Citation: SHI He-xiang, LI Zhi-kai, LIU Ke-feng, XIAO Hai-cheng, KONG Fan-hua, ZHANG Juan, CHEN Jian-gang. Enhanced formation of α-olefins by the pulse process between Fischer-Tropsch synthesis and N₂ purging[J]. Journal of Fuel Chemistry and Technology, ;2016, 44(7): 822-829. shu

Enhanced formation of α-olefins by the pulse process between Fischer-Tropsch synthesis and N₂ purging

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China
3.
Petrochemical Research Institute of Petro China Company Limited, Beijing 100029, China

Corresponding author: CHEN Jian-gang, chenjg@sxicc.ac.cn
Received Date: 3 March 2016
Revised Date: 6 April 2016

Fund Project: The project was supported by the National Natural Science Foundation of China 21373254PetroChina PRIKY15039PetroChina PRIKY15042The project was supported by the National Natural Science Foundation of China 21503256PetroChina PRIKY14006PetroChina PRIKY15038

Figures(7)

The Fischer-Tropsch synthesis has offered an alternative way to convert coal and biomass into chemicals such as α-olefins via sygas comprised of H₂ and CO. A pulse process switching between Fischer-Tropsch synthesis and N₂ purging was carried out when the Fischer-Tropsch synthesis became stable in the fixed bed reactor. The activity and selectivity over Fe-Co catalyst for α-olefins in Fischer-Tropsch synthesis reaction were measured under the normal conditions of 2.0 MPa, 497 K, 2 000 h^-1 and H₂/CO volume ratio of 2.0. It was found that the olefin to paraffin ratio of C₃ for Fe-Co catalyst purged at 517 K and 0.2 MPa was almost nine times higher than that of the fresh one without purging under the same reaction conditions, and the CH₄ selectivity and CO conversion decreased after purging. Two possible reasons were proposed to explain these phenomena. Moreover, a batch experiment by the pulse process in fixed bed reactor was performed. Notably, a high olefins yield was obtained via the pulse process during the Fischer-Tropsch synthesis.
- alpha olefins,
- pulse process,
- N₂ purging,
- Fischer-Tropsch synthesis
1. [1]
  DRY M E. The Fischer-Tropsch process: 1950-2000[J]. Catal Today, 2002,71(3/4):227-241.
2. [2]
  ZHENG S, SUN J, SONG D, CHEN Z, CHEN J. The facile fabrication of magnetite nanoparticles and their enhanced catalytic performance in Fischer-Tropsch synthesis[J]. Chem Commun, 2015,51(55):11123-11125. doi: 10.1039/C5CC03336E
3. [3]
  DUPAIN X, KRUL R A, SCHAVERIEN C J, MAKKEE M, MOULIJN J A. Production of clean transportation fuels and lower olefins from Fischer-Tropsch synthesis waxes under fluid catalytic cracking conditions[J]. Appl Catal B: Environ, 2006,63(3/4):277-295.
4. [4]
  CAVELL R G, CREED B, GELMINI L, LAW D J, MCDONALD R, SANGER A R, SOMOGYVARI A. Design, syntheses and application of new phosphine and dithiophosphinate complexes of nickel: Catalyst precursors for the oligomerization of ethylene[J]. Inorg Chem, 1998,37(4):757-763. doi: 10.1021/ic970798w
5. [5]
  JANARDANARAO M. Direct catalytic conversion of synthesis gas to lower olefins[J]. Ind Eng Chem Res, 1990,29(9):1735-1753. doi: 10.1021/ie00105a001
6. [6]
  LIU Z, SUN C, WANG G, WANG Q, CAI G. New progress in R & D of lower olefin synthesis[J]. Fuel Process Technol, 2000,62(2/3):161-172.
7. [7]
