Oil Yield and Gas Compositions of Oil Shale Samples at Variable Time and Temperature

Transcription

1 Oil Yield and Gas Compositions of Oil Shale Samples at Variable Time and Temperature 1% Conceptual Time - Temperature Yield Relationship for Any Oil Shale Oil Recovery wt% of Fischer Assay 9% 8% 7% 6% 5% 4% 3% Oil Shale Approximate Oil Yield With Temperature at Less Than 3 Minutes Residence Time Approximate Oil Yield Loss Due to Internal Condensation-Reflux-Secondary Pyrolysis 1 C Rise / Day 5 C Rise / Day Approximate Oil Yield Loss Due to Internal Alteration, Metamorphosis and Ultimate Coking Reactions 2% 1% 3 C Rise / Day % 3 C 325 C 35 C 375 C 4 C 425 C 45 C 475 C 5 C Soak Days Presentation to: 29 th Oil Shale Symposium October Golden, Colorado 29 Author: W. Taciuk UMATAC Industrial Processes A Division of AECOM Canada Ltd.

2 Indications of Oil Shale Sensitivity to Temperature and Time Prolonged drying of oil shale at 15 C reduces Fischer assay oil yield. Prolonged drying of lignite coal at 15 C significantly reduces Fischer assay oil yield. Shale exposure to 2 C, as in the ATP preheat zone, results in some odorous gases. Shale exposure to 275 C for short periods results in condensate containing hydrocarbons. Certain shales have a faint bituminous smell when crushed indicating the presence of hydrocarbons.

3 Overall UMATAC Test Program to Evaluate Oil Shale Sensitivity to Time and Temperature Test Series Apparatus Used Vapour Discharge Orientation Duration of Test Temperature of Test ( C) Sample Used A ATP Batch Unit Side Various 15, 225, 3, 35, and 4 5 Oil Shales B Slow Soak Top 5 7 days Oil Shales C ATP Batch Unit Side Various 4 5 Oil Shales D-1 Slow Soak Bottom 1 day 2 56 Utah and Jordan Shales D-2 Slow Soak Bottom 5 2 days 2 56 Utah and Jordan Shales

4 ATP Processor Simplified Schematic Preheat Steam Flue Gas ATP Processor Residence Time (minutes) Preheat Zone 1 15 Retort Zone 5 8 Combustion Zone 6 12 Cooling Zone 1 2 Total Time Cooling Zone Combustion Zone Auxiliary Burner Feed Preheat Zone Evolved Steam Retort Zone Hydrocarbon Vapours Heat Transfer Cooling Zone Solids Coked Solids Combusted Solids Combustion Air Spent Solids The ATP Processor

5 The ATP Processor in Gladstone, Australia 211 t/h ATP Processor at the Stuart Oil Shale Demonstration Facility

6 Characteristics of the Five Oil Shales Tested Item Jordan Utah Fushun Australia Estonia Sample Age (years) Crushed Top Size (mm) Moisture (wt%) Modified Fischer Assay (LTM C 4 +) C 6 + Oil Specific Gravity (g/ml) Modified Fischer Assay (kg/t M) Ultimate Analysis (dry basis) C (wt%) H (wt%) N (wt%) S (wt%) O (diff) (wt%)

7 Characteristics of the Five Oil Shales Tested Typical UMATAC ATP Batch Unit (per 1 kg feed) Item Jordan Utah Fushun Australia Estonia C 6 + Oil (kg) C 6 - Gas (m 3 ) Main Feature High Sulfur Oil High Limestone Lowest Oil Content High Moisture Phenolic Oil

8 Crushed Jordan Oil Shale Sample

9 ATP Batch Unit 25 g Oil Shale Feed Capacity

10 Test Series A Test Results for Jordan Oil Shale Jordan Oil Shale Feed 15 C 225 C 3 C 35 C 4 C Oil (ml) Water (ml) H 2 S (vol %) Trace Trace 1% 3% 6% CO 2 (vol %) 1% 2% 5% 15% 12% C 6 + (vol %) Present.5% 1.5% 2.% 1.5% C 1 C 5 No Peaks Slight All All All H 2 (vol %). Trace Trace.5% 2.% Odour None Musky Faint HC H 2 S Strong H 2 S Feed LOI* (wt%) 25. Product Solids LOI* (wt%) 19.6 LOI* Loss (wt%) 5.4 *LOI is Loss on Ignition at 6 C

