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 2006, 2007 UOP LLC. All rights reserve
3、d. 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 610.83
4、2.9585 PHONE. Chloride in LPG and Gaseous Hydrocarbons by Dry Colorimetry UOP Method 930-07 Scope This method is for determining the sum of organic chloride and hydrogen chloride (HCl) in liquefied petroleum gas (LPG) and refinery gas streams at concentrations ranging from approximately 0.02 to 1000
5、 mass-ppm (mg/kg) for LPG samples or 0.02 to 1000 ng/mL for gas samples. Other halogens present are determined as chloride. References ASTM Practice D 1265, “Sampling Liquefied Petroleum (LP) Gases (Manual Method),” www.astm.org ASTM Method D 1657, “Density or Relative Density of Light Hydrocarbons
6、by Pressure Hydrometer,” www.astm.org ASTM Method D 2421, “Interconversion of Analysis of C5and Lighter Hydrocarbons to Gas-Volume, Liquid-Volume, or Mass Basis,” www.astm.org ASTM Method D 2598, “Calculation of Certain Physical Properties of Liquefied Petroleum (LP) Gases from Compositional Analysi
7、s,” www.astm.org ASTM Practice D 3700, “Obtaining LPG Samples Using a Floating Piston Cylinder,” www.astm.org ASTM Practice D 5287, “Automatic Sampling of Gaseous Fuels,” www.astm.org ASTM Method D 6849, “Storage and Use of Liquefied Petroleum Gases (LPG) in Sample Cylinders for LPG Test Methods,” w
8、ww.astm.org Instrument instruction manual, CI Analytics, PN 2010-Cl-man UOP Method 516, “Sampling of Gasolines, Distillate Fuels and C3- C4Fractions,” www.astm.org UOP Method 539, “Refinery Gas Analysis by Gas Chromatography,” www.astm.org UOP Method 999, “Precision Statements in UOP Methods,” www.a
9、stm.org 2 of 6 930-07 Outline of Method A commercial chloride analyzer utilizing dry colorimetric detection is set up according to the manufacturers specifications. The sample is subjected to pyrolysis during which the organic chlorides are converted to HCl. The pyrolysis product is then passed to a
10、 detector where the HCl produces a color change on sensitized paper. The measured color change is proportional to the quantity of chloride in the sample. Calibration is by blends for LPG samples and permeation tubes for gas samples. Apparatus References to catalog numbers and suppliers are included
11、as a convenience to the method user. Other suppliers may be used. Chloride analyzer, with Dry Colorimetric Detector (DCD), Gas/LPG Introduction Module, and AccuGas Blend Generator (PN 096) , C.I. Analytics, Model 2010L Cylinder, gas sampling, stainless steel, internally coated with Teflon, Siltek, S
12、ulfinert, or other similar inert coating, 500- or 1000-mL, Restek, Cat. No. 24133 or 24144, with valve Cat. No. 24100 and valve with rupture disk Cat. No. 21403, several required Cylinder, LPG sampling, stainless steel, internally coated with Teflon, Siltek, Sulfinert, or other similar inert coating
13、, 500- or 1000-mL, with outage tube, Restek, Cat. No. 24133 or 24144, with valve with outage tube Cat. No. 21402 (specify %-outage, e.g., 30%) and valve with rupture disk Cat. No. 21403, several required Fittings, tube, as needed for connecting gases and sample cylinders to instrument, local supply
14、or Swagelok Gauge, test, pressure, 0 to 2760 kPa gauge (0 to 400 psig), Matheson Tri-Gas, Cat. No. 63-5642 Regulator, air, two-stage, high purity, with stainless steel diaphragm, delivery pressure range 30-700 kPa (4-100 psi), Matheson Tri-Gas, Cat. No. 3122-590 Regulator, nitrogen, two-stage, high
15、purity, with stainless steel diaphragm, delivery pressure range 30-700 kPa (4-100 psi), Matheson Tri-Gas Cat. No. 3122-580 Regulator, nitrogen, two-stage, high purity, with stainless steel diaphragm, delivery pressure range 70-1700 kPa (10-250 psi), Matheson Tri-Gas Cat. No. 3126-580, if needed to p
