REFINERY GAS ANALYSIS BY GAS CHROMATOGRAPHY

Transcription

1 REFINERY GAS ANALYSIS BY GAS CHROMATOGRAPHY UOP Method SCOPE This automated method is for determining the composition of refinery gas samples or expanded liquefied petroleum gas (LPG) samples obtained from refining processes or natural sources. Non-condensable gases, hydrogen sulfide, C 1 through C 4 hydrocarbons and C 5 paraffins are reported individually, while C 5 olefins and C 6 + hydrocarbons are reported as a composite. Oxygen is not separated from argon. Results for hydrogen sulfide, if present, may not be quantitative on some analyzers. The method yields quantitative results from 0.1 to 99.9 mol-% for a single component or composite; except for hydrogen sulfide that yields quantitative results between 0.1 and 25 mol-%. Results may also be reported in mass-% OUTLINE OF METHOD The method requires the use of a dedicated gas chromatographic system that is configured for automated refinery gas analysis, and is capable, via valve switching, of multi-column, multi-detector operation. The sample is injected using two sampling valves, and the analysis is performed under isothermal conditions. Hydrogen and helium are determined on a 13X molecular sieve column using nitrogen carrier gas and a thermal conductivity detector (TCD). The remainder of the sample components are determined using hydrogen carrier gas, a series of four columns connected by 6-port and 10-port rotary valves, and a second TCD. The four columns separate specific portions of the total sample. The first two columns resolve the gases in the C 3 -C 5 boiling range, carbon dioxide, hydrogen sulfide and the C 5 olefins and/or C 6 + hydrocarbon composite. The third column resolves the components in the intermediate boiling range, ethylene and ethane. The light gases, oxygen and/or argon composite, nitrogen, methane and carbon monoxide, are resolved by the fourth column. Quantitative results are obtained from the measured areas of the recorded peaks by the application of individual relative response factors, followed by normalization to 100%. APPARATUS References to catalog numbers and suppliers are included as a convenience to the method user. Other suppliers may be used. IT IS THE USER'S RESPONSIBILITY TO ESTABLISH APPROPRIATE PRECAUTIONARY PRACTICES AND TO DETERMINE THE APPLICABILITY OF REGULATORY LIMITATIONS PRIOR TO USE. EFFECTIVE HEALTH AND SAFETY PRACTICES ARE TO BE FOLLOWED WHEN UTILIZING THIS PROCEDURE. FAILURE TO UTILIZE THIS PROCEDURE IN THE MANNER PRESCRIBED HEREIN CAN BE HAZARDOUS. MATERIAL SAFETY DATA SHEETS (MSDS) OR EXPERIMENTAL MATERIAL SAFETY DATA SHEETS (EMSDS) FOR ALL OF THE MATERIALS USED IN THIS PROCEDURE SHOULD BE REVIEWED FOR SELECTION OF THE APPROPRIATE PERSONAL PROTECTION EQUIPMENT (PPE). COPYRIGHT 1963, 1973, 1987, 1997 UOP LLC ALL RIGHTS RESERVED UOP Methods are available through ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken PA , United States. The Methods may be obtained through the ASTM website, or by contacting Customer Service at service@astm.org, FAX, or PHONE.

