Upgrading of oil shale using Conventional flotation

1. Some Physicochemical Studies
on Egyptian Oil Shale Separation

2. OUTLINE
I. Aim of Work.
II. Introduction.
III. Experimental Work.
IV. Results and Discussion.
V. Conclusions.

3. Aim of Work

4.  Because of tightening energy supply, Egypt
looking for alternative oil sources.
 A significant source for oil is oil shale .
Developing substantial technologies for the oil
shale industry is an important mission.
AIM OF WORK

5. Introductio
n

6. • It is a sedimentary rock containing
organic matter called KEROGEN that
yields substantial amounts of oil and gas
upon destructive distillation.
• The main gangue minerals present in oil
shale are kaolin, quartz, siderite, apatite,
anhydrite and calcite.
WHAT IS OIL SHALE?

7. OIL SHALE SEDIMENTARY ROCKS

8. Oil Shale Deposits All Over The World

9. Canadian Oil Shale
Australian Oil Shale
Estonian and Sweden Oil
Shale
Oil Shale Deposits All Over The world

10. Oil Shale Deposits in Egypt

11. • Gebel Duwi, Wadi El-nakhil , Gebel Ahns (8922 million ton).
• Abu Tundub, Hamadat (5487 million ton).
• Abu Shgela (555 million ton).
Oil Shale in Red Sea Region-Egypt

12. UPGRADING TECHNIQUES
THE APPLIED TECHNIQES
GRAVITY TECHNIQUE
Using
Falcon Concentrator
FLOTATION TECHNIQUE
Using
Conventional and column cells

13. Experimental
Work

14. EXPERIMENTAL WORK
Characterization
of
Oil Shale
Fundamental
Studies on
the Pure
Kerogen
Upgrading
Methods of
Oil Shale

15. CHARACTERIZATION OF THE ORE SAMPLE
XRF Elemental analysis,
XRD Phase Analysis,
Thermal Analysis,
FTIR Analysis,
Petrography and Microscopic Investigation,
Grindability and Work Index Measurements.

16. • The results indicated that the work index of oil
shale sample is 16.82 KW/ton.
• It means that the ore with a feed size (d80 = 80%)
less than 2200 µm (2.2 mm) will consume about
16.82 KW/ton to be grind to (d80) less than 80
µm (0.08 mm).
GRINDABILITY AND WORK INDEX
MEASUREMENTS

17. PETROGRAPHY AND MICROSCOPIC STUDY OF THE ORE
SAMPLE

18. I. Evaluation of Extracted Pure Kerogen
FTIR spectrum of the extracted kerogen showed that, sample contains aromatic
matrix was found due to high organic matter content.
FTIR spectrum of the extracted kerogen
PHYSICOCHEMICAL MEASUREMENTS
PHYSICOCHEMICAL FUNDAMENTAL
MEASUREMENTS

19. PHYSICOCHEMICAL MEASUREMENTS
 Zero point of charge (ZPC) of pure kerogen is 1.2.
 Zero point of charge was increased to 1.3 and 1.4 with kerosene and pine
oil treatment.
 Treatment of kerogen with kerosene or pine oil was slightly increased as
shown but it was more effective with pine oil!!.
II- Zeta-Potential Measurements
PHYSICOCHEMICAL FUNDAMENTAL
MEASUREMENTS
(CONT.)

20. pH
Contact angle
Kerogen +
kerosene
Kerogen + Pine oil Kerogen only
Exp. 136° 113° 93
Ref. -- -- 96° - 100°
This table shows that the higher contact angle was obtained in case of
treating kerogen with kerosene more than in case of treating with pine oil.
III- Contact Angle Measurements
PHYSICOCHEMICAL MEASUREMENTS
PHYSICOCHEMICAL FUNDAMENTAL
MEASUREMENTS
(CONT.)

