UOP 880-2008 Hydrocarbon Types and Distributions in Low Olefin C12 and Lower Endpoint Distillates 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 1991, 1996, 2008 UOP LLC. All rights r

3、eserved. 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, 610.832.9555 FAX, or

4、610.832.9585 PHONE. Hydrocarbon Types and Distributions in Low Olefin C12and Lower Endpoint Distillates by GC UOP Method 880-08 Scope This method is a procedure for calculating paraffin, olefin, naphthene and aromatic hydrocarbon types in hydrocarbon fractions, such as reformer feeds and reformates,

5、 having endpoints of 200C or less (C3through C11). C12paraffins and naphthenes at concentrations totaling less than 3% can be determined. Olefins must be less than 2%. C8minus paraffins and naphthenes are reported individually. C9through C12paraffins and naphthenes are determined by carbon number. A

6、romatics through C10are determined individually with C11+ aromatics determined as a composite. Olefins are reported undistributed. If analysis by carbon number only for all hydrocarbon types over all carbon number ranges is sufficient, use ASTM Method D6839, “Hydrocarbon Types, Oxygenated Compounds,

7、 and Benzene in Spark Ignition Engine Fuels by Gas Chromatography.” Results are reported to the nearest 0.01 mass-%. Conversion to liquid volume-percent (LV-%) is described in the Appendix. References ASTM Method D4052, “Density and Relative Density of Liquids by Digital Density Meter,” www.astm.org

8、 ASTM Method D6839, “Hydrocarbon Types, Oxygenated Compounds, and Benzene in Spark Ignition Engine Fuels by Gas Chromatography,” www.astm.org UOP Method 690, “Octanes and Lower Boiling Hydrocarbons in Olefin Free Gasolines by GC,” www.astm.org UOP Method 744, “Aromatics in Hydrocarbons by GC,” www.a

9、stm.org UOP Method 999, “Precision Statements in UOP Methods,” www.astm.org Outline of Method The sample is analyzed by three gas chromatographic methods: UOP Methods 690, “Octanes and Lower Boiling Hydrocarbons in Olefin Free Gasolines by GC,” 744, “Aromatics in Hydrocarbons by GC,” and ASTM Method

10、 D6839, “Hydrocarbon Types, Oxygenated Compounds, and Benzene in Spark Ignition Engine Fuels by Gas Chromatography.” The sample is analyzed by ASTM Method D6839 to determine total paraffins, naphthenes and aromatics by carbon number. The sample is analyzed by UOP 2 of 7 880-08 Method 690 to determin

11、e the individual C8minus paraffin and naphthene distribution. Total C8minus olefins are also determined by UOP Method 690. The sample is analyzed by UOP Method 744 to determine the individual C6through C10aromatics and the C11+ aromatic composite. Data are combined from each analysis to report the t

12、otal composition of the sample. Apparatus, Reagents, and Materials The apparatus, reagents, and materials required for this analysis are described in the three GC methods listed in References. A spreadsheet or computer program may be developed to automate the calculations. Procedure 1. Determine the

13、 total paraffins, naphthenes and aromatics, by carbon number, of the sample using the equipment for ASTM Method D6839, but run in the PNA mode. The analyzer specified in D6839 reports results in both mass-% and LV-%. Use the mass-% values. Olefins, if present, are hydrogenated and determined as para

14、ffins or naphthenes in this analysis when run in the PNA mode. 2. Determine the C8minus paraffin and naphthene distribution as well as the total C8minus olefin composition of the sample by UOP Method 690. Perform both analysis A and B and the additional calculations required by analysis B as describ

15、ed in the method. This analysis is normally performed on olefin-free samples. However, for the purpose of this determination, any unidentified components eluting before methylcyclohexane are considered to be olefins and totaled. Olefins eluting after methylcyclohexane cannot be determined. If the ol

16、efin content is above 2%, interferences will make the paraffin and naphthene results invalid. The sample may still be analyzed for hydrocarbon types by carbon number using ASTM D6839 run in the PIONA mode. 3. Determine the C6through C10aromatics individually and the total C11+ aromatic composite by

