. Energy, Alternative, renewable and novel feedstocks for producing chemicals, in, 2007.
    • (2007)
  • 19
    • 85096202365 scopus 로고    scopus 로고
    • Innovation and Future Energy Challenges, in: UOP LLC
    • S.A. Gembicki, Innovation and Future Energy Challenges, in: UOP LLC, 2006.
    • (2006)
    • Gembicki, S.A.1
  • 20
    • 84901982793 scopus 로고    scopus 로고
    • Enhancement of catalytic lifetime of nanostructured SAPO-34 in conversion of biomethanol to light olefins
    • Aghaei E., Haghighi M. Enhancement of catalytic lifetime of nanostructured SAPO-34 in conversion of biomethanol to light olefins. Microporous Mesoporous Mater. 2014, 196:179-190.
    • (2014) Microporous Mesoporous Mater. , vol.196 , pp. 179-190
    • Aghaei, E.1    Haghighi, M.2
  • 21
    • 84907741813 scopus 로고    scopus 로고
    • Effect of crystallization time on properties and catalytic performance of nanostructured SAPO-34 molecular sieve synthesized at high temperatures for conversion of methanol to light olefins
    • Aghaei E., Haghighi M. Effect of crystallization time on properties and catalytic performance of nanostructured SAPO-34 molecular sieve synthesized at high temperatures for conversion of methanol to light olefins. Powder Technol. 2015, 269:358-370.
    • (2015) Powder Technol. , vol.269 , pp. 358-370
    • Aghaei, E.1    Haghighi, M.2
  • 24
    • 84949150470 scopus 로고    scopus 로고
    • The design and understanding of the mechanism of formation of nanoporous catalytic materials, in: University College London
    • K. Simmance, The design and understanding of the mechanism of formation of nanoporous catalytic materials, in: University College London, 2011, p. 326.
    • (2011) , pp. 326
    • Simmance, K.1
  • 25
    • 84655167246 scopus 로고    scopus 로고
    • Use of different templates on SAPO-34 synthesis: effect on the acidity and catalytic activity in the MTO reaction
    • Álvaro-Muñoz T., Márquez-Álvarez C., Sastre E. Use of different templates on SAPO-34 synthesis: effect on the acidity and catalytic activity in the MTO reaction. Catal. Today 2012, 179:27-34.
    • (2012) Catal. Today , vol.179 , pp. 27-34
    • Álvaro-Muñoz, T.1    Márquez-Álvarez, C.2    Sastre, E.3
  • 26
    • 0032630545 scopus 로고    scopus 로고
    • The effect of crystal size of SAPO-34 on the selectivity and deactivation of the MTO reaction
    • Chen D., Moljord K., Fuglerud T., Holmen A. The effect of crystal size of SAPO-34 on the selectivity and deactivation of the MTO reaction. Microporous Mesoporous Mater. 1999, 29:191-203.
    • (1999) Microporous Mesoporous Mater. , vol.29 , pp. 191-203
    • Chen, D.1    Moljord, K.2    Fuglerud, T.3    Holmen, A.4
  • 27
    • 34547739470 scopus 로고    scopus 로고
    • Methanol conversion on SAPO-34 catalysts prepared by mixed template method
    • Lee Y.-J., Baek S.-C., Jun K.-W. Methanol conversion on SAPO-34 catalysts prepared by mixed template method. Appl. Catal. A 2007, 329:130-136.
    • (2007) Appl. Catal. A , vol.329 , pp. 130-136
    • Lee, Y.-J.1    Baek, S.-C.2    Jun, K.-W.3
  • 28
    • 84863076581 scopus 로고    scopus 로고
    • Synthesis of SAPO-34 molecular sieves templated with diethylamine and their properties compared with other templates
    • Liu G., Tian P., Liu Z. Synthesis of SAPO-34 molecular sieves templated with diethylamine and their properties compared with other templates. Chin. J. Catal. 2012, 33:174-182.
