1  

SLOVAK UNIVERSITY OF TECHNOLOGY IN BRATISLAVA

FACULTY OF CHEMICAL AND FOOD TECHNOLOGY

DEPARTMENT OF CHEMICAL AND BIOCHEMICAL ENGINEERING

Analysis of crude oil products

REPORT ON TRAINING VISiT

In the frame work of the project

No.SAMRS.2011/10/01

“Development Human Resource Capacity of Engineering Education in Afghanistan”

Fund by

 

 

 

 

 

 

Bratislava 2011                                                                                                  prof.  Abdul Ghafoor  Noorzad‐ 

 

 

2  

 

SLOVAK UNIVERSITY OF TECHNOLOGY IN BRATISLAVA

FACULTY OF CHEMICAL AND FOOD TECHNOLOGY

DEPARTMENT OF CHEMICAL AND BIOCHEMICAL ENGINEERING

REPORT

ON MY ACADEMIC AND SIENTIFIC ACTIVITIES IN TRAINING COURSE AT THE SLOVAK UNIVERSITY OF TECHNOLOGY IN BRATISLAVA

PREPARED BY: Abdul Ghafoor Noorzad, M.S Professor of Chemical Technology Faculty of Kabul Polytechnic University in

Afghanistan

GUIDENCE BY: DOC. ING. Pavol Daučík, PhD

Professor of the department of oil technology and petrochemistry, Faculty of Chemical and Food Technology of Slovak University of Technology in Bratislava

Ing. Michal Hornaček, PhD.

Mgr. Marcela Hadvinová

 

3  

Preface

I am Abdul Ghafoor noorzad professor in general chemistry Department of Chemical Technology Faculty of Kabul Polytechnic University. I attended a two months and fifteen days training visit stay from 1.10.2011 to 15.12.2011 in the Slovak University of Technology in Bratislava, Slovakia. Main purpose of this training stay was familiarity with new pedagogic methods, and collecting new scientific articles and books on chemical technology topics. Activities I've done during this training stay are listed below:

- Visiting and being familiar with chemical engineering laboratories.

- Visiting and being familiar with organic chemistry & organic substances technology laboratories.

-Aanalysis of crude oil products.

- Participating in some lectures, seminars, and laboratorial works of bachelor, master & PHD classes of chemical engineering department.

- Visiting faculty bookstore and library.

- Collecting scientific articles and books (published from 2000 to 2011) in related tire recycling topic.

I want to appreciate and thank, Prof. Dr. Juma Haydary, Professor Dr.Daučík and other teachers of Chemical & Food Technology Faculty for their excellent cooperation and collaboration.

Some parts of collected materials are inserted in continuation of this report.

With Respect

Abdul Gafoor Noozad M.S

 

4  

Contents

Title Page

Introduction 9

Section1: Determination of flash point. 10 Auto Pensky-Martens Closed Cup Flash Point Tester

1.1- Automatic Abel Flash Point Tester 10

1.2- Auto Pensky-Martens Closed Cup Flash Point Tester. 12

1.3- Automatic Abel Flash Point Tester 13

Section 2: Automatic Cleveland Open Cup Flash Point 13 2.1-utomaticTagClosedCupFlashPointTester 14 2.2-Pensky-Martens Closed Cup Flash Tester 14 2.3-ShippingInformationTestmethod 15

2.4-Tag Closed Cup Flash Tester 15 Section 3 :Test Method:For flash and fire points of all petroleum 17 products, except fuel oils and those having an open cup flash below9°C75°F).Cleveland Open-Cup Flash Tester

3.1-FLASH AND FIRE POINT BY CLEVELAND OPEN CUP 17

 

5  

TESTER ASTM D92 IP 36 DIN 51376 ISO 2592 3.2-MAIN UNIT 17

Section4:StandardTestMethodforColdFilterPointof 20

Diesel and Heating Fuels 4.1- Scope 20 4.2-Terminology 20

4.3- Summary of Test Method 20 4.4-Significance and Use 21 4.5-Apparatus 21

4.6- Sampling 25

4.7- Reagents and Materials 26

4.8‐ Preparation of Test Specimen                                                        26 

4.9-Preparation of Apparatus 26

4.10- Procedure 27

4.11- Report 30

4.12- Precision and Bias 30 4.13-keywords 30

 

6  

Section5: standard Test Methods forFlash Point by Pensky-Martens Closed Cup Tester1(D93-02a) 32

5.1-Scope 32

5.2-Terminology 33

5.3-Summary of Test Method 34 5.4- Significance and Use 34 5.5 Apparatus 35 5.6-Reagents and Materials 35 5.7- Sampling 36 5.8 Preparation of Apparatus 37 5.9-VerificationofApparatus 38 5.10-Procedure 38

5.11- Procedure 41

5.12-Calculation 42 5.13- Report 42 5.14- Precision and Bias (Procedure A) 42 5.15- Precision and Bias (Procedure B) 43 5.16- Keywords 44 5.17-APPENDIXES 51

 

7  

Section6 : Standard Test Method for Water in Petroleum 53 Products and Bituminous Materials by Distillation 6.1- Scope 53 6.2- Terminology 53 6.3 Summary of Test Method 54 6.4-Significance and Use 54 6.5 - Solvent-Carrier Liquid 54 6.6- Apparatus 55 6.7-Sampling 58 6.8-Verification 58 6.9- Procedure 59 6.10-Calculation 62 6.11-Report 63 6.12- Precision and Bias 63 6.13- Keywords 63 Sectio.7-Distillationof Petroleum Products at Reduced Pressure 64 7.1-Scope 64 7.2- Summary of Test Method 65 7.3- Summary of Test Method 65

 

8  

7.4-Apparatus 66 7.5-Reagents and Materials 80 7.6-Sample and Sampling Requirements 81 7.7-Preparation,Calibration, and Quantification of Apparatus 81 7.8-Procedure 82 7.9-Calculations and Repotr 84 7.10- Precision and Bias 84 7.11-Keywords 86 7.12-APPENDIX 99 7.13-SUMMARY OF CHANGES 100 Reference 101

 

9  

Introduction

This international standard specifies a procedure for the determination of the kinematic viscosity,of liquid petroleum products.both transparent and opaque by measuring the time for a volume of liqvid to flow under gravity through a clibrated glass capillary viscometer.also method of water in petroleum products and bituminous materials by distillation covers the determination of water in crude petroleum,tars,and products derived from these materials.also softening point of asphalt and tar in ethylene glycol method is covers the determination of the softening point of asphalt and tar ,including tar pitches in the range of 30 to 175 0C using the ring-and-ball apparatus in an ethylene glycol bath. Also cold filter plogging point of destellate fuels method describes a procedure for the determination of the low temperature operabilitay of distillate fules including those containing a flow improving a dditive.also determination of flash point-pensky-martens closed cup method is describes tow procedures \A and B using the pensky-martens closed cup tester for determination the flash point of combustible liquids/liquids with suspended solids/liquids that and to form a surface film under the test conditions and other liquids.it is applicable for liquids with a flash point above 40 0c. also method of crude petroleum and liquid petroleum products laboratory determination of density-hydrometer method is international standard specifies a method for the laboratory determination/using a glass hydrometer/of the density at 150c of crude petroleum/liquid petroleum product /mixtures of petroleum and non-petroleum products normally handled as liquids and having a reid vapour pressure(RVP) of 100 KPa or less.  