  PARK J, LEE Y, JUN K, BAE J W, VISWANADHAM N, KIM Y H. Direct conversion of synthesis gas to light olefins using dual bed reactor[J]. J Ind Eng Chem, 2009,15(6):847-853. doi: 10.1016/j.jiec.2009.09.011
8. [8]
  TORRES GALÜIS H M, BITTER J H, KHARE C B, RUITENBEEK M, DUGULAN A I, DE JONG K P. Supported iron nanoparticles as catalysts for sustainable production of lower olefins[J]. Science, 2012,335(6070):835-838. doi: 10.1126/science.1215614
9. [9]
  MA C, CHEN J. Effect of hydrothermal treatment on precipitated iron catalyst for Fischer-Tropsch Synthesis[J]. Catal Lett, 2015,145(2):702-711. doi: 10.1007/s10562-014-1457-4
10. [10]
  SUN J, ZHENG S, ZHANG K, SONG D, LIU Y, SUN X, CHEN J. The crystal plane effect of CoFe nanocrystals on Fischer-Tropsch synthesis[J]. J Mater Chem A, 2014,2(32):13116-13122. doi: 10.1039/C4TA02425G
11. [11]
  JOYNER R W. The mechanism of chain growth in the Fischer-Tropsch hydrocarbon synthesis[J]. Catal Lett, 1988,1(10):307-310. doi: 10.1007/BF00774872
12. [12]
  MADON R J, IGLESIA E. The importance of olefin readsorption and H₂/CO reactant ratio for hydrocarbon chain growth on ruthenium catalysts[J]. J Catal, 1993,139(2):576-590. doi: 10.1006/jcat.1993.1051
13. [13]
  LINGHU W, LIU X, LI X, FUJIMOTO K. Selective synthesis of higher linear alpha-olefins over cobalt Fischer-Tropsch catalyst[J]. Catal Lett, 2006,108(1/2):11-13.
14. [14]
  JANANI H, REZVANI A R, GRIVANI G H, MIRZAEI A A. Fischer-Tropsch synthesis of hydrocarbons over new Co/Ce bimetallic catalysts derived from dipicolinate and carbonyl metal complexes[J]. J Inorg Organomet Polym, 2015,25(5):1169-1182. doi: 10.1007/s10904-015-0225-2
15. [15]
  RAMASAMY K K, GRAY M, JOB H, WANG Y. Direct syngas hydrogenation over a Co-Ni bimetallic catalyst: Process parameter optimization[J]. Chem Eng Sci, 2015,135:266-273. doi: 10.1016/j.ces.2015.03.064
16. [16]
  SHIMURA K, MIYAZAWA T, HANAOKA T, HIRATA S. Fischer-Tropsch synthesis over alumina supported bimetallic Co-Ni catalyst: Effect of impregnation sequence and solution[J]. J Mol Catal A: Chem, 2015,407:15-24. doi: 10.1016/j.molcata.2015.06.013
17. [17]
  FARZANFAR J, REZVANI A R. Inorganic complex precursor route for preparation of high-temperature Fischer-Tropsch synthesis Ni-Co nanocatalysts[J]. Res Chem Intermed, 2015,41(11):8975-9001. doi: 10.1007/s11164-015-1942-4
18. [18]
  CALDERONE V R, SHIJU N R, FERRE D C, ROTHENBERGA G. Bimetallic catalysts for the Fischer-Tropsch reaction[J]. Green Chem, 2011,13(8):1950-1959. doi: 10.1039/c0gc00919a
19. [19]
  KEYSER M J, EVERSON R C, ESPINOZA R L. Fischer-Tropsch studies with cobalt-manganese oxide catalysts: Synthesis performance in a fixed bed reactor[J]. Appl Catal A: Gen, 1998,171(1):99-107. doi: 10.1016/S0926-860X(98)00083-0
20. [20]
  DUVENHAGE D J, COVILLE N J. Fe:Co/TiO₂ bimetallic catalysts for the Fischer-Tropsch reaction I. Characterization and reactor studies[J]. Appl Catal A: Gen, 1997,153(1/2):43-67.
21. [21]
  DUVENHAGE D J, COVILLE N J. Fe: Co/TiO₂ bimetallic catalysts for the Fischer-Tropsch reaction: part 2. the effect of calcination and reduction temperature[J]. Appl Catal A: Gen, 2002,233(1/2):63-75.
22. [22]
  TIHAY F, ROGER A C, KIENNEMANN A, POURROY G. Fe-Co based metal/spinel to produce light olefins from syngas[J]. Catal Today, 2000,58(4):263-269. doi: 10.1016/S0920-5861(00)00260-1
23. [23]
