Fischer-Tropsch Synthesis for Greener Fuel Oil

Production

CaRE Micro teaching, 15 May 2019

Catalysis and
Reaction Engineering Pertamina University
 Fischer Tropsch Process

Indonesia’s potential resources for oil fuel

 150.39 TSCF
Natural Gas (Ditjen Migas, 2015)
BBM
 32,263.68 JT
Coal
In 2030, fuel oil imports are projected to have (ESDM, 2015)
reached 71.8% of the total demand, or around
2.5 times the national fuel production (ESDM
2018).  200,000 BPD BBN
Biomass (Ditjen EBTKE, 2014)

Fischer Tropsch Process (FTS)

2 2
 Low Temperature Fischer Tropsch (LTFT), What this technology can offer?

Co-based Catalyst
LTFT Development
Operating Cond. : P ~10-45 Bar, T 200-250 0C
Reactor : Fixed bed, SBCR
Product : Middle distillate-wax Goals :
Catalyst : Co-based • High syngas conversion
• high product selectivity towards heavy wax
products C5+ 3
  How to Develop The Catalyst?

Catalyst is a substance that increases the rate of the reaction, without being substantially
consumed in the process.

Catalyst main component How catalyst are prepared?

• Impregnation method
• Copresipitation method
• Sol gel method

4
  How to Develop The Catalyst? PREVIOUS RESEARCH

1. Modified support – pretreatment with reflux system using chemicals

3.5

3
Kondensor
Condenser
2.5

dV[log d] (cc/gr)
2
Thermometer
Termometer 1.5 P
100P
1
Keranjang
Stainless steel
Stainless
basket Steel 0.5
Magnetic Magnet
Pengaduk stirrer 0
hotplate
Hotplate 2.5 7.5 12.5
dpori (nm)

XRD cobalt
BET surface Pore volume Catalysts XCO (%) XH2 (%) particle YC5+ (%))
Catalysts
area (m2/g) (cm3/g) size (nm)
P (Support) 217.3 0.46 Co 36.4 34.2 9.2 19.5
100P 184.7 0.48 Co/100P 85.2 77.3 10.2 51.1
5
 How to Develop The Catalyst? PREVIOUS RESEARCH

2. Promoter Addition – Cu and K

Catalysts XCO (%) XH2 (%) α SC1 (%) SC2-4 (%) SC5+ (%)
Co 36.4 34.2 0.84 8.8 37.7 53.5

Co/100P 85.2 77.3 0.73 7.1 32.9 59.9

•Support
Co-1.2Cu/100P 91.8 81.8 0.76 5.7 28.5 65.8

Co-0.6Cu/100P 98.0 83.7 0.77 5.6 28.0 66.4

Co-1K/100P 98.8 80.7 0.77 5.4 27.2 67.5

•Dry- 6
Co-2K/100P 71.1 69.1 0.83 3.0 17.5 79.6 impregnation
method

•Co-based
Catalyst

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  METHODS – Catalytic Ativity Test

Thermocouple

Exhaust gas
Thermo
Syngas 2:1 controller
Condenser Absorber

Catalyst
Bed

Reactor

Sampling inlet
Product
Vessel
Sampling Product
Pump
Water Cooler

 (Catalyst Reduction : P= 5 bar; T= 400°C; H2 flowrate = 90 mL/min ; t = 6 jam

 (Activity Test : P= 20 bar; T= 250°C; GHSV=1500 jam-1; Syngas Ratio - H2/CO = 2)

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  METHODS – Limitation Diffusion Test

External Diffusion Test Internal Diffusion Test

100
100
90
90
80
80
70
Konversi (%)

70

Konversi (%)
60
60
50
50
40
40
30
XCO 30
XCO
20 XH2 20 XH2
10
10
0
0
10 20 30 40 50 10/20 20/30 40/60
Q (mL/min) Ukuran katalis (mesh)
CO and H2 conversion as a function of linear flowrates at fixed resident CO and H2 conversion as a function of catalyst particle size (Syngas 2:1, Q
time (Syngas 2:1, Q = 25 mL/min, T = 250oC, P = 20 Bar, t = 18 h) = 25 mL/min, T = 250oC, P = 20 Bar, t = 18 h)

