Gas Treatment

& Sulfur Recovery

Process Engineer

Outline

Introduction

Gas Treatment

Some Definitions.
Hazards of (H2S).

Amines.
Amine Process.
Operational Problems.

Sulfur Recovery

Claus Process.
Interesting Aspect.

Introduction
What are the goals of Gas Treatment ( Gas sweetening)?
The goals are:
To produce sweet gas.
To control corrosion and prevent poisoning of catalyst in
down stream facilities.
To meet consumer gas specification.

To meet environmental requirements and regulations.

What about Sulfur Recovery? To recover the sulfur to be

used in fertilizers industry.

Definitions

Absorption: a separation process involving the transfer of a substance

from a gaseous phase to a liquid phase through the phase boundary.

Adsorption:

Sour Gas :

the process by which gaseous components are adsorbed

on solids because of their molecular attraction to solid surface.
gas containing undesired quantities of hydrogen sulfide,

carbon dioxide, and/or mercaptans.

Sweet Gas: gas without sulfur content.

Acid Gas : feed stream to sulfur recovery plant consisting of H2S, CO2,
H2O, and usually less than 2 mol % hydrocarbon.

Hazards of H2S

Highly toxic colorless and flammable gas.

Heavier than air.
At low concentration, it smells like rotten eggs.
Human sense of smell cannot be relied on to
detect hazardous concentration of it.

Concentration & Reaction by Human body

Slight symptoms after
several hours exposure
1 hour without
serious effects
Dangerous after
30 min to I hr
Fatal in less
than 30 min

ppm

Symptoms

0.0001

Detected by odor

10

0.001

Occupational Exposure Level, Threshold Limit Value

(TLV)

100

0.01

Kills sense of smell in 3 to 5 minutes. May burn eyes

and throat.

200

0.02

Kills sense of smell rapidly. Burns eyes and throat

after one hour.

500

0.05

Dizziness, loses sense of reasoning, breathing

ceases in few minutes. Needs prompt artificial
resuscitation

700

0.07

Will become unconscious quickly. Breathing will stop,

death will result if not rescued promptly. Immediate
artificial resuscitation

1000

0.1

Unconscious at once; followed by death

Gas Treatment
(Amines)

Types of Amines:

Monoethanolamine (MEA).
Diethanolamine (DEA).
Methyldiethanolamine (MDEA).

Primary
Secondary
Tertiary

MDEA is better. Why?

HOC2H4NH2
(HOC2H4)2NH
(HOC2H4)2NCH3

Highest selectivity for H2S over CO2

Selectivity is defined as ratio of (mole percent of H2S removed

to mole percent of H2S in feed gas) to (mole percent of CO 2
removed to mole percent of CO2 in feed gas).

MDEA
More

Advantages:

Useful in upgrading acid gas feed to sulfur

recovery unit.
Low solvent losses due to low vapor pressure.
High resistance to degradation.
High energy efficiency.
Low capital and operating cost.
Less corrosive operation.

Amine Process Schematic

Process Description

Sour gas enters the base of the amine absorber, which is sweetened by the lean amine
flowing down the absorber tower. The sweet gas leaves the top for further treatment.

Rich amine leaves the base flowing to the low pressure amine flash tank, where the
dissolved gases and entrained hydrocarbon come off the solution.

The outgoing gas flash gas can be sweetened to be used as fuel gas.

The rich amine leaves the flash tank to the rich-lean exchanger to cool down the lean
amine, then continues to the amine regenerator.

H2S and CO2 are stripped off from the amine by the steam coming from the reboiler.
The vapor flow to the top of regenerator, condensed by the condenser, then proceed to
the reflux separator, where the gas is separated from the liquid.

The acid gas flows to the sulfur plant, while the condensed liquid is pumped back to the
regenerator as reflux.

The regenerated amine solution flows to the rich-lean exchanger to get cooled. It gets
to the surge tank, cooled and pumped to the absorber to repeat the absorption process.

Operational Problems
The

usual problems in all amine systems are

related to:

Corrosion.
Solution degradation.
Solvent losses.
Plugging and Fouling.
Foaming.

Corrosion

Potential problem, it is a function of temperature and liquid velocity.

Combination of H2S and CO2 with water practically ensures that

corrosive conditions will exit in portions of the plant.

Gas streams with high H2S to CO2 ratios are less corrosive than
those having low H2S to CO2 ratios. Why?
H2S dissociate in water to form a weak acid. The acid attacks iron and form insoluble iron
sulfide. The iron sulfide will adhere to the base metal and may provide some protection
from further corrosion.
On the other hand, CO2 will react with water to form carbonic acid. The acid attacks the
iron to form a soluble iron bicarbonate which, upon heating will release CO 2 and an
insoluble iron carbonate to iron oxide.

H2S concentration in the ppmv (parts per million by volume) range

with CO2 concentration of 2 % or more tend to be practically corrosive.