The  method  of    determination  of  distillation  characteristics    at  atmospheric pressure   of   petroleum   products   specifies   a  laboratory   method   of    light   and middle  distillates  derived  from  petroleum  with  initial  boiling  points  above  0  oc   and   end   points   below   approximately   400   0c   utilizing   either manual   or  automated   equipment.and   also    standard     method   of    test    for   ASH    from  petroleum   products   describes   procedure    for   determination    the   ASH    from  distillate   and   residual   fuel   oils/ crude   oils    lubricating   oils   waxes/ and other 

 

10  

petroleum  product   in  which  any ASH‐forming  materials  present  are  normally  considered  to  be  Undesirable impurities  or  contaminants  [Note  i]     

  Section  1:  Determination  of flash  point.                                                               Auto Pensky-Martens Closed Cup Flash Point Tester • Conforms to ASTM D93 and related specifications • Dual flash point detection system (thermal and ionization) for easurement of samples containing water and/or silicone • Gas or electric ignition • Flash point operation range between 0 and 400°C • Simple automation routine for easy operation related specifications Dual flash point detection system (thermal and ization)asurement of samples containing water and/or silicone eiewing screen for observing test status at a distance from the unit • Automatic barometric correction The automated Pensky-Martens flash point tester accurately determines the lowest flash point temperature of fuels, lubricating oils, and homogenous liquids (ASTM D93 A), or liquids containing suspended solids as well as liquids that tend to form a surface film during testing (ASTM D93 B). Flash oint tests are simply conducted by mounting the flash cup filled with sample .into the test position and selecting a pre- or user-programmed test method. A quick search method allows for determination of flash points for unknown samples and a method for asphalts is also included. The automation routines provide accurate test results, even with users inexperienced in flash point test methods. The flash point test result is automatically corrected to standard pressure (101.3 kPa). The unit is equipped with a differential Pt-100 RTD probe designed to duplicate the response time of a mercury-in-glass thermometer as per ASTM D93-02a and E1-03a. The system features multiple sensors for continually monitoring of instrument function and displaying an error message if a problem is detected. The performance of the electrical ignitor is continuously checked, and the user is notified upon the need of replacement due to either damage or the end of its useful life. The system is easily interfaced with an external PC for operation and method updates. When performing a test, the system will display the stirring speed, temperature curve (also printed out), and current test status. The system alerts the user if the first application of the ignitor results in a flash or if no flash point is detected at the end of the test program. If a flash is not detected 30°C above the expected flash point or at 400°C, then the test is automatically aborted for safety. An easy connection to the air ventilation system or external water connection provides a quick cool down between test runs for operational efficiency. Automated Flash Point Testers 1.1-Automatic Abel Flash Point Teste

 

11  

• Conforms to IP 170 and related specifications • Simple automation routine for easy operation The automated Abel flash point tester is used primarily to test flammable and combustible materials for shipping and safety regulations. The flash tester provides an increased temperature range of operation as compared with other testers, allowing reater flexibility in testing samples according to the Abel test method. The unit provides a test range to 110°C and can be extended to –30°C by any appropriate external hiller. The flash point tests are simply conducted by mounting the flash cup filled with sample into the test position and selecting a pre- or user-programmed test method. Automation routines provide accurate test results. A quick search method is available to determine the flash point of unknown samples. The dual detection system (thermal and ionization) allows for testing all types of products. Ignition by gas flame or electrical ignitor is included, along with safety cut-off devices. Test results are matically corrected to standard pressure (101.3 kPa). The system is equipped with a differential Pt-100 RTD probe designed to duplicate the response time of a mercury-in-glass thermometer and with multiple sensors that continually monitor instrument function, displaying an error message if a problem is detected. Supervision software is included. Temperature range of Flash Tester can be extended. Please contact Koehler Customer Service for additional information.

FIG1.Automated Pensky-Martens Flash Point Tester

 

12  

FIG2.pensky-marten flash point tag 1.2-Auto Pensky-Martens Closed Cup Flash Point Tester. • Conforms to ASTM D93 and related specifications • Dual flash point detection system (thermal and ionization) for measurement of samples containing water and/or silicone. • Gas or electric ignition. • Flash point operation range between 0 and 400°C. • Simple automation routine for easy operation. • Large viewing screen for observing test status at a distance from the unit. • Automatic barometric correction. The automated Pensky-Martens flash point tester accurately determines the lowest flash point temperature of fuels, lubricating oils, and homogenous liquids (ASTM D93 A), or liquids containing suspended solids as well as liquids that tend to form a surface

 

13  

film during testing (ASTM D93 B). Flash point tests are simply conducted by mounting the flash cup filled with sample into the test position and selecting a pre- or user-programmed test method. A quick search method allows for determination of flash points for unknown samples and a method for asphalts is also included. The automation routines provide accurate test results, even with users inexperienced in flash point test methods. The flash point test result is automatically corrected to standard pressure (101.3 kPa). The unit is equipped with a differential Pt-100 RTD probe designed to duplicate the response time of a mercury-in-glass thermometer as per ASTM D93-02a and E1-03a. The system features multiple sensors for continually monitoring of instrument function and displaying an error message if a problem is detected. The performance of the electrical ignitor is continuously checked, and the user is notified upon the need of replacement due to either damage or the end of its useful life. The system is easily interfaced with an external PC for operation and method updates. When performing a test, the system will display the stirring speed, temperature curve (also printed out), and current test status. The system alerts the user if the first application of the ignitor results in a flash or if no flash point is detected at the end of the test program. If a flash is not detected 30°C above the expected flash point or at 400°C, then the test is automatically aborted for safety. An easy connection to the air ventilation system or external water connection provides a quick cool down between test runs for operational efficiency. 1.3-Automatic Abel Flash Point Tester • Conforms to IP 170 and related specifications • Simple automation routine for easy operation The automated Abel flash point tester is used primarily to test flammable and combustible materials for shipping and safety regulations. The flash tester provides an increased temperature range of operation as compared with other testers, allowing greater flexibility in testing samples according to the Abel test method. The unit provides a test range to 110°C and can be extended to –30°C by any appropriate external chiller. The flash point tests are simply conducted by mounting the flash cup filled with sample into the test position and selecting a pre- or user-programmed test method. Automation routines provide accurate test results. A quick search method is available to determine the flash point of unknown samples. The dual detection system (thermal and ionization) allows for testing all types of products. Ignition by gas flame or electrical ignitor is included, along with safety cut-off devices. Test results are automatically corrected to standard pressure (101.3 kPa). The system is equipped with a differential Pt-100 RTD probe designed to duplicate the response time of a mercury-in-glass thermometer and with multiple sensors that continually monitor instrument function Customer Service for additional information, Temperature range of Flash Tester can be extended. Please contact Koehler Customer Service for additional information Section 2: Automatic Cleveland Open Cup Flash Point . forms to ASTM D92 and related specifications

 

14  

• Simple automation routine for easy operation • Flash point operation between ambient and 400°C • Gas or electric ignition The automated Cleveland Open Cup flash point tester accurately determines flash and fire point temperatures of viscous petroleum products including oils and bitumens over an extended temperature range. When examining highly viscous specimens, a preheating time and temperature are set in order to liquefy the sample for testing. The surface skin from bituminous samples can be removed with a skimmer. The flash/fire point tests are simply conducted by mounting the flash cup filled with sample into the test position and selecting. a pre-programmed test method or the search mode to determine an approximate flash point. The test results are automatically corrected to standard pressure (101.3 kPa). Equipped with a differential Pt-100 RTD probe,the system is designed to duplicate the response time of a mercury-in-glass lly monitor instrument function,displaying an error message if a problem is detected. The performance of the ionization sensor which detects the flash and fire points is continuously monitored, and the user is notified upon the need of replacement. If a flash is not detected 20°C above the expected flash point or at 420°C, then the test is automatically aborted for safety. The system is easily interfaced with an external PC for operation and method updates. When performing a test, the system will display the stirring speed, temperature curve (also printed out),and current test status. The system alerts the user if the first application of the ignitor results in a flash or if no flash point is detected at the end of the test program. If a flash is not detected 30°C above the expected flash point or at 400°C, then the test is automatically aborted for safety. 2.1-utomatic Tag Closed Cup Flash Point Tester • Conforms to ASTM D56 and related specifications • Simple automation routine for easy operation The automated Tag Closed Cup flash point tester ensures the accuracy and precision required according to the ASTM D56 and related test methods.The test sample is heated at a prescribed rate of temperature increase throughout the standard temperature test range to 100°C. The flash point tests are simply conducted by mounting the flash cup filled with sample into the test position and selecting a pre-programmed test method or the search mode to determine an approximate flash point. The automation routines provide accurate test results. Ignition by gas flame or electrical ignitor is included, along with safety cut-off devices. The easurement range can be extended to –30°C by any appropriate external chiller. Supervision software is included. Customer Service for additional information emperature range of Flash Tester can be extended. Please contact Koehler Test Method For flash point determinations of fuels, lubricating oils, liquids containing suspended solids and liquids that tend to form a surface film during testing. 2.2-Pensky-Martens Closed Cup Flash Tester • Conforms to ASTM D93 and related specifications

 

15  

• Choice of electric or gas heating Determines flash points of a wide range of products by a closed cu . method with two option speed stirring of the sample. Extensively used in shipping and safety regulations for detection of contamination by volatile and flammable materials in fuel oils and lubricating oils, and for characterization of hazardous waste samples. Smooth operating cover mechanism slides shutter open and applies test flame at the turn of a knob. Cover fits over brass test cup and includes pilot flame,test flame reference bead, built-in stirrer and plated brass thermometer ferrule. Electrically heated model is equipped with a 750W nickel-chromium heater with stepless variable control for accurate, repeatable temperature rate of rise settings perfications. Heater unit is enclosed in a stainless steel housing with cooling vents. Includes line cord receptacle and switch for accessory slow speed stirrer. Gas heated model has a built-in nickel plated brass natural gas burner, or can be pplied with an artificial gas burner or liquid propane burner (specify when ordering). Both odels are mounted on a sturdy cast iron base. 2.3-Shipping Information Test method.