  MIRZAEI A A, HABIBPOUR R, KASHI E. Preparation and optimization of mixed iron cobalt oxide catalysts for conversion of synthesis gas to light olefins[J]. Appl Catal A: Gen, 2005,296(2):222-231. doi: 10.1016/j.apcata.2005.08.033
24. [24]
  MA X, SUN Q, YING W, FANG D. Effects of the ratio of Fe to Co over Fe-Co/SiO₂ bimetallic catalysts on their catalytic performance for Fischer-Tropsch synthesis[J]. J Nat Gas Chem, 2009,18(2):232-236. doi: 10.1016/S1003-9953(08)60102-4
25. [25]
  DE LA PENA O'SHEA V A, ÁLÜAREZ-GALÜAN M C, CAMPOS-MARTIN J M, FIERRO J L G. Fischer-Tropsch synthesis on mono-and bimetallic Co and Fe catalysts in fixed-bed and slurry reactors[J]. Appl Catal A: Gen, 2007,326(1):65-73. doi: 10.1016/j.apcata.2007.03.037
26. [26]
  YOKOTA K, FUJIMOTO K. Supercritical phase Fischer-Tropsch synthesis reaction[J]. Fuel, 1989,68(2):255-256. doi: 10.1016/0016-2361(89)90335-9
27. [27]
  SAVOST'YANOV A P, YAKOVENKOA R E, NAROCHNYI G B, LAPIDUS A L. Effect of the dilution of synthesis gas with nitrogen on the Fischer-Tropsch process for the production of hydrocarbons[J]. Solid Fuel Chem, 2015,49(6):356-359. doi: 10.3103/S0361521915060099
28. [28]
  LU X, ZHU X, HILDEBRANDT D, LIU X, GLASSER D. A new way to look at Fischer-Tropsch Synthesis using flushing experiments[J]. Ind Eng Chem Res, 2011,50(8):4359-4365. doi: 10.1021/ie102095c
29. [29]
  SCHULZ H. Major and minor reactions in Fischer-Tropsch synthesis on cobalt catalysts[J]. Top Catal, 2003,26(1/4):73-85.
30. [30]
  SCHULZ H, NIE Z, OUSMANOV F. Construction of the Fischer-Tropsch regime with cobalt catalysts[J]. Catal Today, 2002,71(3/4):351-360.
31. [31]
  WILSON J, DE GROOT C. Atomic-scale restructuring in high-pressure catalysis[J]. J Phys Chem, 1995,99:7860-7866. doi: 10.1021/j100020a005
32. [32]
  LIU Y, CHEN J, FANG K, WANG Y, SUN Y. A large pore-size mesoporous zirconia supported cobalt catalyst with good performance in Fischer-Tropsch synthesis[J]. Catal Commun, 2007,8(6):945-949. doi: 10.1016/j.catcom.2006.06.019
33. [33]
  KHODAKOV A Y, GRIBOVOL-CONSTANT A, BECHARA R, ZHOLOBENKO V L. Pore size efects in Fischer Tropsch synthesis over cobalt-dupported mesoporous silicas[J]. J Catal, 2002,206(2):230-241. doi: 10.1006/jcat.2001.3496
34. [34]
  OLEWSKI T, TODIC B, NOWICKI L, NIKACEVIC N, BUKUR D B. Hydrocarbon selectivity models for iron-based Fischer-Tropsch catalyst[J]. Chem Eng Res Des, 2015,95:1-11. doi: 10.1016/j.cherd.2014.12.015
35. [35]
  YAN F, QIAN W, SUN Q, ZHANG H, YING W, FANG D. Product distributions and olefin-to-paraffin ratio over an iron-based catalyst for Fischer-Tropsch synthesis[J]. React Kinet Mech Cat, 2014,113(2):471-485. doi: 10.1007/s11144-014-0746-7
36. [36]
  TSUBAKI N, FUJIMOTO K. Product control in Fischer-Tropsch synthesis[J]. Fuel Process Technol, 2000,62(2/3):173-186.
37. [37]
  ERKEY C, RODDEN J B, AKGERMAN A. Diffusivities of synthesis gas and n-alkanes in Fischer-Tropsch wax[J]. Energy Fuels, 1990,4(3):275-276. doi: 10.1021/ef00021a010
38. [38]
  IGLESIA E, REYES S C, MADON R J. Transport-enhanced alpha-olefin readsorption pathways in Ru-catalyzed hydrocarbon synthesis[J]. J Catal, 1991,129(1):238-256. doi: 10.1016/0021-9517(91)90027-2
39. [39]
  SCHULZ H, CLAEYS M. Reactions of alpha-olefins of different chain length added during Fischer-Tropsch synthesis on a cobalt catalyst in a slurry reactor[J]. Appl Catal A: Gen, 1999,186(1/2):71-90.
