Thomas G. Braga Manager, Research and Development SulfaTreat, a Business Unit of M I L.L.C. A Smith/Schlumberger Company
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 Amine/Claus SulfaTreat Direct Oxidation 25 TPD sulfur [H2S] 0.2 TPD sulfur SulfaTreat Gas Flowrate, MMscfd
What is SulfaTreat? SulfaTreat is a dry, free flowing iron oxide based media that selectively removes H 2 S and some light mercaptans from vapor and liquid streams. SulfaTreat is environmentally non hazardous 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 SulfaTreat Standard product SulfaTreat HP Faster reaction rates in water saturated gas streams Gas streams with >80 percent relative humidity Removal of some ethyl and methyl mercaptans SulfaTreat 410 HP Product suitable for low pressure applications and odor control SulfaTreat XLP Similar to Standard product with up to 3 x bed life
SulfaTreat Quality Using SPC methodology, SulfaTreat is manufactured to be in control and capable. 2.5 SulfaT reat (410) dp, psi / ' media (@ 1 cfm lab unit) 2.0 1.5 1.0 0.5 0.247(% fines) dp = 0.084e R 2 = 0.931 EPS dp model 0.0 0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 % fines ( 30 m esh)
Why is SulfaTreat Safe? SulfaTreat begins as a safe and stable compound that is environmentally nonhazardous. It reacts with H 2 S to form pyrite, also stable compound. SulfaTreat meets EPA guidelines for classification as non hazardous waste.
Environmental Impact Spent media samples of representative applications were collected and tested. Total Metals Method 6010B: Hg, As, Pb, Se, Ba, Cd, Cr, Ag TCLP Method 6010B: Hg, As, Pb, Se, Ba, Cd, Cr, Ag 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.
Two Vessel Lead Lag Mass Transfer Zone Tower # 1 Tower # 2 1 2 3 4 1 2 3 4 Time Intervals Time Intervals
Lead/lag advantages More efficient use of SulfaTreat Build in guard bed No shutdown during changeout Valve systems allows flexibility
Applications Currently over 1000 applications worldwide.
SulfaTreat Fixed Bed Media
SulfaTreat Products SulfaTreat HC Removes hydrogen sulfide and some light mercaptans from liquid hydrocarbons
SulfaTreat HC Uses Treatment of clear light liquid hydrocarbons and water gasoline kerosene NGL LNG LPG solvents industrial water (non potable)
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 130 94 Most common goal of SulfaClean HC 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 Amine/Claus SulfaTreat Direct Oxidation 25 TPD sulfur 0.2 TPD sulfur SulfaTreat Gas Flowrate, MMscfd
SulfaTreat DO 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. 1 H 2 S ( g ) + + 8 TDA Catalyst 0. 5 O 2 ( g ) S 8 ( g ) H 2 O ( g ) Under properly controlled conditions, little or no SO2 produced.
Process Flow Diagram 1. Liquid is separated INLET GAS Flue gas AIR 2. Gas is heated to 350ºF & air injected if necessary 5. Sulfur mist is removed Liquid knockout Feed Preheater Fuel/air Direct Oxidation Reactor Sulfur Quench 6. H 2 S is polished. 3. 85 95% of H2S is catalyzed to gaseous sulfur SULFUR Sulfur Condenser SulfaTreat 4. Gas is cooled to 200 to 250ºF to condense liquid sulfur OUTLET GAS
Catalyst Development The commercial catalyst has been developed and tested under the following conditions. Laboratory bench scale testing Field bench scale testing Field full scale Pilot Test
Pilot Test 1,200+ hour continuous operation: Gas Source: Associated gas Flow Rate: up to 710 Nm 3 /hr Operating Conditions 0.8% H 2 S 20% methane 15% ethane 10% propane Balance CO 2 >2300 ppm BTEX ~100 ppm mercaptans 400 lbs/day of sulfur Heater Reactor Condenser
Full Scale Pilot Test Actual Unit Electric heater attaches here Sulfur storage pots Reactor Sulfur condenser Flare line Gas inlet not attached in this photo
Full Scale Pilot Test Unit Process Conditions Reaction Temperature 100 100 98 96 H S conversion (%) 96 94 92 88 S selectivity (%) 92 84 90 80 180 185 190 195 200 205 210 Temperature ( C)
Full Scale Pilot Test Unit Process Conditions Sulfur Dew Point 0.008 kmol S File: C:\STEVE GEBHARD\SG_ PROJECTS\SULFUR project 0.007 0.006 0.005 0.004 0.003 0.002 0.001 0.000 S8(g) S6(g) S2(g) S7(g) S5(g) 0 50 100 150 200 250 Temper C
Pilot Test Results Gas Chromatography Analysis Component Mol% (inlet) Mol% (outlet) Component Mol% (inlet) Mol% (outlet) H 2 S 0.8000 0.095 cyclohexane 0.17 0.14 N 2 1.6 2.9 n heptane 0.09 0.07 CH 4 17.7 17.8 methylcyclohexane 0.05 0.04 CO 2 58.6 58.7 toluene 0.02 0.01 Ethane 8.7 8.6 n octane 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 n butane 2.38 2.32 o xylene 0.0007 0.0004 isopentane 0.74 0.71 n nonane 0.0022 n pentane 0.77 0.75 cyclopentane 0.01 0.01 Mercaptans (ppm) 101.00 20 2 methylpentane 0.15 0.14 3 methylpentane 0.13 0.12 Specific gravity (air =1 ) 0.45 n hexane 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 88 % removal of H2S 80 % removal of mercaptans No change in hydrocarbon content
Applications Two units scheduled for commissioning in 1 st Quarter 2006
SulfaTreat Technology Amine/Claus SulfaTreat Direct Oxidation 25 TPD sulfur [H2S] 0.2 TPD sulfur SulfaTreat Gas Flowrate, MMscfd