21.  The sample was crushed using pilot 56 "Denver
Jaw crusher” to less than 3.3 mm. Then it was
divided into representative samples of about 50 kg
each.
 Then it is ground to less than 50 µm by “Rod Mill”
then by “Attrition Mill ” to less than 20 µm.
SAMPLE PREPARATION FOR PROCESSING

22.  Falcon concentrator is an enhanced
gravity separator which uses a
spinning bowel design to generate a
force up to 300 G's and more.
 The Falcon is designed to separate
and concentrate relatively fine
particles, according to differences in
specific gravity.
FALCON CONCENTRATOR

23. Denver
Flotation Cell
CONVENTIONAL FLOTATION

24. Schematic diagram of column flotation cell.
COLUMN FLOTATION TECHNIQUE

25.  The column flotation technique has many advantages such as:
• Production of cleaner concentrate.
• Lower energy consumption.
• Lower capital costs.
• Small space.
• Wash Water & Froth depth.
 The water stream applied at the top of the column for washing the
entrained non-floatable bubble-particle aggregate. The concentrate
grade can be controlled by the amount of the wash water employed.
Advantages of column flotation
COLUMN FLOTATION TECHNIQUE

26. Results
&
Discussion

27. XRF ANALYSIS OF OIL SHALE SAMPLE
 Chemical analysis of the sample was determined using X-ray
fluorescence. The sample has a high content of calcium oxide,
sulfur, silica, alumina and iron oxide
Constituent Wt., %
SiO2 18.89
CaO 20.84
Al2O3 4.02
Fe2O3 3.48
P2O5 3.08
SO3 7.48
L.O.I 42.2
Total 99.99
 Ignition loss at 1000C = 42.2% due to organic matter and
inorganic carbonates.
XRF ANALYSIS OF THE ORE SAMPLE

28. The non-clay minerals present in the oil shale sample include;
quartz, siderite, apatite, anhydrite and calcite. The clay mineral is
mainly represented by kaolinite.
X-RAY DIFFRACTION PHASE ANALYSIS (XRD)

29. THERMAL ANALYSIS

30.  The FTIR spectrum showed that the sample is rich in carbon and oxygen.
 It contains characteristic peaks and bands for OH, aliphatic CH, CH2, CH3, carboxyl
and carbonyl groups.
 Finally, it contains aromatic matrix.
FTIR SPECTRUM OF OIL SHALE SAMPLE

31. RESULTS AND DISCUSSION
Upgrading of oil shale using
Falcon concentrator

32. ENHANCED GRAVITY SEPARATION
Effect of frequency and water pressure on grade & recovery of kerogen
Kerogen Recovery, %
B: Water Pressure, Psi
A:
Frequency,
Hz
1.00 2.00 3.00 4.00 5.00
60.00
65.00
70.00
75.00
80.00
23.6672
40.7851
57.903
75.0209
92.1481
2
2
Kerogen Grade, %
B: Water Pressure, Psi
A:
Frequency,
Hz
1.00 2.00 3.00 4.00 5.00
60.00
65.00
70.00
75.00
80.00
34.4586
36.7282
36.7282
38.9977
38.9977
41.2672
41.2672
43.5367
43.5367
2
2
50 %
82 %

34. .
 The floatability of the pure kerogen increased with increasing kerosene or pine oil concentration.
 The addition of kerosene has much greater effect than that of pine oil.
 These results meet the data obtained by zeta-potential and contact angle measurements which showed
the better action of kerosene on the pure kerogen especially increasing the contact angle.
FLOATABILITY OF PURE KEROGEN
FLOATABILITY OF KEROGEN AS A FUNCTION OF COLLECTOR CONCENTRATION

35.  FLOATABILITY OF KEROGEN AS A FUNCTION OF PH IN PRESENCE
OF KEROSENE OR PINE OIL AS COLLECTOR.
The floatability of kerogen was increased by increasing pH up to 9.
The maximum floatability was achieved at pH 9 - 10 for pine oil while the maximum floatability was
achieved at pH 9.5 for kerosene.
 The maximum recovery of kerogen was 70% and 95% for pine oil and kerosene,
FLOATABILITY OF KEROGEN

36. RESULTS AND DISCUSSION
Upgrading of oil shale using
Conventional flotation

37. CONVENTIONAL FLOTATION
Particle size 50 m
Cell volume 1 Liter
Frother type MIBC or Pine oil
Collector type Pine oil or Kerosene
Flotation speed 900 rpm
Conditioning speed 2000 rpm
Conditioning time 10 min
Flotation time 3 min
Experimental conditions for flotation tests

