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Gpa - 2165 - 1995

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327 views12 pages

Gpa - 2165 - 1995

Uploaded by

Alberto
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GPA Standard 2165-95 Analysis of Natural Gas Liquid Mixtures by Gas Chromatography Adopted as Tentative Standard, 1965 Revised and Adopted as a Standard, 1968 Revised 1975, 1995 Gas Processors Association 6526 East 60th Street Tulsa, Oklahoma 74145 DISCLAIMER GPA publications necessarily address problems of a general nature and may be used by anyone desiring to do so. Every effort has been made by GPA to assure accuracy and reliability of the information contained in its publications. With respect to particular circumstances, local, state, and federal laws and regulations should be reviewed. It is not the intent of GPA to assume the duties of employers, manufacturers, or suppliers to warn and properly train employees, or others exposed, concerning health and safety risks or precautions. GPA makes no representation, warranty, or guarantee in connection with this publication and hereby expressly disclaims any liability or responsibility for loss or damage resulting from its use or for the violation of any federal, state, or municipal regulation with which this publication may conflict, or for any infringement of letters of patent regarding apparatus, equipment, or method so covered. Method for Analysis of Natural Gas Liquid Mixtures by Gas Chromatography 1. SCOPE 1.1. This method is intended for the analysis of wide-range NGL mixtures, such as commercial decthanized and depropanized natural gasoline mixtures, that can not readily be entered into the chromatograph as a liquid by syringe, or as a vapor at atmospheric pressure, because of the presence of both highly volatile and heavy-end components (Note 1 ) . This, method is intended to determine ethane and heavier hydrocarbons. Hydrogen sulfide, carbon dioxide, air, and methane are not determined. 2. SUMMARY OF METHOD 2.1 A sample of pressurized natural gasoline is trapped as a liquid in a sampling valve and flashed into the carrier gas flowing to the analyzer column and detector cell. The composition is determined by comparing the peaks of the sample chromatogram with the corresponding peaks of a chromatogram of a mixture of known composition, 3. APPARATUS. 3.1 Major items comprising the gas chromatograph shall conform to the following specifications: 3.1.1 Detector—Thermal conductivity or flame ionization \ype, sufficiently sensitive to produce a peak height on the recorder chart equivalent to atleast 10 mm for 0.1 liquid volume per cent n-butane in a S microliter sample when using a S mv recorder witha full-scale range of 10 inches, 3.1.2 Recorder—A strip chart recorder with a full-scale range of 5 mv or less, a maximum full-scale balance time of 2 seconds, and a minimum chart speed of I inch (2.54 em) per minute, 3.1.3 Autenuator—A multistep attenuator for the detector output signal, accurate in any position to 0.5 percent for the system. 3.1.4 Sample Inlet System—A liquid sampling valve with sample repressure arrangement to entrap a liquid sample and center it into the carrier gas ahead of the analyzer column, Figure | shows a suitable system using a sample cylinder with a valve fon each end. Figure 2 shows an alternate system using another type of sample cylinder. The sample volume must be no larger than 5 microliters and must be repeatable such that successive ‘ns on the same sample agree within 2 mm or 2%, whichever is larger, on each component peak height (Note 2). 