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

8

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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