One-step catalyst for the preparation of light olefins and liquid fuels from syngas
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摘要: 以合成气作为平台化合物一步法制备低碳烯烃和液体燃料是有效利用碳资源的重要路径,具备流程短、能耗低的特点,有着良好的工业应用前景。合成气一步法直接转化制备低碳烯烃和液体燃料包括两条工艺路线:费托合成路线和双功能催化路线。本综述简述了两种路线的反应机理,重点阐述了费托合成路线中采用添加助剂和惰性载体对铁基和钴基催化剂的优化设计,费托金属粒径、反应条件、催化剂界面结构对催化剂性能和反应过程的影响。详细解析了双功能催化路线中,一氧化碳活化组分和酸性分子筛的选择、金属氧化物粒径与元素比例、分子筛酸度与孔径大小以及一氧化碳活化组分和酸性分子筛的耦合方式对于催化剂性能的影响。总结了两条路线所具备的优势和面临的挑战,并对未来高效催化剂的发展方向进行了展望。Abstract: One-step synthesis of light olefin and liquid fuel using syngas as platform compound is an important way to effectively utilize carbon resources. It has the characteristics of short process, low energy consumption, and is of good industrial application prospects. The one-step direct conversion of syngas to prepare light olefins and liquid fuels consists of two process routes: the Fischer-Tropsch (F-T) route and the bifunctional catalytic route. In this paper, the reaction mechanisms of both routes are briefly described. The optimal design of Fe-based and Co-based catalysts by inert supports, the effect of F-T metal particle size, reaction conditions, and catalyst structure on the catalytic performance and reaction process have been elaborated. In the bifunctional catalytic route, the influences of the CO activation components, zeolite type, the proportion and particle size of the metal oxide elements, the acidity and pore size of zeolites and the methods for coupling the CO activation components and zeolite on the performance of the catalysts were analyzed in detail. The advantages and challenges of the two routes are summarized. The development trends of efficient catalysts in the future have also been prospected.
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Key words:
- syngas /
- catalyst /
- light olefins /
- liquid fuels /
- bifunctional catalysis /
- Fischer-Tropsch synthesis
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表 1 费托合成反应
Table 1 Fischer-Tropsch synthesis reaction