2 2 of 17 Chromatographic columns: Column 1A, 30 foot, inch OD, 20% Sebaconitrile on 80/100 Chromosorb PAW, modified with phosphoric acid, Hewlett Packard, Cat. No Column 1B, 2 foot, inch OD, 20% Sebaconitrile on 80/100 Chromosorb PAW, modified with phosphoric acid, Hewlett Packard, Cat. No Column 2, 6 foot, inch OD, Porapak Q, 80/100 mesh, Hewlett Packard, Cat. No Columns 3 and 4, 10 foot, inch OD, molecular sieve 13X, 45/60 mesh, Hewlett Packard, Cat. No , two required Gas purifier, hydrogen, used to remove oxygen from carrier gas, UOP Mat/Sen, Cat. No. P200-1 Gas purifier, nitrogen, used to remove CO 2, CO, H 2 O, O 2, and hydrocarbons, UOP Mat/Sen, Cat. No. P300-1 Integrator, electronic, or equivalent equipment for obtaining peak areas (may be included with the gas chromatographic system) LPG expansion apparatus, for quantitative expansion of LPG from a liquid to a gas phase, see LPG Sampling and list immediately below: Fitting, male connector, stainless steel, 0.25-inch tube fitting to 0.25-inch male NPT, Swagelok, Dearborn Valve & Fitting, Cat. No. SS , four required. Sample cylinders having an outlet fitting other than 0.25-inch female NPT will require a different fitting. Fitting, port connector, stainless steel, 0.25-inch tube fitting, Swagelok, Dearborn Valve & Fitting, Cat. No. SS-401-PC, two required Fitting, union tee, stainless steel, 0.25-inch, Swagelok, Dearborn Valve & Fitting, Cat. No Tubing, stainless steel, 9 inches of Type 304, 0.25-inch OD x 0.21-inch ID, Alltech Associates, Cat. No Vacuum pump, capable of achieving a vacuum of 0.1-mm Hg, Fisher Scientific, Cat. No Valve, stainless steel, 0.25-inch Swagelok, Whitey, Dearborn Valve & Fitting, Cat. No. SS-1RS4 LPG expansion cylinder, sample cylinder for containing expanded LPG sample: Cylinder, 4- x 6-inches, 316 stainless steel, 1380 kpa (200 psi) internal pressure, double connection, 0.25-inch pipe hex bored through, Arthur Harris, Cat. No. B-270 Fitting, hex nipple, stainless steel, 0.25-inch NPT, Cajon, Dearborn Valve & Fitting, Cat. No. SS-4- HN, four required Fitting, tee, stainless steel, 0.25-inch NPT, Cajon, Dearborn Valve & Fitting, Cat. No. SS-4-T Gauge, stainless steel, vacuum-pressure, -100 through +200 kpa (-14.5 to psi) range, Matheson Gas Products, Cat. No

3 3 of 17 Valve, stainless steel, 0.25-inch NPT inlet, 0.25-inch tube fitting outlet, Whitey, Dearborn Valve & Fitting, Cat. No. SS-1RM4-S4, two required Recorder (optional), used to supplement integrator plot Refinery gas analyzer. The analyzer used in this method is based on a commercially available 6890 Hewlett Packard Gas Chromatograph with electronic pneumatic control, dual thermal conductivity detectors, configured for automated refinery gas analysis, complete with four rotary valves, two restrictor valves and five columns to perform the method as written. Fig. 1 shows a flow diagram of the system. Various vendors that provide pre-configured refinery gas analyzers are listed in the APPENDIX. Other vendors also supply similar systems. Confirm with the selected vendor that the required separations are provided for the specific sample types to be analyzed. Regulator, air, two-stage, high purity, Matheson Gas Products, Model Regulator, hydrogen, two-stage, high purity, Matheson Gas Products, Model Regulator, nitrogen, two-stage, high purity, Matheson Gas Products, Model Restrictor, fine metering valve, inch Swagelok, Nupro, Dearborn Valve & Fitting, Cat. No. SS-1- SG, two required Leak detector, gas, Alltech Associates, Cat. No Valve, 6-port (two required), 8-port and 10-port rotary valves, Valco Instrument, models C6UWE, C8UWE and C10UWE, respectively Sample loop, stainless steel, 100-µL, Valco Instrument, Cat. No. SL100CUW, two required Tubing, stainless steel, inch OD, Alltech Associates, Cat. No REAGENTS AND MATERIALS All reagents shall conform to the specifications established by the committee on Analytical Reagents of the American Chemical Society, when such specifications are available, unless otherwise specified. References to catalog numbers and suppliers are included as a convenience to the method user. Other suppliers may be used. Air, compressed, to actuate column switching valves Hydrogen, 99.95% minimum purity, total hydrocarbons less than 0.5 ppm as methane (zero gas) Nitrogen, 99.99% minimum purity, total hydrocarbons less than 0.5 ppm as methane (zero gas) Blend, qualitative, for determining cut times, containing approximately equal concentrations of hydrogen, argon, nitrogen, carbon monoxide, carbon dioxide, methane, ethane, ethylene, propane, n-pentane and 1,3-butadiene, Matheson Gas Products. CAUTION: 1,3-Butadiene is a suspected human carcinogen. Avoid exposure while sampling, handling or venting any blend or sample that may contain this component. If analysis of 1,3-butadiene is not required, delete it from the Qualitative Blend and Blend 2 (increase nitrogen to 16 mol-%). Substitute n-pentane for 1,3-butadiene in the Qualitative Blend and use the n-pentane peak in place of the 1,3-butadiene peak where cited under Cut Time Determination.