17、UOP Method 744. Calculations The composition of the sample is calculated and reported to the nearest 0.01 mass-%. See Table 1 for a listing of the components and composites typically reported. 1. Olefins, mass-%, are totaled and reported directly from UOP 690. 2. Correct the C8minus saturated from A

18、STM D6839 for hydrogenated olefins using Equation 1: Corrected C8minus saturates, mass-% = C-D (1) where: C = sum of the C8minus paraffins and naphthenes by ASTM D6839, mass-% D = total C8minus olefins by UOP 690, mass-% 3. Normalize the C8minus paraffins and naphthenes from ASTM D6839 to the percen

19、tage determined in Step 2. Report the C9through C12paraffins and naphthenes from the original ASTM D6839, as well as any heavy material, called Poly Naphthenes or C12P+N by the method. 4. Normalize each individual C8minus component from UOP 690 to the corresponding carbon number and type total perce

20、ntage determined in Step 3. Report the C8minus components individually. 5. Report the C9through C12paraffins and naphthenes from the original ASTM D6839, as well as any heavy material, called Poly Naphthenes or C12P+N by the method. 3 of 7 880-08 6. Report benzene and toluene directly from ASTM D683

21、9 results. 7. Normalize and report individual C8aromatic components from UOP 744 to the total C8aromatic percentage from ASTM D6839. 8. Normalize and report the C9+ aromatics from UOP 744 to the total C9+ aromatic percentage from ASTM D6839. Report as individual C9and C10aromatic components and tota

22、l C11+ aromatics. 9. Sum all the reported components. Rounding each of the components to the nearest 0.01% may cause the grand total to differ slightly from 100.00. If this occurs, adjust the value of the highest concentration component such that the grand total is exactly 100.00. Table 1 Typical Co

23、mponents Reported The numbers in parentheses behind the paraffin and naphthene components are not reported, but may be used as an aid in distributing paraffins (P) and naphthenes (N) from the UOP 690 analysis to the group totals from ASTM D6839. Component Component Component Total Olefins Propane (P

24、3) 1,1,2-Trimethylcyclopentane (N8) Isobutane (P4) 2-Methyl-3-ethylpentane (P8) Benzene n-Butane (P4) 2-Methylheptane (P8) Toluene Isopentane (P5) 4-Methylheptane (P8) Ethylbenzene n-Pentane (P5) 3,4,Dimethylhexane p-Xylene Cyclopentane (N5) + 3-Methyl-3-ethylpentane (P8) m-Xylene 2,2-Dimethylbutane

25、 (P6) 1-cis-2-trans-4-Trimethylcyclopentane o-Xylene 2,3-Dimethylbutane (P6) + 1-cis-2-cis-4-Trimethylcyclopentane (N8) Cumene 2-Methylpentane (P6) 3-Methylheptane (P8) n-Propylbenzene 3-Methylpentane (P6) 1-cis-3-Dimethylcyclohexane 1-Methyl-4-ethylbenzene n-Hexane (P6) + 1-cis-2-trans-3-Trimethylc

26、yclopentane (N8) 1-Methyl-3-ethylbenzene 2,2-Dimethylpentane (P7) 1-trans-4-Dimethylcyclohexane (N8) tert-Butylbenzene Methylcyclopentane (N6) 1,1-Dimethylcyclohexane (N8) iso-Butylbenzene 2,4-Dimethylpentane (P7) 1-Methyl-trans-3-ethylcyclopentane (N8) 1,3,5-Trimethylbenzene 2,2,3-Trimethylbutane (

27、P7) 1-Methyl-cis-3-ethylcyclopentane (N8) sec-Butylbenzene 3,3-Dimethylpentane (P7) 1-Methyl-trans-2-ethylcyclopentane (N8) Styrene Cyclohexane (N6) 1-Methyl-1-ethylcyclopentane (N8) 1-Methyl-2-ethylbenzene 2-Methylhexane (P7) 1-trans-2-Dimethylcyclohexane (N8) 1-Methyl-3-isopropylbenzene 2,3-Dimeth

