Co-production of Diesel and Synthetic Natural Gas from the...
Transcript of Co-production of Diesel and Synthetic Natural Gas from the...
![Page 1: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/1.jpg)
Co-production of Diesel and Synthetic Natural Gas from the Olive Oil Industry Waste
Javier Barrientos KTH – Chemical Technology
![Page 2: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/2.jpg)
Outline
1. Setting the scene
2. The fuel production process
3. The Fischer-Tropsch synthesis - Diesel
production
4. Methanation – Synthetic natural gas (SNG)
production
2
![Page 3: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/3.jpg)
1. Setting the scene
Branches
Olive tree
Olives Olive oil
Seeds Pomace
3
![Page 4: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/4.jpg)
1. Setting the scene Olive production uses a significant part of the available land in Mediterranean countries
Algeria Greece
Italy
Morocco
Portugal
Spain
Syrian Arabic
Republic
Tunisia
Turkey
Harvested area 2010 > 8 000 000 Ha Residues > 14 Mt! 4
Ref: European Commission. Environment. Life among the olives. Good practice in improving environmental performance in the olive oil sector. [Online] 26-01-2010
![Page 5: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/5.jpg)
1. Setting the scene
• Alternative to fossil fuels
• Reduction of greenhouse gas emissions
5
![Page 6: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/6.jpg)
2. The fuel production process
PHYSICAL PRETREATMENT
CHEMICAL PRETREATMENT
FUEL SYNTHESIS Diesel
SNG
Waste
Pellets
Synthesis gas (CO and H2)
6
![Page 7: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/7.jpg)
2. The fuel production process
PHYSICAL PRETREATMENT
Waste
Drying Grinding Mixing Pelletizing
Pellets
7
![Page 8: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/8.jpg)
2. The fuel production process
CHEMICAL PRETREATMENT
Tar removal
CO2 removal
Purification (e.g. H2S removal)
Synthesis
gas
Gasification Pellets
8
![Page 9: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/9.jpg)
2. The fuel production process
FUEL SYNTHESIS
Synthesis
gas
Fischer-Tropsch Methanation
Compression
Liquid
fuels
(diesel)
SNG
9
![Page 10: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/10.jpg)
3. The Fischer-Tropsch Synthesis
𝐶𝑂 + 2𝐻2 → −𝐶𝐻2 −+𝐻2𝑂 (∆𝐻 ° = −165 𝑘𝐽/𝑚𝑜𝑙)
C1-C2 C3-C4 C5-C10 C11-C21 C22+
SNG LPG Gasoline Diesel Wax
𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 ↑ 𝑆𝑒𝑙𝑒𝑐𝑡𝑖𝑣𝑖𝑡𝑦 𝑡𝑜 𝑙𝑜𝑛𝑔 𝑐ℎ𝑎𝑖𝑛 ℎ𝑦𝑑𝑟𝑜𝑐𝑎𝑟𝑏𝑜𝑛𝑠 ↓
𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 ↑ 𝑆𝑒𝑙𝑒𝑐𝑡𝑖𝑣𝑖𝑡𝑦 𝑡𝑜 𝑙𝑜𝑛𝑔 𝑐ℎ𝑎𝑖𝑛 ℎ𝑦𝑑𝑟𝑜𝑐𝑎𝑟𝑏𝑜𝑛𝑠 ↑
10
![Page 11: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/11.jpg)
3. The Fischer-Tropsch Synthesis
0.0 0.2 0.4 0.6 0.8 1.00.0
0.2
0.4
0.6
0.8
1.0
Wei
ght
frac
tio
n
= f(P, T, catalyst)
C1-C2
C3-C4
C5-C10
C11-C21
C22+
It is impossible to only produce hydrocarbons in the carbon number range of C11-C21!
