microwave pyrolysis for yaojie oil shale · 1 microwave pyrolysis for yaojie oil shale yonghui...
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MICROWAVE PYROLYSIS FOR
YAOJIE OIL SHALE
Yonghui Song2 , Jianmei Zhe2 ,
Xinzhe Lan2 , Xicheng Zhao2 ,
Wenzhi Shang 3 ,
Rick Sherritt 1, Jimmy Jia 1,
1 PROCOM Consultants Ltd.
2 School of Metall. Eng., Xi' an Univ. of Arch. & Tech., Research Center
of Metallurgical Engineering & Technology of Shaanxi Province
3Shenmu Shanjiang Coal Chemical Co.
31st Oil Shale Symposium
October 17-19, 2011
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Microwave is a promising technology for oil shale
processing;
Previous studies in:
Biomass pyrolysis;
Coal pyrolysis;
Sewage sludge pyrolysis;
Waste material (tiers, medical plastic waste etc.)
Oil shale---- surface process and in-situ process;
Theory and findings:
Microstructure and composition of feed stock,
Added oxides for improved thermal efficiency ;
Heat distribution – hot spots;
Microwave Pyrolysis Review
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Advantages
Short heating time--- it takes seconds to minutes to increase temperature to 1000 C;
Heat value of retort gas is higher;
Less water consumption;
Less waste water production;
Less dust in gas/oil stream;
Potential for lower CO2 emissions (use solar power/wind power);
Disadvantages
Heat distribution – not even;
Power consumption;
Carbon residue utilization (low);
Advantages of Microwave
Pyrolysis
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EXPERIMENT SETUP
1
2
3
4
5
67
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1- Microwave power generator, 2- K- thermal couple,3- Quartz
reactor,4- Conical Flask,5- cooling bath,6- U tube cooler,7- On-
line GC,8- temperature controller
Fig 1. illustration of experimental facility.
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YAOJIE LOCATION
①
②
③④⑦
⑤
⑥ ⑧
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Yaojie Location and Resource
260 M ton of oil shale reserves;
FA Oil yield average >10%;
By-product of coal mining;
Underground mining;
Location: very dry, 100’s mm rain annually – very sunny;
Altitude 2100 m (elevation above sea level) – very windy;
Landscape: Loess Plateau landscape;
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Oil Shale Property
Proximate analysis Ultimate analysis
Mad Aad Vad FCad Cad Had Nad St,ad
0.84 64.73 22.50 11.93 23.88 2.26 0.54 0.89
Proximate and ultimate analyses of oil shale (%)
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OIL & GAS YIELD CHANGES VS
MICROWAVE POWER
Yield from Microwave pyrolysis (2450 MHz) vs. Fischer Assay
Power Product yield / % (mass)
/W Semi-coke Oil Gas
160 99.4 0 0.6
320 84.6 8.5 6.6
400 77.2 13.3 9.2
480 76.2 13.5 10
640 74.4 11.7 13.6
800 72.3 12 15
FA 79.95 12.67 7.40
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POWER VS PRODUCT YIELD
0
20
40
60
80
100
0 500 1000
Pro
du
ct
Yie
ld (
% w
)
Power (W)
Coke
Oil
Gas
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PYROLYSIS TEMPERATURE PROFILES
Temperature Profile with Varied Power
0
200
400
600
800
1000
0 10 20 30
Reto
rt
Te
mp
era
ture (
˚C)
Reaction Time (min)
480W
600W
800W
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PYROLYSIS TEMPERATURE PROFILES
Temperature Profile with Varied Power
0
200
400
600
800
1000
0 5 10 15 20 25 30 35
Re
tort
Te
mp
era
ture
(˚C
)
Reaction Time (min)
400W
600W
800W
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SPENT SHALE ANALYSIS WITH
DIFFERENT POWER
Power/W
Proximate analysis/% Ultimate analysis/%
Mad Aad Vad FCad Cad Had Nad St,ad
160 0.40 60.60 26.00 13.00 17.40 0.50 0.29 0.74
320 0.52 76.03 9.38 14.07 17.72 0.80 0.34 0.74
400 0.56 79.69 5.10 14.65 19.13 0.66 0.34 0.75
480 0.53 81.07 1.38 17.02 18.20 0.82 0.42 1.03
640 0.52 82.46 0.14 16.88 27.80 1.86 0.57 0.92
800 0.21 80.91 0.14 18.74 19.80 0.24 0.23 0.65
Proximate and ultimate analyses of char under different microwave power
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OIL COMPOSITION GC-MS
REPORT AT 480W
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00
400000
500000
600000
700000
800000
900000
1000000
1100000
1200000
1300000
1400000
1500000
Time-->
Abundance
TIC: S1.D
4.35
4.49
4.61
5.91
6.05 6.23
6.40
6.51 6.59 8.08
8.51
8.71
8.94 10.10 10.60
11.15
11.37
12.76 13.40
13.93
14.14
14.54
16.70
16.91
17.61
18.14
19.38
19.58
21.09
21.95
22.13
24.40
24.56
25.15 25.32
26.73
26.88
27.02
28.74
28.93
29.07
29.99
30.85
30.94
31.04
31.16
32.37 32.52 32.71 32.95
33.05
33.16
35.01
35.13
