CCQTA-COQA Joint Meeting in Edmonton, 2016 Characterization and Refinery Processing of Partially-upgraded Bitumen Tomoki Kayukawa JGC Corporation 1
Outline Background Properties of Partially Upgraded Product Characterization Olefin Saturation by Hydrotreating Olefin Analysis Refinery Processing Compatibility Test Heat Exchanger Fouling Desalting Performance Summary 2
Heavy Oil Transportation Diluent Well Dilution Pipeline Dil-Bit Refinery Diluent shortage High diluent price Full Upgrader Sweet SCO Complex scheme Large oil field Partial Upgrader Sour SCO Simple scheme No diluent 3
Partial Upgrading of Bitumen Advantage over Dilution Diluent cost can be reduced Pipeline size can be reduced Environmentally safe (diluent easily vaporized) Advantage over Full Upgrading Lower capital cost Smaller foot print Smaller by-product 4
Ongoing Partial Upgrading Project Process (Licensor) Process type CCU (UOP) RFCC HTL (Ivanhoe) Thermal (Coking) I Y Q (ETX) Thermal (Coking) HI-Q (MEG) Thermal + SDA Eureka (Chiyoda) Thermal HSC (TEC) Thermal SDA (KBR) SDA SCWC (JGC) Thermal + Extraction Many partial upgrading technologies are existing Most of them are thermal cracking and/or extraction (SDA) 5
Properties of Partially-upgraded Bitumen SCO produced by thermal cracking and extraction (5BPD scale pilot plant, SCO yield : ~70vol%) ANALYSIS METHOD UNIT Upgraded Bitumen TARGET OLEFIN 1H-NMR wt% 3.67 <1.0 SPECIFIC GRAVITY KINETIC VISCOSITY ELEMENTAL ANALYSIS TYPE ANALYSIS SIMDIS DENSITY ASTM D4052 g/ml 0.9166 API - o 22.9 > 19 @ 10C (Calc.) ASTM D7042 cst 32.1 < 350 Sulfur ASTM D4294 wt% 3.23 SATURATES wt % 37.2 AROMATICS ASTM D2007M wt % 37.3 POLARS wt % 9.9 ASPHALTENE ASTM D4055M wt % 0.05-360 o C wt% 55 360-540 o C ASTM D2887 wt% 41 MCRT TAN DIENE VALUE 540 o C+ wt% 4 ASTM D4530 wt% 0.5 ASTM D664 mg KOH/g 2.87 UOP326 g I2/100g 1.94 6
Properties of Partially-upgraded Bitumen Boiling point [degc] SCO produced by thermal cracking and extraction (5BPD scale pilot plant, SCO yield : ~70vol%) 700 600 500 400 300 200 100 0 Fraction BP Yield wt% Naphtha IBP-200 10 Distillate 200-343 39 HGO 343+ 51 343degC 200degC 10wt% 0 20 40 60 80 100 Fraction [wt%] 49wt% 7
Objectives of Study Investigate product quality of partial upgrading Characterization Olefin Saturation by Hydrotreating Olefin Analysis Address refinery issues in processing partially upgraded oil Refinery Processing Compatibility Test Heat Exchanger Fouling Desalting Performance 8
Characterization Olefin Saturation by Hydrotreating Olefin Analyses 9
Olefin Saturation by Hydrotreating Target olefin content: < 1.0wt% (1H-NMR) Less hydrogen consumption Less cracking, less desulfurization, less saturation of aromatic compounds Maximize liquid yield Test unit : bench scale hydrotreating (packed bubble column reactor, 30cc of catalyst) 10
Product Quality Reactor WABT 1 H-NMR Olefin Desulfurization Aromatics Saturation RUN No. LHSV Sulfur Aromatics degc 1/hr wt% wt% % wt% % Feedstock - - 3.67 3.2 37.3 - RUN 1 BASE-25 BASE x 0.5 0.78 2.6 19.3 - - RUN 2 BASE BASE 0.79 2.3 28.0 36.8 1.2 RUN 3 BASE+25 BASE x 2 0.82 1.9 41.0 35.1 5.8 RUN 4 BASE+50 BASE x 3 0.63 1.6 50.3 33.5 10.1 Target olefin content was achieved at all conditions Lower desulfurization and aromatic saturation were observed at lower temp. Feedstock Product 11
Fraction Yields Boiling point [degc] 700 600 500 400 300 200 100 0 Feedstock RUN 2 Product 0 20 40 60 80 100 Fraction [wt%] Distillation curve does not change FEED STOCK RUN 2 PRODUCT Fraction BP Yield wt% Yield wt% Naphtha IBP-200 10 11 Distillate 200-343 39 39 HGO 343+ 51 50 12
Olefin Conversion in Fraction Olefin [wt%] 4.5 4 3.5 3 2.5 2 1.5 1 3.67wt% Loss Naphtha Distillate HGO 0.80wt% Conversion % Naphtha 77.2 Distillate 74.2 HGO 100 0.5 0 Feedstock 15-B14-Product (R02, R03, R04) Olefin in naphtha and distillate fraction was drastically reduced 13