3.1.5 Temperature Control—A means to maintain the analyzer column and detector at a constant temperature as required to attain repeatability specified in 3.1.4 and to obtain a stable baseline, 3.16 Carrier Gas System—Facilities to provide a flow of helium or other suitable carrier gas through the analyzer column, and detector at a constant flow rate as required to attain repeatability specified in 3.1.4 and to obtain a stable base line. 3.1.7 Column—An analyzer column to provide peak resolution equivalent to or better than that shown by Figure 3 (Note 3) 3.1.8 Reversing Valve—A four-port valve to reverse the direction of flow of the carrier gas through the column, 4. CALIBRATION STANDARD 4. A known blend prepared by weights of high purity components (99+ per cent with known impurities) to an accuracy within 0.05 per cent (of the total blend) for each component is required for calibration runs (Note 4). The concentration of a component in the calibration blend should be not less than one-half of the concentration of the corresponding component in the unknown; and, in addition, corresponding ‘components in the calibration blend and in the unknown should not differ by more than five liquid volume per cent (of the total mixture) if the peak height calculation method is used, nor by ‘more than 20 liquid volume per cent (of the total mixture) if the peak area calculation method is used. In applying the rules of this section the values for the hexanes and heavier components ‘may be totaled and considered as a single component. NOTE 1—This method is not intended to be used for LP. Gas analysis since LP-Gas mixtures are more easily analyzed by ASTM method D 2163. NOTE 2—On instruments with an accessible gas sampling valve having changeable sample loops, the liquid sampling valve can replace the gas sample loop. Apply heat to carrier ow from carrier gas outlet of liquid sampling valve to oven by ‘wrapping flow line with electrical heating tape. Do not heat liquid sampling valve or carrier flow line to liquid sampling valve, NOTE 3—See Appendix for method of preparation of the silicone 703 column used to obtain the Figure 3 chromatogram, {In Figure 3, major components are listed above each peak. ‘Minor or trace components that may also be included in the peaks are shown in parentheses. It has been reported that "iso- ‘ctane" (2,2,4 trimethylpentane) would elute with cyclohexane or immediately ahead of n-heptane on this column if it were resent in the sample, However, this component is not known to exist as a normal constituent of natural gas liquids. NOTE 3a—Apiezon B is a suitable stationary phase for this ‘material with hydrogen flame ionization detectors. The Apiezon eliminates deposits in the burner orifice commonly experienced with silicone fluids as the stationary phase. NOTE 4—Calibration blends may be prepared as described in Appendix A or purchased from a supplier, provided blends are prepared by weights of high purity components to an ‘accuracy within 0.05 percent on each component (considering hhexanes and heavier grouped as one component). Figure I — Repressure System and Liquid Sampling Valve. Figure 2 — Alternate Repressure System. -- \ | Sturcearunecnsre INLET PRESSURE~35 PSIG | SAMPLE SIZE-S MICROLITERS ‘FRIMETHYCBUTANE) 2 METHVLPENTANE & 2,2 OMETHYLBUTANE FT METHYLPENTANE b (CYCLOPENTANE) METHYLCYCLOPENTANE (RARE TRACE 2.2.2 HEPTANE & DIMETHYLEYCLOPENTANE CYCLOHEXANE (2 ETHYLPENTANE) ‘3 METHYLHEXANE (2,9. DIMETHYLPENTANE) 2 METHYEHEXANE (2,3 DIMETHYLPENTANE) fuoster cat | J REVERSE CARRIER FLOW DENZENE Trane © AR Figure 3 Chromatogram of Natural Gasoline, 5. ANALYTICAL PROCEDURE 5.1 Apparatus Preparation—Place the apparatus in ‘operation and adjust operating conditions as determined by trial runs t0 be suitable for the column used. Allow adequate watm- Up time to establish equilibrium and provide a stable base line. 5.2. Sample Preparation—Connect the sample cylinder B (Figure 1 or Figure 2) to cylinder A so that repressure liquid can be entered into the bottom of cylinder B, and sample withdrawn from within the hydrocarbon layer (Note 5). Pressurize and maintain a pressure on cylinder A that is at least SO psi higher than the hydrocarbon sample vapor pressure and open valves to admit the repressure liquid into cylinder B (Note 6). Gently rotate cylinder B from vertical to nearly horizontal about ten times to mix the repressured hydrocarbon, and then fix it in the vertical position by means of a ringstand or other holder. Attach outlet valve of cylinder B to inlet of liquid sampling valve using small diameter metal tubing as short as practical to minimize required