11 Slow Soak Test Units Pictured on the left are stainless steel containers used for the slow soak tests Pictured on the right are the insulated and assembled stainless steel test units used for the slow soak tests

12 Gas Analysis Shown on the right is a tedlar gas bag, pump, and gas meter used during the analysis Shown on the left are UMATAC s gas chromatographs one is used to measure refinery gas and the other for hydrogen and methane

13 Series B Jordan Oil Shale Slow Soak Testing Jordan 58 Day Soak Oil and Gas Accumulations Jordan 58 Day Soak Off Gas Compositions 6 Jordan Oil Shale Slow Soak Oil and Gas Accumulation 24 6 Jordan Slow Soak Gas Compositions C 6 +, H 2 S, CO 2, C 1 & H Soak Temperature (deg C) Soak Temperature Gas Accumulation Oil Accumulation Amount - Oil (g), Gas (L) Soak Temperature (deg C) H 2 S SoakTemperature H 2 CO 2 C 1 C Gas Composition (wt%) Soak Time (days) Soak Time (days)

14 Series B Utah Oil Shale Slow Soak Testing Utah 7 Day Soak Oil and Gas Accumulations Utah 7 Day Soak Off Gas Compositions 6 Utah Slow Soak Oil and Gas Accumulation 24 6 Utah Slow Soak C 6 +, H 2 S, CO 2, C 1 & H Soak Temperature (deg C) Soak Temperature Gas Accumulation Oil Accumulation Amount - Oil (g), Gas (L) Soak Temperature (deg C) CO 2 H 2 S H 2 Soak Temperature C 1 C Gas Composition (wt%) Soak Time (days) Soak Time (days)

15 Series B Fushun Oil Shale Slow Soak Testing Fushun 61 Day Soak Oil and Gas Accumulations Fushun 61 Day Soak Off Gas Compositions Soak Temperature (deg C) FMG Slow Soak Oil and Gas Accumulation Soak Temperature Oil Accumulation Gas Accumulation Soak Time (days) Amount - Oil (g), Gas (L) Soak Temperature (deg C) FMG Slow Soak C 6 +, H 2 S, CO 2, C 1, & H Soak Temperature H CO 2 C H 2 S C Soak Time (days) Gas Composition (wt%)

16 Series B Estonia Oil Shale Slow Soak Testing Estonia 48 Day Soak Oil and Gas Accumulations Estonia 48 Day Soak Off Gas Compositions Soak Temperature (deg C) Estonia Oil Shale Slow Soak Oil and Gas Accumulation Soak Temperature Gas Accumulation Oil Accumulation Amount - Oil (g), Gas (L) Soak Temperature (deg C) Estonia Oil Shale Slow Soak C 6 +, H 2 S, CO 2, C 1 & H 2 Soak Temperature CO 2 H 2 S C 6 + H 2 C Gas Composition (wt%) Soak Time (days) Soak Time (days)

17 Series B Australia Oil Shale Slow Soak Testing Australia 62 Day Soak Oil and Gas Accumulations Australia 62 Day Soak Off Gas Compositions 6 Australia Oil Shale Slow Soak Oil and Gas Accumulation 24 6 Australia Oil Shale Slow Soak C6+, H2S, CO2, C1 & H Soak Temperature (deg C) Soak Temperature Gas Accumulation Amount - Oil (g), Gas (L) Soak Temperature (deg C) Soak Temperature C 1 H Gas Composition (wt%) Oil Accumulation CO 2 H 2 S C Soak Time (days) Soak Time (days)

18 Series B Gas Chromatograph Traces Utah Oil Shale Slow Soak Top Discharge Gas C C4 C3 C3= H2S C4 Aromatics Range C5 C5 Aromatics Range C6+ C6 C6 Aromatics Range CO2 C2= C2 C1 CO O2 N2 Second GC: H2.45% C1.29% Second GC.: H2 39% C1 17% Second GC: H2 64% C1 9.5% Second GC: H2 67% C1 15% Second GC: H2 37% C1 42% Second GC: H2 23% C1 26%

19 Series B Slow Soak Tests Oil Yield Results C 6 + Liquid (LTM kg/t) Fischer ATP Batch Slow Soak % Recovery Slow Soak (referenced to Fischer) Jordan % Utah % Fushun % Australia % Estonia %

20 Series B Slow Soak Tests Gas Yield Results Gas Volume (m 3 /t) Fischer ATP Batch Slow Soak Ratio Referred to ATP Batch Jordan Utah Not measured directly but Fushun included in the Australia overall weight loss Estonia