Detail Analysis for Olefin in Naphtha Naphtha(IBP-200 ): GCxGC, TOF-MS Alkenes Diene/Cycloalkenes wt% 5 4 3 2 1 Before Hydrotreating After Hydrotreating wt% 5 4 3 2 1 Before Hydrotreating After Hydrotreating 0 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 0 C5 C6 C7 C8 C9 C10 C11 C12 C13 C14 Alkenes in naphtha were reduced significantly Diene/Cycloalkenes were reduced only close to 50% 14
Detail Analysis for Olefin in Distillate Distillate (200-343 ): HPLC, GCxGC, TOF-MS Alkenes Diene/Cycloalkenes wt% 0.5 0.4 0.3 0.2 0.1 Before Hydrotreating 0.4 After Hydrotreating 0.3 wt% 0.5 0.2 0.1 Before Hydrotreating After Hydrotreating 0.0 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 0.0 C11 C12 C13 C14 C15 C16 C17 C18 C19 C20 C21 Alkenes in distillate were reduced significantly Diene/Cycloalkenes slightly increased. Cycloalkenes were formed by hydrogenation of aromatics?? 15
Characterization of Olefin Olefin target (<1.0wt%) can be achieved at various operating conditions. Lower temperature would be preferred to reduce hydrogen consumption. Olefin is concentrated mostly in naphtha. Alkenes in naphtha and distillate were reduced significantly by hydrotreating 16
Refinery Processing Compatibility Test Heat Exchanger Fouling Desalting Performance 17
Test Method for Compatibility Test Test Method : Wiehe s oil compatibility model I N : Insolubility number S BN : Solubility blending number Blending partially-upgraded Bitumen (SCO) with WCS 18
Total Insolubles 100 80 S BNmix SBNmix, IN 60 40 20 0 WCS SCO I N 33.1 0 S BN 93.34 65.52 0 20 40 60 80 100 Blending ratio of SCO [vol%] Blended samples were compatible at any ratios. I N 19
Test Method for Fouling Evaluation Test unit : Alcor unit Test conditions : 400, 4 hours Criterion for fouling [Defined by Brons, (400, 3hours)] Low fouling : ΔT < 15 Medium fouling : 15 < ΔT < 30 High fouling : ΔT > 30 [Defined by Shell Canada, (400, 4hours)] Low fouling : %F < 23% 20
Equipment for Fouling Evaluation Schematic diagram of experimental unit Heating Section Heater Tube Movable TC (Ts) Outlet Temp (To) Spent Sample Fresh Sample PUMP Inlet Temp (Ti) TC1 (Inlet) TC2 (Outlet) TC3 (Heated Tube) TC4 (Room Temp) 21
450 400 Temperature Trend during Test Sample: SCO before hydrotreating ΔT = 10ºC Temperature, T (ºC) 350 300 250 200 150 100 50 0 280ºC 270ºC Tc1 Tc2 Tc3 Tc4 0 15 30 45 60 75 90 105 120 135 150 165 180 195 210 225 240 255 270 285 300 315 330 345 Elapsed Time (min) ΔT=10 is defined as low fouling 22
Test Method for Desalting Test Method : Mixing and Settling Test Sample : 20ml of water and 80ml of oil ph 5~8 23
Pictures during Settlement Sample: SCO before hydrotreating 1 minute 5 minutes Separation was carried out within 5 minutes at various ph. Water in oil were 0.18~0.25%. 24
<Characterization> Conclusion Olefin target can be achieved by hydrotreating. Olefin is concentrated mostly in the naphtha. <Refinery Processing> No problem was found for blending, fouling tendency or desalting performance with SCO before hydrotreating. This study will be continued for understanding about quality of cracked products 25
Acknowledgement This study was consulted by OMNICON Consultants Inc.. Hydrotreating, heat exchanger fouling tests and analytical works were performed by CanmetENERGY. Detail analysis of olefins was performed by NHMFL at FSU. Desalting test was performed by Nalco Champion. 26
Test Method for Storage Stability Test Method : ASTM D4625 (Accelerated Stability Test) Conditions: 43.5 for 24 weeks 28
Total Insolubles Total Insolubles [mg/100ml] 100 90 80 70 60 50 40 30 20 10 0 長期貯蔵安定性 Storage Stability (ASTM D4625) 0 5 10 15 20 25 30 Weeks Total insoluble increased with the time. But leveled off after 12 weeks 29