11
![Page 12: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/12.jpg)
3. The Fischer-Tropsch Synthesis
C1-C2
C3-C4
C5-C10
C11-C21
C22+ (wax)
Hydrocracking
Fischer-Tropsch
Diesel production optimization
Diesel
Reforming
Synthesis gas
Diesel is maximized by optimizing the selectivity to C22+ 12
![Page 13: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/13.jpg)
3. The Fischer-Tropsch Synthesis
Reactor optimization
Goal: Isothermal operation
Slurry bed reactor Multitubular fixed
bed reactor
T = 200-250 °C P = 20-40 bar
𝐻𝑜𝑡 𝑠𝑝𝑜𝑡𝑠 𝑆𝑒𝑙𝑒𝑐𝑡𝑖𝑣𝑖𝑡𝑦 𝑡𝑜 𝑙𝑜𝑛𝑔 𝑐ℎ𝑎𝑖𝑛 ℎ𝑦𝑑𝑟𝑜𝑐𝑎𝑟𝑏𝑜𝑛𝑠 ↓↓↓
13
![Page 14: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/14.jpg)
3. The Fischer-Tropsch Synthesis
Catalyst optimization Slurry bed reactor
• High activity, selectivity and
stability
• High attrition resistance
Catalyst particle size: 50-100 µm
14
![Page 15: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/15.jpg)
3. The Fischer-Tropsch Synthesis
Catalyst optimization Multitubular fixed
bed reactor
• High activity, selectivity and
stability
• Mass transfer
Catalyst particle size: > 1mm
Egg-shell catalyst:
15
![Page 16: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/16.jpg)
16
3. The Fischer-Tropsch Synthesis
0 2 4 6 8 10 120
5
10
15
20
25
30
35Yi
eld
of
CO
to
Hyd
roca
rbo
ns
(NL/
day
per
gra
m o
f ca
taly
st)
Time on Stream (days)
FT conventional conditions:
20 bar synthesis gas
20 bar synthesis gas + 15 bar He
![Page 17: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/17.jpg)
17
3. The Fischer-Tropsch Synthesis
0 200 400 600 800 1000 1200
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Rela
tive a
ctivity
Sulphur loading (g S/g cat)
![Page 18: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/18.jpg)
18
3. The Fischer-Tropsch Synthesis
0
10
20
30
40
50
60
70
80
90
100
SC5+
CO
convers
ion/
Sele
ctivity (
%)
Fresh
10 ppm S
100 ppm S
250 ppm S
1000 ppm S
XCO
SCH4
SC2-C4
Operating conditions: 20 bar, 210 °C and H2/CO=2.1
![Page 19: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/19.jpg)
4. Methanation
𝐶𝑂 + 3𝐻2 → 𝐶𝐻4 +𝐻2𝑂 (∆𝐻 ° = −206 𝑘𝐽/𝑚𝑜𝑙)
0.0 0.2 0.4 0.6 0.8 1.00.0
0.2
0.4
0.6
0.8
1.0W
eigh
t fr
acti
on
= f(P, T, catalyst)
C1-C2
C3-C4
C5-C10
C11-C21
C22+
𝐓 ↑↑ 𝐒𝐞𝐥𝐞𝐜𝐭𝐢𝐯𝐢𝐭𝐲 𝐭𝐨 𝐂𝐇𝟒 ↑↑↑ 19
![Page 20: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/20.jpg)
4. Methanation
𝐓 ↑↑ 𝐒𝐞𝐥𝐞𝐜𝐭𝐢𝐯𝐢𝐭𝐲 𝐭𝐨 𝐂𝐎𝟐 ↑↑↑
𝐶𝑂 + 𝐻2𝑂 → 𝐶𝑂2 +𝐻2 (∆𝐻 ° = −41 𝑘𝐽/𝑚𝑜𝑙)
100 200 300 400 500 600 700 80050
60
70
80
90
100C
O c
onvers
ion (
%)
T (° C)
CO conversion
P = 20 bar
Initial conditions: molar H2/CO = 3
0
20
40
60
80
100
CH4 selectivity
CO2 selectivity
Sele
ctivity (
%)
20
![Page 21: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/21.jpg)
4. Methanation
Reactor/process optimization T = 250-650 °C P = 20-40 bar
650 °C
300 °C
550 °C 450 °C
300 °C 300 °C 300 °C
350 °C
21
![Page 22: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/22.jpg)
4. Methanation
Catalyst optimization Minimize catalyst deactivation!
T=250-350 °C Nickel carbonyl formation T=300-450 °C Carbon formation T=450-650 °C Sintering
Preeminent methanation catalyst: Nickel-based
22
![Page 23: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/23.jpg)
4. Methanation
23
0 2 4 6 8 10 12 14 16 18 20 22 24
0
10
20
30
40
50
60
70
80
90
100
Catalyst 1
Catalyst 2
Catalyst 3
Catalyst 4
Catalyst 5
CO
convers
ion (
%)
Time on stream (h)
Operating conditions: 20 bar, 310 °C and H2/CO=3
![Page 24: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/24.jpg)
4. Methanation
24
200 400 600 800 1000 1200
Am
ou
nt
of
ca
rbo
n (
a.u
.)
T (K)
Isothermal
great!
![Page 25: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/25.jpg)
Acknowledgements
This research has received funding from the European Union Seventh Framework Programme (FP7/2013) under grant agreement n° 308733.
25
![Page 26: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/26.jpg)
FFW partners:
26
![Page 27: Co-production of Diesel and Synthetic Natural Gas from the ...web.abo.fi/projekt/poke/Saarenmaa/Co-production of... · Good practice in improving environmental performance in the](https://reader034.fdocuments.in/reader034/viewer/2022042408/5f247bd01879396c7c3431f8/html5/thumbnails/27.jpg)
Thank you for your attention
27