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Sulfur Recovery

Chapter 16
Based on presentation by Prof. Art Kidnay
Plant Block Schematic

Adapted from Figure 7.1,


Fundamentals of Natural Gas Processing, 2nd ed.
Kidnay, Parrish, & McCartney

Updated: January 4, 2019


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Topics
Introduction
Properties of sulfur
Sulfur recovery processes
▪ Claus Process
▪ Claus Tail Gas Cleanup
Sulfur storage
Safety and environmental considerations

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Introduction &
Properties of Sulfur

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Sulfur Crystals

http://www.irocks.com/minerals/specimen/34046

http://www.mccullagh.org/image/10d-5/sulfur.html

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Molten Sulfur

http://www.kamgroupltd.com/En/Post/7/Basic-info-on-elemental-Sulfur(HSE)

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World Consumption of Sulfur
Primary usage of sulfur
to make sulfuric acid
(90 – 95%)
▪ Other major uses are
rubber processing,
cosmetics, &
pharmaceutical
applications
China primary market

Ref: https://ihsmarkit.com/products/sulfur-chemical-economics-handbook.html
Report published December 2017

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Sulfur Usage & Prices
Natural gas & petroleum
production accounts for the
majority of sulfur production
Primary consumption is
agriculture & industry
▪ 65% for farm fertilizer:

sulfur → sulfuric acid →


phosphoric acid → fertilizer

$50 per ton essentially


disposal cost
▪ Chinese demand caused run-
up in 2007-2008

Ref: http://ictulsa.com/energy/
“Cleaning up their act”, Gordon Cope, Updated December 24, 2018
Hydrocarbon Engineering, pp 24-27, March 2011

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U.S. sulfur production

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Sulfur Chemical Structure
Pure sulfur exists as SX where X =
1 to 8
▪ The dominant species are S2, S6, &
S8
May be in ring structure or open
chain
Species determined by
temperature

This composition greatly affects


its properties! Octasulfur, S8

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Sulfur Vapor Species
1.0

S8
Mol Fraction of Species

0.8
S2

0.6

0.4

S6
0.2

0.0
200 400 600 800 1000 1200 1400
Temperature, °F

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Viscosity of Molten Sulfur
105
Pure
Sulfur

104
Viscosity, cp

103

102

101

100
300 400 500 600 700 800
Temperature, °C

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Viscosity of Molten Sulfur
105
Pure
Sulfur
H2S Partial
104 Pressure,
psia
0.0015
Viscosity, cp

0.015
103
0.15
1.5
102
14.7

101

100
300 400 500 600 700 800
Temperature, °C

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Viscosity of liquid sulfur

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Sulfur recovery processes

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Copyright © 2017 John Jechura (jjechura@mines.edu)
Sulfur Recovery
Typically a modified Claus process
▪ H2S rich stream burned with 1/3 stoichiometric air. Hot gases are then
passed over alumina catalyst to produce free sulfur
Combustion: H2S + 1.5·O2 H2O + SO2
Claus Reaction: 2·H2S + SO2 D 2·H2O + 3·S
▪ Sulfur formation reaction mildly exothermic
▪ Sulfur conversion reactors kept above 400oF (sulfur dew point)
The Claus reaction is reversible – therefore, 100% conversion can
never be achieved
▪ Practically, Claus units are limited to about 96% recovery
▪ Tail gas units are used to provide improved conversion

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Modified Claus Process

Petroleum Refining Technology & Economics – 5th Ed.


by James Gary, Glenn Handwerk, & Mark Kaiser, CRC Press, 2007

Converters
400 – 700oF
Burner & Reactor above 1800oF
2300-2700oF for NH3 destruction

GPSA Engineering Data Book, 13th ed.,


Fig. 22-2, 2012

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Temperature Regimes for the Claus Process

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Straight-through Claus Process
gas reheat gas reheat gas reheat
waste heat
boiler HP 450°F 420°F 400°F
steam
Claus #1 Claus #2 Claus #3
acid
gas 600°F LP 590°F LP 453°F LP 300°F 407°F
steam 375°F 350°F steam 270°F
110°F steam
8 psig
condenser condens condenser
condenser condenser
er
air boiler feed
water (BFW)
BFW BFW BFW
reaction
sulfur sulfur sulfur sulfur
furnace
1700 - 2400°F
tail gas

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Equilibrium Conversion of H2S to S
Temperature, o C
Percent Conversion of H2S to Sulfur

204 427 649 871 1093 1316 1538


100

80

60 melting point

boiling point

40
0 400 800 1200 1600 2000 2400 2800
Temperature, °F

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Equilibrium Conversion of H2S to S
Percent Conversion of H2S to Sulfur

100
Claus #3
Furnace & waste heat boiler
Claus #2 Claus #1 1700 - 2400F
80

60
melting point

boiling point

40
0 400 800 1200 1600 2000 2400 2800
Temperature, °F
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Hydrocarbons in the Claus Process