35.23 37.27
37.40
37.51 40.03
40.17
43.60
47.90
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OIL GC-MS REPORT AT 640W
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00
100000
150000
200000
250000
300000
350000
400000
450000
500000
550000
600000
650000
Time-->
Abundance
TIC: S82.D
4.58
4.72
6.13
6.28 6.49 6.68
6.79 6.87 8.51
8.98 9.20
9.42 11.23
11.80
12.03
13.51 14.12
14.70
14.93
15.31
17.55
17.77
18.47
18.99
20.28
20.48
22.00
22.88
23.06
25.34
25.51
26.25
27.68
27.83
29.90
30.04
30.96
32.01
32.14
33.94
34.03
34.13
35.99
36.11
38.26
38.38
40.78 41.01
41.14
44.56
48.87
54.34
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OIL GC-MS REPORT AT 800W
5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00
60000
80000
100000
120000
140000
160000
180000
200000
220000
240000
260000
280000
300000
320000
340000
360000
Time-->
Abundance
TIC: S92.D
4.58
4.71
6.13
6.29
6.49
6.67
6.87 8.51
8.98
9.20
9.42 11.23
11.80
12.03
14.70
14.93
17.55
17.76
18.47 18.98
20.28
20.48
21.89 21.99 22.11
22.88
23.06
25.34
25.51
27.68
27.83
29.90
30.03
30.97
32.01
32.13
33.70
34.03
34.13
35.99
36.10
36.20
38.26
38.38
40.78 41.00
41.14
44.56
48.88
54.32
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OIL GC-MS REPORT AT 800W
Peak
Power /W
480 W 640 W 800 W
Retension
/min Compond
Concerntr
ation /% Retension /min Compond
Concerntr
ation /% Retension
/min Compond
Concerntr
ation /%
1 4.354 Toluene 2.647 4.581 1-Octene 1.033 4.58 1-Octene 1.677
2 4.494 1-Octene 1.577 4.715 Octane 1.38 4.714 Octane 2.557
3 4.615 Octane 1.579 6.126 Ethylbenzene 0.785 6.13 Ethylbenzene 0.718
4 5.909 Ethylbenzene 0.651 6.285
Benzene,1,3-
dimethyl- 1.777 6.285 p-xylene 1.64
5 6.054 p-Xylene 1.531 6.486 1-Nonene 1.599 6.491 1-Nonene 1.711
6 6.228 1-Nonene 1.539 6.676 Nonane 1.755 6.676 Nonane 2.319
7 6.397 Nonane 2.033 6.79 Styrene 1.064 6.867
Benzene,1,2-
dimethyl- 0.771
8 6.508 Styrene 0.005 6.867
Benzene,1,2-
dimethyl- 0.82 8.514 Phenol 1.172
9 6.59
Benzene,
1,3-dimethyl- 0.593 8.51 Phenol 1.242 8.978 1-Decene 1.517
10 8.078
Benzene,1-
ethyl-3-
methyl- 0.628 8.978 1-Decene 1.637 9.199 Decane 1.973
11 8.507 1-Decene 1.338 9.205 Decane 1.707 9.426
Benzene,1,3,
5-trimethyl- 0.688
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OIL COMPOSITION VS POWER
Power
/W Parafin Aromatics Oleffin Phenols Alkyl ketone
480 36.033 16.234 17.789 3.795 0.997
640 47.288 17.030 25.402 6.150 0
800 59.256 13.973 24.726 2.048 0
Oil Composition (wt %) with Varied Power
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GAS COMPOSITION VS POWER
0
10
20
30
40
50
60
70
0 200 400 600 800 1000
Ga
s C
om
po
sit
ion
(v
%)
Power Applied ( W)
CO2
CO
CH4
CnHm
H2
H2+CH4+CO
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SUMMARY
Results from Microwave Pyrolysis of oil shale:
Pyrolysis temperature is achieved within 3 minutes;
Achieved higher yield than Fischer Assay;
Oil & gas yield and composition is determined by
microwave power applied;
480W is suitable microwave power for 50 g oil shale
sample to maximize oil yield;
At 480 W, oil yield reaches 13.5% (peak);
More than 36.03% of the oil is paraffinic;
More than 55% of gas is H2+CH4+CO;
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FUTURE WORK
A new larger pilot facility has been established;
Continuous feed and discharge operation;
Economical evaluation of microwave pyrolysis;
Challenges ahead:
Scale up design and economics study.
Availability of larger Microwave power generator with
even heat distribution;
Heat recovery from spent shale;
Utilization of remaining carbon in spent shale;
Hybrid technology with Microwave pyrolysis
BACKGROUND
The company was founded in 2005, and has been profitable
throughout this period.
Our customer base is broad and we seek a close arrangements with
our clients to foster long term relationships.
Our employees come from a wide range of industries and
experiences. 21
THANK YOU
1/38 Limestone St Darra, QLD 4076 Australia P +61 7 3715 8473 F +61 7 3715 6032 www.procom-consultants.com
• PROCOM Consultants is a niche Australian engineering company that provides process engineering and plant commissioning services in several energy industry sectors.
• PROCOM was founded in 2005 following the closure of the Stuart Shale Oil Plant in Queensland Australia. PROCOM’s directors and several key employees worked on the project.
• PROCOM has provided engineering and consulting services to oil shale, UCG, CSM, Refinery in USA, Estonia, China, Jordan and Australia.
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