28、ylpentane (P7) 1-cis-2-cis-3-Trimethylcyclopentane (N8) 1-Methyl-4-isopropylbenzene 1,1-Dimethylcyclopentane (N7) n-Octane (P8) 1,2,4-Trimethylbenzene 3-Methylhexane (P7) 1-cis-4-Dimethylcyclohexane (N8) 1-Methyl-2-isopropylbenzene 1-cis-3-Dimethylcyclopentane (N7) 1-trans-3-Dimethylcyclohexane (N8)

29、 + 1,3-Diethylbenzene 1-trans-3-Dimethylcyclopentane (N7) Isopropylcyclopentane (N8) 1-Methyl-3-n-propylbenzene 3-Ethylpentane (P7) 1-Methyl-cis-2-ethylcyclopentane (N8) 1-Methyl-4-n-propylbenzene 1-trans-2-Dimethylcyclopentane (N7) 1-cis-2-Dimethylcyclohexane (N8) 1,4-Diethylbenzene 2,2,4-Trimethyl

30、pentane (P8) Ethylcyclohexane (N8) n-Butylbenzene n-Heptane (P7) n-Propylcyclopentane (N8) 1,3-Dimethyl-5-ethylbenzene Methylcyclohexane (N7) 1,2-Diethylbenzene 1-cis-2-Dimethylcyclopentane (N7) C9 Naphthenes 1-Methyl-2-n-propylbenzene 1,1,3-Trimethylcyclopentane (N8) C9 Paraffins 1,2,3-Trimethylben

31、zene 2,2-Dimethylhexane (P8) C10 Naphthenes 1,4-Dimethyl-2-ethylbenzene Ethylcyclopentane (N7) Paraffins 1,3-Dimethyl-4-ethylbenzene 2,5-Dimethylhexane (P8) C11 Naphthenes 1,2-Dimethyl-4-ethylbenzene 2,4-Dimethylhexane C11 Paraffins Indane + 2,2,3-Trimethylpentane (P8) C12 Naphthenes 1,3-Dimethyl-2-

32、ethylbenzene 1-trans-2-cis-4-Trimethylcyclopentane (N8) C12 Paraffins 1,2-Dimethyl-3-ethylbenzene 3,3-Dimethylhexane (P8) 1,2,4,5-Tetramethylbenzene 1-trans-2-cis-3-Trimethylcyclopentane Poly Naphthenes 1,2,3,5-Tetramethylbenzene 2,3,4-Trimethylpentane (P8) 200 P + N 1,2,3,4-Tetramethylbenzene 2,3,3

33、-Trimethylpentane (P8) C11+ Aromatics 2,3-Dimethylhexane (P8)4 of 7 880-08 Precision Precision statements were determined using UOP Method 999 from precision data obtained using an autosampler. Repeatability and Site Precision A nested design was carried out for determining components in two samples

34、 with two analysts in one laboratory. Each analyst carried out tests on two separate days, performing two tests each day. The total number of tests for each component in each sample was 8. The precision data are summarized in Table 2. Two tests performed by the same analyst on the same day should no

35、t differ by more than the repeatable allowable difference with 95% confidence. Two tests performed in one laboratory by different analysts on different days should not differ by more than the site precision allowable difference with 95% confidence. Table 2 Repeatability and Site Precision, Reformer

36、Feed, mass-% Repeatability Site Precision Component Mean Conc. Within- Day esd Allowable Difference Within- Lab esd Allowable Difference Benzene 1.16 0.006 0.02 0.011 0.04 Toluene 2.83 0.005 0.02 0.005 0.02 C11+ Aromatics 0.19 0.004 0.01 0.004 0.01 Cyclopentane 0.03 0.004 0.02 0.005 0.02 2-Methylpen

