Challenges and Solutions for Shale Oil Upgrading

Transcription

1 Challenges and Solutions for Shale Oil Upgrading Don Ackelson UOP LLC, A Honeywell Company 32 nd Oil Shale Symposium Colorado School of Mines October 15-17, UOP LLC. All rights reserved. UOP

2 Method of Extraction Can Impact Difficulty of Upgrading Oxygen-free gas flow? Above ground versus In-situ Vertical versus horizontal Rapid versus slow Heating methods Internal combustion Hot recycled solids Wall conduction Externally-generated hot gas Reactive fluid Radio waves, microwaves, etc. UOP

3 UOP

4 Sulfur Nitrogen Hydrogen Oxygen Arsenic 0.80 Wt-% 1.8 Wt-% Wt-% 1.0 Wt-% 40 wppm UOP

5 Sulfur 0.80 Wt-% Sulfur 0.72 Wt-% Nitrogen Hydrogen Oxygen Arsenic 1.8 Wt-% Wt-% 1.0 Wt-% 40 wppm Nitrogen Hydrogen Oxygen Arsenic Wt-% 9.73 Wt-% 7.2 Wt-% 4 wppm UOP

6 Sulfur 0.80 Wt-% Sulfur 0.72 Wt-% Nitrogen Hydrogen Oxygen Arsenic 1.8 Wt-% Wt-% 1.0 Wt-% 40 wppm Nitrogen Hydrogen Oxygen Arsenic Wt-% 9.73 Wt-% 7.2 Wt-% 4 wppm Sulfur Wt-% Nitrogen Wt-% Hydrogen Wt-% Oxygen 3-7 Wt-% UOP

7 Sulfur 0.80 Wt-% Sulfur 0.72 Wt-% Nitrogen Hydrogen Oxygen Arsenic 1.8 Wt-% Wt-% 1.0 Wt-% 40 wppm Nitrogen Hydrogen Oxygen Arsenic Wt-% 9.73 Wt-% 7.2 Wt-% 4 wppm Sulfur Wt-% Nitrogen Wt-% Hydrogen Wt-% Oxygen 3-7 Wt-% Sulfur Nitrogen Hydrogen Oxygen Arsenic Wt-% Wt-% 9.73 Wt-% 2.4 Wt-% 29 wppm UOP

8 Sulfur 0.80 Wt-% Sulfur 0.72 Wt-% Nitrogen Hydrogen Oxygen Arsenic 1.8 Wt-% Wt-% 1.0 Wt-% 40 wppm Nitrogen Hydrogen Oxygen Arsenic Wt-% 9.73 Wt-% 7.2 Wt-% 4 wppm Sulfur Nitrogen Hydrogen Oxygen 0.68 Wt-% 1.06 Wt-% 12.0 Wt-% 2.0 Wt-% Sulfur Wt-% Nitrogen Wt-% Hydrogen Wt-% Oxygen 3-7 Wt-% Sulfur Wt-% Nitrogen Wt-% Hydrogen Oxygen Arsenic 9.73 Wt-% 2.4 Wt-% 29 wppm UOP

9 Shale Oils and Upgrading Requirements Vary, but There are Some Common Challenges Upgrading Challenge Potential Problems Particulates Arsenic Oxygen Nitrogen Di-Olefins Plugging Deactivation Gum Formation Instability Plugging UOP

10 UOP/Unocal Pilot Plant Studies Covered All Aspects of Extraction and Upgrading Full slate of pilot plants 3 ton per day retort De-ashing and de-arseniting Coking, fractionation Hydrotreating and hydrocracking UOP

11 Broad Range of Shale Sources and Processing Goals Was Studied Processed many different shale oils from Variety of retorting processes Variety of locations Including Colorado, Utah, Bulgaria, Russia, Australia, Morocco, Israel and others Pilot plant objectives Arsenic removal Naphtha, Jet, Diesel yields and quality Catalyst optimization Cold flow improvement Capability for high nitrogen & ammonia environment UOP