40. [40]
  CHENG J, SONG T, HU P, LOK C M, ELLIS P, FRENCH S. A density functional theory study of the α-olefin selectivity in Fischer-Tropsch synthesis[J]. J Catal, 2008,255(1):20-28. doi: 10.1016/j.jcat.2008.01.027
41. [41]
  KUIPERS E W, VINKENBURG I H, OOSTERBEEK H. Chain-length dependence of alpha-olefin readsorption in Fischer-Tropsch synthesis[J]. J Catal, 1995,152(1):137-146. doi: 10.1006/jcat.1995.1068
1. [1]
  Hui Li , Yanxing Qi , Jia Chen , Juanjuan Wang , Min Yang , Hongdeng Qiu . Synthesis of amine-pillar[5]arene porous adsorbent for adsorption of CO₂ and selectivity over N₂ and CH₄. Chinese Chemical Letters, 2024, 35(11): 109659-. doi: 10.1016/j.cclet.2024.109659
2. [2]
  Yating Yang , Ming Xu , Ze Gao , Ting Wang , Zhaoxing Li , Yuqi Wang , Daming Yang , Ming Feng . Oxygen vacancy engineering of Fe₂O₃ nanospindles via cobalt incorporation for enhanced electrocatalytic N₂ reduction towards NH₃ synthesis. Chinese Chemical Letters, 2026, 37(11): 112580-. doi: 10.1016/j.cclet.2026.112580
3. [3]
  Rui Hu , Yidan Qi , Xingyu Wang , Yunhui Yang , Congyang Wang . Titanium-promoted conversion of N₂ into N-methylimides. Chinese Chemical Letters, 2026, 37(1): 111197-. doi: 10.1016/j.cclet.2025.111197
4. [4]
  Zhen Zhang , Rui Su , Xiongjun Xiao , Jiaxin Yang , Yuwei Li , Tiemin Sun , Yang Liu , Chengjun Wu . A continuous-flow process for the synthesis of balsalazide disodium. Chinese Chemical Letters, 2026, 37(7): 111965-. doi: 10.1016/j.cclet.2025.111965
5. [5]
  Sanmei Wang , Yong Zhou , Hengxin Fang , Chunyang Nie , Chang Q Sun , Biao Wang . Constant-potential simulation of electrocatalytic N₂ reduction over atomic metal-N-graphene catalysts. Chinese Chemical Letters, 2025, 36(3): 110476-. doi: 10.1016/j.cclet.2024.110476
6. [6]
  Bin Chen , Chaoyang Zheng , Dehuan Shi , Yi Huang , Renxia Deng , Yang Wei , Zheyuan Liu , Yan Yu , Shenghong Zhong . p-d orbital hybridization induced by CuGa2 promotes selective N2 electroreduction. Chinese Journal of Structural Chemistry, 2025, 44(1): 100468-100468. doi: 10.1016/j.cjsc.2024.100468
7. [7]
  Chang LIU , Chao ZHANG , Tongbu LU . Small-size Au nanoparticles anchored on pyrenyl-graphdiyne for N₂ electroreduction. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 174-182. doi: 10.11862/CJIC.20240305
8. [8]
  Chaozheng He , Menghui Xi , Chenxu Zhao , Ran Wang , Ling Fu , Jinrong Huo . Highly N₂ dissociation catalyst: Ir(100) and Ir(110) surfaces. Chinese Chemical Letters, 2025, 36(3): 109671-. doi: 10.1016/j.cclet.2024.109671
9. [9]
  Ping Wang , Tianbao Zhang , Zhenxing Li . Reconstruction mechanism of Cu surface in CO2 reduction process. Chinese Journal of Structural Chemistry, 2024, 43(8): 100328-100328. doi: 10.1016/j.cjsc.2024.100328
10. [10]
  Jingtai Bi , Yupeng Cheng , Mengmeng Sun , Xiaofu Guo , Shizhao Wang , Yingying Zhao . Efficient and selective photocatalytic nitrite reduction to N₂ through CO₂ anion radical by eco-friendly tartaric acid activation. Chinese Chemical Letters, 2024, 35(11): 109639-. doi: 10.1016/j.cclet.2024.109639
11. [11]
  Lijun Yan , Shiqi Chen , Penglu Wang , Xiangyu Liu , Lupeng Han , Tingting Yan , Yuejin Li , Dengsong Zhang . Hydrothermally stable metal oxide-zeolite composite catalysts for low-temperature NO_x reduction with improved N₂ selectivity. Chinese Chemical Letters, 2024, 35(6): 109132-. doi: 10.1016/j.cclet.2023.109132
