WSA Technology

a competitive solution for sulfur management

Livia Sierra Llorens – lisl@topsoe.com

 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

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 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

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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
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What to do with H2S?
The direct way

H2S

Sulfuric acid plant (WSA)

Sulfuric acid
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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
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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

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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.

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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

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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
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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
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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
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 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

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WSA condenser

Clean gas outlet

Cooling air inlet

SO3 gas Hot air outlet

inlet

Sulfuric acid
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WSA condenser – modular construction
Clean Gas Outlet

Cooling Air
Inlet

Hot Air Outlet

Acid Gas
Inlet

Product Acid Outlet

18
WSA condenser design

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 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

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 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
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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.
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