Shipping Weight: 30 lbs (13.6kg)imensions: 3.1 Cu. ft.

FIG1. Closed cup flash tester For flash point determinations of liquids with a viscosity of below 5.5 centistokes (cSt) at 104°F (40°C) or below 9.5cSt at 77°F (25°C), and a flash point below 200°F (93°C) except cut-back asphalts, those liquids which tend to form a surface film under test conditions and materials which contain suspended solids. 4-Tag Closed Cup Flash Tester • Conforms to ASTM D56 and related specifications • Gas or electrical heating Determines flash points of liquid products by the Tag Closed Cup method. Features stepless variable heat control with reference dial for accurate repeat setting of temperature rate of rise per specifications. Also available with gas burner instead of electric heater. Precision machined cover mechanism simultaneously opens slide

 

16  

shutter and applies test flame to sample at the turn of a knob. Includes liquid bath with constant level overflow, brass test cup, plated brass thermometer ferrules and test flame reference bead. Bath and cover mechanism are constructed of plated brass. Heater is enclosed in a cast aluminum base assembly. FIG2.tag closed cup flash tester

 

17  

Section 3 :Test Method: For flash and fire points of all petroleum products, except fuel oils and those having an open cup flash below 79°C (175°F). Cleveland Open-Cup Flash Tester • Conforms to ASTM D92 and related specifications • For flash points above 79°C (175°F) Determines flash and fire points by the Cleveland Open-Cup method. Consists of test flame applicator, brass test cup, thermometer support,heating plate and electric heater. Applicator is precisely aligned per specifications and pivots for test flame application at specified temperature intervals. Hinged thermometer support raises to facilitate placement and removal of test cup. Adjust flame size using built-in needle valve and comparison bead. Equipped with a 1000W nickel-chromium heater with stepless variable heat control for accurate repeat setting of temperature rate of rise per specifications.Heater unit is enclosed in a stainless steel housing with cooling vents. Test flame applicator and thermometer support are constructed of 3.1-FLASH AND FIRE POINT BY CLEVELAND OPEN CUP TESTER ASTM D92 IP 36 DIN 51376 ISO 2592 SCOPE Flash and Fire Point on petroleum products, gas oils, fuel oils, lubrificants. Suitable for flash and fire point detection on different substances and waste materials, having a flash point over 79°C. 3.2-MAIN UNIT. 880/AUT AUTOMATIC CLEVELAND Measuring Cleveland PrincipleThe sample is warmed up according the methods. When the sample reaches the selected test temperature, the flame is passed automatically above the sample. When the flash point is reached, the detection is done by an ionisation detector. For fire point detection, the sample continues to be heated until permanent flame is detected by the second PT100 probe, then the auto extinguisher will be placed on the top of the test cup.Measuring Cleveland Devices - Analyser equipped with automatic flame exposure device - Measurement of the Flash Point detected by an ionisation detector - Analyser equipped with 2 electrical ignitors and a pilot flame - Measurement of the Fire Point detected by PT100 detector Measuring Temperature Probe - Platinum resistance PT100 Class A Measuring Parameters - Temperatures: in °C

 

18  

- Measuring range: +79°C … +400°C - Resolution: 0.06 °C - Accuracy: ± 0.1 °C - Repeatability / Reproducibility: as per standards methods or better Software Features The LabLink software is Windows ® Based (Windows ® 2000, XP, Vista) and is able to manage up to 10 analytical heads simultaneously - User friendly interface - All analytical parameters recoded - Customisable analysis parameters and methods - Customizable results report - Printable graphs and results - Self-identification of the typology of the analysers connected The software includes:Analysis Menu - Standard method as per ASTM / IP / ISO / EN / DIN… norms of reference - - Audible alarm and displayed messages (at the end of the analysis and in Unknow sample case of errors

FIG2.cleveland open –cup flash tester c 880/AUT AUTOMATIC CLEVELAND measuring Cleveland Principle The sample is warmed up according the methods. When the sample reaches the selected test temperature, the flame is passed automatically above the sample. When the flash point is reached, the detection is done by an ionisation detector. For fire point detection, the sample continues to be heated until permanent flame is detected by the second PT100 probe, then the auto extinguisher will be placed on the top of the test cup.Measuring Cleveland Devices - Analyser equipped with automatic flame exposure device - Measurement of the Flash Point detected by an ionisation detector

 

19  

- Analyser equipped with 2 electrical ignitors and a pilot flame - Measurement of the Fire Point detected by PT100 detector Measuring Temperature Probe - Platinum resistance PT100 Class A Measuring Parameters - Temperatures: in °C - Measuring range: +79°C … +400°C - Resolution: 0.06 °C - Accuracy: ± 0.1 °C - Repeatability / Reproducibility: as per standards methods or better software Features The LabLink software is Windows ® Based (Windows ® 2000, XP, Vista) and is able to manage up to 10 analytical heads simultane-ously. - User friendly interface. - All analytical parameters recoded. - Customisable analysis parameters and methods. - Customizable results report. - Printable graphs and results. - Self-identification of the typology of the analysers connected The software .includes: Analysis Menu. - Standard method as per ASTM / IP / ISO / EN / DIN… norms of reference.

FIG3. Cleveland open flash and fir cup tag.

 

20  

Section 4 : Standard Test Method for Cold Filter Plugging Point of Diesel and Heating Fuels This standard is issued under the fixed designation D 6371; the number mediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A superscript epsilon (e) indicates an editorial change since the last revision or reapproval. 4.1- Scope This test method covers the determination of the cold flter plugging point (CFPP) temperature of diesel and domestic heating fuels using either manual or automated apparatus. NOTE—This test method is technically equivalent to test methods IP309 and EN 116. The manual apparatus and automated apparatus are both suitable for referee purposes. This test method is applicable to distillate fuels, including those containing a flow-improving or other additive, intended for use in diesel engines and domestic heating installations. This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. For specific hazardstatements, see Section 4.2-Terminology. Definitions of Terms Specific to This Standard: cold filter plugging point, n—highest temperature,expressed in multiples of 1°C, at which a given volume of fuel fails to pass through a standardized filtration device in a specified time when cooled under the conditions prescribed in this test method. certified reference material, n—a stable petroleum product with a method-specific nominal CFPP value established by a method-specific inter laboratory study following RR:D02-10079 guidelines or ISO Guides 34 and 35.7 4.3- Summary of Test Method. A specimen of the sample is cooled under specified conditions and, at intervals of 1°C, is drawn into a pipet under a controlled vacuum through a standardized wire mesh filter.The procedure is repeated, as the specimen continues to cool,for each 1°C below the first test temperature. Testing is continued until the amount of

 

21  

wax crystals that have separated out of solution is sufficient to stop or slow down the flow so that the time taken to fill the pipet exceeds 60 s or the fuel fails to return completely to the test jar before the fuel has cooled bya further 1°C. This test method is under the jur is diction of ASTM Committee D-2 on Petroleum Products and Lubricants and is the direct responsibility of mittee D02.07.0D on Wax-Related Viscometric Properties of Fuels and Oils.urrent dition approved Feb. 10, 1999. Published April 1999. 2 Annual Book of ASTM Standards, Vol 05.01. 3 Annual Book of ASTM Standards, Vol 05.02. 4 Annual Book of ASTM Standards, Vol 05.03. 5 Annual Book of ASTM Standards, Vol 14.03. 6 Available from Institute of Petroleum, 61 New Cavendish St., London, W. I., England. 7 Available from American National Standards Institute, 11 W. 42nd St., New York, 10036. 8 Available from European Committee for Standardization, Central Secretariat, Rue Bréderode 2, B-1000, Brussels, Belgium. 9 Available from ASTM Headquarters.2 The indicated temperature at which the last filtration was commenced is recorded as the CFPP. 4.4-Significance and Use The CFPP of a fuel is suitable for estimating the lowesttmperature at which a fuel will give trouble-free flow in certain fuel systems. In the case of diesel fuel used in European light dutytrucks, the results are usually close to the temperature of failure in service except when the fuel system contains, for example,a paper filter installed in a location exposed to the weather or if the filter plugging temperature is more than 12°C below the cloud point value in accordance with Test Method D 2500,D 5771, D 5772, or D 5773. Domestic heating installations are usually less critical and often operate satisfactorily at temperatures somewhat lower than those indicated by the test results. The difference in results obtained from the sample as received and after heat treatment at 45°C for 30 min can beused to investigate complaints of unsatisfactory performanceunder low temperature conditions. 4.5-Apparatus Manual Apparatus: The apparatus, as detailed in 6.1.2-6.1.13, shall be arranged as shown in Fig. 1. Test Jar, cylindrical, of clear glass, flat bottomed, with an internal diameter of 31.5 6 0.5 mm, a wall thickness of 1.25,60.25 mm and a height of 120 6 5 mm. The jar shall have a permanent mark at the 45 6 1 mL level.