21 Series B Slow Soak Tests Specific Gravity of Oil Produced C 6 + Oil Specific Gravity (g/ml) Fischer ATP Batch Slow Soak 325 C 375 C Jordan Utah Fushun Australia Estonia

22 12 Jordan Oil Shale Batch Tests - Oil Yield (g/kg, dry basis) Test Series C 11 1 Jordan oil shale 4 C soak to accelerate alteration reaction on kerogen then rapid heating to 56 C to observe oil remaining. Oil Yield (g/kg) C 4 C Total Oil Yield Oil 4 C Ramp Run to 56 C 1 1/2 hour 4 C then to 56 C 3 hour 4 C then to 56 C 5 hour 4 C then to 56 C 7 hour 4 C then to 56 C 18 hour 4 C then to 56 C 44 hour 4 C then to 56 C 6 hour 35 C then to 56 C

23 Test Series C 12 Utah Oil Shale Batch Tests - Oil Yield (g/kg, dry basis) Utah oil shale 4 C soak to accelerate alteration reaction on kerogen then rapid heating to 56 C to observe oil remaining. Oil Yield (g/kg) C Total Oil Yield Oil 4 C Note Fushun, Estonia, and Australia results are similar 2 1 Batch Run Ramp Run Hot Run Fast 3 Hour 4 C then to 56 C 4 C 2 hour 4 C then to 56 C 4 hour 4 C then to 56 C

24 Top Vapour Discharge on Slow Soak Test Units

25 Bottom Vapour Discharge on Slow Soak Test Units Test Series D tests were carried but with vapour bottom discharge to eliminate effects of oil condensing and refluxing back into hot oil shale charge. Only Jordan and Utah oil shales tested to date.

26 15 Utah Oil Shale Oil Different Soak Conditions C C Fast Soak Bottom Discharge Fischer Assay = 12.7wt% ATP Batch Unit Test = 12.1wt% Oil Yield (%wt) h 3 h 4 h 455 C 5.25 h 6.25 h 5 C 4 C 8.25 h 44 C 4C 1.5 h h 15 h h 19.5 h 35C h C Fast Soak Top Discharge Special Medium C Bottom Discharge Time (Hour) 3C 4 32C 7 5 C 53 C 45 C Medium C 4C Bottom Discharge C C 19 35C Special 32 C Bottom Discharge 5 C Slow Soak Top Discharge Time (Day) C C C 64 67

27 1 Gas Make (L/kg) C 45C 4C 4C h 2.25 h 3.25 h 4 h 4.75 h 5.5 h 6.25 h 8 h 9 h 1.5 h 12 h 13.5 h 15 h 16.5 h 18 h 19.5 h 21 h 22.5 h 13 Utah Shale Soak Gas Different Soak Conditions Fast Soak Bottom Discharge ATP Batch=31.9 L/kg 44C Fast Soak Top Discharge 35C 275 C 535C Medium C Bottom Discharge 53C 572 C 45C C 3C 5 C Slow Soak Top Discharge Special 32 C Bottom Discharge 475C 35C 425C Special Medium C Bottom Discharge 55 C 45C Time (Hour) Time (Day)

28 15 Jordan Oil Shale Oil Different Soak Conditions Oil Yield (%wt) C Fast Soak Bottom Discharge 44 C 45 C 4 C 4 C 54 C 52C Fast Soak Top Discharge 4 C 35 C 315 C High 4 C Bottom Discharge 375 C 3C 475 C 45 C 35 C High 375C Bottom Discharge Medium Bottom Discharge h 2.25 h 3.75 h 5.25 h 6.75 h 8.25 h 9.75 h h h h h h h 2.25 h h h C 4 C 525 C 3 C Fisher Assay = 12.5%wt Batch Unit Test = 11.77%wt Special Medium Bottom Discharge Jordan 1 Slow Soak Top Discharge 45 C 55 C 35 C 4 C 45 C 5 C Jordan 2 Slow Soak Top Discharge Time(Hour) Time (Day)