4 4 of 17 Blends, calibration, quantitative, primary standard, Matheson Gas Products, at the nominal levels shown in Table 1. If the composition of the samples to be analyzed varies significantly from the specified Calibration Blends, an alternative blend may be utilized that more closely resembles the composition of the samples. Single point calibrations are acceptable for normalized composition. If hydrogen sulfide is not present in the sample types being analyzed, it may be deleted from Blend 3 (increase nitrogen to 50.0 mol-%). Table 1 Calibration Blend Nominal Concentrations, mol-% Component Blend 1 Blend 2 Blend 3 Hydrogen Nitrogen Argon Methane Ethane Ethylene Propane Propylene Propadiene n-butane Isobutane Butene Isobutylene trans-2-butene cis-2-butene ,3-Butadiene n-pentane Isopentane Carbon Dioxide Carbon Monoxide Helium Hydrogen Sulfide PREPARATION OF APPARATUS If the pre-configured refinery gas analyzer is purchased, follow the instrument set-up procedure provided by the manufacturer. For a refinery gas analyzer built in-house, refer to the following procedures for the instrument set-up on a HP 6890 based system.

5 5 of 17 Instrument Set-up Install the four rotary valves, two restrictor valves and five columns on the GC as shown in Fig. 1. CAUTION: Leakage of hydrogen into the confined volume of the column and valve compartments can cause a violent explosion. It is, therefore, mandatory to test for leaks each time a connection is made and periodically thereafter. All connecting lines are to be of minimum length and must be in the heated zone. The restrictors are required to minimize any flow disruption when the flow path through the rotary valves is changed and must be set to provide constant system pressure at Columns 2 and 3 when they are cut out of the system. Use the electronic pneumatic control in the constant flow mode. Establish the column flows in the following manner. Rotate valve 4 to the off position (solid line position, flow through the column) and set the column 4 flow rate to 25 ml/min (nitrogen carrier gas flow rate). Rotate valves 1, 2, 3 to the off position (solid line position, flow through the column) and set the column flow rate on columns 1A, 1B, 2, and 3 to 40 ml/min (hydrogen carrier gas flow rate). Restrictor Adjustment Needle valve restrictors are plumbed into Valves 2 and 3 to provide constant pressure when columns 2 and 3 are out of the flow path. Restrictors are adjusted by monitoring the inlet pressure. Record the inlet pressure when all valves are off, then turn on Valve 2 and allow 5 to 10 minutes for the flow to equilibrate. Adjust the restrictor to bring the inlet pressure back to the original value. Allow 5 minutes for flow to equilibrate between restrictor adjustments. Turn Valve 2 off. Repeat the procedure for Valve 3. Cut Time Determination Prior to sample injection, all valves are in the off position as shown in Fig. 1. Analysis of Hydrogen The analysis of hydrogen is accomplished by injecting samples from the sample loop on Valve 4. Hydrogen eluted from Column 4 (13X sieve column) is detected by TCD A and the rest of the components injected are back flushed before the next analysis. Cut Time A - the time the signal switches from TCD A to TCD B after hydrogen has been completely eluted from Column 4 and the time to close Valve 4, back flushing the rest of components after the signal is switched. Enter the following commands into the Run Table: Run Time 0.01 min Valve 4 On Run Time 1.40 min Signal 1 Switch to TCD B Cut Time A Run Time 1.43 min Signal 1 Zero Run Time 1.43 min Valve 4 Off Back flush Run Time 5 min Stop Flush the qualitative blend containing hydrogen, nitrogen, argon, carbon monoxide, carbon dioxide, ethane, ethylene, propane, n-pentane and 1,3-butadiene through the sample loops and start the run. Check the elution time of hydrogen. The time to switch the signal to TCD B should be after hydrogen has