 

22  

NOTE .Test jars of the required dimensions may be obtained by selection from jars conforming to Test Method D 2500, which specifies a wider diameter lerance. Jacket, brass, watertight, cylindrical, flat bottomed, to be used as an air bath. It shall have an inside diameter of 45 ,60.25 mm, outside diameter of 48 6 0.25 mm, and a height of 115 6 3 mm (see Fig. 2). Insulating Ring, made from oil-resistant plastics or other suitable material, to be placed in the bottom of the jacket) to provide insulation for the bottom of the test jar.It shall fit closely inside the jacket and have a thickness of 6 +,0.3 - 0.0 mm. Spacers (two), approximately 5-mm thick, made of oil-resistant plastics or other suitable material, to be placed as shown in Fig. 1 around the test jar to providensulation for the test jar from the sides of the jacket. Thespacers shall fit closely to the test jar and closely inside the jacket. The use of incomplete ings, each with a 2-mm circumferential gap, will accommodate variations in test jar diameter. The spacers and insulating ring may be made as a single part as shown in Fig. 2. Supporting Ring, of oil resistant plastics or other suitable non-metallic, non-absorbent, oil-resistant material used to suspend the jacket in a stable and upright position in the cooling bath and to provide a concentric location for the stopper A design is for guidance, but this design may be modified to suit the ooling bath. Stopper, of oil-resistant plastics or other suitable non-metallic, non-absorbent, oil-resistant material, to fit the test jar and the support ring It shall have three holes to accommodate the pipet and the thermometer and to allow venting of the system. If necessary, when using the high-range thermometer FIG. 1 Arrangement of Manual CFPP Apparatu s NOTE.All dimensions are in millimetres, and the comma (,) is used as the imal point.FIG. 2 Watertight Brass Jacket the upper part of the stopper shall have an indentation to permit the thermometer to be read down to a temperature of -30�‹C. A pointer shall be fitted to the upper surface of the stopper to facilitate location of the thermometer in relation to the bottom of the test jar. A spring wire clip shall be used to retain the thermometer in the correct position. Pipet with Filter Unit: A Pipet,, of clear glass with a calibration mark corresponding to a ontained volume of 20 6 0.2 mL at a point 149 6 0.5 mm from the bottom of the pipet shall be connected to the filter unit A Filter Unit containing the followingelements: (a) A Brass Body, with a threaded cavity that houses the wiremesh holder. The cavity shall be fitted with an O-ring of oil-resistant plastics. The internal diameter of the central tube shall be 4 6 0.1 mm;

 

23  

(b) A Brass Screw Cap, to connect the upper part of the bodyof the filter unit to the lower part of the pipet to ensure a leak-free joint. An example of satisfactory connection

FIG 1 cold filter Jacket tester

 

24  

fig2.watertight brassjacket (c) A Disc, 15 6 0.1-mm diameter, of plain weave stainless steel wire mesh gauze with a nominal aperture size of 45 ƒÊm The nominal diameter of the wire shall be 32 ƒÊm, and the tolerance for the size of an individual aperture shall be as follows: (1) No aperture size shall exceed the nominal size by more than 22 ƒÊm;(2) The average aperture size shall be within 6 3.1 ƒÊm of the nominal size;(3) Not more than 6 % of the apertures shall be above the nominal size by more than 13 ƒÊm.

.The requirements for the wire mesh are taken from ISO 3310,to which reference may be made for methods for testing the gauze.

All dimensions are in millimetres, and the comma (,) is used as the decimal point. FIG. 2pacers

All dimensions are in millimetres, and the comma (,) is used as the ecimal point. All dimensions are in millimetres, and the comma (,) is used as the ecimal point.

(d) A Filter Holder of Brass, in which the disc of wire mesh gauze is firmly lamped by a retaining ring pressed into the filter holder. The diameter of the exposed part of the gauze shall be 12 + 0.1 - 0.0 mm (A Brass Cylinder, threaded on the outside, that can be screwed into the cavity of the body (a)) to clamp the filter holder against the O-ing (a)), The lower end shall have four slots to allow the specimen to flow into the filter unit. Thermometers, having ranges shown below and conforming to the requirements prescribed in Specification E 1 or Specifications for IP Standard Thermometers.Thermometer Number Thermometer Temperature Range ASTM IP High-range for CFPP down to .30�‹C .38�‹C to +50�‹C 5C 1C Low-range from CFPP below .30�‹C .80�‹C to +20�‹C 6C 2CCooling bath .80�‹C to +20�‹C 6C 2C Cooling Bath: The type of cooling bath is optional, but it shall be of a shape and size suitable for containing the jacket in a stable and upright position at the required 6depth. . The bath shall be fitted with a cover with one or more holes in it to accommodate the supporting ring The jacket may be permanently mounted in the cover. The bath temperature shall be maintained at the required value and tolerance by a refrigeration unit or by the use of suitable freezing mixtures, ensuring a omogenous temperature in the bath by stirring or other means of agitation. Table 1 lists the bath temperature set-points required in the CFPP procedure. If only one bath is

 

25  

utilized, it must have the ability to change down to the next lower set-point temperature in a time period not exceeding 2 min 30 s. All dimensions are in millimetres, and the comma (,) is used as the decimal point. All dimensions are in millimetres, and the comma (,) is used as the decimal point. All dimensions are in millimetres, and the comma (,) is used as the decimal point. Stopcock, glass, with double oblique bore of 3-mm diameter. Vacuum Source, vacuum pump or water pump fower ful enough to ensure an air flow rate in the vacuum regulator of 15 6 1 L/h for the duration of the test. Vacuum Regulator, consisting of a glass bottle, at least 350-mm high, not less than 5 L capacity, partially filled with water. It shall be closed by a stopper with three holes of convenient diameters for glass tubes. Two tubes shall be short and shall not go below the water level. The third tube, with an internal diameter of 10 6 1 mm, shall be long enough for one end to be approximately 200 mm beneath the surface of the water while the other end reaches a few centimetres above the stopper. The depth of the immersed part shall then be adjusted to obtain a depression of 200 6 1 mm of water (2 6 0.05 kPa) on the manometer, which shall contain water. A second empty 5 L bottle shall be fitted in the line to serve as a vacuumreservoir to ensure a constant depression. The arrangement is shown in Fig.1 Stopwatch, with a graduation or reading of 0.2 s or lower, with an accuracy of 0.1 % over a period of 10 min. 6.2 Automated Apparatus: The automated apparatus shall include elements conforming to 6.1.1-6.1.8, platinum resistance thermometers,cooling bath(s), vacuum pump, and suitable electronic control and measurement devices. Cooling Bath, a refrigeration unit capable of maintaining the cooling bath at the required temperature and also of automatically changing the bath temperature within 2 min 30 sat the appropriate stage Vacuum Pump, powerful enough to ensure an air flow rate in the vacuum regulator of a minimum of 15 6 1 L/h, and to maintain a constant vacuum of 200 6 1 mm (2 6 0.05 kPa) for the duration of the test. For multi-position testers using the same vacuum pump, the flow rate shall be checked when several positions are operating simultaneously. 4.6- Reagents and Materials. Heptane, clean commercial or reagent grade. NOTE 4.Warning: Flammable. Harmful if inhaled. Acetone, clean commercial or reagent grade. NOTE 5.Warning: Extremely flammable.