Reaction type Reaction name Reaction equation Main reaction paraffin formation $n{\rm{CO}} + \left(2n + 1\right){{\rm{H}}}_{2}\to {{\rm{C}}}_{n}{{\rm{H}}}_{2n + 2} + n{{\rm{H}}}_{2}{\rm{O}}$ olefin formation $n{\rm{CO}} + 2n{{\rm{H}}}_{2}\to {{\rm{C}}}_{n}{{\rm{H}}}_{2n} + n{{\rm{H}}}_{2}{\rm{O}}$ water-gas shift reaction ${\rm{CO}} + {{\rm{H}}}_{2}{\rm{O}}\rightleftharpoons {\rm{C}}{{\rm{O}}}_{2} + {{\rm{H}}}_{2}$ Side reaction alcohol formation $n{\rm{CO}} + 2n{{\rm{H}}}_{2}\to {{\rm{C}}}_{n}{{\rm{H}}}_{2n + 1}{\rm{O}} + \left(n + 1\right){{\rm{H}}}_{2}{\rm{O}}$ boudard reaction $2{\rm{CO}}\rightleftharpoons {\rm{C}} + {\rm{C}}{\rm{{O}}}_{2}$ 表 2 不同CO活化组分与酸性分子筛相结合的双功能催化剂
Table 2 Bifunctional catalysts with different CO activated components combined with acidic molecular sieves
CO activation
componentsZeolite CO conv./% Selectivity of hydrocarbonsm/% Reference CH4 ${\rm{C}}_{2}^=-{\rm{C}}_{4}^= $ ${\rm{C}}_{2}^{0}-{\rm{C}}_{4}^{0}$ C5 + Ru meso-ZSM-5 29.6a 5.9 − − 79.0 [69] Co meso-ZSM-5 43.0a 7.7 − − 70.0 [70] Fe ZSM-5 48.0a 27.0 − − 51.0 [71] Co ZSM-5 29.0b 15.0 − − 53.0 [72] MnOx SAPO-34 8.5c 2.0 79.2 12.9 − [73] ZnCrOx SAPO-34 17.0d 2.0 80.0 14.0 4.0 [74] Zn-Cr SAPO-34 30.0e 16.0 38.0 45.0 − [67] Zn-Al2O3 SAPO-34 4.5f 10.4 77.0 12.6 0 [68] Zn-Cr2O3 SAPO-34 1.8f 16.0 37.2 46.8 0 [68] Zn-ZrO2 SAPO-34 5.3f 30.2 11.2 58.6 0 [68] Zn-CeO2 SAPO-34 2.1f 34.4 55.8 9.8 0 [68] Zr-Zn SAPO-34 7.5g 11.0 37.0 48.0 3.2 [75] MgAl2O4 SAPO-34 1.0h 9.9 62.0 33.0 0.1 [76] MgGa2O4 SAPO-34 6.8h 6.5 68.0 18.0 7.7 [76] MgCr2O4 SAPO-34 4.2h 4.4 62.0 33.0 0.1 [76] Mn-Ga SAPO-34 14.0i 2.0 88.0 8.0 2.0 [77] ZnxCe2-yZryO4 SAPO-34 6.0j 5.0 83.0 4.0 9.0 [78] ZnO-ZrO2 SAPO-34 7.0k 4.0 69.0 25.0 2.0 [79] ZnGa2O4 SAPO-34 30.0l 5.0 77.0 17.0 2.0 [80] a: H2/CO=1.0,360 ℃,2.0 MPa,GHSV=2400 mL/(h·gcat);b: H2/CO=1.0,280 ℃,2.1 MPa,GHSV=1153 mL/(h·gcat);c: H2/CO=2.5, 400 ℃,2.5 MPa,GHSV=4800 mL/(h·gcat);d: H2/CO=2.5,400 ℃,2.5 MPa,GHSV=7714 mL/(h·gcat);e: H2/CO=1.0,400 ℃,2.0 MPa,GHSV=1125 mL/(h·gcat);f: H2/CO=1.0,390 ℃,4.0 MPa,GHSV=1800 mL/(h·gcat);g: H2/CO=2.0,360 ℃,1.0 MPa,GHSV=3600 mL/(h·gcat);h: H2/CO=2.0,400 ℃,3.0 MPa,GHSV=1800 mL/(h·gcat);i: H2/CO=2.0,400 ℃,2.5 MPa,GHSV=4875 mL/(h·gcat);j: H2/CO=2.0,300 ℃,1.0 MPa,GHSV=5400 mL/(h·gcat);k: H2/CO=1.0,360 ℃,2.0 MPa,GHSV=1600 mL/(h·gcat);l: H2/CO=2.0,400 ℃,3.0 MPa,GHSV=3600 mL/(h·gcat);m:Product obtained based on C mole calculations, excluding CO2 表 3 不同比例金属元素与酸性分子筛相结合的双功能催化剂
Table 3 Bifunctional catalysts with different ratios of metal elements combined with acidic molecular sieves
