Sulfa Treat

SulfaTreat, a Business Unit of MI L.L.C. A Smith/Schlumberger Company

Thomas G. Braga Manager, Research and Development

© 2004 Copyright MI L.L.C.

Who is SulfaTreat?

A World Leader in H 2 S Removal for More than a Decade Today there are over 1,000 SulfaTreat installations worldwide in more than 20 countries. Almost 3 trillion cubic feet of gas is processed by SulfaTreat annually.


SulfaTreat Technology

Gas Flowrate, MMscfd Gas Flowrate, MMscfd

0.2 TPD sulfur

25 TPD sulfur

Amine/Claus

SulfaTreat Direct Oxidation SulfaTreat Direct Oxidation

[H2S

]

SulfaTreat


What is SulfaTreat?

SulfaTreat is a dry, freeflowing iron oxide based media that selectively removes H 2 S and some light mercaptans from vapor and liquid streams.

SulfaTreat is environmentally nonhazardous and safe in unreacted and reacted forms.

SulfaTreat has uniform shape and size between 4 and 40 mesh.

SulfaTreat has a density of 70 lbs/ft 3

SulfaTreat is available in 50 lb and 2000 lb bags.


SulfaTreat Fixed Bed Media


SulfaTreat Products

Product suitable for low pressure applications and odor control SulfaTreat 410 HP

Faster reaction rates in water saturated gas streams Gas streams with >80 percent relative humidity Removal of some ethyl and methyl mercaptans

SulfaTreat HP

Similar to Standard product with up to 3 x bed life SulfaTreat XLP

Standard product SulfaTreat


SulfaTreat Quality

§Using SPC methodology, SulfaTreat is manufactured to be “in control” and “capable”.

SulfaTreat (410)

dP = 0.084e 0.247(% fines)

R 2 = 0.931

0.0

0.5

1.0

1.5

2.0

2.5

0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0

% fines (30 mesh) dP

, psi / ' m

edia (@

1 cfm

lab un

it)

EPS dP model


Why is SulfaTreat Safe?

SulfaTreat begins as a safe and stable compound that is environmentally non hazardous . It reacts with H 2 S to form “pyrite”, also stable compound.

SulfaTreat meets EPA guidelines for classification as nonhazardous waste.


Environmental Impact

Spent media samples of representative applications were collected and tested. l Total Metals Method 6010B: Hg, As, Pb, Se, Ba, Cd, Cr, Ag

l TCLP Method 6010B: Hg, As, Pb, Se, Ba, Cd, Cr, Ag

l Volatile Organics Method 8260B


Environmental Impact

"The chemical analyses of these representative samples have shown that in no instance has the spent media absorbed enough material and subsequently released it upon undergoing the “hazardous metals test” or VOC test to be deemed hazardous waste, as defined by the U.S. Environmental Protection Agency. Many states have their own limitations, frequently lower than that of the federal government, that must be adhered to when disposal of a material occurs and this must be investigated in each case in order to ensure compliance. However, the levels obtained by independent analysis thus far are well below currently existing state levels."


How is SulfaTreat Used?

The SulfaTreat System should be placed upstream of dehydration.


How is SulfaTreat Used?

Typical SulfaTreat vessel


Single Vessel Mass Transfer Zone

1 2 3 Time Intervals


What is a Lead/Lag System?

The Lead/Lag arrangement allows more efficient use of the SulfaTreat material with no interruption in unit service and greater process reliability.


TwoVessel LeadLag Mass Transfer Zone

1 2 3 4 1 2 3 4

Tower # 1 Tower # 2

Time Intervals Time Intervals


Lead/lag advantages

§ More efficient use of SulfaTreat § Buildin guard bed §No shutdown during changeout §Valve systems allows flexibility


Applications

Currently over 1000 applications worldwide.


SulfaTreat Fixed Bed Media


SulfaTreat Products

Removes hydrogen sulfide and some light mercaptans from liquid hydrocarbons SulfaTreat HC


SulfaTreatHC Uses

gasoline • industrial water kerosene (non potable) NGL LNG LPG solvents

Treatment of clear light liquid hydrocarbons and water


Use Specifications

§ Reduction and conversion of aggressive sulfur contaminants to meet copper strip corrosion test for liquid fuels.

