WSA Technology
a competitive solution for sulfur management
Agenda
▪ A few words about Haldor Topsoe
▪ Handling sulfurous streams
✓ the traditional way
✓ the WSA way
▪ Introduction to WSA technology
▪ WSA process and lay-outs
▪ References
▪ Summary
2
3
Haldor Topsoe Company
• Established in 1940 by Dr. Haldor Topsoe. Private 100%
family owned company
• Global market leader in heterogeneous catalysis with a 75
year long track record
• ~2,700 employees in 11 countries across five continents.
• HQ in Lyngby, Denmark, HT Inc. located in Houston ̴ ~250
employees
• Revenue about $1 billion.
Services:
• Catalysts
• Technology/licensing
• Engineering
• Hardware
3
Active phase Pore structure Catalyst Reactor • Operation assistance
Synergies in the Topsoe business model
• Founded on the belief that applied
fundamental research is key to
build and retain a leading position Process
in catalysis and technology supply design
• Basic research and catalyst
characterization done by 300+
world class scientists Marketing,
R&D Catalyst
production
• Approx. 10% of revenues annually sales and
support
applied to support R&D efforts
• Bringing science to the market
• Improving our products through Engineering
& Hardware
costumer interaction
4
Refinery Overview Topsoe WSA plant
Gas, LPG Spent/fresh H2SO4
Alkylation
SRU Tailgas
H2S
SRU
Naphta
Atmospheric
Kero
distillation
Crude oil Gasoline, jet fuels
Gas oil
HDT
Steam H2SO4
Vacuum Gas oil HDT FCC Fuel Oils Steam
distillation
MHC
Vacuum
H2S
Lubricating oils
Power
HC
Delayed coker
Visbreaker
H2SO4
Topsoe SNOXTM plant
5
What to do with H2S? Other uses
The traditional way of sulfur
~ 10 %
H2S
Sulfur
Claus plant
~ 90 %
of all sulfur
Sulfuric acid plant
Sulfuric acid
6
What to do with H2S?
The direct way
H2S
Sulfuric acid plant (WSA)
Sulfuric acid
7
Four times more energy
when producing sulfuric acid instead of sulfur
222
S
H2S
(solid)
Sulfur:
222 kJ/mole
H2SO4 H2SO4
H2S 519 SO2 99 SO3 101
(gas)
85
(liquid)
Sulfuric acid:
804 kJ/mole
-2 0 +4 +6 +6 +6
Oxidation state of sulfur
8
Limitations when producing sulfur in a Claus plant
• Minimum H2S content in feed gas of 20 vol.-%
• Other combustibles than H2S (like NH3 and
hydrocarbons) make air control more complex
• Ammonia requires very high furnace temperature
• Hydrocarbons give risk of carbon formation and
catalyst deactivation
• COS and CS2 require special design
• Sulfur solidifies below 120°C and gets viscous
9 above 160°C.
Comparison WSA vs. Claus 3 x more steam
Operating expenses (OPEX) and better quality
10
Comparison WSA vs. Claus
Summary
▪ WSA offers larger revenues and less CAPEX
▪ WSA produces 3 times as much steam; this means
saving in fuel consumption and CO2 emissions
▪ WSA produces HP steam; Claus produces mostly MP
steam
▪ WSA handles NH3, COS and hydrocarbons
▪ DeNOx is conveniently included in the WSA process,
when required
▪ Smaller plot area for WSA than for Claus
▪ Less equipment is required
▪ WSA is simple and easy to operate.
11
What is WSA - Wet gas Sulfuric Acid
A process for cleaning sulfur containing streams under production of
concentrated sulfuric acid
Lean H2S gas
Rich H2S gas
SRU tail gas Clean gas …No need to dry the gas
SWS gas …No water consumption
SO2 H2SO4 …No need to use chemicals or other
additives
SO3
…No generation of waste products
Elemental sulfur
WSA HP steam …With high energy efficiency.
CS2 / COS
Spent H2SO4
12
WSA process lay-out
H2S gas Reaction:
H2SO4 (g) → H2SO4 (liq) + heat
Superheated steam
Cleaned gas
Blower
Combustion air
SO2 converter
BFW Blower
Steam Air
drum
Interbed
cooler
WSA
WHB Interbed
H2S gas condenser
cooler
Combustor Gas
cooler
Reaction:
Acid cooler
H2S + 1½O2 → SO2 + H2O + heat
CW
Reaction:
Reaction:
Product acid
SO2 + ½O2 → SO3 + heat
SO3 + H2O → H2SO4 (g) + heat
13
WSA process lay-out
H2S gas + SWS gas
Superheated steam
Cleaned gas
Blower
Combustion air
SO2 converter
BFW Blower
Steam Air
drum
SCR Interbed
cooler
H2S gas WSA
WHB Interbed condenser
cooler
SWS gas Combustor Gas
cooler
Acid cooler
CW
Additional reaction:
NH3 + 1.25 O2 → NO + 1.5 H2O + heat Reaction: Product acid
14
NO + NH3 + 0.25 O2 → N2 + 1.5 H2O + heat
WSA process lay-out
Spent acid regeneration
Superheated steam
Cleaned gas
Blower
Combustion air
SO2 converter
BFW Blower
Steam Air
drum ESP Interbed
cooler
Dust WSA
H2S gas WHB Interbed condenser
Spent cooler
acid
Atom. air Combustor Gas
cooler
Fuel gas
Acid cooler
CW
Product acid
15
SO2 conversion catalyst series VK-W
VK-WSX / VK-WL VK-WSA VK-WSA / VK-WH
9 mm Daisy 25 mm Daisy 12 mm Daisy
16
WSA condenser
Clean gas outlet
Cooling air inlet
SO3 gas Hot air outlet
inlet
Sulfuric acid
17
WSA condenser – modular construction
Clean Gas Outlet
Cooling Air
Inlet
Hot Air Outlet
Acid Gas
Inlet
Product Acid Outlet
18
WSA condenser design
19
WSA/SNOXTM references
March 2018
Acid production: 4 – 1,140 MTPD
155+ references
1 1 41
2
3 11 13 5 24
1 26 18
12 16 1 14 8
8
5 2 15 25
4 6 1
29 4 14 31
3 5
2
4 4 7 17 7
2 4 10 8 9
2
Oil refining 2
9 10 28
19
30
11
19
24 31
22
32 14
29 17
16
24
35 23
17 30
8 10 47
12
18 23
6 20 11 12 33 37
26 3 3 4
11 22 3 38 40
25 28
27 8 7 5 46 45
Coking 10 18 25
27 26 19 15 6 21 13 16 32
5 21 9 13 29 28 20
6 39 15 31 7
6
51 33 32
Gasification
27
42
Metallurgy 22 23
8
1 5
6 7
9
13
Viscose
21
12
14 7
Sundry applications 44 34
3 9
43 36
20
Refinery WSA plants
Irving Oil Limited, NB, OSC Slavneft (YaNOS)
Canada Yaroslavl, Russia
Claus plant Spent acid regeneration
tail gas treatment
260 t/d sulfuric acid
21
40 t/d sulfuric acid
Too good to be true??
Conclusions
Traditional SRU
WSA technology – a better solution
• Attractive OPEX and CAPEX
• Simple process and easy to operate
• Proven and reliable technology (155+ references)
• Low emissions and no waste materials
• No issues with NH3 and hydrocarbons.
22