purging. Slightly open the needle vent valve and open cylinder B outlet valve to slowly flow liquid to purge and fill the sampling valve, Clase the needle vent valve 5.3 Calibration Run—Enter a sample of the calibration mixture and adjust the attenuator at each peak for maximum, peak height within the recorder chart range. Reverse the carrier flow after benzene is eluted or later. If repeatability has not been established, make a second calibration run to determine that performance specified in 3.1.4 is met. For the peak height calculation method, make the calibration run and the sample runs while she instrument is in continuous operation. For the peak area calculation method, check the area response factors periodically by calibration runs. Determine new response factors for each new analyzer column or for each replacement in the detector components 5.4 Sample Run—Enter a sample of the deethanized or de- propanized natural gasoline and obtain a chromatogram under conditions of the corresponding calibration run, 6. CALCULATIONS 6.1 Peak Area Method—Obiain the area of exch component and of the reverse flow peaks. An integrator can be used if its repeatability has been established. If an acceptable integrator is not available, carefully draw the base line, measure the peak height and width at half-height of each peak on forward flow. Use a magnifying glass to aid in measuring the peak width from the outside edge of one fine to the inside edge of the other. Measure the reverse-flow area by geometric construction of planimeter. Obtain corresponding peak areas from the sample ‘and calibration runs by the same method and apparatus and the same units of measurement, NOTE 5—Attach the connecting tubing t0 cylinder A and ‘open valve to slowly flow liquid to completely fill tubing before ‘attaching to cylinder B. Loop the connecting tubing to allow moving cylinder B through a 90 degree arc without strain to tubing. NOTE 6—A gage press of about 200 psi is usually adequate. Caution! Be certain that working pressure of cylinders, valves, fiutings, and tubing is higher than the pressure Calculate the composition as follows s C=PxMx —S— ae PsMs Where: (C= liquid volume per cent of component in sample P= peak area of component in sample P= peak area of component in calibration standard 'M = attenuation multiplier for component in sample M = attenuation multiplier for component in calibration standard liquid volume percent of component in calibration standard (Note 7) ‘Total values and normalize results to 100.0 6.2 Peak Height Method—The peak height calculation method may be used for the forward flow components if retention times for corresponding peaks of the sample and calibration runs agree within 1/2%, as measured along the base line from the point of sample entry to the maximum peak height for each component. In this case express P and Ps in 6.1 in peak hheight in millimeters or other convenient units 7. PRECISION 7.1 Repeatability—Duplicate results obtained on the same apparatus should not differ by more than the following: Concentration Range Vol. % o1 008 15 0.10 5-20 020 20-30 028 Over 30 030 7.2. Reproducibility—Results on the same sample by different laboratories should not differ by more than the following: Concentration Range Liquid Vol. % Reproducibility os] oo7 1s ous 5-20 030 20-30 0.40 Over 30 0.50 NOTE 7—Ht would be equally acceptable to express S and C in mole or weight percent if desired. APPENDIX A. A, Preparation of Silicone 703 Column, ‘Add 12 grams of silicone 703 to 60 grams of dry 35-80 mesh chromosorb P in a clean screw cap bottle. Shake for about five minutes until it appears homogeneous. Clean a 20-ft. (6m.) Tength of 1/4 in, copper or aluminum tubing by flushing it with acetone and drying it by purging with a stream of clean, dry air or inert gas. Bend the tubing into a U-shape and fill with the packing by admitting it into one end and then the other using a funnel and electric vibrator to completely fill the tubing. Plug each end with 1/2 in, of glass wool and shape the tubing so that it may be conveniently mounted in the chromatograph. 