Data was taken at Q > 25 mL/min with particle size between 30 – 50 mesh”
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 METHODS – Calculation

Catalyst mass in bed Conversion

Mass balance in PFR Reactor

ASF Product Selectivity

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 



C5+ product
FTS Product

Light hydrocarbon (Gas product)

2. HK Product C21+ wax fraction, (white)

0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0

-0.5
1. HK Product C6-C20 liquid phase (clear yellowish)

2.702
4.263 3.758
4.203
5.333 5.526
uV(x10,000)

6.084 6.452
6.6537.149 6.383
7.876 7.999 5.687 8.045 8.300
9.153
10

8.872 8.787 9.437

Chromatogram

8.119
8.978
10.785 10.845
11.04710.937
11.233
12.664
11.76812.443
12.855 12.164
13.160
13.63311.939
13.481 13.812
14.055 13.925
14.77815.441 15.168
15.67915.787
15.977 14.245
14.921 16.662
16.84916.717
17.406
17.622
16.535 17.506
17.809 17.684 17.16616.983
18.660 18.322 18.520 18.054
18.965
19.125 18.798
19.024
20

19.42419.504
19.635
19.95419.775
20.297
20.548 20.792
21.05820.445
21.513 21.195
22.065
22.284 22.147
22.59822.421
23.060
21.651
23.54423.656
23.746 23.385
23.839
24.52424.570
23.15424.659
24.929 24.798
25.621 25.842
27.043 25.102
26.89026.955
27.179
27.307
27.950 27.479
28.450 28.171
29.134
30

29.220
29.445 29.309
29.734 29.566
30.385
31.27631.716
31.882 32.495
33.323
33.766 34.507
35.278
36.432
37.148
38.945 38.273
40

40.038
41.733
43.363
44.934
46.448
47.909
50

49.324
GC-FID Characterization

55.643
60

63.109
63.150
min

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  Characterization- Physical Properties of The Prepared Catalyst Composition

BET Characterization
5

4.5

4
P
dV[log d] Pore volume (cm3/gr)

BET surface area Pore volume

3.5 100P Catalysts
(m2/g) (cm3/g)
3 Co/100P P (Support) 217.3 0.46
Co-0.6Cu/100P 100P 184.7 0.48
2.5
Co-1.2Cu/100P Co 144.9 0.37
2 Co-1K/100P Co/100P 273.1 0.64
Co-2K/100P Co-0.6Cu/100P 228.9 0.59
1.5
Co-1.2Cu/100P 292.8 0.80
1 Co-1K/100P 157.8 0.39
Co-2K/100P 34.5 0.88
0.5

0
2.5 4.5 6.5 8.5 10.5 12.5 14.5
Pore diameter (nm)

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 Characterization - Cobalt Particle Size (dp Co) of The Prepared Catalyst Composition

X-ray Diffraction Characterization

Co3O4 cobalt particle size

Co-2K/100P γ-Al2O3 Catalysts
(nm)
P (Support) -
Co-1K/100P
100P 10,2
Co 92
Co-1.2/100P
Intensity (a.u)

Co-1.2Cu/100P 8.6
Co-0.6Cu/100P 9.5
Co-0.6/100P
Co/100P 9.2
Co-1K/100P 11
Co/100P
Co-2K/100P 9.2

Co

0 10 20 30 40 50 60 70 80
2 thetha (θ)
 Characterization – Acidity Of The Prepared Catalyst Composition

TPD Characterization 1.2

Co
0.8
Co/100P
Co-1K/100P

( )
Co-2K/100P
Signal (a.u)

Co-0.6Cu/100P
Co-1.2Cu/100P 0.4

0.0
Co- Co-
Co Co/100P Co-1K/100P Co-2K/100P
1,2Cu/100P 0,6Cu/100P
Lkat/Lco-0 1.00 1.00 0.84 0.66 0.61 0.72

0 100 200 300 400 500 600 700 800 *Lcat/LCo-0: Relative acidity, measured by comparing
o
Temperature ( C) the area percent of catalyst sample and divide it by
the area percent of catalyst reference (Co)

• Modification changes the surface acid amount

• So our next research topic is about surface acidity properties
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