    • (2012) Chin. J. Catal. , vol.33 , pp. 174-182
    • Liu, G.1    Tian, P.2    Liu, Z.3
  • 29
    • 66149129226 scopus 로고    scopus 로고
    • Size control of SAPO-34 crystals and their catalyst lifetime in the methanol-to-olefin reaction
    • Nishiyama N., Kawaguchi M., Hirota Y., Van Vu D., Egashira Y., Ueyama K. Size control of SAPO-34 crystals and their catalyst lifetime in the methanol-to-olefin reaction. Appl. Catal. A 2009, 362:193-199.
    • (2009) Appl. Catal. A , vol.362 , pp. 193-199
    • Nishiyama, N.1    Kawaguchi, M.2    Hirota, Y.3    Van Vu, D.4    Egashira, Y.5    Ueyama, K.6
  • 30
    • 53949086529 scopus 로고    scopus 로고
    • Comparison of four catalysts in the catalytic dehydration of ethanol to ethylene
    • Zhang X., Wang R., Yang X., Zhang F. Comparison of four catalysts in the catalytic dehydration of ethanol to ethylene. Microporous Mesoporous Mater. 2008, 116:210-215.
    • (2008) Microporous Mesoporous Mater. , vol.116 , pp. 210-215
    • Zhang, X.1    Wang, R.2    Yang, X.3    Zhang, F.4
  • 31
    • 84890502450 scopus 로고    scopus 로고
    • Methanol conversion to light olefins over nanostructured CeAPSO-34 catalyst: thermodynamic analysis of overall reactions and effect of template type on catalytic properties and performance
    • Aghamohammadi S., Haghighi M., Charghand M. Methanol conversion to light olefins over nanostructured CeAPSO-34 catalyst: thermodynamic analysis of overall reactions and effect of template type on catalytic properties and performance. Mater. Res. Bull. 2014, 50:462-475.
    • (2014) Mater. Res. Bull. , vol.50 , pp. 462-475
    • Aghamohammadi, S.1    Haghighi, M.2    Charghand, M.3
  • 32
    • 80055106218 scopus 로고    scopus 로고
    • Improvement of light olefins selectivity and catalyst lifetime in MTO reaction; using Ni and Mg-modified SAPO-34 synthesized by combination of two templates
    • Salmasi M., Fatemi S., Taheri Najafabadi A. Improvement of light olefins selectivity and catalyst lifetime in MTO reaction; using Ni and Mg-modified SAPO-34 synthesized by combination of two templates. J. Ind. Eng. Chem. 2011, 17:755-761.
    • (2011) J. Ind. Eng. Chem. , vol.17 , pp. 755-761
    • Salmasi, M.1    Fatemi, S.2    Taheri Najafabadi, A.3
  • 33
    • 84896701442 scopus 로고    scopus 로고
    • Hydrothermal synthesis of nanosized SAPO-34 molecular sieves by different combinations of multi templates
    • Najafi N., Askari S., Halladj R. Hydrothermal synthesis of nanosized SAPO-34 molecular sieves by different combinations of multi templates. Powder Technol. 2014, 254:324-330.
    • (2014) Powder Technol. , vol.254 , pp. 324-330
    • Najafi, N.1    Askari, S.2    Halladj, R.3
  • 34
    • 84891776131 scopus 로고    scopus 로고
    • Aluminium chloride: a new aluminium source to prepare SAPO-34 catalysts with enhanced stability in the MTO process
    • Álvaro-Muñoz T., Márquez-Álvarez C., Sastre E. Aluminium chloride: a new aluminium source to prepare SAPO-34 catalysts with enhanced stability in the MTO process. Appl. Catal. A 2014, 472:72-79.
