UOP 539-2012 Refinery Gas Analysis by GC.pdf

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1、 IT IS THE USERS 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 PRESCRIB

2、ED 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, 2012 UOP LLC.

3、All rights reserved. Nonconfidential UOP Methods are available from ASTM International, 100 Barr Harbor Drive, P.O. Box C700, West Conshohocken, PA 19428-2959, USA. The UOP Methods may be obtained through the ASTM website, www.astm.org, or by contacting Customer Service at serviceastm.org, 610.832.9

4、555 FAX, or 610.832.9585 PHONE. Refinery Gas Analysis by GC UOP Method 539-12 Scope This method is for determining the composition of refinery gas streams or vaporized liquefied petroleum gas (LPG) using a preconfigured, commercially available gas chromatograph. At a minimum, the following component

5、s are reported: non-condensable gases, individual C1 through C4 hydrocarbons and C5 paraffins. C5 olefins and C6+ hydrocarbons are reported as a composite. Some configurations of the analyzer will separate the C5 olefins and certain C6+ hydrocarbons. Oxygen is not separated from argon. Results for h

6、ydrogen sulfide, if present, may not be quantitative on some analyzers. The lower limit of quantitation for each component or composite is 0.05 mol-%. If the measurement of lower concentrations of hydrocarbons are needed, use UOP Method 899, “Trace Hydrocarbons in Hydrogen, Hydrocarbon Gases, or LPG

7、 by GC.” LPG samples may be analyzed by UOP Method 373, “Composition of C2 through C5 Hydrocarbon Mixtures by GC,” or UOP Method 980, “C5 and Lower Boiling Dienes, Olefins, and Paraffins in Naphthas by GC.” Alternatively, LPG samples may be expanded to the gas phase and run by this method. Reference

8、s Analyzer manufacturers operating manual UOP Method 373, “Composition of C2 through C5 Hydrocarbon Mixtures by GC,” www.astm.org UOP Method 899, “Trace Hydrocarbons in Hydrogen, Hydrocarbon Gases, or LPG by GC,” www.astm.org UOP Method 980, “C5 and Lower Boiling Dienes, Olefins, and Paraffins in Na

9、phthas by GC,” www.astm.org UOP Method 999, “Precision Statements in UOP Methods,” www.astm.org Outline of Method The sample is injected into a GC configured for refinery gas analysis with multiple valves and columns, and, usually, more than one detector. The included data system controls the operat

10、ing sequence, measures the resultant peaks, and performs component quantitation based upon calibration with known gas blends. Apparatus References to catalog numbers and suppliers are included as a convenience to the method user. Other suppliers may be used. 2 of 7 539-12 Analyzer, refinery gas. Ref

11、inery gas analyzers are available pre-configured, including a data system, from several suppliers. A partial list of suppliers is included in Appendix A, and includes instrument features as described in the suppliers website, as of publication of this method. Other vendors also supply similar system

12、s. Confirm with the supplier that the analyzer is appropriate for the streams to be analyzed and the analysis required. Instrument gas supply regulators; not all instruments will require all the regulators listed below. Regulator, air, two-stage, high purity, delivery pressure range 30-700 kPa (4-10

13、0 psi), Matheson Tri-Gas, Model 3122-590 Regulator, argon, two-stage, high purity, delivery pressure range 30-700 kPa (4-100 psi), Matheson Tri-Gas, Model 3122-580 Regulator, helium, two-stage, high purity, delivery pressure range 30-700 kPa (4-100 psi), Matheson Tri-Gas, Model 3122-580 Regulator, h

14、ydrogen, two-stage, high purity, delivery pressure range 30-700 kPa (4-100 psi), Matheson Tri-Gas, Model 3122-350 Regulator, nitrogen, two-stage, high purity, delivery pressure range 30-700 kPa (4-100 psi), Matheson Tri-Gas, Model 3122-580 Leak detector, gas, Grace Davison, Cat. No. 60229 Reagents a

15、nd Materials References to catalog numbers and suppliers are included as a convenience to the method user. Other suppliers may be used. Calibration blends, as specified by the analyzer operating manual, Matheson Tri-Gas, or local supply. For increased accuracy, one calibration blend should have a co

16、mposition close to that of the samples to be analyzed, but not less than 1 mol-% of each component of interest. Table 1 lists a set of calibration blends that would be generally applicable to a variety of sample types. Gas purifier, for carrier gases, to remove oxygen and moisture, VICI Mat/Sen, Cat

17、. Nos. P100-1 (helium), P200-1 (hydrogen), P300-1 (nitrogen), and (optional) indicating oxygen traps, Restek, Cat. No. 22010 Instrument gases, as needed; not all instruments will require all the gases listed below. Air, zero gas, total hydrocarbons less than 2.0 ppm as methane, local supply Argon, 9

