IEA-MOST Workshop: Advances in deployment of fossil fuel technologies Efficient oil and gas refining with oil shale: Technology overview and new development Guangwen Xu Institute of Process Engineering, Chinese Academy of Sciences State Key Laboratory of Multiphase Complex System Advanced Energy Technology Group（AETG） June 24, 2014, Beijing AET Group Contents Highlight on world oil shale resource and technologies Highlight on China oil shale resource and technologies A new refining technology development in IPE-CAS Concluding remarks IPE CAS Highlight on world oil shale resource and technologies IPE CAS World energy resource in 2013 1011 equivalent barrel Resource Reserves Crude oil 13.1～16.3 Oil sand (including char) 3.3～4.9 Heavy oil 4.9～8.2 Oil shale (including char and gas) 16.3～24.5 Others 4.9～16.3 * The int. exploitation and processing of oil shale, 2014,1, SINO-GLOBAL ENERGY Crude oil Oil Sand Heavy oil Oil Shale Oil shale: A sedimentary rock contains a solid organic material known as kerogen. It has low organic content (<35 wt.%), high ash content (50～85 wt.%) and H/C is above 1.2. IPE CAS World Shale oil distribution Country Potential oil reserve (107 t) Annual oil production (104 t/a) America 30000 —— Russia 3900 —— Zaire 1400 —— Brazil 1200 20 Canada 630 —— Jordan 520 —— Morocco 500 —— Australia 450 —— China 4760 80 Estonia 250 66 Italy 140 —— Total 43750 166 * The int. exploitation and processing of oil shale, 2012, SINO-GLOBAL ENERGY. IPE CAS History of oil shale utilization Combustion for energy Year Retorting for oil and gas Shale oil and gas production 1900s Directly used as solid fuel by combustion. 1970s Commercial production of shale oil and gas by retorting. 1990s Petroleum oil industry suppressed shale oil production. 2000s High price and shortage in petroleum, the shale oil production has been renewed. IPE CAS Major countries refining oil shale Brazil • Petrosix process • Total shale oil production is about 200 kt/a. China • Fushun retort • Total shale oil production is about 1000 kt/a. Estonia • Kiviter and Galoter process • The 2nd largest shale oil producer after China • The total shale oil production is about 600 kt. Other countries: USA, Australia, Jordan, Russia IPE CAS Retorting / Pyrolysis technology True in-situ retorting In-situ underground retorting Modified (half) in-situ retorting Gas heat carrier Direct heating Solid heat carrier Aboveground retorting Indirect heating IPE CAS In-situ underground retorting For deep low-grade oil shale, being economic possible. Polluting underground water and rack stratum. Research mainly in America, but no industrial appl. Heating method Conductive heating (ICP): Electric heating sticks Convective heating (EGL): Aeration of hot flue gas Radiant heating (Lawrence Livermore): Radio frequency IPE CAS Reported major technologies Technology Shell’s Conversion Process (ICP) Exxon mobil ElectrofracTM American Shale Oil (AMSO, previously known as EGL) Heating supply Electric heating Electric conducting material Pyrolysis gas 2 10 —— 340～400 —— 300～425 Complex, high electricity consumption Combine retorting and sodium carbonate production. Difficult for moisture-removing Heating rate (℃/day) Retorting temperature (℃) Features Schematic diagram 1,000 feet Surface processing Overburden Producers Heater holes Oil shale IPE CAS Difficulty for in-situ retorting No mature technology for industrial utilization Low heating rate and heat transfer efficiency Pollution of underground water and rack stratum around the working section Low permeability of oil shale layers Low oil yield (60% against Fischer Assay) Problems for ground subsidence