2. Preparation of Calibration Standard, Major equipment and materials required: ‘8, Blend eylinder, two-valve, S00 ml or larger. b, Balance, 2,000 gram or larger capacity, 0.1 gm or better sensitivity ‘¢. Pure hydrocarbons, ethane through n-pentane, 99 + % pure. 4. Depentanized natural gasoline Run a chromatogram on each pure component to check on its given purity, Run a chromatogram on the depentanized natural gasoline to obtain a composition breakdown as shown by the Cg and heavier peaks in Figure 3. Calculate the approximate ‘composition breakdown by assuming that weight percentages of the Cy and heavier components equal area percentages of the peaks (Note 1). Calculate the weight of each pure component and the weight of the depentanized natural gasoline required to make 400 ml (80 percent of blend cylinder capacity) of the desired blend, Evacuate the blend cylinder to 1 mm Hg or less and weigh accurately. Admit the approximate amount of natural gasoline required for the blend into the weighed cylinder. This can be conveniently done as follows, Butt-end a glass funnel to a small length of metal tubing by means of Tygon and connect to the cylinder. Pour some of the natural gasoline into the funnel to fill iva little above the top of the stem. Slightly loosen the fitting at the cylinder valve and allow liquid to seep out to expel all “Tighten fitting when the gasoline level is at top of the funnel stem of in the stem where the level can be marked. Pour the volume of natural gasoline equivalent to the needed weight into the funnel and slowly admit it into the cylinder by cracking the inlet valve and closing it when the gasoline level is at the pre-set level. Remove the fitting and thoroughly clean out any gasoline romaining in the end of the cylinder valve and again weigh the cylinder {o obtain the precise weight of gasoline added. Similarly, admit the required amount of pure n-pentane into the blend cylinder and obtain its weight Evacuate and weigh a small eylinder ( usually 100 ml ) that, ‘will hold the amount of iso-pentane to be blended. Admit the approximate weight plus about 5 grams of pure iso-pentane into this eylinder by rial-and-error, adding or venting small amounts Of iso-pentane and re-weighing until the approximate desired weight is contained in the small cylinder. Attach to the blend cylinder valve using a minimum length of metal tubing. Slightly loosen the fitting at the blend cylinder valve and open the small cylinder valve to purge air from the connection to fil it with iso- pentane. Tighten the fitting and open the blend cylinder valve to admit iso-pentane into the blend cylinder until cylinder pres- sures are equalized. Close valves and remove the fitting. Clean the blend cylinder valve and weigh the blend cylinder to obtain the precise weight of iso-pentane in it. Similarly, add pure n- butane, iso-butane, and propane into the blend cylinder, weighing it afier each addition to obtain the precise weight of ceach component, Connect the blend cylinder to a cylinder of pure ethane with ‘a metal connection of calculated length to contain approximately the amount of ethane to be added. Flush the connection with the ethane by slightly loosening the fitting at the blend cylinder valve. Tighten the fitting. Close the ethane cylinder valve and ‘open the blend cylinder valve to admit the ethane from the con- nection and then close. Disconnect and weigh the blend cylinder to obtain the weight of ethane added. From the weights and purities of all components added, calculate the composition of the blend in weight percent, breaking down the Cg and heavier by applying the weight per cent composition determined on the depentanized natural ‘gasoline, Convert to liquid volume per cent using specific ‘gravity values given in Table I NOTE 1—The approximate breakdown of the Cy and heavier components is a means of calculating the ‘chromatogram. The objective in this instance is an accurate value for the total of the Ce and heavier components Table 1 Relative Density ponent 6060 F (Vacuum) Ethane 035619 Propane 0.50698 N-butane 58402 Iso-butane 0.56286 N-pentane 