12 Parachute Creek, Colorado, USA UOP

13 Retort Located on Bench Next to Mine Entrance UOP

14 Upgrader Located Several Miles from Retort UOP

15 Unocal Produced and Upgraded Colorado Shale Oil from Facility built at Parachute Creek in lower Piceance Basin in Colorado Design throughput was 12,800 tpd shale rock Produced 10,000 bpd raw shale oil Key challenges identified & solved Produced 4,500,000 barrels of SCO 1986 to 1989 synthetic crude processed as blend stock with normal crude slate in Unocal refinery in Illinois 1989 to 1990 synthetic crude sold to Gary Western States & Crysen (USA) which processed it to transportation fuels (diesel, light blends) Operations halted due to economic reasons (Oil price <$20/barrel) Catalyst over entire operating cycle Showed little deactivation Did not require regenerating UOP

16 Parachute Creek Produced SCO Superior to Arabian Light Crude SCO from Shale Oil Arabian Light Crude Gravity, API Sulfur, wppm 5 17,000 Nitrogen, wppm Heavy Metals, wppm (V + Ni + Fe) Nil 20 Distillation, Vol% < 1000 F > 1000 F Nil 15 UOP

17 Boiling Range Distribution Was Favorable C4's Diesel ( C) Gasoline (C5-350 F) VGO (650 F+) UOP

18 Effective Solutions for Key Problems Have Been Found Particulates in shale oil Dependence on mining, crushing, extraction, tankage Range of sizes; some sub-micron Organic & inorganic Significant effort involved in successful removal UOP s approach can include mechanical filtration, de-ashing, guard beds Arsenic Powerful poison for hydroprocessing catalysts Catalyst developed for high As Colorado shale oil Reactor outlet As content consistently below 0.5 wppm Total capacity expected to be 40-50% of fresh catalyst weight UOP

19 Effective Solutions for Key Problems Have Been Found Cold Flow Upgraded shale oils with paraffinic character can require dewaxing Dewaxing catalyst developed to work in high N and NH 3 Parachute Creek full range shale oil pour point reduced from +80 o F to +10 o F Fuel yields & qualities also improved through dewaxing Fuel Specifications Shale oil properties can be challenging Jet smoke point and diesel cetane require significant saturation for many shale oils Oxidation and sediment stability of fuels requires careful attention to hetero compound concentrations UOP

20 Effective Solutions for Key Problems Have Been Found Olefins & dienes in feed Potential plugging with most shale oils Recent pilot plant work demonstrated value of protective beds 500 Reactor Pressure Drop, psig Shutdown Days on Stream UOP

21 Effective Solutions for Key Problems Have Been Found Olefins & dienes in feed Potential plugging with most shale oils Recent pilot plant work demonstrated value of protective beds 500 Reactor Pressure Drop, psig Days on Stream UOP

22 Shale Oil Upgrading Steps Shale Oil Pretreatment High Pressure Hydrotreating Hydrocracking and / or Dewaxing Particulates Arsenic Other Metals Olefins Nitrogen Sulfur Oxygen Paraffins Nitrogen Sulfur Oxygen Paraffins VGO, Resid Spec S, N, Paraffins VGO, Resid Premium Synthetic Crude Finished Products Catalysts & Guard Beds Based on Proven Commercial Solutions Newest Generation HT Catalysts from UOP/Albemarle UOP Unicracking TM Technology Dewaxing from UOP/ExxonMobil UOP

23 Molecular Evolution in the Hydrotreating Reactor Sulfur Nitrogen Aromatics S-S NH 2 SH R2 R1 S S N N NH R1 R1 R2 NH 3 H 2 S N R1 R1 R2 R2 NH 3 H 2 S S S R1 R2 R2 S NH R1 R1 NH 3 H 2 S UOP

24 Viru Keemia Grupp (VKG) Pilot Plant Demonstration UOP

25 We Evaluated Three Configuration Options: Case Volume Percent FF Raw Shale Oil Feed De-Arseniting Pretreating Unit UOP VGO Unionfining TM Unit 61.5 Volume Percent FF 27.0 Volume Percent FF Total Naphtha 20.2 Volume Pct. Total Diesel 61.5 Volume Pct. Total Fuel Oil 27.0 Volume Pct. Total C 4 + Product Volume Pct. UOP

26 Parallel Hydrotreating Option Case 2 Fractionating Column 18.4 Volume Percent FF Raw Shale Oil Feed De-Arseniting Pretreating Unit Integrated Distillate/VGO Unionfining Unit 53.5 Volume Percent FF 33.4 Volume Percent FF Total Naphtha 18.4 Volume Pct. Total Diesel 53.5 Volume Pct. Total Fuel Oil 33.4 Volume Pct. Total C 4 + Product Volume Pct. UOP