6 6 of 17 completely eluted from Column 4. Readjust signal switch time and Valve 4 Off time in the Run Table if it is needed. Record this time as Cut Time A. Analysis of Fixed Gas and Light Hydrocarbons The analysis of fixed gas and light hydrocarbons is established by injecting samples through the sample loop on Valve 1 right after hydrogen is injected from Valve 4. Note: Valve 1 is switched shortly after Valve 4 to prevent hydrogen carrier gas from backing up into the sample loop on Valve 4 eliminating the error in the hydrogen analysis. When sample is introduced into two analysis paths after injection, hydrogen is eluted first and measured at TCD A. Then, the signal is switched to TCD B to measure fixed gases and hydrocarbons. The determination of the following cut times is required for the separation of fixed gases and hydrocarbons. Cut Time B - the time that Valve 1 closes to back flush C 6 + heavies so that all the 1,3-butadiene and the components lighter than 1,3-butadiene enter into Column 1A, and C 6 + heavies elute in the Column 1B back flush. Enter the following commands into the Run Table: Run Time 0.01 min Valve 4 On Injection Run Time 0.10 min Valve 1 On Injection Run Time 0.10 min Valve 2 On Run Time 0.10 min Valve 3 On Run Time 1.40 min Signal 1 Switch to TCD B Cut Time A Run Time 1.43 min Signal 1 Zero Run Time 1.43 min Valve 4 Off Run Time 1.50 min Valve 1 Off Cut Time B Run Time 30.0 min Stop Flush the same qualitative blend used to determine Cut Time A through the sample loops and start the run. Valves 2 and 3 are switched to the On position during the injection to isolate Columns 2 and 3 from the flow path, and fixed gases (except for hydrogen) and hydrocarbons are separated only by the Sebaconitrile columns. A chromatogram similar to that shown in Fig. 2 should be obtained. Identify the peaks by comparing your chromatogram to that shown in Fig. 2. Check the chromatogram for the appearance of a peak in the C 6 + heavies region. If there is a peak in the C 6 + region and the 1,3-butadiene peak is smaller than expected or does not appear, delete the Run Time and enter a later time for switching Valve 1 to the Off position. Repeat the run as above until there is no C 6 + peak and the maximum area is obtained for the 1,3-butadiene peak. Record the final time for switching Valve 1 Off as Cut Time B. Cut Time C - the time that Valve 3 is switched to the Off position while Valve 2 stays on. The 13X sieve column is in the flow path to collect the composite Ar/O 2 /N 2 /CH 4 /CO peak. Based on the chromatogram obtained in Cut Time B, determine Cut Time C by subtracting 0.1 minutes from the time that the composite Ar/O 2 /N 2 /CH 4 /CO peak started. Record this time as Cut Time C. Cut Time D - the time that Valve 2 is switched off while Valve 3 is turned on. The Porapak column is in the flow path to collect the composite C 2 = /C 2 peak.

7 7 of 17 Based on the chromatogram obtained in Cut Time B, also determine the time at the valley between the carbon monoxide peak and the ethane peak. This time can be established quite accurately by taking one half of the difference between the retention times of the two peaks and adding this value to the retention time of the first peak. Record this time as Cut Time D. Cut Time E - the time that Valve 2 is returned to the On position while both Columns 2 and 3 are isolated from the flow path. Components CO 2 to 1,3-butadiene are eluted from the Sebaconitrile columns and detected by TCD B. Based on the chromatogram obtained in Cut Time B, also determine the time at the valley between the ethane/ethylene peak and carbon dioxide peak and record this as Cut Time E. Cut Time F - the time that Valve 2 is turned back off to elute the C 2 = /C 2 from Column 2 after 1,3- butadiene has completely eluted from the Sebaconitrile column. Based on the chromatogram obtained in Cut Time B, also determine the time for Valve 2 to switch to the Off position by adding three minutes to the retention time of the 1,3-butadiene peak. Record the time as Cut Time F. Cut Time G - the time that Valve 3 is turned back off to elute O 2, N 2, CH 4 and CO from Column 3 after ethane has completely eluted from the Porapak column. Based on the chromatogram obtained in Cut Time B, also determine the time for Valve 3 to switch to the Off position by adding five minutes to Cut Time F. Ethylene and ethane are expected to be eluted in five minutes, and then Valve 3 is turned off to elute O 2, N 2, methane and carbon monoxide from Column 3. Record this time as Cut Time G. Enter the Cut Times determined above in a new Run Table, such as: Run Time 0.01 min Valve 4 On Run Time 0.10 min Valve 1 On Run Time 0.10 min Valve 2 On Run Time 0.10 min Valve 3 On Run Time 1.40 min Signal 1 Switch to TCD B Cut Time A Run Time 1.43 min Signal 1 Zero Run Time 1.43 min Valve 4 Off Run Time 1.50 min Valve 1 Off Cut Time B Run Time 2.60 min Valve 3 Off Cut Time C Run Time 3.20 min Valve 3 On Cut Time D Run Time 3.20 min Valve 2 Off Cut Time D Run Time 3.70 min Valve 2 On Cut Time E Run Time 15.0 min Valve 2 Off Cut Time F Run Time 20.0 min Valve 3 Off Cut Time G Run Time 30.0 min Stop Re-inject the qualitative blend to check the cut times. If necessary, adjust the timing to ensure the proper separations.