37、tane 0.69 0.000 0.00 0.010 0.04 n-Heptane 6.75 0.013 0.05 0.016 0.06 1,1,3-Trimethylcyclopentane 0.17 0.004 0.01 0.004 0.01 n-Octane 7.86 0.009 0.03 0.011 0.04 Ethylcyclohexane 1.12 0.010 0.04 0.010 0.04 C9Paraffins 12.56 0.013 0.05 0.014 0.05 C11Naphthenes 1.05 0.004 0.01 0.004 0.01 Repeatability a

38、nd Site Precision, Reformate, mass-% Repeatability Site Precision Component Mean Conc. Within- Day esd Allowable Difference Within- Lab esd Allowable Difference Benzene 11.13 0.052 0.20 0.067 0.26 Toluene 24.23 0.031 0.12 0.044 0.17 C11+ Aromatics 1.63 0.004 0.01 0.007 0.03 Cyclopentane 0.17 0.004 0

39、.01 0.005 0.02 2-Methylpentane 2.75 0.032 0.12 0.033 0.13 n-Heptane 1.21 0.004 0.02 0.005 0.02 C9Paraffins 0.07 0.004 0.01 0.005 0.02 C11Naphthenes 0.02 0.006 0.02 0.008 0.05 The data in Table 2 are a short-term estimate of repeatability. When the test is run routinely, a control standard and chart

40、should be used to develop a better estimate of the long-term repeatability. 5 of 7 880-08 Reproducibility There is insufficient data to calculate reproducibility of the test at this time. Time for Analysis The elapsed time and labor requirement for the calculations described in this method are ident

41、ical. A fully manual calculation could require up to one hour. If programming for automated data transfer and calculation is developed, the calculation time could be reduced to a few minutes. Suggested Suppliers Refer to the individual methods referenced. 6 of 7 880-08 Appendix Calculation of Result

42、s in Liquid Volume Percent Scope The Appendix describes the calculation of the results in liquid volume-% (LV-%) instead of the usual mass-%. It also describes the conversion of existing mass-% results to LV-%. References ASTM Method D4052, “Density and Relative Density of Liquids by Digital Density

43、 Meter,” www.astm.org ASTM Publication DS 4B, “Physical Constants of Hydrocarbon and Non-Hydrocarbon Compounds,” www.astm.org Outline of Method The sample is analyzed by three GC methods as in the body of the method. The LV-% results of ASTM D6839 are used along with the results of the other methods

44、 to calculate results in LV-%. Alternatively, existing mass-% results are converted to LV-% using a formula incorporating published density values for individual components. Apparatus, Reagents, and Materials The apparatus, reagents, and materials required for this analysis are described in the meth

45、od listed in References. A spreadsheet or computer program may be developed to automate the calculations. Procedure Procedure A, Calculation from the Individual GC Analyses Procedure A takes advantage of the fact that the ASTM D6839 analysis is programmed to report both mass- and LV-%. For purposes

46、of this analysis, the densities of all the components of a specific carbon number and hydrocarbon type group (e.g., C8naphthenes) are taken to be the same. 1. Determine the total paraffins, naphthenes and aromatics, by carbon number, of the sample by ASTM Method D6839 run in the PNA mode. The analyz

47、er specified in D6839 reports results in both mass-% and LV-%. Use the LV-% values. Olefins, if present, are hydrogenated and determined as paraffins or naphthenes in this analysis. 2. Determine the paraffin, naphthene, and aromatic distributions as described in Steps 2 and 3 under Procedure in the

48、body of the method. 3. Obtain the density of the sample by ASTM D4052, “Density and Relative Density of Liquids by Digital Density Meter.” 4. Proceed with the calculation under Calculations for Procedure A, below. Procedure B, Calculation from a Completed Mass-% Report Procedure B uses a completed m

49、ass-% report along with known densities of individual components and averaged group densities to obtain an LV-% report. 7 of 7 880-08 1. Obtain the density of each individually reported component from ASTM Publication DS 4B, “Physical Constants of Hydrocarbon and Non-Hydrocarbon Compounds,” or other reference. For grouped components, use an average of the individual listed components. 2. Proceed with the calculation under Calculations for Procedure B, below. Calculations The composition of the sample is calculated and reported to the nearest 0.01 LV-%. Ca