IPE CAS Aboveground Retorting Technology Oil shale Oil shale Shale oil Oil shale 热灰 Oil Heating gas Gas 油气 半焦 Char Indirectly heated Low heat transfer efficiency and Difficult for scale-up Flue gas Combustion Furnace 煤 Hot ash Gas heat carrier For big particles and Relatively low yield O2 Char Solid heat carrier For small particles but high dust contamination IPE CAS Kiviter Retorting (Estonia) Oil shale 1981, a 1000t/d Kiveter furnace was completed in Estonia. Feeding Shale oil yield: 75~80% of Fischer assay yield. Oil and gas Circulating gas Combustor Advantages: ● Gas heating, heat-binding and heat-dusting oil shale ● Easy to scale up and control Disadvantages: ● Big particles ( 25~125 mm) ● Low gas heating value ● Low utilization rate of char Burner Burner Fireproof Cold gas circulation Char controller Char IPE CAS Petrosix Retorting (Brazil) Precipitator Oil shale Compressor Oil and gas Retorting furnace Gas Cyclone Gas Spray tower Oil Oil Oil Char Heating furnace Fuel gas Water Gasoline Distillation Cold circulating gas Liquid fuel 1) Running rate: 95%; 2) High-HHV gas; 3) Large capacity (6000 t/d); 4) Steady running; 5) High oil yield (85~90% Fischer assay yield). But a) Large particles (12~80 mm); b) Wasting char potential heat. IPE CAS Galoter Retorting (Russia) For 0~25 mm particle, Oil yield: 90%, High-HHV gas, Actually applied. High investment, Complex operation, Extensive maintenance. Hot ash and flue gas Dust removal Ash Power plant Combustor Separator Mixer Separator Dryer Pyrolyzer Oil shale Oil and gas recovery Char Water Air Power plant Shale oil IPE CAS Enefit-280 (Germany & Estonia) Oil shale (<6 mm) Stack Dust Combustion Pyrolysis gas Dryer Shale oil Heavy oil Retorting Cooler Hot air making Air Air Extra-heavy oil Condenser Modified Galoter: 6000t/d IPE CAS Tosco-Ⅱ Technology (America) Heat carrier: porcelain balls at 680 ℃ Porcelain balls Flue gas Oil shale (<12.7 mm) Preheated to 260 ℃ Pyrolysis gas Naphtha Air Pyrolysis at 480 ℃ Light oil Retorting Dryer Heavy oil Hot oil shale Porcelain balls Hot gas Vapor Combustion Heater Water Oil yield: > 90% (Fischer assay yield) High investment Char not used Water Hardly for large scale Cooler Shale High oil sludge IPE CAS Alberta Taciuk Process (ATP, Canada & Austrilia) 62.5 m Combustion 8.2 m Oil and gas Retorting Seal Preheating Cooling Oil shale (0~25 mm) 500℃ 750℃ 250 ℃ It was said to have 6000 t/d with oil yield > 90% (Fisher assay), but meeting many problems in China , such as complex operation and maintenance, low running rate, high dust contamination. IPE CAS Lurgi-Ruhrgas (Germany) Ash : oil shale = 4:1 Flue gas Pyrolysis gas Air preheater Dryer Air Oil shale (0~5 mm) Pyrolysis at 520 ℃ Cooler Combustion Feeding Oil Water Pyrolysis Circulated ash: 720 ℃ Oil yield: > 90% (Fischer assay yield) High-HHV pyrolysis gas Oil Pyrolysis gas Char Finished 8-24t/d pilot, but no industrial plant. Char used in the system Complex system High investment High dust in oil IPE CAS Comparison of existing technologies In-situ Parameter retorting Gas heat carrier Petrosix Kiviter Solid heat carrier Galoter Enefit-280 Tosco-Ⅱ ATP Lurgi-Ruhrgas Reactor Under ground Scale (t/d) ─ 6200 1000 3000 6000 900 6000 8-24 Size (mm) ─ 6-50 10-125 0-25 0-6 0-12.7 0-16 0-5 Oil yield 60 85-90 75-80 85-90 90 90 85-90 90 High HHV Low HHV High HHV High HHV High HHV High HHV High HHV Heated Pyrolysis gas Ash Ash Balls Ash Char Gas product Low HHV Moving bed Heat supply Char & gas combustion Flue gas Problem Many issues to concern Large particles Rotating oven Moving bed High ash contamination, large oil sludge IPE CAS Highlight on world oil shale resource