    • (2014) Appl. Catal. A , vol.472 , pp. 72-79
    • Álvaro-Muñoz, T.1    Márquez-Álvarez, C.2    Sastre, E.3
  • 35
    • 84879920139 scopus 로고    scopus 로고
    • Synthesis of SAPO-34 with small and tunable crystallite size by two-step hydrothermal crystallization and its catalytic performance for MTO reaction
    • (e61-62.e68)
    • Wang P., Yang D., Hu J., Xu J.A., Lu G. Synthesis of SAPO-34 with small and tunable crystallite size by two-step hydrothermal crystallization and its catalytic performance for MTO reaction. Catal. Today 2013, 212:62. (e61-62.e68).
    • (2013) Catal. Today , vol.212 , pp. 62
    • Wang, P.1    Yang, D.2    Hu, J.3    Xu, J.A.4    Lu, G.5
  • 36
    • 84874942839 scopus 로고    scopus 로고
    • Effects of ultrasound-related variables on sonochemically synthesized SAPO-34 nanoparticles
    • Askari S., Halladj R. Effects of ultrasound-related variables on sonochemically synthesized SAPO-34 nanoparticles. J. Solid State Chem. 2013, 201:85-92.
    • (2013) J. Solid State Chem. , vol.201 , pp. 85-92
    • Askari, S.1    Halladj, R.2
  • 37
    • 41749085301 scopus 로고    scopus 로고
    • Synthesis, characterization and catalytic properties of SAPO-34 synthesized using diethylamine as a template
    • Liu G., Tian P., Li J., Zhang D., Zhou F., Liu Z. Synthesis, characterization and catalytic properties of SAPO-34 synthesized using diethylamine as a template. Microporous Mesoporous Mater. 2008, 111:143-149.
    • (2008) Microporous Mesoporous Mater. , vol.111 , pp. 143-149
    • Liu, G.1    Tian, P.2    Li, J.3    Zhang, D.4    Zhou, F.5    Liu, Z.6
  • 39
    • 0033613493 scopus 로고    scopus 로고
    • Synthesis of Ga-incorporated SAPO-34s (GaAPSO-34) and their catalytic performance on methanol conversion
    • Kang M., Lee C.-T. Synthesis of Ga-incorporated SAPO-34s (GaAPSO-34) and their catalytic performance on methanol conversion. J. Mol. Catal. A Chem. 1999, 150:213-222.
    • (1999) J. Mol. Catal. A Chem. , vol.150 , pp. 213-222
    • Kang, M.1    Lee, C.-T.2
  • 40
    • 0034739382 scopus 로고    scopus 로고
    • Methanol conversion on metal-incorporated SAPO-34s (MeAPSO-34s)
    • Kang M. Methanol conversion on metal-incorporated SAPO-34s (MeAPSO-34s). J. Mol. Catal. A Chem. 2000, 160:437-444.
    • (2000) J. Mol. Catal. A Chem. , vol.160 , pp. 437-444
    • Kang, M.1
  • 41
    • 0036958131 scopus 로고    scopus 로고
    • Substitution of transition metal ions into aluminophosphates and silicoaluminophosphates: characterization and relation to catalysis
    • Hartmann M., Kevan L. Substitution of transition metal ions into aluminophosphates and silicoaluminophosphates: characterization and relation to catalysis. Res. Chem. Intermed. 2002, 28:625-695.
    • (2002) Res. Chem. Intermed. , vol.28 , pp. 625-695
    • Hartmann, M.1    Kevan, L.2
  • 45
    • 84890023281 scopus 로고    scopus 로고
    • 2 nanocatalyst used for toluene abatement from waste gas streams at low temperature: conventional vs. plasma-ultrasound hybrid synthesis methods
    • 2nanocatalyst used for toluene abatement from waste gas streams at low temperature: conventional vs. plasma-ultrasound hybrid synthesis methods. Microporous Mesoporous Mater. 2014, 185:213-223.
    • (2014) Microporous Mesoporous Mater. , vol.185 , pp. 213-223
    • Rahmani, F.1    Haghighi, M.2    Estifaee, P.3
  • 46
    • 84895072206 scopus 로고    scopus 로고
    • 3 nanocatalyst used in hydrogen purification: effect of Pd loading and ultrasound irradiation time
    • 3nanocatalyst used in hydrogen purification: effect of Pd loading and ultrasound irradiation time. Ultrason. Sonochem. 2014, 21:1155-1165.