Metal oxides (scale) Zeolite CO conv./% Selectivity of hydrocarbonsc/% Reference CH4 ${\rm{C} }_{2}^= - {\rm{C} }_{4}^=$ ${\rm{C} }_{2}^{0} - {\rm{C} }_{4}^{0}$ C5 + ZnO SAPO-34 3.3a 43.0 8.1 4.9 0 [75] Zr-Zn(1∶1) SAPO-34 7.5a 11.0 37.0 48.0 3.2 [75] Zr-Zn(2∶1) SAPO-34 9.5a 6.0 63.0 29.0 2.2 [75] Zr-Zn(4∶1) SAPO-34 6.8a 4.2 69.0 25.0 2.1 [75] ZrO2 SAPO-34 1.0a 4.0 90.0 5.5 1.1 [75] ZrO2 SSZ-13 3.9a 2.0 80.0 10.0 8.0 [80] Zn-ZrO2(1∶64) SSZ-13 18.0b 1.8 75.2 2.0 10.0 [80] Zn-ZrO2(1∶32) SSZ-13 21.0b 2.0 74.0 4.0 10.0 [80] Zn-ZrO2(1∶16) SSZ-13 23.0b 2.0 75.0 4.0 9.0 [80] Zn-ZrO2(1∶4) SSZ-13 26.0b 2.0 66.0 21.0 11.0 [80] Zn-ZrO2(1∶1) SSZ-13 28.0b 3.0 59.0 20.0 18.0 [80] Zn-ZrO2(2∶1) SSZ-13 28.0b 4.0 54.0 26.0 16.0 [80] Zn-ZrO2(4∶1) SSZ-13 22.0b 5.0 35.0 44.0 16.0 [80] ZnO SSZ-13 6.0b 8.0 24.0 58.0 10.0 [80] a: H2/CO=2,360 ℃,1.0 MPa,GHSV=3600 mL/(h·gcat);b: H2/CO=2,400 ℃,3.0 MPa,GHSV=2700 mL/(h·gcat);c Product obtained based on C mole calculations, excluding CO2 表 4 CO活化组分粒径对反应的影响
Table 4 Effect of CO activation component particle size on the reaction
CO activation
componentParticle size/ nm Zeolite CO conv.
/%CO2 sel.
/%Selectivity of hydrocarbonsc/% Reference CH4 ${\rm{C}}_{2}^= - {\rm{C}}_{4}^= $ ${\rm{C}}_{2}^{0} - {\rm{C}}_{4}^{0} $ C5–C9 C10–C20 Co 4.9 Na-meso-Y 40.0a − 12.0 − − 29.0 45.0 [64] Co 6.5 Na-meso-Y 38.0a − 5.0 − − 27.0 47.0 [64] Co 8.4 Na-meso-Y 34.0a − 5.0 − − 18.0 60.0 [64] Co 14.0 Na-meso-Y 39.0a − 5.0 − − 18.5 52.0 [64] Co 20.0 Na-meso-Y 36.0a − 4.5 − − 18.3 51.0 [64] Co 27.0 Na-meso-Y 30.0a − 4.0 − − 18.0 48.0 [64] ZnO 23.0 SAPO-34 31.9b 42.0 3.1 76.7 15.5 − − [81] ZnO 24.0 SAPO-34 33.2b 41.0 3.0 76.5 15.9 − − [81] ZnO 25.0 SAPO-34 33.5b 41.0 2.9 76.1 16.4 − − [81] ZnO 33.0 SAPO-34 29.7b 41.0 2.6 75.6 17.4 − − [81] ZnO 40.0 SAPO-34 24.4b 41.0 2.5 74.3 18.9 − − [81] ZnO 53.0 SAPO-34 17.4b 40.0 2.4 67.0 24.8 − − [81] ZnO 62.0 SAPO-34 11.8b 37.0 2.7 60.0 30.1 − − [81] ZnO 79.0 SAPO-34 6.5b 32.0 2.4 61.0 28.6 − − [81] a: Co/zeolite=0.15∶1 (mass ratio),H2/CO=1,230 ℃,2.0 MPa,GHSV=1800 mL/(h·gcat);b: ZnO/zeolite =2∶1 (mass ratio),H2/CO=2.5,400 ℃,4 MPa,GHSV =1600 mL/(h·gcat);c Product obtained based on C mole calculations, excluding CO2 表 5 双功能催化剂中分子筛结构对合成气催化转化的影响
Table 5 Effect of zeolite structure in bifunctional catalysts on the catalytic conversion of syngas
CO activation
componentZeolite Topology Orifice structure CO conv.
