Determination of chlorine/chlorides using MWD- XRF

Transcription

1 Determination of chlorine/chlorides using MWD- XRF Ranzy Morgan Director, Sales & Marketing Petroleum Analyzers Scott Blumenshine Senior Chemist Technical Support Flint Hills Resources

2 XOS, Inc. East Greenbush, Upstate NY Sales office in Houston Texas Founded in Employees Market Focus: Application specific X-Ray Analyzers X-ray Optics and Beam Systems. X-Ray Analysis Elemental Analysis Crystalline Structure Analysis

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4 2005 R&D 100 Awards Related to XOS Invention of the Year of Eastern New York 2006 Beckman Founder Award of International Instrumentation, Systems, and Automation Society

5 Monochromatic WD XRF ASTM D 7039 Counts Counts E E S E S E Counts Counts DCC DCC

6 Monochromatic WD XRF Used in BT and OL DCC Optic1 DCC Optic2 Very high signal-tobackground. LOD 0.4 ppm wt. Lab Sulfur LOD 0.6 ppm wt. OL Sulfur LOD ppm wt. Chlorine Simplified configuration - No moving parts in basic system No special gases needed X-ray Beam Sample X-ray Counter Low Power Air-Cooled Tube Enables On-Line and Bench- Top Systems No combustion required Sulfur reading in ppm wt. No density effects Insensitive to changes in Matrix. Gasoline and Diesel same cal curve

7 ASTM D 7039 Statement

8 Bench-top Design for Terminals and Laboratories Compact Size Minimum Sample Preparation Plug and Play, No Gas Utilities Wide Dynamic Range for Linearity, 0 to 3000ppm X-tended Range up to 10% available Hundreds in operation world wide

9 Bench-top Design for Terminals and Laboratories Compact Size Minimum Sample Preparation Plug and Play, No Gas Utilities Wide Dynamic Range for Linearity, 0 to 3000ppm X-tended Range up to 5% available Suitable for hydrocarbon and aqueous samples

10 Sample Cup Preparation

11 Clora Analyzer s LOD and LOQ LOD (ppm) LOQ (ppm) Matrix 300s 600s 300s 600s Water Crude Xylene or Iso-Octane

12 Weighted Linear Fit Parameters H 2 O Crude oil Xylene IsoOctane Slope count/sec/ppm 0.333± ± ± ±0.005 Intercept count/sec 0.54± ± ± ±0.1 correlation coefficient

13 Calibration Curves Cl COUNTS/300s Xylene Iso Octane Crude oil H2O Cl CONCENTRATION (PPM)

14 Accuracy Cl Standards Reference Value (ppm) Measured Value (ppm) Bias (ppm) Xylene, gravimetric Isooctane, gravimetric Water, gravimetric Lubricant oil, NIST SRM 234±

15 Chloride Repeatability Matrix Crude oil Iso Octane Norminal Cl level (ppm) < Measurement time (s) Measured Cl (ppm) Mean (ppm) Stand. Dev. σ (ppm)

16 Chloride Repeatability Crude oil Cl concentration in crude oil (ppm) Crude 1 Crude 2 Crude Average Standard Dev

17 Stdev. (ppm) average (ppm) ppm 5ppm 1ppm 0.5 ppm 300s measurement 600s measurement Sample # Cl concentration in Xylene

18 Screening Crude Oil for Organic Chloride Techniques for analyzing crude oil for organic chloride are time consuming and labor intensive. Microcoulometry Electron Capture Detector Crude Oil can not be analyzed directly by these methods. Sample prep is key to removing interferences in any method. Inorganic chloride is one of the main interferences in determining organic chloride.

19 Evaluation of Clora Analyzer for Organic Chloride 6 different types of crude oil were selected The relative amount of salt was determined for each sample and compared to ASTM D6470 results. Whole crude salt content could be determined but we concentrated on organic chloride determination. Sample # Crude Type Wyoming Domestic South American Crude North Sea Crude Heavy Canadian Louisiana Domestic Louisiana Domestic Salt Content

20 Comparison of Salt Content Salt Content Salt Clora, Cl 0 Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6

21 Procedure to Remove Inorganic Chloride The sample with the highest salt content was used to determine a suitable technique for salt removal Several methods were tried: Spinning the whole crude Spinning the whole crude with water Filtering Extraction / Filtering A more labor intensive method would be the extraction from ASTM D6470

22 Results of Different Extraction Methods Technique Neat Crude Spun Crude Spun w/ Water Filter 1 micron Filter 0.2 micron 1.0 Filter / Extract 0.2 Filter / Extract Clora Result, ppm Cl

23 Organic Chloride Determination The easiest, fastest and most effective extraction method was chosen. The low salt North Sea crude was chosen. Organic Chloride was spiked into the crude at different levels. The crude was extracted and filtered and then the organic chloride was determined by the Clora analyzer.

24 Results of Organic Chloride Determinations Actual Measured Corrected STD STD STD STD Measured, ppm Organic Chloride y = x R 2 = Actual, ppm

25 The XOS Family

26 Summary The XOS MWD XRF technique is a viable alternative to UV Fluorescence for low level sulfur measurements Incredibly wide dynamic range for sulfur measurement without dilution 0.4 ppm/wt 10%/wt This technique can be used for laboratory and on line applications The XOS Sindie is widely accepted worldwide A compact bench-top chloride analyzer was developed, that is has the same user friendly approach as the SINDIE Sulfur Bench top system. The Minimum LOD has been determined to be ppm (150 ppb/wt) Can be used for quick screening of organic chlorides It is demonstrated that this analyzer can be used for direct measurements of low level chloride in crude oil, aromatics, distillates, water and other liquid samples with minimal sample preparation

27 Thank you very much! Contact Information Ranzy Morgan