16、ressurize an LPG sample Regulator, oxygen, two-stage, high purity, with stainless steel diaphragm, delivery pressure range 30-700 kPa (4-100 psi), Matheson Tri-Gas, Cat. No. 3122-540 Tubing, 316 stainless steel, 3.18-mm OD (1/8-inch) x 2.16-mm ID (0.085-inch), Alltech Associates, Cat. No. 30105 Reag
17、ents and Materials References to catalog numbers and suppliers are included as a convenience to the method user. Other suppliers may be used. Air, compressed gas, 99.99% minimum purity Nitrogen, compressed gas, 99.99% minimum purity 3 of 6 930-07 Oxygen, compressed gas, 99.99% minimum purity Calibra
18、tion blends, certified, LPG, 0.5- and 50-mass-ppm (as chloride) 2-chlorobutane in isobutane, Matheson Tri-Gas. Adjust concentrations and components to fit typical samples. Reference blank, gas or LPG, less than 10 ppb chloride Permeation devices, for gas-phase calibration; select one or more from: 1
19、,2-Dichloropropane, C.I. Analytics, Cat. No. PN-per-cl2-003a 1,1,1-Trichloroethane, C.I. Analytics, Cat. No. PN-per-cl2-002a 1,1,2-Trichloroethane, C.I. Analytics, Cat. No. PN-per-cl2-002b 1,1,2-Trichloroethylene, C.I. Analytics, Cat. No. PN-per-cl2-002aa 1,2,3-Trichloropropane, C.I. Analytics, Cat.
20、 No. PN-per-cl2-003c Purifiers, compressed gas, removes hydrocarbons and moisture, Alltech, Cat. No. 81350, three required Procedure The analyst is expected to be familiar with general laboratory practices and with the equipment being used. Preparation of Apparatus Install the analyzer as recommende
21、d by the manufacturer and perform any required performance tests. Figure 1 shows a general diagram of the instrument and Figure 2 shows a diagram of the LPG and gas sampling module. Establish operating parameters as recommended by the manufacturer for the sample types to be analyzed. When not in use
22、, keep the analyzer in Stand-By Mode (reactor at 600C and heater at 200C with nitrogen gas flowing). Without the flow of nitrogen gas, the Teflon fittings at the end of the reactor tube may be damaged. When the analyzer is to be turned off, maintain flow of reactor gas until the reactor temperature
23、is below 400C. Otherwise damage to the Teflon fittings may occur. 4 of 6 930-07 Calibration For gas-phase samples, calibrate using the AccuGas Blend Generator and the permeation devices as described in the instrument manual. For LPG samples, calibrate using the LPG calibration blends as described in
24、 the instrument manual. After all required parameters are entered into the instrument, the calibration factors are calculated by the instrument software. Sample Analysis Collect the LPG or gas samples in the stainless steel cylinders. For LPG samples follow the procedures as described in ASTM Practi
25、ce D 1265, “Sampling Liquefied Petroleum (LP) Gases (Manual Method),” ASTM Practice D 3700, “Obtaining LPG Samples Using a Floating Piston Cylinder,” or UOP Method 516, “Sampling of Gasolines, Distillate Fuels and C3- C4Fractions.” See also ASTM Method D 6849, “Storage and Use of Liquefied Petroleum
26、 Gases (LPG) in Sample Cylinders for LPG Test Methods.” For gas samples follow the procedures as described in ASTM Practice D 5287, “Automatic Sampling of Gaseous Fuels,” or other reliable technique. Analyze the samples according to the instrument manufacturers instructions. Calculations For gas sam
27、ples, the instrument is calibrated in mol-ppm using permeation tubes. All calculations are performed by the instrument software and printed out automatically. Report the results to one significant figure below one ng/mL, and to two significant figures at or above one ng/mL. 5 of 6 930-07 For LPG sam
28、ples, the instrument is calibrated in mass-ppm using calibration blends. If the calibration blend is prepared in the same matrix as the sample matrix, all calculations are performed by the instrument software and printed out automatically. If the blend matrix differs from the sample matrix, calculat