/%CO2 sel.
/%Selectivity of hydrocarbonsh/% Reference CH4 ${\rm{C}}_{2}^= - {\rm{C}}_{4}^= $ ${\rm{C}}_{2}^{0} - {\rm{C}}_{4}^{0} $ C5 + ${\rm{C}}_{5} - {\rm{C}}_{11}$ Co SSZ-13 CHA 3D 8-MR 27.4a − 17.5 − − 71.1 − [83] Co ZSM-22 TON 1D 10-MR 5.0a − 32.5 − − 48.5 − [83] Co ZSM-11 MEL 3D 10-MR 54.8a − 15.4 − − 72.7 − [83] Co ZSM-5 MFI 3D 10-MR 56.7a − 15.6 − − 71.7 − [83] Co Y FAU 3D12-MR 50.6a − 15.9 − − 72.3 − [83] Co MOR MOR 2D 8&12-MR 29.5a − 14.3 − − 76.3 − [83] Zn2MnOx ZSM-35 FER 2D 8&10-MR 23.0 b 48.7 20.3 − − − 11.7 [82] Zn2MnOx SAPO-11 AEL 1D 10-MR 20.3b 50.0 2.3 − − − 76.7 [82] Zn2MnOx ZSM-22 TON 1D 10-MR 19.3b 48.7 4.2 − − − 64.2 [82] Zn2MnOx ZSM-12 MTW 1D 12-MR 20.7b 48.5 2.1 − − − 70.2 [82] Zn2MnOx ZSM-5 MFI 3D 10-MR 22.9b 48.9 2.0 − − − 67.4 [82] Zn2MnOx ZSM-11 MEL 3D 10-MR 22.6b 48.9 1.8 − − − 63.5 [82] Zn-ZrO2 ZSM-5 MFI 3D 10-MR 9.3 c 39.0 1.9 2.9 13.0 − 1.0 [66] Zn-ZrO2 Beta BEA 3D12-MR 7.5 c 41.0 7.5 13.0 73.0 − 1.8 [66] Zn-ZrO2 MOR MOR 2D 8&12-MR 9.2c 40.0 9.2 43.0 26.0 − 4.3 [66] Zn-ZrO2 SAPO-34 CHA 3D 8-MR 7.4 c 40.0 7.4 61.0 29.0 − 5.5 [66] Zn-ZrO2 SSZ-13 CHA 3D 8-MR 29.0d 42.0 2.0 77.0 18.0 − 3.0 [80] ZnCrOx SAPO-34 CHA 3D 8-MR 17.0e 41.0 2.0 80.0 14.0 − 4.0 [74] ZnCrOx MOR MOR 2D 8&12-MR 9.0e − 5.0 89.0 5.5 − 0.5 [73] ZnAl2O4 SAPO-34 CHA 3D 8-MR 6.9f 33.1 5.5 77.0 14.5 − − [84] ZnAl2O4 MOR MOR 2D 8&12-MR 10.0g 44.0 5.2 77.0 12.0 − − [85] a: H2/CO=2.0,240 ℃,2.5 MPa,GHSV=7714 mL/(h·gcat);b: H2/CO=1.0,360 ℃,4.0 MPa,GHSV=1000 mL/(h·gcat);c: H2/CO=2.0,400 ℃,3.0 MPa,GHSV=1500 mL/(h·gcat);d: H2/CO=2.0,400 ℃,3.0 MPa,GHSV=2700 mL/(h·gcat);e: H2/CO=2.5,400 ℃,2.0 MPa,GHSV=4000 mL/(h·gcat);f: H2/CO=1.0,390 ℃,4.0 MPa,GHSV=12000 mL/(h·gcat);g: H2/CO=1.0,330 ℃,3.0 MPa,GHSV=1500 mL/(h·gcat);h Product obtained based on C mole calculations, excluding CO2 -
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