 

26  

Lintless Filter Paper, (5 6 1 ƒÊm retention). Certified Reference Materials. 4.7- Sampling. Unless otherwise specified in the commodity specification,samples shall be taken as described in Practice D 4057 or D 4177 in accordance with the requirements of national standards or regulation for the sampling of the product under test,or both. 4.8- Preparation of Test Specimen. Filter approximately 50 mL of the sample at laboratory ambient temperature, but in any case not at a temperature less than �‹C, through dry filter paper 5.10- 4.9-Preparation of Apparatus. Prepare the manual apparatus or the automated apparatus for operation in accordance with the manufacturer�fs instructions for calibrating, checking, and operating the equipment.See Fig. 1 for manual apparatus. Before each test, dismantle the filter unit and wash the pieces and the test jar the pipet and the thermometer for manual apparatus and 6.2 for platinum resistance used in automated equipment)with heptane then rinse with acetone and dry in a stream of filtered air. Check the cleanliness and dryness of all elements, including the jacket Examine the wire mesh (c)) and the joints (a) and 6.1.8.2(b) for damage; if necessary renew them.Check that the screw cap is tight enough to prevent leakage. . Calibration and Standardization. Adjust the automated CFPP apparatus (when used) in accordance with the manufacturer�fs instructions. Calibrate the temperature measuring device in accordance with the nufacturer�fs

instructions. Periodically verify the correct functioning of manual and automated apparatus

using a certified reference material or in-house secondary reference material, such as fuel of known CFPP value.

It is preferable that verification be carried out at least two times a year, where possible, using certified reference materials. The apparatus should be checked more frequently (for example, weekly) using a condary verification material.

When the CFPP values obtained using a verification material deviate by more than the test repeatability (see 15.2),or an unacceptable statistical quality control bias is

observed, check the condition and operation of the apparatus to ensure

 

27  

conformity with the specification as stated in this test method.The anufacturer fs instruction manual should provide guidance on ensuring that the apparatus is correctly set up and calibrated. 4.10- Procedure. Manual Apparatus: Establish the cooling bath temperature at .34 6 0.5�‹C.Place the insulating ring on the bottom of the jacket If spacers are not mounted on the insulating ring position them approximately 15 and 75 mm above the bottom of the test jar Pour the filtered specimen into the clean and dry test jar to the mark (45 mL). Close the test jar with the stopper carrying th (Use a low-range thermometer if the expected CFPP is below .30�‹C. Thermometers shall not be changed during the test. Adjust the apparatus in such a way that the bottom of the filter unit rests on the bottom of the test jar, and position the thermometer so that its lower end is 1.5 6 0.2 mm above the bottom of the test jar. Take care to ensure that no part of the thermometer is not in contact with the side of the test jar or the filter body. NOTE.The precise positioning of the thermometer in the test jar is a critical parameter of this test method. The position of the lower end of the thermometer above the bottom of the test jar can be indirectly measured by marking the stem of the thermometer flush with the stopper when the lower end of the thermometer is just touching the bottom of the test jar, and then pulling the thermometer up such that the reference lineis 1.5 6 0.2 mm above the top of the stopper. If the jacket is not an integral part of the cooling bath,place the jacket vertically to a depth of 85 6 2 mm in the cooling bath which is maintained at the temperature of .34 6 0.5�‹C. Insert the test jar assembly in a stable vertical position into the jacket. With the stopcock open to atmosphere, connect the pipet to the vacuum system by means of flexible tubing attached to the stopcock (see Fig. 1). Switch on the vacuum source and regulate to ensure an air flow rate of 15 L/h in the vacuum regulator. Before starting a test, check that the U-tube manometer indicates a 200 6 1 mm of water depression (2 6 0.05 kPa). Start the test immediately after inserting the test jar assembly into the jacket, but if the cloud point of the sample is known, it is permitted to wait until the specimen has cooled to a temperature of not less than 5�‹C above its cloud point. When the specimen temperature reaches a suitable integer value, turn the stopcock so that the filter assembly is connected to the vacuum source, causing the specimen to be drawn through the wire mesh into the pipet;

 

28  

simultaneously start the stopwatch. When the specimen reaches the mark on the pipet,stop the stopwatch and turn the stopcock to its initial position to vent the pipet and so allow the specimen to return to the test jar. If the time taken to reach the mark exceeds 60 s on the first filtration, abandon the test and repeat it on a fresh portion, starting at a higher temperature. Repeat the operations for each 1�‹C decrease of the specimen temperature until the temperature is reached at which the pipet is not filled to the 20 mL mark within 60 s. Record the temperature at which this last filtration was commenced as CFPP NOTE 8.A small minority of samples may exhibit anomalous aspiration behavior, which can be detected by examining the observed aspiration times. This behavior is marked by an unexpected reduction in the time taken to fill the pipet, after which aspiration time again continues to increase progressively, until the failure limit of 60 s is reached. If the filter has not plugged when the temperature of the specimen reaches .20�‹C, continue the test by using a second cooling bath maintained at .51 6 �‹C, quickly transferring the test jar and filtration assembly to a new jacket placed on the second cooling bath. Alternatively, for single new temperature must be reached within 2 min 30 s of the adjustment. Repeat the operations 12.1.9 to to each 1�‹C decrease of the specimen temperature. If the filter has not plugged when the temperature of the specimen reaches .35�‹C, continue the test by using a third cooling bath maintained at .67 6 2�‹C by quickly transferring the test jar and filtration assembly to a new jacket placed on the second cooling bath. Alternatively, for single bath apparatus,adjust the refrigeration unit to .67 6 2�‹C. The new temperature must be reached within 2 min 30 s of the adjustment.Repeat the operations 12.1.9 to 12.1.10 at each 1�‹C decrease of the specimen temperature. If the filter has not plugged when the temperature of the specimen reaches .51�‹C, discontinue the test If, after cooling in accordance with 12.1.12,, and 12.1.14, the specimen fills the pipet to the mark in less than 60 s, but does not flow back completely into the test jar when the pipet is vented to atmosphere through the stopcock before the start of the next aspiration,record the temperature at the commencement of the filtration as the CFPP Automated Apparatus: Check that the cooling bath is operating and has reached the temperature required as specified in the manufacturer�fs instructions. Pour the filtered specimen into the clean and dry test jar to the 45 mL mark. Close the test jar with the stopper carrying the pipet with filter unit platinum resistance thermometer. Adjust the apparatus in such a way that the bottom of the filter unit rests on the bottom of the test jar, and position the thermometer so that

 

29  

its lower end is 1.5 6 0.2 mm above the bottom of the test jar. Take care to ensure that no part of the thermometer is in contact with the side of the test jar or the filter body. NOTE.The precise positioning of the thermometer in the test jar is a critical parameter of this test method. The position of the lower end of the thermometer above the bottom of the test jar can be indirectly measured by marking the stem of the thermometer flush with the stopper when the lower end of the thermometer is just touching the bottom of the the reference lineis 1.5 6 0.2 mm above the top of the stopper. If necessary, reconnect the pipet to the vacuumsystem. Switch on the vacuum source and regulate to ensure an air flow rate of 15 L/h in the vacuum regulator. Check that the U-tube manometer (if used) indicates a 200 6 1 mm depression(2 6 0.05 kPa) or that the electronic vacuum regulator indicates a pressure of 2 6 0.05 kPa.Press the start button immediately after insertion of the test jar assembly. If the cloud point is known, aspiration of the specimen through the filter may be set to start when it has cooled to a temperature not less than 5�‹C above the cloud point. The apparatus will carry out the test procedure filtering the specimen at each 1�‹C decrease if temperature and measuring the filtering time. If the time to reach the 20 mL mark exceeds 60 s on the first filtration, the test is to be abandoned and repeated on a fresh specimen starting at a higher temperature.The apparatus will record the first temperature at which D 6371 . 99. the specimen fails to reach the 20 mL mark in less than 60 s or fails to flow back into the test jar when the vacuum is cut off as CFPP The test will be discontinued if the specimen reaches .51�‹C without plugging During the procedure, the apparatus will automatically change the cooling bath temperature as indicated below. Bath Temperature Start of test .34 6 0.5�‹C When (if) specimen reaches .20�‹C .51 6 1�‹C When (if) specimen reaches .35�‹C .67 6 2�‹C small minority of samples may exhibit anomalous aspiration behavior, which can be detected by examining the aspiration times recorded in the test printout for signs of an unexpected reduction in the time taken to fill the pipet, after which aspiration time again continues to increase progressively until the failure limit of 60 s is reached.12.2.6 If the automated CFPP apparatus used does not incorporate a lower light sensor, it shall only be used if the test sequence is observed as in the manual procedure (see 12.1.16),so that any fuels not flowing back into the test jar as described are detected and reported accordingly.