18、9.99% minimum purity, local supply Helium, 99.99% minimum purity, local supply Hydrogen, zero gas, 99.99% minimum purity, total hydrocarbons less than 0.5 ppm as methane, local supply Nitrogen, zero gas, 99.99% minimum purity, total hydrocarbons less than 0.5 ppm as methane, local supply Procedure T

19、he analyst is expected to be familiar with general laboratory practices, the technique of gas chromatography, and the equipment being used. Dispose of used reagents, materials, and samples in an environmentally safe manner according to local regulations. 3 of 7 539-12 Table 1 Calibration Blend Examp

20、le Concentrations, mol-% Component Blend 1 Blend 2 Blend 3 Hydrogen 50.0 - 20.0 Nitrogen 15.0 15.0 45.0 Argon 5.0 - 5.0 Methane 5.0 10.0 - Ethane 5.0 10.0 - Ethylene - 5.0 - Propane 12.0 12.0 - Propylene - 6.0 - Propadiene - 1.0 - n-Butane 3.0 10.0 - Isobutane 3.0 10.0 - 1-Butene - 5.0 - Isobutylene

21、 - 5.0 - trans-2-Butene - 5.0 - cis-2-Butene - 5.0 - 1,3-Butadiene - 1.0 - n-Pentane 1.0 - - Isopentane 1.0 - - CarbonDioxide - - 5.0 CarbonMonoxide - - 10.0 Helium - 10.0 HydrogenSulfide - - 5.0 If specific components, e.g., hydrogen sulfide, helium, or 1,3-butadiene are known to be not present in

22、the sample types being analyzed, they may be deleted from the blends, and the composition of the other components adjusted to total 100%. Chromatographic Technique 1. Install the gas purifier in the supply line between the carrier gas source and the carrier gas inlets on the gas chromatograph. Colum

23、n life is significantly reduced if gas purifiers are not used. Replace the gas purifiers at intervals determined by good laboratory practice. Indicating oxygen traps may be placed downstream of the gas purifiers. When the indicator shows one-half used, replace both the gas purifier and the indicatin

24、g trap. 2. Follow the instrument set-up procedure provided by the manufacturer and establish the recommended operating conditions. CAUTION: Hydrogen leakage into the confined volume of the column oven can cause a violent explosion. Therefore, it is mandatory to check for leaks each time a connection

25、 is made and periodically thereafter. 3. Connect the sample cylinder or calibration blend cylinder to the sample inlet and purge the system with the gas to be analyzed. If LPG samples are to be analyzed, they must be expanded to the gas phase before analysis, see Appendix B. LPG samples that contain

26、 significant quantities of C5+ material may not vaporize quantitatively and are beyond the scope of this method. 4. Stop the flow, allow 5 to 10 seconds for the pressure to equilibrate, and start the analysis. Calibration Response factors are required to relate detector response for each sample comp

27、onent to mol-%. Response factors are determined by the analysis of one or more calibration blends as directed by the 4 of 7 539-12 analyzer operating manual. Analyze the blends in triplicate or as directed by analyzer operating manual and determine the response factors according to the instructions

28、in the analyzer operating manual. For increased accuracy, a calibration blend should have a composition close to that of the samples to be analyzed, but not less than 1 mol-% of each component of interest. The peak areas from each of the triplicate blend runs should not deviate from the average by m

29、ore than 3% (relative) of the value. If greater deviations occur, make certain that there are no problems with the equipment and then make additional runs until the required repeatability is obtained on three consecutive runs. Confirm the stability of the chromatographic system by analyzing a refere

30、nce sample or blend each day when samples are analyzed. If the results differ by more than 5% from the average of previous analyses, a problem has developed with the chromatographic system, and the series of samples must be rerun after the problem is resolved. Calculations Component identifications

31、and calculations are performed by the instrument data system. Report each measured component or group of components to the nearest 0.01 mol-%. Precision Precision statements were determined using UOP Method 999, “Precision Statements in UOP Methods.” Repeatability, Site Precision, and Reproducibilit

32、y A nested design was carried out for determining impurities in a synthetic refinery gas blend on three instruments, each by two analysts, with each analyst performing analyses on two separate days, performing two analyses each day for a total of 24 analyses. Using a stepwise analysis of variance pr

33、ocedure, the within-day, within-lab, and between-lab estimated standard deviations (esd) were calculated at the concentration means listed in Table 2. Two analyses performed in one laboratory by the same analyst on the same day should not differ by more than the repeatability allowable differences s