    • (2014) Ultrason. Sonochem. , vol.21 , pp. 1155-1165
    • Estifaee, P.1    Haghighi, M.2    Mohammadi, N.3    Rahmani, F.4
  • 47
    • 84888138326 scopus 로고    scopus 로고
    • 3 over HZSM-5: effect of precursor and irradiation power on nanocatalyst properties and catalytic performance for direct syngas to DME
    • 3over HZSM-5: effect of precursor and irradiation power on nanocatalyst properties and catalytic performance for direct syngas to DME. Ultrason. Sonochem. 2014, 21:663-673.
    • (2014) Ultrason. Sonochem. , vol.21 , pp. 663-673
    • Allahyari, S.1    Haghighi, M.2    Ebadi, A.3    Hosseinzadeh, S.4
  • 53
    • 73649094133 scopus 로고    scopus 로고
    • Effect of mesoporosity against the deactivation of MFI zeolite catalyst during the methanol-to-hydrocarbon conversion process
    • Kim J., Choi M., Ryoo R. Effect of mesoporosity against the deactivation of MFI zeolite catalyst during the methanol-to-hydrocarbon conversion process. J. Catal. 2010, 269:219-228.
    • (2010) J. Catal. , vol.269 , pp. 219-228
    • Kim, J.1    Choi, M.2    Ryoo, R.3
  • 54
    • 84864921835 scopus 로고    scopus 로고
    • Methanol conversion to light olefins over sonochemically prepared SAPO-34 nanocatalyst
    • Askari S., Halladj R., Sohrabi M. Methanol conversion to light olefins over sonochemically prepared SAPO-34 nanocatalyst. Microporous Mesoporous Mater. 2012, 163:334-342.
    • (2012) Microporous Mesoporous Mater. , vol.163 , pp. 334-342
    • Askari, S.1    Halladj, R.2    Sohrabi, M.3
  • 55
    • 32844465143 scopus 로고    scopus 로고
    • Post-mortem characterization of coke-induced deactivated alumina-supported Co-Ni catalysts
    • Hardiman K.M., Cooper C.G., Adesina A.A., Lange R. Post-mortem characterization of coke-induced deactivated alumina-supported Co-Ni catalysts. Chem. Eng. Sci. 2006, 61:2565-2573.
    • (2006) Chem. Eng. Sci. , vol.61 , pp. 2565-2573
    • Hardiman, K.M.1    Cooper, C.G.2    Adesina, A.A.3    Lange, R.4
  • 56
    • 0038636540 scopus 로고    scopus 로고
    • Structural characterization of coke deposits on industrial spent paraffin dehydrogenation catalysts
    • Sahoo S.K., Rao P.V.C., Rajeshwer D., Krishnamurthy K.R., Singh I.D. Structural characterization of coke deposits on industrial spent paraffin dehydrogenation catalysts. Appl. Catal. A 2003, 244:311-321.
    • (2003) Appl. Catal. A , vol.244 , pp. 311-321
    • Sahoo, S.K.1    Rao, P.V.C.2    Rajeshwer, D.3    Krishnamurthy, K.R.4    Singh, I.D.5
  • 57
    • 0034615439 scopus 로고    scopus 로고
    • Studies of catalyst deactivation in methanol conversion with high, medium and small pore silicoaluminophosphates
    • Campelo J.M., Lafont F., Marinas J.M., Ojeda M. Studies of catalyst deactivation in methanol conversion with high, medium and small pore silicoaluminophosphates. Appl. Catal. A 2000, 192:85-96.
    • (2000) Appl. Catal. A , vol.192 , pp. 85-96
    • Campelo, J.M.1    Lafont, F.2    Marinas, J.M.3    Ojeda, M.4


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