 

30  

4.11- Report: Report the temperature read or indicated at the beginning of the last filtration to the nearest 1�‹C as the CFPP. If the specimen has reached .51�‹C without plugging report as �gNot plugged at .51�‹C.�h The report shall contain at least the following information: The type and identification of the product under test;A reference to this test ethod; The sampling procedure used The result of the test 13.3.5 Any deviation from the procedure described 8 and and the date of the test. 4.12- Precision and Bias The precision of this procedure as determined by the statistical examination of the interlaboratory test results is as follows: Repeatability.The difference between results obtained on the same day by the same operator with the same apparatus under constant operating conditions on identical test material, would in the long run, with normal and correct operation of the test method, exceed 1.76�‹C only in one case in twenty. Reproducibility.The difference between two single and independent results obtained by different operators working in different laboratories on identical test material, would in the long run, in the normal and correct operation of the test method, exceed the values indicated by the formula: 0.102 (25.X)�‹C where: X is the average of the two results being compared,only in one case in wenty. NOTE 11.The interlaboratory test program used to determine the precision of this test method was carried out in 1988 by the IP. The program involved 46 boratories and 5 samples, ranging in CFPP values from 0�‹C to .33�‹C. Extrapolations to measurements more than a few degrees outside this range are unsupported by the data. The raw data from the 1988 program was re-analyzed in 1997 using the ASTM D2PP program. The report of the re-evaluation is available from ASTM Headquarters RR:D02-1452. Bias.The procedure in this test method has no bias because the value of CFPP can be defined only in terms of a test method . Relative Bias.The current interlaboratory tests confirm that there is no relative bias between the manual and automated apparatuses. Both apparatuses are suitable for reference purposes. 4.13-keywords. Automate4 d cold filter plugging point; cold filter plugging point (CFPP); diesel; domestic heating fuels; filterability;manual cold filter plugging point.

 

31  

ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk of infringement of such rights, are entirely their own responsibility. This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards and should be addressed to ASTM ternational Headquarters. Your comments will receive careful consideration at a meeting of the responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should make your views known to the ASTM Committee on Standards, at the address shown below. This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above address or at 610-832-9585 (phone), 610-832-9555 (fax), or service@astm.org (e-mail); or through the ASTM website(www.astm.org)..

 

32  

Section 5 : standard Test Methods forFlash Point by Pensky-Martens Closed Cup Tester1(D93-02a) This standard is issued under the fixed designation D 93; the number immediately following the designation indicates the year of original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A superscript epsilon (e) indicates an editorial change since the last revision or reapproval. This standard has been approved for use by agencies of the Department of Defense. INTRODUCTION This flash point test method is a dynamic test method and depends on definite rates of temperature increases to control the precision of the test method. The rate of heating may not in all cases give the precision quoted in the test method because of the low thermal conductivity of certain materials. To improve the prediction of flammability, Test Method D 3941, an equilibrium method, was developed in which the heating rate is slower. This allows the vapor above the test specimen and the test specimen to be at about the same temperature. If your specification requires Test Method D 93, do not substitute Test Method D 3941 or any other test method without obtaining comparative data and agreement from the specifier. Flash point values are a function of the apparatus design, the condition of the apparatus used, and the operational procedure carried out. Flash point can therefore only be defined in terms of a standard test method, and no general valid correlation can be guaranteed between results obtained by different test methods, or with test apparatus different from that specified. 5.1-Scope These test methods cover the determination of the flash point of petroleum

 

33  

products in the temperature range from 40 to 360°C by a manual Pensky-Martens closed-cup apparatus or an automated Pensky-Martens closed-cup apparatus. NOTE—Flash point determination as above 250°C can be performed ,however, the precisions have not been determined above this temperature. For residual fuels, precisions have not been determined for flash points above 100°C. Procedure A is applicable to distillate fuels (diesel,kerosine, heating oil, turbine fuels), new lubricating oils, and other homogeneous petroleum liquids not included in the scope of Procedure B. Procedure B is applicable to residual fuel oils, cutback residua, used lubricating oils, mixtures of petroleum liquids with solids, petroleum liquids that tend to form a surface film under test conditions, or are petroleum liquids of such kinematic viscosity that they are not uniformly heated under the stirring and heating conditions of Procedure A. These test methods is applicable for the detection of contamination of relatively nonvolatile or nonflammable materials with volatile or flammable materials. The values stated in SI units shall be regarded as the standard. The values given in parentheses are provided for information only. This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. For specific hazards statements. 5.2-Terminology Definitins:dynamic, adj—in petroleum products—the condition    where the vapor above the test specimen and the test specimen  are not in temperature equilibrium at the time that the ignition  source is applied. Discussion—This is primarily caused by the heating of the test specimen at the constant prescribed rate with the vapor temperature lagging behind the test specimen temperature. equilibrium, n—in petroleum products—the condition where the vapor above the test specimen and the test specimen are at the same temperature at the time the ignition source is applied. Discussion—This condition may not be fully achieved in practice, since the temperature may not be uniform throughout the test specimen, and the test cover and shutter on the apparatus can be cooler. flash point, n—in petroleum products, the lowest temperature corrected to a barometric pressure of 101.3 kPa (760 mm Hg), at which application of an ignition source causes the vapors of a specimen of the sample to ignite under specified conditions of test.

 

34  

Discussion—The test specimen is deemed to have flashed when a flame appears and instantaneously propagates itself over the entire surface of the test specimen. Discussion—When the ignition source is a test flame, the application of the test flame may cause a blue halo or an enlarged flame prior to the actual flash point. This is not a flash point and shall be ignored. 5.3-Summary of Test Method A brass test cup of specified dimensions, filled to the inside mark with test pecimen and fitted with a cover of specified dimensions, is heated and the specimen stirred atspecified rates, by either of two defined procedures (A or B). An ignition source is directed into the test cup at regular intervals with imultaneous interruption of the stirring, until a flash is detected flash point is reported as defined in 3.1.3. 5.4- Significance and Use The flash point temperature is one measure of the tendency of the test specimen to form a flammable mixture with air under controlled laboratory conditions. It is only one of a number of properties which must be considered in assessing the overall flammability hazard of a material. Flash point is used in shipping and safety regulations to define flammable and combustible materials. One should consult the particular regulation involved for precise definitions of these classifications. NOTE—The U.S. Department of Transportation (DOT)9 and U.S.Department of Labor (OSHA) have established that liquids with a flash point under 37.8°C (100°F) are flammable, as determined by these test methods, for those liquids which have a kinematic viscosity of 5.8 mm 2/s (cSt) or more at 37.8°C or 9.5 mm 2/s (cSt) or more at 25°C (77°F), or that contain suspended solids, or have a tendency to form a surface film while nder test. Other classification flash points have been established by these departments for liquids using these test methods. These test methods should be used to measure and describe the properties of materials, products, or assemblies in response to heat and an ignition source under controlled laboratory conditions and should not be used to describe or appraise the fire hazard or fire risk of materials, products, or assemblies under actual fire conditions. However, results of these test methods may be used as elements of a fire risk assessment which takes into account all of the factors which are pertinent to an assessment of the fire hazard of a particular end use. These test methods provides the only closed cup flash point test procedures for temperatures up to 370°C (698°F).

 

35  

5.5 Apparatus Pensky-Martens Closed Cup Apparatus (manual)—This apparatus consists of the test cup, test cover and shutter, stirring device, heating source, ignition source device, air bath, and top plate described in detail in Annex A1. The assembled manual apparatus, test cup, test cup cover, and test cup assembly are illustrated in Figs. A1.1-A1.4, respectively. Dimensions are listed respectively. Pensky-Martens Closed Cup Apparatus (automated)—This apparatus is an automated flash point instrument that is capable of performing the test in accordance with Section 11 (Procedure A) and Section 12 (Procedure B) of these test methods. The apparatus shall use the test cup, test cover and shutter, stirring device, heating source, and ignition source device described in detail in Annex A1. Temperature Measuring Device—Is a thermometer having a range as shown as follows and conforming to the requirements prescribed in Specification E 1 or in Annex A3, or an electronic temperature measuring device, such as resistance thermometers or thermocouples. The device shall exhibit the same temperature response as the mercury thermometers. Annual Book of ASTM Standards, Vol 14.03. Annual Book of ASTM Standards, Vol 15.05. Annual Book of ASTM Standards, Vol 14.02. Available from American National Standards Institute (ANSI), 25 W. 43rd St., 4th Floor, New York, NY 10036. For information on U.S. Department of Transportation regulations, see Codes of U.S. Regulations 49 CFR Chapter 1 and the U.S. Department of Labor, see 29 CFR Chapter XVII. Each of these items is revised annually and may be procured from the Superintendent of Documents, Government Printing Office, Washington, DC 20402. Ignition Source—Natural gas flame, bottled gas flame,and electric ignitors (hot wire) have been found acceptable for use as the ignition source. The gas flame device described in detailed in Fig. A1.4 requires the use of the pilot flame described in A1.1.2.3. The electric ignitors shall be of the hot-wire type and shall position the heated section of the ignitor in the aperture of the test cover in the same manner as the gas flame device. (Warning—Gas pressure supplied to the apparatus should not be allowed to exceed 3 kPa (12 in.) of water pressure.) 5.6-Reagents and Materials Cleaning Solvents—Use suitable solvent capable of cleaning out the specimen from the test cup and drying the test cup and cover. Some commonly used solvents are toluene and acetone. (Warning—Toluene, acetone, and many solvents are flammable and a health hazard. Dispose of solvents and waste

