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Clean, high quality
Diesel and Gasoline
Production with
Topsøe Upgrading Process
8th International Freiberg Conference, June 2016
Angélica Hidalgo Vivas and Rasmus G. Egeberg
2
For each 100,000 TPY of tar, a potential revenue of 60 MM Euro, an up-grade value of 46 million Euro
Coke oven
or gasifi cation
Tar
wash
20 million USD
Coal
COKE
TAR
GAS treat ment
GAS
H2 Balance of plant 100 million USD
Diesel Naphtha
Lube base stock
Haldor Topsoe’s technology and catalysts
Tar Hydroprocessing
Clean
tar
Coal tar is a low value by-product
3
Challenges in tar hydroprocessing
4
Coal Tar vs Crude Oil Comparison
Chinese Coal Tar
(C5 to 588°C)
Brent Blend Crude
(C5 to 815°C)
S.G. 60/60°F 1.003 0.837
Sulphur wt% 0.17 0.400
Nitrogen wt ppm 6075 1000
Oxygen Wt% 7.1 < 0.15
C/H ratio wt/wt 8.8 6.4
Diesel cetane index D4737 24 55.7
Pour Point °C +27 -19
Total Acid Number mg KOH/g 4.7 0.1
Arsenic wt ppm 0.2 nil
Chloride wt ppm 10 nil
Iron wt ppm 110
Calcium wt ppm 210
Low sulfur
Low hydrogen, high density,
high nitrogen,
sulfur / nitrogen <1 high oxygen content,
high aromaticity
high total acidity, metal impurities and
dispersed fines
5
Haldor Topsoe compendium of coal tar samples: Fe and As content is high Also Ca, Mg, Si and other metals depending on source of coal
0
20
40
60
80
100
120
140
160
180
200
Iro
n c
on
ten
t, w
t p
pm
0
2
4
6
8
10
Ars
en
ic c
on
ten
t, w
t p
pm
6
What can Topsøe do? Metals impurities challenge
7
We can wash with acid to remove majority of metals
Heating Mixing Centrifugal separation
High metals tar
Cleaned Tar
Sulfuric acid + water
We have patents applications and collaborate with 3rd parties
Membrane
Centrifugal separation tests with Alfa Laval
8
Acid treatment to remove metal impurities
Filtration
Water wash
Removal
Ca Fe Mg
Filtration 60-95% 0-11% 0-8%
Water wash 19% 24% 60%
H2SO4 wash 94% 92% >69% The acid wash method removes more than 90% metals
Simple filtration only removes particles/ash
Water wash only removes inorganic salts
9
Acid wash also reduces organic nitrogen Organic nitrogen – in particular basic nitrogen – inhibits catalyst activity
Untreated tar
Tar treated with H2SO4
Nitrogen, wtppm 5970 3157
Basic nitrogen, wtppm 3682 1326
%N removal 47%
%Basic N removal 64%
10
Low hydrogen, high density, high oxygen,
high aromatics
Tar properties challenges
11
Hydrogen and density Target: diesel product SG=0.845
High temperature tars
Medium T tars
Shale oil
Light oil
Light oil Light oil
Wash oil
High density reduction
High hydrogenation
High H2 consumption
Target
Diesel SG
12
Hydrodeoxygenation (HDO) is highly exothermic Catalyst loading must be tailored to reactivity of feed
Heat of reaction 120 KJ/mol
Associated high heat release = high exotherm 350 - 500 °C in total
13
Coal tar upgrading process Diesel and gasoline production
Guards HDT
C5- 150oC
Naphtha
150-390oC
Diesel
390oC+
Lube
base stock
H2SO4
HDT/HDC Separation
Hydrogen LPG
Acid wash
Tar
Diolefins guard
Metals guard
Arsenic guard
HDS, HDO
HDN
HDN
Aromatics saturation
HDC
14
Hydrotreating and hydrocracking Once-through hydrotreating and hydrocracking at two pressures
Make-up
hydrogen
Feed
Hydro-
cracking
reactor
Naphtha
Diesel
Fractionator
Unconverted oil
(API Group III
Lube base oil)
Metals
guard
system
Hydrotreating reactors
Optional
heavy
residue
Recycle gas
compressor
Optional recycle
Optional recycle Ammonia, Water, H2S
Separa
tor
Heater
Diolefins
guard
15
Upgrading of Middle Section Oil Example 1
16
Middle section oil is a fraction
100
200
300
400
500
0 20 40 60 80 100
Te
mp
era
ture
, °C
Percentage fractionated, wt%
Property Method Unit
SG 60/60 D 4052 1.0144 Sulfur D 4294 ppm 2498
Nitrogen D 4629 ppm 6605
Hydrogen D 7171 H wt % 8.85
Oxygen Elemental wt % 5.72
Carbon By diff. wt % 84.5
17
Only Hydrotreatment gives high diesel yield
Good quality diesel and outstanding lube basestock
10 vol% TK-743T
20 vol% TK-47T
70 vol% TK-609 HYBRIM™
>70 wt%FF diesel S< 10 ppm SG=0.860- 0.865 CCI= 38-39 CP/PP = -4 / -6 oC
<20 wt%FF naphtha
<10 wt%FF lube base stock
18
Test results Aromatics saturation & oxygen removal achieves a vast shift in boiling point
Kero Diesel Naphtha UCO
19
Hydrocarbons by GC x GC - FID HDT product at 168 barg
Area %
Naphthenes_C5-C9 0.2
Naphthenes_C10-C24_1 56.4
Aromatics_C10-C24 1.2
Paraffins_C10-C24 20.7
Napthenes_C10-C24_2 10.3
Naphthenes_C25+ 2.8
Paraffins_C25+ 6.4
DIESEL
• Diesel after HDT • About 1 % aromatics
• Requires HDC to improve cetane
• 75% naphthenic
• 24% paraffinic
• UCO • No aromatics
• Very paraffinic high quality lube base stock
DIESEL
20
Upgrading of full boiling range tar Example 2
21
Feed characterization
Distributions
100
150
200
250
300
350
400
450
500
550
600
0 20 40 60 80 100
Te
mp
era
ture
, °C
Percentage distilled, wt%
Boiling point distribution by SimDist
Feed
b.p. <260°C
b.p. 260-390°C
b.p. >390°C
22
GC×GC-ToFMS in a reversed column Paraffins/olefins and phenols and other oxygenated compounds dominate
23
HDT/HDC test Full boiling range tar
High diesel yield
5 vol% TK-743T
10 vol% TK-47T
35 vol% TK-609T HYBRIM™
50 vol% TK-931T
>60 wt%FF diesel S< 5 ppm SG=0.856 CCI= 43.8
<15 wt%FF naphtha
<15 wt%FF lube base stock
<3 wt%FF C1-C4
60 wt% true conversion
• Diesel yield
• Good quality but not ULSD
Water
24
TEST 2 HDT/HDC test More active HDC catalyst but less of it
10 vol% TK-743T
15 vol% TK-47T
50 vol% TK-609T HYBRIM™
25 vol%TK-951T
>60 wt%FF diesel S< 5 ppm SG=0.857 CCI= 45.8 CN= 49.8
<15 wt%FF naphtha
<15 wt%FF lube base stock
<3 wt%FF C1-C4
60 wt% true conversion
• Diesel yield
• Better diesel cetane
Water
25
To conclude…
26
Coal tar upgrading process Diesel and gasoline production
Improving overall coal utilization
Catalyst with high HDN and HDA activity Enables high cetane and low density even with only HDT
Flexible process Enables max diesel or max naphtha operation
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Questions ?
Thank you. [email protected] +45 2275 4294
