+ Catalysts O Temperature Pressure

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2 Franz Fischer & Hans Tropsch A catalytic reaction process to convert syngas (H 2 +CO) into hydrocarbons nco + {2n(+1)}H 2 C n H 2n(+2) + nh 2 O H H + Catalysts O Temperature Pressure C Exothermic Complicated Key Technologies: Reactors & Catalysts 2/22

3 Syngas H 2 /CO 2 H 2 /CO < 2 H 2 /CO 2 + CO 2 H 2 /CO < 2 Cobalt LT-FTS ( ºC) Iron LT-FTS ( ºC) Iron HT-FTS ( ºC) Product Upgrade Product Upgrade LPG (2%) Naphtha (30%) Diesel (68%) LPG (3%) Naphtha (33%) Diesel (33%) PL Others (26%) (5%) 3/22

4 HT-FTS LT-FTS F-Fe P-Fe S-Co F-Fe Old Fused Iron-Based Catalysts P-Fe Precipitated Iron-Based Catalysts Advanced F-Fe P-Fe S-Co S-Co Supported Cobalt-Based Catalysts <Figure Source: A.P. Steynberg. M.E. Dry, Fischer-Tropsch Technology, Elsevier, Amsterdam (2004).> 4/22

5 LT-FTS SBCR (Slurry Bubble Column Reactors) + P-Fe (Precipitated Iron-Based Catalysts) HT-FTS <Figure Source: A.P. Steynberg. M.E. Dry, Fischer-Tropsch Technology, Elsevier, Amsterdam (2004).> 5/22

6 Hydrodynamic Behavior Scale-Up Factors Scale-Up Bench-Scale Pilot-Scale Catalyst Lab-Scale Catalyst = g Catalyst = g Catalyst = kg Catalyst = 4-6 kg Catalyst = kg 6/22

7 Step 1: Pre-Activation Step 2: FT Synthesis Fe Fe α-fe 2 O 3 O 4 3 O 4 3 (H 2 +CO)-L Fe x C (H 2 +CO)-H Fe x C or CO As-Prepared Activated Stabilized <Reduction> 3Fe 2 O 3 + H 2 2Fe 3 O 4 + H 2 O 3Fe 2 O 3 + CO 2Fe 3 O 4 + CO 2 <Reduction and Carburization> xfe 3 O 4 + (4x+6)CO 3Fe x C + (4x+3)CO 2 Minor Phase Change (H 2 +CO)-L: Low Pressure Syngas (H 2 +CO)-H: High Pressure Syngas 7/22

8 FT Synthesis without Pre-Activation Fe α-fe 2 O 3 O 4 3 High Pressure Syngas (H 2 +CO) Fe x C As-Prepared Spontaneous Activation in the FT Synthesis Condition <Reduction> 3Fe 2 O 3 + H 2 2Fe 3 O 4 + H 2 O 3Fe 2 O 3 + CO 2Fe 3 O 4 + CO 2 <Reduction and Carburization> xfe 3 O 4 + (4x+6)CO 3Fe x C + (4x+3)CO 2 Spontaneously Activated 7/22

9 In-Situ Pre-Activation Pre-Activation & Subsequent FTS in a Single Reactor Ex-Situ Pre-Activation Pre-Activation As-Prepared Catalysts (No Withdrawal) FTS Deactivated Catalysts Facility Simplification: Good Operation Efficiency: Bad Facility Simplification: Bad Operation Efficiency: Good 8/22

10 New Catalysts New Process Spontaneous Activation of As-Prepared Catalysts in FTS <M. Dong et al., Appl. Catal. A-Gen. 345 (2008) > As-Prepared Catalysts Deactivated Catalysts Highly Reducible & Carburizable Iron-Based Catalysts Facility Simplification: Excellent Operation Efficiency: Excellent <B.H. Davis, Catal. Today 84 (2003) 83-98> 9/22

11 New Catalysts New Process <B.H. Davis, Catal. Today 84 (2003) 83-98> Overcoming Limitation Spontaneous Activation of As-Prepared Catalysts in FTS As-Prepared Catalysts Deactivated Catalysts Highly Reducible & Carburizable Iron-Based Catalysts Facility Simplification: Excellent Operation Efficiency: Excellent <B.H. Davis, Catal. Today 84 (2003) 83-98> 9/22

12 SponCat (Spontaneously Activatable Iron-Based Catalysts in the FTS Condition) - Lab-Scale: Discovery of SponCat in LT-FTS Application to HT-FTS - Pilot-Scale: Feasibility of SponCat in LT-FTS (6 bbl/d) and HT-FTS (9 bbl/d) 10/22

13 Conventional Catalysts KIER SponCat 275, 114hr 275, 5hr GHSV(H 2 +CO) = 5.1 NL/g (Fe) -h H 2 /CO = 1.0 P(H 2 +CO) = 1.5 MPa T = ºC Fresh, RT Mg Mg Mg hr hr 275 Hm Hm Fresh, RT θ ( o ) Mg Mg Mg Mg χ = Active Phase θ ( o ) Mg Hm Hm Hm Fh Fh Fh Hematite Magnetite (Fe 2 O 3 ) (Fe 3 O 4 ) GHSV(H 2 +CO) = 5.1 NL/g (Fe) -h H 2 /CO = 1.0 P(H 2 +CO) = 1.5 MPa T = ºC Ferrihydrite Magnetite + Fe 5 C 2 (Fe 9 O 2 (OH) 23 ) (Fe 3 O 4 ) /22