29 Gas Make (L/kg) C 44 C Jordan Oil Shale Gas Different Soak Conditions Fast Soak Top Discharge High Bottom Discharge 4 C 35 C 4 C 335C h 1.5 h 2.25 h 3 h 3.75 h 4.5 h 5.25 h 6 h 6.75 h 7.5 h 8.25 h 9 h 9.75 h 1.5 h h 12 h h 13.5 h h 15 h h 16.5 h h 18 h h 19.5 h 2.25 h 21 h h 22.5 h h C Fast Soak BTM Discharge 54C 525C High 5C ATP Batch = 39.5 L/kg Bottom Discharge 45C 275 C 3 C C 375 C Jordan 1 Slow Soak Top Discharge 4C 45C 35 C Special Medium Bottom Discharge 325 C Jordan 2 Slow Soak Top Discharge 5C 55C 45C 4C Medium Bottom Discharge Time (Hour) Time (Day)

30 Accumulative Weight Percentage (%wt) 1% 95% 9% 85% 8% 75% 7% 65% 6% 55% 5% 45% 4% 35% 3% 25% 2% 15% 1% 5% % Utah Shale Oil Boiling Point Distribution Soak 33C #2 Soak 33C #4B Soak 315C #7 Fischer Assay ATP Batch Test 17 C 27 C 34 C 4 C 45C 49 C 52 C C7 C8 C8 C9 C9 C1 C1 C11 C11 C12 C12 C13 C13 C14 C14 C15 C15 C16 C16 C17 C17 C18 C18 C19 C19 C2 C2 C21 C21 C22 C22 C23 C23 C24 C24 C25 C25 C26 C26 C27 C27 C28 C28 C29 C29 C3 C3 C31 C31 C32 C32 C33 C33 C34 C34 C35 C35 C36 C36 C37 C37 C38 C38 C39 C39 C4 C4 Plus Carbon Number

31 Percentage of Fischer Assay (wt%) Utah Shale Oil BP Curve vs Soak Curves Related to Temperature Top Discharge Oil BP Curve ATP Batch BP Curve Temperature (deg C) Special Medium Soak Bottom Discharge Medium Soak Bottom Discharge Fast Soak Bottom Discharge Fast Soak Top Discharge Special 32C Slow Soak Top Discharge 7 Days

32 1% Conceptual Time - Temperature Yield Relationship for Any Oil Shale Oil Recovery wt% of Fischer Assay 9% 8% 7% 6% 5% 4% 3% Oil Shale Approximate Oil Yield With Temperature at Less Than 3 Minutes Residence Time Approximate Oil Yield Loss Due to Internal Condensation-Reflux-Secondary Pyrolysis 1 C Rise / Day 5 C Rise / Day Approximate Oil Yield Loss Due to Internal Alteration, Metamorphosis and Ultimate Coking Reactions 2% 1% 3 C Rise / Day % 3C325C35C375C4C425C45C475C5C Soak Days

33 Conclusions to Date Based on Results of UMATAC Tests 1) Jordan, Utah, Estonia, China, and Australia oil shales have very similar time, temperature, product composition characteristics. 2) Measurable quantities of oil and gas released at 3 C. 3) Kerogen decomposition becomes rapid beyond 32 C. 4) Kerogen decomposition accelerates as temperature is increased. 5) Inefficient removal of oil and gas products (oil reflux) remarkably reduces oil yield.

34 Conclusions to Date Based on Results of UMATAC Tests 6) During kerogen decomposition the oil quality and the off gas composition trends are remarkably similar for different oil shales. 7) During soak time secondary alteration reactions occur which tend to reduce oil yield tending towards ultimate coking. 8) Long term soak periods of 6 day duration with reflux reduce oil yield by 5 to 8% referenced to Modified Fischer assay.

35 Comments by Author UMATAC s technical paper searches regarding this type of slow soak research has turned up very little information on oil yields, gas yields and product comparison under our test conditions. The presentation of our test methods, our test data, and findings is to stimulate discussion with other researchers in aid of understanding the complex nature of oil shale kerogen.

36 Comments by Author The author recognizes that UMATAC s test programs were performed under conditions using a prepared crushed oil shale and operating at atmospheric pressure. Based on the conclusions reached in this paper regarding kerogen alternation, reaction and the effect of reflux, the author has a much better appreciation of the complexity of modeling, designing and operating a large scale in-situ type oil shale operation where the additional factors of pressure, viscosity, bed permeability, heat transfer co-efficient, potential for multiple refluxing of oil products, catalytic action and potential for gasification are at least some of the additional considerations. The oil resources are there in the oil shales but collectively we need to develop means to recover this oil in a safe, environmentally friendly, and economic fashion.

37 UMATAC Industrial Processes telephone (43)