8 8 of 17 PROCEDURE Chromatographic Technique The first time the columns are installed, or any time the columns are replaced, condition the columns according to the manufacturers instructions. Table 2 Operating Conditions for In-House Built Analyzer Oven temperature (isothermal) 55 o C Injection port temperature 100 o C Detector temperature 160 o C Carrier gas (A) nitrogen Flow rate 25 ml/min Carrier gas (B) hydrogen Flow rate 40 ml/min Detector A* Reference gas Flow rate Makeup gas Flow rate TCD nitrogen 40 ml/min nitrogen 3 ml/min Detector B* TCD Reference gas hydrogen Flow rate 55 ml/min Makeup gas hydrogen Flow rate 3 ml/min *Consult the manufacturer s instrument manual for suggested flow rates. 1. Install the gas purifiers in the supply line between the carrier gas source and the carrier gas inlet on the gas chromatograph. The column life is significantly reduced if the gas purifiers are not used. 2. Establish the recommended operating conditions for the in-house built analyzer (see Table 2). Other conditions may be used if they produce the required sensitivity and chromatographic separations equivalent to those shown in the typical chromatogram (Fig. 3). 3. Connect the sample or calibration blend cylinder to the sample inlet (Fig. 1) and purge the sample loops with the gas to be analyzed. 4. Stop the flow, allow 5 to 10 seconds for the pressure to equilibrate, and start the analysis. 5. Identify the sample components by comparing the resultant chromatogram with the typical chromatogram (Fig. 3).

9 9 of 17 LPG Sampling Liquefied petroleum gas (LPG) must be carefully expanded to ensure that a representative sample is analyzed. Various procedures are used to quantitatively expand LPG from a liquid phase into a representative gas phase prior to analysis. The following is the recommended procedure that has been proved to be satisfactory. 1. Assemble the LPG Expansion Cylinder consisting of a small stainless steel expansion cylinder, a stainless steel gauge with a reading range from vacuum to 200 kpa (gauge) and two stainless steel shut-off valves (see Fig. 4). Some expansion cylinders have two valves (C and D) as shown in Fig. 4, some have only one (Valve C). The version shown in Fig. 4 is easier to clean, but either may be used. 2. Connect the apparatus to the vacuum system and evacuate the cylinder assembly to kpa (0.1- mm Hg). 3. Connect two small pieces of clean stainless steel tubing, a tee and Valve B to the evacuated cylinder as shown in Fig. 4 (LPG Expansion Apparatus). 4. Determine if the LPG sample cylinder contains a dip tube. If not, place the LPG sample cylinder in a vertical position in a hood or well-vented area. Briefly open the bottom valve (A) to check that no water or sediment is present in the LPG. If the sample cylinder contains a dip tube, invert the cylinder (both valves on the bottom) and briefly open the valve not connected to the dip tube to check that no water or sediment is present. If water or sediment is determined to be present, discontinue the analysis and obtain a clean sample. LPG samples are usually contained in a cylinder having valves on both ends or, in some cases, a cylinder where one of the valves is connected to a dip tube. 5. Connect the bottom valve or the valve connected to the dip tube of the LPG sample cylinder with a short stainless steel connector to the expansion apparatus. Fully open Valve B in Fig Open (about 1/4 turn) Valve A, rapidly, on the sample cylinder until only liquid comes out of Valve B. Important: The valve must be opened wide enough so that a portion of liquid sample enters the stainless steel tubing before it vaporizes. Fractionation must not take place at the valve, or the composition of the sample will change. 7. Close Valve B and then Valve A and open Valve C (Fig. 4). 8. Close Valve C on the apparatus and disconnect the apparatus from the sample vessel. A positive pressure of 69 to 103 kpag (10 to 15 psig) should be displayed on the expansion cylinder gauge. If not, repeat Steps 1 through 8 with a longer or shorter piece of stainless steel tubing in the expansion apparatus. The cylinder now contains a gas phase sample that is representative of the LPG sample in the original pressurized cylinder. 9. Inject the expanded sample following Steps 3 through 5 under Chromatographic Technique. Calibration Response factors are required to relate detector response for each sample component to mol-%. Response factors for hydrogen, oxygen and/or argon composite, isopentane and n-pentane are calculated from