 

36  

material in accordance with local regulations.) 5.7- Sampling Obtain a sample in accordance with instructions given in Practices D 4057, D 4177, or E 300. At least 75 mL of sample is required for each test. Refer to Practice D 4057. When obtaining a sample of residual fuel oil, the sample container shall be from 85 to 95 % full. For other types of samples, the size of the container shall be chosen such that the container is not more than 85 % full or less than 50 % full prior to any sample aliquot being taken. Successive test specimens can be taken from the same sample container. Repeat tests have been shown to be withi n the precisions of the method when the second specimen is taken with the sample container at least 50 % filled. The results of flash point determinations can be affected if the sample volume is less than 50 % of sample container capacity. Erroneously high flash points may be obtained if precautions are not taken to avoid the loss of volatile material. Do not open containers unnecessarily, to prevent loss of volatile material or possible introduction of moisture, or both. Avoid storage of samples at temperatures in excess of 35°C or 95°F.Samples for storage shall be capped tightly with inner seals. Do not make a transfer unless the sample temperature is at least the equivalent of 18°C or 32°F below the expected flash point. Do not store samples in gas-permeable containers, since volatile material may diffuse through the walls of the enclosure. Samples in leaky containers are suspect and not a source of valid results. Samples of very viscous materials shall be heated in their containers, with lid/cap slightly loosened to avoid buildup of dangerous pressure, at the lowest temperature adequate to liquefy any solids, not exceeding 28°C or 50°F below the expected flash point, for 30 min. If the sample is then not completely liquefied, extend the heating period for additional 30 min periods as necessary. Then gently agitate the sample to provide mixing, such as orbiting the container horizontally, before transferring to the specimen cup. No sample shall be heated and transferred unless its temperatures is more than 18°C or 32°F below its expected flash point. When the sample has been heated above this temperature, allow the sample to cool until its temperature is at least 18°C or 32°F below the expected flash point before transferring. NOTE—Volatile vapors can escape during heating when the sample container is not properly sealed.

 

37  

Some viscous samples may not completely liquefy even after prolonged periods of heating. Care should be exercised when increasing the heating temperature to avoid unnecessary loss of volatile vapors, or heating the sample too close to the flash point. Samples containing dissolved or free water may be dehydrated with calcium chloride or by filtering through a qualitative filter paper or a loose plug of dry absorbent cotton. Warming the sample is permitted, but it shall not be heated for prolonged periods or greater than a temperature of 18°C 32°Fbelow its expected flash point. If the sample is suspected of containing volatile contaminants,the atment described in 8.6 and 8.7 should be omitted. 5.8 Preparation of Apparatus Support the manual or automated apparatus on a level steady surface, such as a table. Tests are to be performed in a draft-free room or compartment. Tests made in a laboratory hood or in any location where drafts occur are not reliable. A shield, of the approximate dimensions 460 mm (18 in.)square and 610 mm (24 in.) high, or other suitable dimensions, and having an open front is recommended to prevent drafts from disturbing the vapors above the test cup. With some samples whose vapors or products of pyrolysis are objectionable, it is permissible to place the apparatus along with a draft shield in a ventilation hood, the draft of which is adjustable so that vapors can be withdrawn without causing air currents over the test cup during the ignition source application period. Prepare the manual apparatus or the automated apparatus for operation in accordance with the manufacturer’s instructions for calibrating, checking, and operating the equipment. (Warning—Gas pressure should not be allowed to exceed 3 kPa (12 in.) of water pressure.) Thoroughly clean and dry all parts of the test cup and its accessories before starting the test, to ensure the removal of any solvent which had been used to clean the apparatus. Use suitable solvent capable of removing all of the specimen from the test cup and drying the test cup and cover. Some commonly used solvents are toluene and acetone. (Warning—Toluene, acetone, and many solvents are flammable. Health hazard.Dispose of solvents and waste material in accordance withlocal regulations.)

 

38  

5.9- Verification of Apparatus Adjust the automated flash point detection system (when used) in accordance with the manufacturer’s instructions. Verify that the temperature measuring device is in accordance with 6.3. Verify the performance of the manual apparatus or the automated apparatus at least once per year by determining the flash point of a certified reference material (CRM) such as those listed in Annex A4, which is reasonably close to the expected temperature range of the samples to be tested. The material shall be tested according to Procedure A of these test methods and the observed flash point obtained in 11.1.8 or 11.2.2 shall be corrected for barometric pressure The flash point obtained shall be within the limits stated in Table A4.1 for the identified CRM or within the limits calculated for an unlisted CRM 10.4 Once the performance of the apparatus has been verified, the flash point of secondary working standards (SWSs) can be determined along with their control limits. These secondary materials can then be utilized for more frequent performance checks 10.5 When the flash point obtained is not within the limits stated in 10.3 or 10.4, check the condition and operation of the apparatus to ensure conformity with the details listed in Annex A1, especially with regard to tightness of the lid (A1.1.2.2), the action of the shutter, the position of the ignition source (A1.1.2.3), and the angle and position of the temperature measuring device (A1.1.2.4). After any adjustment, repeat the test in 10.3 using a fresh test specimen, with special attention to the procedural details prescribed in these test methods. PROCEDURE A; 5.10- Procedure Manual Apparatus: Ensure that the sample container is filled to the volume capacity requirement specified in 8.2. Fill the test cup with the test specimen to the filling mark inside of the test cup.The temperature of the test cup and test specimen shall be at least 18°C or 32°F below the expected flash point. If too much test specimen has been added to the test cup, remove the excess using a syringe or similar device for withdrawal of fluid. Place the test cover on the test cup and place the assembly into the apparatus. Be sure the locating or locking device is properly engaged. If the temperature measuring device is not already in place, insert the device into its holder. Light the test flame, and adjust it to a diameter of 3.2 to 4.8 mm (0.126 to 0.189 in.), or switch on the electric igniter and adjust the intensity in accordance with the manufacturer’s instructions. (Warning—Gas pressure should not be allowed to exceed 3 kPa (12 in.) of water pressure.) (Warning— Exercise care when using a gas test flame. If it should be

 

39  

extinguished it will not ignite the vapors in the test cup, and the gas for the test flame that then enters the vapor space can influence the result.) (Warning—The operator should exercise and take appropriate safety precautions during the initial application of the ignition source, since test specimens containing low-flash material can give an abnormally strong flash when the ignition source is first applied.) (Warning—The operator should exercise and take appropriate safety precautions during the performance of these test methods. The temperatures attained during these test methods, up to 370°C (698°F), are considered hazardous.) Apply the heat at such a rate that the temperature, as indicated by the temperature measuring device, increases 5 to 6°C (9 to 11°F)/min. Turn the stirring device at 90 to 120 rpm, stirring in a downward direction. (Warning—Meticulous attention to all details relating to the ignition source, size of test flame or intensity of the electric ignitor, rate of temperature increase, and rate of dipping the ignition source into the vapor of the test specimen is desirable for good results.)Application of Ignition Source: If the test specimen is expected to have a flash point of 110°C or 230°F or below, apply the ignition source when the temperature of the test specimen is 23 6 5°C or 41 6 9°F below the expected flash point and each time thereafter at atemperature reading that is a multiple of 1°C or 2°F. Discontinue the stirring of the test specimen and apply the ignition source by operating the mechanism on the test cover which controls the shutter so that the ignition source is lowered into the vapor space of the test cup in 0.5 s, left in its lowered position for 1 s, and quickly raised to its upward position. If the test specimen is expected to have a flash point above 110°C or 230°F, apply the ignition source in the manner described in 11.1.5.1 at each temperature increase of 2°C or 5°F, beginning at a temperature of 23 6 5°C or 41 6 9°F ,below the expected flash point. When testing materials to determine if volatile material contamination is present, it is not necessary to adhere to the temperature limits for initial ignition source application as stated in 11.1.5. When testing materials where the expected flash point temperature is not known, bring the material to be tested and the tester to a temperature of 15 6 5°C or 60 6 10°F. When the material is known to be very viscous at this temperature, heat the specimen to a starting temperature as described in 8.6. Apply the ignition source, in the manner described in 11.1.5.1, beginning at least 5°C or 10°F higher than the starting temperature. NOTE 8—Flash Point results determined in an “unknown expected flash point mode” should be considered approximate. This value can be used as the expected flash point when a fresh specimen is tested in the standard mode of operation.