29、e the density of the Calibration Blend using ASTM Method D 2421, “Inter-conversion of Analysis of C5and Lighter Hydrocarbons to Gas-Volume, Liquid-Volume, or Mass Basis,” and ASTM Method D 2598, “Calculation of Certain Physical Properties of Liquefied Petroleum (LP) Gases from Compositional Analysis
30、.” If the matrix of the sample is known, calculate the density of the sample in the same manner. If the matrix of the sample is unknown, analyze the sample by UOP Method 539, “Refinery Gas Analysis by Gas Chromatography,” and then calculate the density of the sample as above. Alternatively, the dens
31、ity of the sample may be determined directly using ASTM Method D 1657, “Density or Relative Density of Light Hydrocarbons by Pressure Hydrometer.” Using the densities of the Calibration Blend and the sample, calculate the density correction factor using Equation 1 and enter it into the instruments c
32、omputer. Results will print automatically. Report the results to one significant figure below one mass-ppm, and to two significant figures at or above one mass-ppm. Density correction factor = SD(1) where: D = liquid density of the Calibration Blend, g/mL S = liquid density of the sample, g/mL Notes
33、 1. In refinery applications it may be advantageous to analyze for chloride using an online analyzer. Similar online analyzers using dry colorimetric detection are available from the suggested supplier and may be substituted. 2. Some loss of HCl can occur in the equipment particularly in the presenc
34、e of water. When the most accurate determination of the HCl is required, a known quantity of the sample is sparged through a known quantity of water to dissolve the HCl quantitatively. The water is injected directly into the instrument for chloride determination. Precision Analyses of the samples us
35、ed for the precision statement were performed by the suggested vendor and another company. The testing protocols of UOP Method 999, concerning the number of analysts and days were not used, but the calculation protocols for UOP Method 999 were used. Repeatability Analysts performed replicate analyse
36、s as shown in the Table. The precision data are summarized in the Table. Two tests performed by the same analyst on the same day should not differ by more than the repeatability allowable difference with 95% confidence. The data in the Table is a short-term estimate of repeatability. When the test i
37、s run routinely, a control standard and chart should be used to develop a better estimate of the long-term repeatability. Reproducibility There is insufficient data to calculate the reproducibility of the test at this time. 6 of 6 930-07 Table Repeatability, Chloride, ng/mL (gas) Number of Repeatabi
38、lity Sample Instrument Number Number of Days Replicates per Day Mean Chloride Concentration Within- Day esd Allowable Difference A 4 1 30 0.13 0.006 0.01 B 1 1 10 0.78 0.037 0.08 C 4 1 51 0.88 0.025 0.05 D 1 1 10 0.90 0.050 0.11 E 2 1 20 3.24 0.454 0.95 F 4 1 66 3.73 0.099 0.20 G 1 1 10 4.02 0.125 0
39、.28 H 3 3 5 4.13 0.105 0.29 I 1 2 10 7.44 0.139 0.31 J 2 1 10 14.71 0.183 0.41 K 1 1 10 17.16 0.254 0.58 L 2 1 10 22.56 0.231 0.52 M 2 1 10 45.07 0.555 1.26 Time for Analysis The elapsed time and labor requirement for one analysis of an LPG or gaseous sample, including calibration, are identical, 1
40、hour. Each succeeding analysis requires 0.3 hour. An additional 0.5 hour is required for sampling. Suggested Suppliers Alltech Associates, Inc., 2051 Waukegan Rd., Deerfield, IL 60015 (847-948-8600) C.I. Analytics, 2085 Industrial Blvd., Chambly, Quebec, Canada J3L 4C5 (450-658-4965) Matheson Tri-Gas, 166 Keystone Drive, Montgomeryville, PA 18936 (215-648-4000) Restek, 110 Benner Circle, Bellefonte, PA 16823 (814-353-1300) Swagelok Company, 29500 Solon Rd., Solon, OH 44139 (440-248-4600)