27 Hydrocracking to Obtain Maximum Diesel Yield Case Volume Percent FF Raw Shale Oil Feed De-Arseniting Pretreating Unit Unicracking Unit 82.5 Volume Percent FF 1.2 Volume Percent FF Total Naphtha Total Diesel Total Fuel Oil Total C 4 + Product 28.9 Volume Pct Volume Pct. 1.2 Volume Pct Volume Pct. UOP

28 Case Comparison Case 1 Case 2 Case 3 Naphtha, BPSD 20.2 Vol % 18.4 Vol % 28.9 Vol % Diesel, BPSD 61.5 Vol % 53.5 Vol % 82.5 Vol % Fuel Oil, BPSD 27.0 Vol % 33.4 Vol % 1.2 Vol % Hydrogen Consumption, Wt-% Base Base x 0.56 Base x 1.12 CAPEX, MM US$ Base Base x 0.90 Base x 1.09 UOP

29 Selected For Final Evaluation Integrated Distillate/VGO Unionfining Unit Case 2 Reactors HT H H P S CHPS 370 C + Feed H C - Feed HT H F D To Fuel Oil Stripper H H P S H F D To Product Fractionator UOP

30 Configuration and Conditions Were Optimized in the Pilot Plant Good example of optimization Evaluate configuration options Test selected configuration to demonstrate Removal of contaminants Maximum production of most valued products Euro V diesel Low sulfur fuel oil Unique Feed Characteristics High tail-end boiling points Moderate sulfur & nitrogen contents High contents of unsaturates Very high concentration of oxygen Feedstock Properties Property Value 15.6 o C Sulfur, Wt % Nitrogen, wppm 1796 Hydrogen, Wt % 9.73 Oxygen, Wt-% 7.2 Arsenic, wppm 4 Final Boiling Pt., o C 728 Diesel Cetane Number Feed Product UOP

31 Configuration and Conditions Were Optimized in the Pilot Plant Feedstock Properties Good example of optimization Evaluate configuration options Test selected configuration to demonstrate Removal of contaminants Maximize production of most valued products Euro V diesel Low sulfur fuel oil Unique Feed Characteristics High tail-end boiling points Moderate sulfur & nitrogen contents High contents of unsaturates Very high concentration of oxygen Property Value 15.6 o C Sulfur, Wt-% Nitrogen, wppm 1796 Hydrogen, Wt-% 9.73 Oxygen, Wt-% 7.2 Arsenic, wppm 4 Final Boiling Pt., o C 728 wppm Diesel Sulfur Feed Product 0 UOP

32 Configuration and Conditions Were Optimized in the Pilot Plant Feedstock Properties Good example of optimization Evaluate configuration options Test selected configuration to demonstrate Removal of contaminants Maximize production of most valued products Euro V diesel Low sulfur fuel oil Unique Feed Characteristics High tail-end boiling points Moderate sulfur & nitrogen contents High contents of unsaturates Very high concentration of oxygen Property Value 15.6 o C Sulfur, Wt-% Nitrogen, wppm 1796 Hydrogen, Wt-% 9.73 Oxygen, Wt-% 7.2 Arsenic, wppm 4 Final Boiling Pt., o C 728 wppm VGO Sulfur Feed Product 0 UOP

33 Reactor Pressure & Temperature Impacted Product Quality 50 Diesel Cetane Number Reactor ABT = 360 o C Reactor ABT = 370 o C Reactor Pressure, barg above Base UOP

34 Changing Space Velocity Was More Effective 54 Diesel Cetane Number LHSV, Relative to Base Value UOP

35 Capability to Produce Specification Products Was Successfully Demonstrated De-arseniting/Pretreating unit very effective at removing contaminant metals from the feed Feed metals (except Fe) reduced to very low levels 5 wppb Arsenic remaining in the product Chlorides in the feed reduced from more than 60 wppm to less than 7 wppm Capability to produce Euro V diesel confirmed Diesel aromatics are reduced to low levels while producing specification diesel Cold flow properties of the specification diesel product meet specifications; cloud point = -30 o C VGO-range material (370 C+) met fuel oil specifications UOP

36 UOP