§ Liquid phase treatment for odor control and reduction of total sulfur content


Use Specifications

Copper Strip Tarnish Test ASTM D 13094 Most common goal of SulfaCleanHC Use Grade 1 criteria, 1A if necessary


Use Specifications

Odor Control §Commonly used in solvents § Industrial / Process water

Reduction of Total Sulfur Content “Removal” of mercaptans §Only methyl and ethyl mercaptans removed §50% reacted ; 50% converted to disulfides §Important in total S reduction


SulfaTreat Process


Market Analysis


0.2 TPD sulfur

25 TPD sulfur

SulfaTreat

Amine/Claus

SulfaTreat Direct SulfaTreat Direct Oxidation Oxidation


SulfaTreatDO Partners

•Uses a proprietary, patented catalyst developed by TDA Research, Inc. •Engineering / Fabrication support from Westfield Engineering.


Direct Oxidation Process

•Catalytic oxidation of hydrogen sulfide to elemental sulfur and water.

•Under properly controlled conditions, little or no SO2 produced.

) ( 2 ) ( 8 ) ( 2 ) ( 2 8 1 5 . 0 g g

Catalyst TDA g g O H S O S H + → +


AIR

INLET GAS

SULFUR

Feed Preheater

Fuel/air Direct Oxidation Reactor

Sulfur Condenser

Flue gas

Liquid knockout

SulfaTreat

OUTLET GAS

Process Flow Diagram

1. Liquid is separated

2. Gas is heated to 350ºF & air injected if necessary

3. 8595% of H2S is catalyzed to gaseous sulfur

4. Gas is cooled to 200 to 250ºF to condense liquid sulfur

Sulfur Quench

5. Sulfur mist is removed

6. H 2 S is polished.


Catalyst Development

•Laboratory bench scale testing •Field bench scale testing •Field full scale Pilot Test

The commercial catalyst has been developed and tested under the following conditions.


1,200+ hour continuous operation: l Gas Source: Associated gas l Flow Rate: up to 710 Nm 3 /hr l Operating Conditions ü 0.8% H 2 S ü 20% methane ü 15% ethane ü 10% propane ü Balance CO 2 ü >2300 ppm BTEX ü ~100 ppm mercaptans ü 400 lbs/day of sulfur

Pilot Test

Heater Reactor Condenser


Full Scale Pilot Test Actual Unit

Sulfur condenser

Reactor

Electric heater attaches here

Flare line

Gas inlet not attached in this photo

Sulfur storage pots

Sulfur condenser

Reactor

Electric heater attaches here

Flare line

Gas inlet not attached in this photo

Sulfur storage pots


Full Scale Pilot Test Unit Process Conditions – Reaction Temperature

90

92

94

96

98

100

180 185 190 195 200 205 210

Temperature ( C)

H S con

version (%

)

80

84

88

92

96

100

S se

lectivity

(%)


Full Scale Pilot Test Unit Process Conditions – Sulfur Dew Point

0 50 100 150 200 250 0.000

0.001

0.002

0.003

0.004

0.005

0.006

0.007

0.008 File: C:\STEVE GEBHARD\SG_ PROJECTS\SULFUR projects\WHITING FIELD TEST\sulfurDP.OGI

C

kmol

Temperature

S

S8(g) S6(g) S2(g)

S7(g) S5(g)


Pilot Test Results Gas Chromatography Analysis

• 88 % removal of H2S • 80 % removal of mercaptans • No change in hydrocarbon content

Component Mol% (inlet) Mol% (outlet) Component Mol% (inlet) Mol% (outlet) H2S 0.8000 0.095 cyclohexane 0.17 0.14 N2 1.6 2.9 nheptane 0.09 0.07

CH4 17.7 17.8 methylcyclohexane 0.05 0.04 CO2 58.6 58.7 toluene 0.02 0.01

Ethane 8.7 8.6 noctane 0.005 0.003 Propane 6.5 6.3 ethyl benzene 0.003 0.002

isobutane 0.98 0.92 p and m xylene 0.003 0.003 nbutane 2.38 2.32 oxylene 0.0007 0.0004

isopentane 0.74 0.71 nnonane 0.0022 npentane 0.77 0.75

cyclopentane 0.01 0.01 Mercaptans (ppm) 101.00 20 2methylpentane 0.15 0.14 3methylpentane 0.13 0.12 Specific gravity

(air =1 ) 0.45

nhexane 0.27 0.24 Gross BTU/CF dry 731.00 methylcyclopentane 0.14 0.12 Gross BTU/CF wet 718.00

benzene 0.21 0.17


Applications

§Two units scheduled for commissioning in 1 st Quarter 2006


SulfaTreat Technology


0.2 TPD sulfur

25 TPD sulfur

Amine/Claus

SulfaTreat Direct Oxidation SulfaTreat Direct Oxidation

[H2S

]

SulfaTreat

Documents

Sulfa Treat