0.63108, Iso-pentane 62441 N-hexane 0.66404 2-methylpentane os7a8 3-methylpentane 0.66909 2, 2-dimethylbutane (neohexane) 0.65408, 2, 3dimethyloutane 0.66630, Ne-heptane o.6s805 2-methylhexane 0.68316 $3:methylhexane 0.69165 2, 2-dimethylpentane o.e7es2 2, 4-dimethylpentane 067721 1, Feimethyleyclopentane 0.75920 Neoetane 0.70678 Cyclopentane 0.75077 Methyleyclopentane 0.75467 Cyclohexane 0.78339 Methyleyclonexane 077395 Benzene o.nsass Toluene os7i91 ‘Values from GPA Standard 2145-95 and the GPSA Engineering Data Book, Revised 10th Edition. Appendix B Calculations Performed in Association with Liquid Product Analyses PREFACE All physical constants used in these calculations should come from the most recent edition of GPA 2145. The constants used in the examples that follow are from GPA 2145-95, The following physical constants not listed in GPA 2145 have been used in some of the calculations 0.25636 = vapor pressure of HO (psia) @ 60°F (reference: U.S. Bureau of Standards) 1230 = vapor pressure of CO, (psia) @ 100°F 5000 = vapor pressure of Np (psia) @ 10°F B= Gas Constant = 1545.3504 fi. —Ibylb — mot Cufto—mot of any gas a 14696 prin and 607 = V = RT (1545.3504\459.67 + 60) (144)(14.696) = 379.48357 Constant values for hexanes plus (C*) of heptanes plus (C;*) if not actually determined by extended analysis should be mutually agreed upon by all concerned partes For ease of hand calculations in the examples shown the number of significant figures does not match those shown in GPA. 2145. Precision of numbers in computer generated calculations should match that of GPA-2145, Rounding of numbers can cause some differences in final results. Computer generated calculations should only round those final numbers displayed on analyses, ‘not numbers generated in intermediate calculations. For those calculations that are pressure dependent, the mathematics should be carried out using the constants ata pressure base of 14.696 and the final result converted to the desired pressure base after all other mathematical functions are completed. Conversion of the physical constants to equivalent values at other pressure bases or the use of generated secondary factors prior to performing calculations is not recommended. It is further recommended that computer software be written to follow these methods and recommendations and that hardbound documentation of the software programs be maintained and available at all times. For use in these calculations, mol fraction shall be equal to: mol%/100, B1 Calculation of Weight Fraction, Liquid Volume Fraction, Molecular Weight and Relative Density of Liquifed Product from Mol Fraction Analysis [___ San Gakime Sam—_Goend Geen Gon Oem? Came — Goma] Sample Molecular Wt. Weight Lbs. ‘Sample Lbs./Gal__ Lig. Vol. Lig, Vol Relative Relative | Nel Elchon NORCHEE. Wet e elon SMG siooe Piacton ensty Bens Ccomponers GPA2IES Cok 1xC0l.2 Cal BVabes GPAZIES 100x014 Col.6 Values GPAZIS Cal. 7x00. 8 oh To CoS Col 6 Tota ivogon coos 301s cot —=—swance = 7am ans 0.000 ae anar waa cess goss Gas? «Sans 2o000Osse©—scowes ooo ans CaponDoxde 00120 aaora. «= sas=sorrs = Gersy oes 0070 Baten csr Eitane oan oor sban0= Oras 2aume «Sauter seamen Fsogon Sufde 0.0000 Shogo «0.000 «(0000 «eet «0000 «0.0000 ««aore © conn Propane cst Ssoor—teaoe,=s Gast? «fanaa! ossoy strat (oobuore «ows gags aa) Oey dese? pate at01S Osean a7 Naane coo aes Saar Ori7e amet 2ats crows osmaoGases (soporte ome T2N80.«=«200-=«soage«==««Sz0se 108 ==«(soe=Daeae ats Neenare bows «7a v00.«=«dts——«soees«Szet 1188 sor ast oate MovanesPus 088 «se00 «4400 anaSeaaot titre Oars Mar | ois 1.0000 Molecular wt 1.0000 23713 1.0000 Relative density =0.5059 | ~ Aviva assumed vale (used if average value not deterined) 2 Cafeulation of Liquid Density (LbGal of Liquifed Product. Liquid Density (Ibgal) = Relative Density x gal fH z 05059 x 83372 = 4278 B3 Calculation of API Gravity of Liquifed Product. APIGravity. = (141.5 + Relative Density)- 131.5 = (141.5 + 0.5059) - 131.5 = 1482 BA Calculation of Cu F, VaporfGallom of Liqufed Produc. Iigal x 379.48357 14.696 ‘mol wt.

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