10 10 of 17 Calibration Blend 1. The response factors for C 1 to C 4 hydrocarbons and nitrogen are calculated from Calibration Blend 2, while the response factors for hydrogen sulfide (if present), carbon monoxide and carbon dioxide are determined from Calibration Blend 3. Analyze each calibration blend three times as described under Chromatographic Technique. The three replicates should repeat with 3% (relative). If not, rerun until three replicates are obtained with the desired repeatability. Based on the average of the three replicate analyses, determine the average relative response factor for each component, to three significant figures, using nitrogen as reference and the following formula: F = AB (1) CD where: A = component of interest, mol-% B = area of nitrogen peak C = nitrogen, mol-% D = average peak area for a component of interest F = relative response factor The response factor for argon is used for the unresolved oxygen and/or argon composite peak. Extrapolate a relative response factor for a C 6 hydrocarbon from the relative response factors of propane, n- butane and n-pentane. Use that factor for the C 5 olefin and/or C 6 + hydrocarbon peak. CALCULATIONS Calculate the actual mol-% concentration of each component or composite (assuming all components present in the sample are detected) to the nearest 0.1 mol-% using Eq. 2. FG Component or Composite, mol-% = 100 (2) H where: F = previously defined, Eq. 1 G = peak area of the component H = sum of the products FG for all recorded peaks 100 = factor to convert to mol-% When mass-% concentrations are required, the conversion can be made using Eq. 3. Report results to the nearest 0.1 mass-%. YZ Component or Composite, mass-% = 100 (3) T

11 11 of 17 where: T = sum of the products YZ for all components Y = component concentration, mol-% Z = molecular weight of component, g/mole 100 = factor to convert to mass-% PRECISION Repeatability Based on two tests performed by each of two analysts on each of two different days (8 tests), the withinlaboratory estimated standard deviations (esd) were calculated for components at specific concentrations in a synthetic refinery gas blend and are listed in Table 3. Two tests performed in one laboratory by different analysts on different days should not differ by more than the allowable differences in Table 3 at the concentrations listed (95% probability). The data listed in Table 3 are an estimate of short-term repeatability of the method. When the test is run routinely in the field, a control standard and individual-range chart should be used to develop a better estimate of the long-term repeatability. Reproducibility There is insufficient data to calculate reproducibility of the test at this time. TIME FOR ANALYSIS The elapsed time for the analysis of a gas sample is 0.5 hour, with a 0.1 hour labor requirement. The elapsed time for the analysis of a LPG sample (including expansion of the sample) is 1.0 hour, with a 0.5 hour labor requirement. Table 3 Repeatability Component or Composite Concentration, mol-% Within-Lab esd, mol-% Allowable Difference, mol-% Hydrogen Nitrogen Methane Ethane Propane n-butane Isobutane n-pentane Isopentane Oxygen/Argon Hydrogen Sulfide

12 12 of 17 SUGGESTED SUPPLIERS The suggested suppliers for the refinery gas analyzer are listed in the APPENDIX. Alltech Associates, Inc., 2051 Waukegan Rd., Deerfield, IL ( ) Arthur Harris and Co., 210 N. Aberdeen St., Chicago, IL ( ) Dearborn Valve & Fitting Co., 1540 Old Rand Rd., P.O. Box 847, Wauconda, IL ( ) Fisher Scientific, 711 Forbes Ave., Pittsburgh, PA ( ) Hewlett Packard Co., 2850 Centerville Rd., Wilmington, DE ( ) Matheson Gas Products, Inc., P.O. Box 96, Joliet, IL ( ) UOP Mat/Sen, 4509 Golden Foothill Pkwy., El Dorado Hills, CA ( ) Valco Instruments Co. Inc., P.O. Box 55603, Houston, TX ( )