and technology IPE CAS Unconventional energy resource in China Name Amount Equivalent oil and gas Coal bed gas 36.8×1012 Nm3 36.8×1012 Nm3 gas Shale gas 35×1012 Nm3 35×1012 Nm3 gas Oil shale 7199×108 476×108 t oil 20-50×1012 Nm3 gas Oil sand 59.7×108 t 3-6×108 t oil Heavy oil >100×108 t ~50×108 t oil Tight oil >74×108 t ~74×108 t oil t Shale oil (476×108 t): about 2 times of petroleum reserves (233×108 t). IPE CAS Oil shale distribution in China Oil shale distribution North East (Liaoning, Jilin) 48% Middle (Shanxi) 22% 3.5%-5% Qinghai / Tibet 17% 5%-10% West (Xinjiang) 10% >10% South (Guandong) 3% IPE CAS Oil shale refinery in China Back to 80 years ago, current shale oil production: ～80×104; Only technology: Fushun retort for particles > 12 mm; Being about 60% of the world total shale oil production. Region Oil yield (104 t/a) Fushun 35.0 Beipiao 7.0 Diaobingshan 2.5 Longkou 12.0 Huadian 9.0 Wangqing 5.0 Dongning 1.5 Yaojie 5.0 Total Technology Scale (t/d) Number 220 Fushun retort (internally heated moving bed) 140 100 20 40 Fushun retort Fushun retort Gas combustion 100/300 32/12 100 40 100 4 300 8 ～800,000 t/a shale oil by retorting >15 mt/a large-size oil shale IPE CAS Fushun retorting technology First plant in 1930 at 50 t/d, 100 t/d in 1940; Low oil yield (<72 wt.%); Low gas heating valve; Low shale oil yield (65% of Fischer Assay yield); Hardly scaling up (still ～ 100 t/d per furnace); Hardly use char and ash / water pollution; Only for large-size oil Well industrialized, simple, low cost. shale (12-75 mm). IPE CAS Actual furnace and refieary IPE CAS Oil shale of different sizes From mining Small-size oil shale IPE CAS Another refinery in construction In Shanxi Tongchuan IPE CAS DaGong (DG) process From coal pyrolysis (started in 1980s, 150 t/d in 1992 for lignite); Ash/char heat carrier, as Lurgi-Ruhrgas process for 0-10 mm fuel; Pyrolysis at 500 ℃, Oil yield: 92 % of Fischer Assay yield. 1) High dust in oil; 2) Blocking duct; 3) High heavy species content. Drying Combustion Hot flue gas Pyrolysis Combustor IPE CAS Fluidized bed retorting Developed in 1969, and a 24 t/d was stopped in 1975 (by Maoming); Retorting at 475～480 ℃, combusting at 590～605 ℃; High shale oil yield, high-HHV gas, easy for scale-up, but high dust in oil. Cold water Waster gas Hopper Oil Steam Air Ash Air Ash Water Crusher Separator Ash Absorption Oil shale Scrubbing Distillation Combustor Pyrolysis gas Retorting Hot flue gas 24t/d Light oil Steam Residue Light shale oil Heavy shale oil IPE CAS A new refining technology development in IPE-CAS IPE CAS Concluding remarks 1) Oil shale is the unconventional oil resource that has the biggest reserves. 2) There are a few commercial refining technologies allowing shale oil yields of 80-90%. While the gas heat carrier technologies only treat largesize oil shale (>10 mm) in moving bed, the solid heat carrier technologies can accept fine oil shale by using rotating oven reactors, but there is usually serious dust contamination. 3) Worldwide there is not any technology which can convert fine oil shale to produce low-dust shale oil in high yield, which producing high heating gas simultaneously. 4) Currently China has only the small moving bed retorting technology (Fushun retorting furnace), which suffers from lots of problems including low oil yield (65-72%), low gas heating value, and difficulty in using char. 5) A new technology is under development in IPE, CAS to treat fine oil shale to produce shale oil in yield of about 90% of Fisher assay value and almost free of dust. IPE CAS Thank you for your attention! IPE CAS
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