34、hown in Table 2 with 95% confidence. Two analyses performed in one laboratory by different analysts on different days should not differ by more than the site precision allowable differences shown in Table 2 with 95% confidence. Two analyses performed in different laboratories by different analysts o

35、n different days should not differ by more than the reproducibility allowable differences shown in the Table with 95% confidence. Table 2 Repeatability, Site Precision, and Reproducibility, mol-% Repeatability Site Precision Reproducibility Component Mean Within- Day esd Allowable Difference Within-

36、 Lab esd Allowable Difference Between- Lab esd Allowable Difference Hydrogen 40.12 0.191 0.59 0.193 0.60 0.204 0.63 Oxygen 4.99 0.019 0.06 0.019 0.06 0.019 0.06 Nitrogen 14.95 0.056 0.17 0.062 0.19 0.063 0.19 Carbon Dioxide 1.95 0.016 0.05 0.017 0.05 0.037 0.17 Methane 9.97 0.039 0.12 0.042 0.13 0.0

37、46 0.14 Ethane 4.99 0.018 0.05 0.020 0.06 0.021 0.07 Propane 20.96 0.080 0.25 0.083 0.26 0.089 0.27 Isobutane 2.05 0.010 0.03 0.010 0.03 0.110 0.67 5 of 7 539-12 The data in Table 2 represent short-term estimates of the repeatability of the method. When the test is run routinely, use of a control st

38、andard and a control chart is recommended to generate an estimate of long-term repeatability. Time for Analysis The elapsed time for one analysis is 0.9 hour. The labor requirement is 0.3 hour. Suggested Suppliers Grace Davison Discovery Sciences, 2051 Waukegan Rd., Deerfield, IL 60015, USA (847-948

39、-8600) Matheson Tri-Gas, 166 Keystone Dr., Montgomeryville, PA 18936, USA (215-641-2700) Restek, 110 Benner Circle, Bellefonte, PA 16823, USA (814-353-1300) VICI Mat/Sen, 7806 Bobbitt, Houston, TX 77055, USA (713-688-9345) 6 of 7 539-12 Appendix A List of Suggested Suppliers for Refinery Gas Ana

40、lyzers Suggested Supplier Model Features Agilent Technologies Refinery Gas Analyzer Complete range of analyzers for refinery and other petroleum gases containing H2, O2, N2, CO, H2S, CO2 and C1-C5 plus higher chain length hydrocarbons Expandable to the analysis of liquefied gases with addition of an

41、 optional micro-gasifier MicroGC Refinery Gas Analyzer 4 channel, multi-dimensional system based on the 490 Micro GC Suitable for sample streams with low sample component concentration Analytical Controls (PAC) HiSpeed RGA - Refinery Gas Components A high speed solution that determines and reports t

42、he composition of refinery gas streams in only five minutes Separation Systems Refinery Gas Analyzer Analysis of C6+ Individual Analysis up to Benzene Complete Separation of C4 Olefins Hydrogen Analysis from 100 ppm to 99.9% Wasson ECE Hyper-Extended Refinery Gas Analysis (RGA) C1 C7, hydrogen, carb

43、on dioxide, hydrogen sulfide, oxygen, nitrogen, carbon monoxide Standard Refinery Gas Analysis (RGA) C1 C7, hydrogen, carbon dioxide, hydrogen sulfide, oxygen, nitrogen, carbon monoxide Suggested Suppliers Agilent Technologies, 2850 Centerville Rd., Wilmington, DE 19808-1610, USA (302-633-8000) PAC

44、, 8824 Fallbrook Dr., Houston, TX 77064, USA ( 281.940.1803) Separation Systems, 100 Nightingale Ln., Gulf Breeze, FL 32561, USA (850-932-1433), Wasson-ECE Instrumentation, 101 Rome Ct., Fort Collins, CO 80524, USA (970-221-9179) www.wasson- 7 of 7 539-12 Appendix B LPG Sampling Liquefied petroleu

45、m gas (LPG) must be carefully expanded to ensure that a representative sample is analyzed. This can be accomplished using an electrically heated pressure reducing vaporizing regulator. The apparatus listed below is one such device. Apparatus References to catalog numbers and suppliers are included a

46、s a convenience to the method user. Other suppliers may be used. LPG vaporization system, Micro-GC Gasifier, Agilent Technologies, Model CP-4900 Procedure 1. Install the LPG vaporization system according to the manufacturers instructions, and allow the system to warm up. 2. Connect the LPG cylinder

47、as directed, start the flow of the sample, and start the analysis. The cylinder must be connected so that the sample is taken from the liquid phase. 3. Calibration and calculations are the same as in the body of the method. Note LPG samples that contain significant quantities of C5+ material may not vaporize quantitatively and are beyond the scope of this method.