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Claus Process
Use multiple stages to obtain highest conversion
▪ Typically three
Various flow patterns
▪ Straight-through – best, used whenever possible
▪ Split flow – best at low H2S feed concentrations (5 to 30 mol% H2S)
▪ Sulfur recycle < 5% H2S
▪ Direct oxidation < 5% H2S

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Claus Process
Claus unit feed usually contains H2S and CO2
High concentrations of noncombustible components (CO2, N2)
▪ Lower flame temperature
▪ Difficult to maintain stable combustion furnace flame temperatures below
1700oF
Solutions include
▪ Preheating air
▪ Preheating acid gas feed
▪ Enriching oxygen in air
▪ Using split-flow process

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Split-flow Claus Process
gas reheat gas reheat gas reheat

HP
steam
2/3 flow Claus #1 Claus #2
Claus #2 Claus #3

1/3 flow LP LP LP
acid gas steam steam steam

condenser condenser
condenser condenser
condenser condenser
condenser
air
boiler feed
water (BFW)

BFW BFW
reaction sulfur sulfur sulfur sulfur
furnace

tail gas

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Typical Claus Configurations
Approximate
concentration of
Process variation
H2S in feed
(mol%)
55 - 100 Straight-through
30 - 55 Straight-through + acid gas and/or air preheat
15 - 30 Split-flow or acid gas and/or air preheat
10 - 15 Split-flow with acid gas and/or air preheat
5 - 10 Split-flow with fuel added, O2 enrichment, or with
acid gas and air preheat

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Tail Gas Clean Up
Three process categories:

Direct oxidation of H2S to sulfur (Superclaus)

2 H2S + O2 → 2 S + 2 H2O

Sub-dew point Claus processes (Cold Bed Adsorption)

SO2 reduction and recovery of H2S (SCOT)

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Claus Tail Gas Cleanup
Conventional 3-stage Claus units recover 96 to 97.5% of sulfur
▪ Remainder was burned to SO2 and vented
▪ Adding fourth stage results in 97 to 98.5% recovery
Regulations now require 99.8 to 99.9% recovery
Meeting regulations requires modified technology

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Shell Claus Offgas Treating (SCOT)
Four step process:
▪ Mix feed with reducing gas (H2 and CO)
▪ Convert all sulfur compounds to H2S
▪ Cool the reactor gas
▪ Strip H2S using amine To Stack
Claus Tail Gas H2S Recycle

Quench tower
Reducing Gas

Regenerator
Absorber
Catalytic Reactor
Air

Furnace
Fuel
Low Pressure Low Pressure
Steam Steam Reboiler
H2O

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SCOT Process
To Stack
Claus Tail Gas H2S Recycle

Quench tower
Reducing Gas

Regenerator
Absorber
Catalytic Reactor
Air

Furnace
Fuel
Low Pressure Low Pressure
Steam Steam Reboiler
H2O

Mix Claus tail Catalytically convert all Cool reactor gas Strip H2S from gas & recycle to
gas with H2 and sulfur compounds to H2S (exiting at ~570oF Claus
CO and heat in Reactions: in waste heat Typically use MDEA – can get to
inline burner SO2 + 3H2 → H2S + 2H2O exchanger and low H2S levels in Stack Gas &
S2 + 2H2 → 2H2S water wash to slip CO2 so it doesn’t build up in
COS + H2O → CO2+ H2S complete cooling. the recycle gas
CS2 + 2H2O → CO2 + H2S

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Alternate Conversion & Sulfur Removal
Processes
SelectoxTM
▪ Proprietary catalyst removes need for furnace
CrystaSulf
▪ Uses modified liquid-phase Claus reaction
▪ Elemental sulfur removed by filtration
▪ Mid-range process to handle sulfur amounts between 0.1 and 20 tons per
day

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Sulfur storage

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Copyright © 2017 John Jechura (jjechura@mines.edu)
Sulfur Piles
Sulfur pile at North Vancouver, B.C., Canada, brought by rail from
the province of Alberta

Ref: Wikimedia Commons

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Sulfur “Blocking”

Fort McMurray oil sands operations, Alberta, Canada

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Summary

Updated: January 4, 2019


Copyright © 2017 John Jechura (jjechura@mines.edu)
Summary
Natural gas & petroleum production accounts for the majority of sulfur
production
▪ Primary consumption is agriculture & industry, 65% for farm fertilizer.
▪ $50 per ton essentially disposal cost
Sulfur properties depends upon which sulfur species are present
▪ Dominant species are S2, S6, & S8
Dominant sulfur recovery process is modified Claus
▪ Extent controlled by chemical equilibrium, so can only get 96% conversion
▪ Tail Gas Cleanup process required for very low sulfur emissions
Sulfur storage
▪ Temporary storage as hot liquid
▪ Shipping in pellets & long-term bulk storage as blocks

Updated: January 4, 2019


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