38. CONVENTIONAL FLOTATION
Effect of kerosene dose as a collector for oil shale flotation
90%
35%
32%

39. CONVENTIONAL FLOTATION
Effect of MIBC dose as a frother on oil shale flotation
9.5
37%

40. Effect of pulp pH on oil shale flotation
CONVENTIONAL FLOTATION

41. CONVENTIONAL FLOTATION
Effect of pulp solid % on oil shale flotation
5
Increasin
g solid %
Crowded of
Particles

42. CONVENTIONAL FLOTATION
Effect of Pine oil dose as a frother on oil shale flotation

43. CONVENTIONAL FLOTATION
 The optimum Conditions of conventional flotation are:
5kg kerosene as a collector and 9kg of MIBC as a frother at pH 9
for one ton ore.
 Under these conditions kerogen grade of 38% with recovery of
88.5% was obtained from oil shale sample of 28%.

45. RESULTS AND DISCUSSION
Upgrading of oil shale using
Column flotation

46. COLUMN FLOTATION
 The pulp density has a significant impact on the recovery and grade .
 The grade of kerogen increased with increasing solid % up to 15%.
Superficial wash water velocity (cm/s) and solids (%) with kerosene

47. COLUMN FLOTATION
Froth depth and superficial air flow velocity with
Kerosene
 The recovery of kerogen increased with increasing froth depth up to 40 cm.
57%
46%

48. COLUMN FLOTATION
Solid concentration and Collector Dosage
Kerosene
The recovery of kerogen was decreased sharply with increasing collector
dosage even at lower solids concentration (% 5 solids) and at higher solids
concentration (% 15 solids).

49. COLUMN FLOTATION
A:Solids conc. (%Solids) = 15.00
5.00 15.00
B:Wash water velocity (cm/s) = 0.00
0.00 0.36
C:Feed velocity (cm/s) = 0.49
0.07 0.49
D:Frother concentration (ppm) = 40.00
10.00 40.00
E:Froth depth (cm) = 40.00
10.00 40.00
F:Air velocity (cm/s) = 0.67
0.50 1.50
G:Collector type = Kerocene
Treatments
1 2
H:Collector dosage (kg/ton) = 0.50
0.50 1.50
Kerogen grade (%) = 52.3521
29.9 55.3
Tailing grade = N/A
20 30
Yield, % = N/A
28.93 94.94
Enrichment ratio = N/A
1.01 1.65
Kyrogen recovery (%) = 78.4063
38.3793 96.224
Desirability = 0.793
Ramp report showing the optimum parameters for upgrading of
Egyptian oil shale via column flotation.
Maximum kerogen grade of 52.35% and kerogen recovery of 78.41% was achieved using
kerosene as collector.
The calculated optimum parameters were :
15% solid concentration, 0.5 cm/s superficial wash water velocity, 0.49 cm/s feed superficial
velocity, 40 ppm frother concentration, 40 cm froth depth, 0.67 cm/s superficial air velocity,
0.5 kg/ton collector dosage(kerosene).

50. Conclusions

51. .
An Egyptian oil shale ore sample from the Eastern Desert was
directed to investigation to increase its kerogen content.
The associated minerals were quartz, pyrite and phosphate.
The frother type and dose, and the pulp pH were playing effective
roles in enhancing the kerogen flotation efficiency.
 By using 5g/kg kerosene as a collector and 9g/kg of MIBC as a
frother at pH 9, a kerogen product assaying 38% with recovery of
88.5% was obtained from an original oil shale ore sample
containing 28% using the conventional flotation technique.
CONCLUSIONS

52. CONCLUSIONS
 The results were analyzed using specialized computer programs in
both techniques.
A fine concentrate kerogen product assaying 38.4% kerogen with
85.4 % recovery was produced at 70 Hz (equivalent to G-force 243)
and water pressure of 2 Psi from a feed sample containing 30 %
kerogen using Falcon Cocentrator.
A final concentrate kerogen product containing 55% kerogen with
a recovery 73% was obtained from a starting feeding material
containing 29 % kerogen using Column Flotation Technique.

53. CONCLUSIONS
 Results showed that the grinding of the oil shale ore sample,
under investigation, to less than 20 m is a must to produce a
kerogen product with satisfied grade and recovery either by the
enhanced gravity technique using the Falcon Concentrator or via
the column flotation technique.