14 With Pre-Activation Without Pre-Activation KIER SponCat 90 SponCat 80 KIER SponCat COConversion (%) Conventional <Pre-Activation> GHSV(H 2 +CO) = 5.1 NL/g (Fe) -h H 2 /CO = 1.0 P(H 2 +CO) = Ambient T = 280 ºC Time = 5 h COConversion (%) Conventional Time (h) Time (h) GHSV(H 2 +CO) = 5.1 NL/g (Fe) -h H 2 /CO = 1.0 P(H 2 +CO) = 1.5 MPa T = 275 ºC GHSV(H 2 +CO) = 5.1 NL/g (Fe) -h H 2 /CO = 1.0 P(H 2 +CO) = 1.5 MPa T = 275 ºC 12/22

15 Overall FTS Performance Overall Performance ( h) Conv-Cat (275 C) Pre-Activation SponCat (275 C) Conv-Cat (230 C) No Pre-Activation Conv-Cat (275 C) SponCat (275 C) CO Conversion (%) CO 2 Selectivity (%) HC Distribution (wt%) CH 4 C 2 -C 4 C 5 -C 11 C 12 -C 18 C C 5+ Productivity (g/g (cat) -h) /22

16 CO Conversion vs. Time CO Conversion (%) SponCat: 320 o C Gradual Decrease SponCat: 275 o C SponCat: 290 o C SponCat: 305 o C SponCat: 320 o C Conventional Catal: 275 o C Time (h) Temperature ( C) GHSV (NL/g (cat) -h) H 2 /CO = 1.0, Pressure = 1.5 MPa <No Pre-Activation> HC Distribution HC Distribution (wt%) C 19+ C 5 -C 18 C 2 -C 4 =(O) CH 4 C 2 -C -(P) Temperature ( o C) <Major Products> Future Work Future Work 1 LT-FTS (275 C): Wax + Oil HT-FTS (320 C): Oil + C 2 -C 4 Olefin /22

17 ASF Distribution GC GC Analysis Log(W n /n) α 1 SponCat: 275 o C SponCat: 290 o C SponCat: 305 o C SponCat: 320 o C -2.5 α T ( C) α α n Liquid Hydrocarbons are enriched with LAOs (Linear α-olefins). - e.g. 1-Octene in C 305 C: 54.6 wt% 15/22

18 Syngas Cleaning System (Designed 1000 Nm 3 /h) Control Room Coal Gasifier (Designed 10 t/d) FT Reactor: SBCR (Designed 15 bbl/d) 16/22

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20 LT-FTS: October, 2015 HT-FTS: October, CO Conversion (%) bbl/d GHSV = 9.8 NL/g (cat) -h P(H 2 +CO) = 1.6 MPa H 2 /CO = 1.0 CO 2 in Feed Gas = 11% T = ºC KIER SponCat <No Pre-Activation> Time (h) CH 4 C 2 -C 4 Oil Wax CO Conversion (%) Heat-Exchanger Problem 9 bbl/d KIER SponCat Time (h) Steady State GHSV = 13 NL/g (cat) -h P(H 2 +CO) = 1.9 MPa H 2 /CO = 1.2 CO 2 in Feed Gas = 10% T = ºC <No Pre-Activation> <HC Distribution (wt%): 1-13 h> <HC Distribution (wt%): h> CH 4 C 2 -C 4 -(P) C 2 -C 4 =(O) Oil Wax /22

21 Even though no activation pre-treatment was carried out, KIER SponCat showed high catalytic performance for LT-FTS. In LT-FTS condition, wax and liquid oil were obtained as major products. The SponCat successfully worked in HT-FTS condition, generating liquid oil and lower (C 2 -C 4 ) olefins as major products. This means that we can predictably control the major products by adjusting the reaction temperature. We successfully demonstrated both LT-FTS and HT-FTS using SponCat in a pilot-scale slurry phase reactor (6-9 bbl/d). We can conclude that the SponCat is highly advantageous for industrial HT-FTS as well as LT-FTS because the as-prepared catalysts can be used for FTS without requiring an extra preactivation process. 19/22

22 This work was supported in part by the Research and Development Program of the Korea Institute of Energy Research (GP /B ) and the National Research and Development Program of the Korea Institute of Energy Technology Evaluation and Planning (NP /B7-3209). 20/22

23 SponCat More Reliable More Novel Synchrotron-Based Characterization Mössbauer Spectroscopy In-Operando Characterization - XRD, TEM, XANES, EXAFS <Looking for Partners> Feasibility Test ( h) Long-Term Test (1,000-10,000 h) Lab (Catal.: g) Bench (Catal.: kg) Pilot (Catal.: kg) In-Progress In the Future In-Progress In the Near Future In the Future Looking for Partners 21/22

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