13 13 of 17 APPENDIX List of Suggested Suppliers for Refinery Gas Analyzers Suggested Supplier, Model # Application Instrument Specifications Address Separates hydrogen, C 6 +, C 1 -C 5 Hewlett-Packard Company, Model HP/AC, Model G2329A AC Analytical Controls Inc., AC/HP RGA, Model 1029 (Turnkey) EG&G Chandler Engineering, Carle Series 400: Model A, Cat. No Model A, Cat. No Wasson ECE Instrumentation, Model Model Model Varian Analytical Instruments, Varian 3800 GC Renaissance Analytical, LLC, System 1 System 2 Separates hydrogen, C 6 +, C 1 -C 5 range per component and fixed gases Refinery Gas Analysis for Low C 5 + Samples (enhanced C 4 unsaturates separation) Refinery Gas Liquids Analysis of C 1 -C 5 saturates and unsaturates, with initial backflush of C = 5 and C 6 Standard Refinery Gas: analysis of C 1 - C 5 paraffins & olefins with initial backflush of C 6 + hydrocarbons Extended Refinery Gas Analysis: analysis of C 1 -benzene paraffins & olefins followed by initial backflush of toluene & C 8 + heavies as composite Refinery Gas by TCD: C 1 -C 5 paraffins and olefins, an initial composite C 5 olefin/c 6 + backflush, fixed gases and hydrogen It provides the separations of oxygen, nitrogen, carbon dioxide, H 2 S and hydrocarbons from C 1 through C 16 Extended Accelerated Refinery Gas Analysis: Initial composite backflush of toluene & C 8 + followed by C 1 -C 7 paraffins & olefins and benzene (fast analysis) Standard Refinery Gas Analysis: analysis of C 1 -C 5 paraffins & olefins with initial backflush of C 6 + heavies System 3 Refinery Gas Analysis: analysis of C 1 - C 5 paraffins & olefins with initial backflush of C 6 heavies (slow analysis) Separation Systems, Inc., Refinery Gas Analyzer C 3 -C 6 hydrocarbons are determined by the FID. Hydrogen, nitrogen, oxygen, carbon monoxide, carbon dioxide, and C 1 to C 2 are determined by TCD Equipped with HP 6890 Series GC with EPC, HP 3365 ChemStation or HP 3396B Integrator, Packed Columns, TCD/TCD Equipped with HP 6890 Series GC with EPC, HP 3365 ChemStation or HP 3396B Integrator, Packed Columns, TCD/TCD 426 Gallimore Dairy Rd., Greensboro, NC Tel: (800) Progress Dr., Bensalem, PA Tel: (215) Fax: (215) TCD/TCD P.O. Box , Tulsa, OK Tel: (918) Fax: (918) TCD/TCD HP 5890 II GC, one capillary and one packed column, TCD/FID same as above TCD/TCD Varian 3800 GC, TCD/TCD, Star Chromatography Workstation HP6890 GC, two capillary and one packed column, dual TCD/FID HP6890 GC, packed columns only, dual TCD/FID HP6890 GC, packed columns only, TCD/TCD HP GC, TCD/FID 1305 Duff Dr., Fort Collins, CO Tel: (303) Fax: (303) Varian Chromatography Systems, 2700 Mitchell Dr., Walnut Creek, CA Tel: (510) Fax: (510) P.O. Box 373, Pearland, TX Tel: (281) Fax: (281) Nightingale Ln., Gulf Breeze, FL Tel: (904) Fax: (904)

14 14 of 17 Figure 1 Instrument Configuration and Flow Diagram

15 15 of 17 Figure 2 Valve Timing, First Chromatogram (A,B, C and D refer to Cut Times, see text)

16 16 of 17 Figure 3 Typical Chromatogram (E,F,G and H refer to Cut Times, see text)

17 17 of 17 Figure 4 Sample Expansion Setup