Corrosion

Because of the temperature relation to corrosion, the

reboiler, the rich side of the amine-amine exchanger,
stripper overhead condensing loop tend to experience
high corrosion rates.

Hydrogen sulfide stress cracking (SSC) is a critical form

of corrosion during the few months of operation. It takes
place in pipes, valves and fittings. This is typically the
outcome of improper material choice and no
consideration to stress relieving or critical piping.

Some Guidelines to Minimize The

Problem

Using of corrosion inhibitors in combination with operating practices,

which will offer potential saving in both capital and operating costs.

Some Guidelines are the following:

Maintain the lowest possible reboiler temperature.

Minimize solids and degradation products through reclaimer and

effective filtration.

Keep oxygen out of the system by providing a gas blanket on all

storage tanks and maintain a positive pressure on the suction of
all pumps.

Monitor corrosion rates with coupon or suitable corrosion probes.

Maintain adequate solution level above reboiler tube bundle and

fire tubes; a minimum submergence of 6 is recommended.

Foaming

The most troublesome problem on a day-to-day basis.

When foaming occurs, there is poor contact between the

gas and the chemical solution.

It reduces treating capacity and sweetening efficiency,

possible to the point that outlet specification cannot be met.

Symptoms

Sudden increase in differential pressure across the

absorber/regenerator.
Amine carry over.
Unstable temperature in the absorber and regenerator.
Unstable flash tank level and flow to regenerator.
Unstable acid gas flow to the Sulfur Recovery Unit.

Foaming
Reasons

Suspended solids.

Organic acids in the feed gas.

Condensed hydrocarbons.

Corrosion inhibitors.

Make-up water impurities.

Amine degradation products.

Lube oil.

Soap-based valve greases.

Foaming
Guidelines

Contaminants from upstream operations can be minimized

through adequate inlet separation.

Condensation of hydrocarbons in the absorber can usually be

avoided be maintaining the lean solution temperature at least
(10 F) above the hydrocarbon dew point of the outlet gas.

Temporary upsets can be controlled by the addition of antifoam

chemicals ( silicon or long-chain alcohol ).

Foaming tests should be done to check the compatibility and

effectiveness of new anti-foam before using them.

Sulfur Recovery

Sulfur Recovery

H2S should be converted to non-toxic and useful

elemental sulfur that can be used in fertilizer
industry.

Clause Process : a process in which 1/3 of the

H2S in the acid gas feed is burned to SO2 which
is then reacted with the remaining H2S to
produce sulfur.

The modified Claus process, developed by

London chemist Carl Friedrich Claus in 1883

Claus Process
Sulfur

is recovered
by 3 steps:

Thermal.
Catalytic.
Cold Bed Adsorption.

Claus Process Schematic

Cold Bed Adsorption

Schematic

Claus Process

Thermal: The H2S is partially oxidized with air,

producing the H2S and SO2 in a 2:1 ratio.

This is done in a reaction furnace at high
temperatures (1000-1400 C). Sulfur is formed,
but some H2S remains unreacted, and some
SO2 is made.
H2S + 3/2 O2
Overall

SO2 + H2O

(1)

2 H2S + SO2 3/n Sn + 2 H2O

(2)

3 H2S + 3/2 O2 3/n Sn + 3 H2O

(3)

This step gives sulfur recovery of about 60 % .

Claus Process

Catalytic : The remaining H2S is reacted with the SO2 at

lower temperatures (about 200-350 C) over a catalyst to
make more sulfur.
2 H2S + SO2 3/n Sn + 2 H2O
(2)

The most widely used Claus catalyst in sulfur recovery units is

non-promoted spherical activated alumina, such as Al2O3

Properties associated with optimum non-promoted Claus

catalyst include high surface area, appropriate pore size
distribution, and enhanced physical properties.

This step gives sulfur recovery of about 35 % ,so the overall

sufur recovery is 95%.

Claus Process

Cold Bed Adsorption: The CBA reactor is operated at low

temperature (121-148 C) initially so that it is below the sulfur
dewpoint of the reaction products, The H2S and SO2 in the gas will
react via reaction (2) to form sulfur, which condenses due to the low
operating temperature and is adsorbed on the catalyst.

Each CBA reactor contains a 36"-48" deep bed of sulfur conversion

catalyst, usually alumina-based.

The tailgas from the second CBA reactor is routed to a Tailgas

Thermal Oxidizer to incinerate all of the sulfur compounds to SO 2
before dispersing the effluent to the atmosphere.

This step gives overall sulfur recovery of about 98-99 %.

Interesting Aspect of Claus

The strange behavior of

molten sulfur.

The temperature of
molten sulfur must be
controlled carefully. If the
sulfur is allowed to cool
too much it can begin to
polymerize.

Characteristic Viscosity Curve Associated

with Molten Sulfur