12. [12]
  Shanyuan Bi , Jin Zhang , Dengchao Peng , Danhong Cheng , Jianping Zhang , Lupeng Han , Dengsong Zhang . Improved N₂ selectivity for low-temperature NO_x reduction over etched ZSM-5 supported MnCe oxide catalysts. Chinese Chemical Letters, 2025, 36(5): 110295-. doi: 10.1016/j.cclet.2024.110295
13. [13]
  Jinzhou Zheng , Chaozheng He , Chenxu Zhao . Rational catalyst design for N₂ electro-reduction: Regulation strategies and quick screen towards enhanced conversion efficiency. Chinese Chemical Letters, 2025, 36(7): 111056-. doi: 10.1016/j.cclet.2025.111056
14. [14]
  Fangxiang SUN , Qing ZHANG , Yifan ZHANG , Haoyi SUN , Akim V. Shmal′ko , Sergey A. Anufriev , Igor B. Sivaev , Deshuang TU , Hong YAN . Pd-catalyzed B—H bond activation and annulation of nido-carborane with terminal olefins: Facile construction of 2D-3D fused polycyclic compounds. Chinese Journal of Inorganic Chemistry, 2026, 42(3): 467-478. doi: 10.11862/CJIC.20250347
15. [15]
  Jijoe Samuel Prabagar , Kumbam Lingeshwar Reddy , Dong-Kwon Lim . Visible-light responsive gold nanoparticle and nano-sized Bi2O3-x sheet heterozygote structure for efficient photocatalytic conversion of N2 to NH3. Chinese Journal of Structural Chemistry, 2025, 44(4): 100564-100564. doi: 10.1016/j.cjsc.2025.100564
16. [16]
  Jingtao Bi , Yupeng Cheng , Mengmeng Sun , Xiaofu Guo , Shizhao Wang , Yingying Zhao . Corrigendum to “Efficient and selective photocatalytic nitrite reduction to N₂ through CO₂ anion radical by eco-friendly tartaric acid activation” [Chinese Chemical Letters 35 (2024) 109639]. Chinese Chemical Letters, 2025, 36(7): 110867-. doi: 10.1016/j.cclet.2025.110867
17. [17]
  Yangyang Sun , Tianyu Huang , Houqiang Ji , Tian Tian , Xingwang Zhu , Wenlin Xu , Huan Pang . Efficient charge separation by Ti₃C₂ MXene modified nano MIL-125(Ti) Schottky photocatalysts for N₂ reduction and tetracycline hydrochloride removal. Chinese Chemical Letters, 2026, 37(3): 111391-. doi: 10.1016/j.cclet.2025.111391
18. [18]
  Yiqian Jiang , Zihan Yang , Xiuru Bi , Nan Yao , Peiqing Zhao , Xu Meng . Mediated electron transfer process in α-MnO₂ catalyzed Fenton-like reaction for oxytetracycline degradation. Chinese Chemical Letters, 2024, 35(8): 109331-. doi: 10.1016/j.cclet.2023.109331
19. [19]
  Xueyang Zhao , Bangwei Deng , Hongtao Xie , Yizhao Li , Qingqing Ye , Fan Dong . Recent process in developing advanced heterogeneous diatomic-site metal catalysts for electrochemical CO₂ reduction. Chinese Chemical Letters, 2024, 35(7): 109139-. doi: 10.1016/j.cclet.2023.109139
20. [20]
  Xiao-Kai Li , Si-Hao Fu , Yi Yue , Rui-Jing Pang , Jia Feng , Ren-Rong Liu . C₂-Symmetric N–N atropisomeric diphosphines: Synthesis and application in enantioselective dearomatization of heteroaryls. Chinese Chemical Letters, 2026, 37(5): 111430-. doi: 10.1016/j.cclet.2025.111430

Get Citation

PDF

XML

Metrics

PDF Downloads(2)
Abstract views(1518)
HTML views(116)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Enhanced formation of α-olefins by the pulse process between Fischer-Tropsch synthesis and N2 purging

Metrics

通讯作者: 陈斌, bchen63@163.com

Enhanced formation of α-olefins by the pulse process between Fischer-Tropsch synthesis and N₂ purging