 

40  

Record as the observed flash point the reading on the temperature measuring device at the time ignition source application causes a distinct flash in the interior of the test cup. The sample is deemed to have flashed when a large flame appears and instantaneously propagates itself over the entire surface of the test specimen. (Warning—For certain mixtures containing halogenated hydrocarbons, such as, methylene chloride or trichloroethylene, no distinct flash, as defined, is observed. Instead a significant enlargement of the test flame (not halo effect) and change in color of the test flame from blue to yellowish-orange occurs. Continued heating and testing of these samples above ambient temperature can result in significant burning of vapors outside the test cup, and can be a potential fire hazard. See Appendix X1 and Appendix X2 for more information.) When the ignition source is a test flame, the application of the test flame may cause a blue halo or an enlarged flame prior to the actual flash point. This is not a flash and shall e ignored. When a flash point is detected on the first application, the test shall be iscontinued, the result discarded, and the test repeated with a fresh test specimen. The first application of the ignition source with the fresh test specimen shall be 23 5°C or 41 6 9°F below the temperature at which a flash point was detected on the first application. When a flash point is detected at a temperature which is greater than 28°C or 50°F above the temperature of the first application of the ignition source, or when a flash point is detected at a temperature which is less than 18°C or 32°F above the temperature of the first application of the ignition source, the result shall be onsidered approximate, and the test repeated with a fresh test specimen. Adjust the expected flash point for this next test to the temperature of the pproximate result. The first application of the ignition source with the fresh test specimen shall be 23 6 5°C or 416 9°F below the temperature at which the approximate result was found. When the apparatus has cooled down to a safe handling temperature, less than 55°C (130°F), remove the test cover and the test cup and clean the apparatus as recommended by the manufacturer. NOTE 9—Exercise care when cleaning and positioning the lid assembly so not to damage or dislocate the flash detection system or temperature measuring device. See the manufacturer’s instructions for proper care and maintenance. Automated Apparatus: The automated apparatus shall be capable of performing the procedure as described in, including control of the heating rate, stirring of the test specimen, application of the ignition source, detection of the flash point, and recording the flash point.

 

41  

Start the automated apparatus in accordance with the manufacturer’s instructions. The apparatus shall follow the procedural details described in through ROCEDURE B: 5.11- Procedure. Manual Apparatus: Ensure that the sample container is filled to the volume capacity requirement specified in 8.2. Fill the test cup with the test specimen to the filling mark inside of the test cup. The temperature of the test cup and test specimen shall be at least 18°C or 32°F below the expected flash point. If too much test specimen has been added to the test cup, remove the excess using a syringe or similar device for withdrawal of fluid. Place the test cover on the test cup and place the assembly into the apparatus. Be sure the locating or locking device is properly engaged. If the temperature measuring device is not already in place, insert the device into its holder. Light the test flame and adjust it to a diameter of 3.2 to 4.8 mm (0.126 to 0.189 in.), or switch on the electric igniter and adjust the intensity in accordance with the manufacturer’s instructions. (Warning—Gas pressure should not be allowed to exceed 3 kPa (12 in.) of water pressure.) (Warning—extinguished it will not ignite the vapors in the test cup and the gas for the test flame that then enters the vapor space can influence the result.) (Warning—The operator should exercise and take appropriate safety precautions during the initial application of the ignition source, since test specimens containing low-flash material may give an bnormally strong flash when the ignition source is first applied.) (Warning—The operator should exercise and take appropriate safety precautions during the performance of these test methods. The temperatures attained during these test methods, up to 370°C (698°F), are considered hazardous.) Turn the stirring device at 250 6 10 rpm, stirring in a downward direction. Apply the heat at such a rate that the temperature as indicated by the temperature measuring device increases 1 to 1.6°C (2 to 3°F)/min. Proceed as prescribed in Section, with the exception of the preceding requirements for rates of stirring and heating. Automated Apparatus: The automated apparatus shall be capable of performing the procedure as described in 1, including control of the heating rate, stirring of the test specimen, application of the ignition source, detection of the flash point, and recording the flash point. Start the automated apparatus in accordance with the manufacturer’s instructions. The apparatus shall follow the procedural details in accordance with through

 

42  

PRECISION, CALCULATION, AND REPORT FOR PROCEDURES A AND B. 5.12- Calculation. Observe and record the ambient barometric pressure (see Note 10) at the time of the test. When the pressure differs from 101.3 kPa (760 mm Hg), correct the flash point as follow: where: C = observed flash point, °C, F = observed flash point, °F, P = ambient barometric pressure, mm Hg, and K = ambient barometric pressure, kPa.

pressure for the laboratory at the time of the test. Many aneroid barometers, such as those used at weather stations and airports, are precorrected to give sea level readings and would not give the correct reading for this test. 13.2 After correction for barometric pressure, round the temperature to the nearest 0.5°C (1°F) and record. 5.13- Report Report the corrected flash point as the ASTM D 93–IP 34, Procedure A or Procedure B Pensky-Martens Closed Cup Flash Point of the test specimen. 5.14- Precision and Bias (Procedure A) Precision—The precision of this procedure as determined by the statistical examination of the interlaboratory test results, is as follows: Repeatability—The difference between successive results, obtained by the same operator with the same appa atus under constant operating conditions on identical test material, would in the long run, in the normal and correct operation of the test method, exceed the following values in 1 case in 20. r 5 AX, (4)A 5 0.029,X 5 mean result in °C, and r 5 repeatability. Reproducibility—The difference between two single and independent results, obtained by different operators working in different laboratories on identical material, would in the long run, in the normal and correct operation of the test method, exceed the following values only in 1 case in 20.

 

43  

R 5 BX, (5) B 5 0.071,X 5 mean result in °C, and R 5 reproducibility. 15.1.3 Bias—Since there is no accepted reference material suitable for determining the bias for the procedure in these test methods, bias has not been determined. Relative Bias—Statistical evaluation of the data did not detect any significant difference between the reproducibilitY variances of manual and automated Pensky-Martens flash point results for the samples studied. Evaluation of the data did not detect any significant difference between averages of manual and automated Pensky-Martens flash point for the samples studied with the exception of cycle oil and fuel oil which showed some bias. In any case of dispute, the manual procedure shall be considered the referee test. The precision statements were derived on clear liquids only. Refer to the research report10 for information regarding relative bias and types of samples. Additional studies are in progress concerning relative bias. The precision data were developed from a combined 1991ASTM cooperative test program10 using 5 samples of fuel and lubricating oils (Twelve laboratories participated with the manual apparatus and 21 laboratories participated with the automated equipment) and a 1994 IP cooperative test program using 12 fuel samples and 4 pure chemicals. (Twenty-six laboratories participated with manual and automated equipment. The apparatus used either a gas test flame or an electric resistance (hot wire) device for the ignition source. Information on the type of samples and their average flash point are in the research report.10 5.15- Precision and Bias (Procedure B) Precision—The precision of this procedure as determined by the statistical examination of the interlaboratory test results, is as follows: Repeatability—The difference between successive results obtained by the same operator with the same apparatus under constant operating conditions on identical test materials would, in the long run, in the normal and correct operation of the test method, exceed the following value in 1 case in 20: Residual fuel oil 2°C ~5°F! Other types 5°C ~9°F! (6)Reproducibility—The difference between two single and independent results obtained by different operators working in different laboratories on identical material would, in the long run, exceed the following value only in 1 case in 20. Residual fuel oil 6°C ~12°F! Other types 10°C ~18°F! (7)Bias—Since there is no accepted reference material suitable for determining the bias for the procedure in these test methods, bias has not been determined. The precision data for residual fuel oils were developed in a 1996 cooperative test program conducted by the IP using 12 samples of residual fuel and 40 laboratories

 

44  

worldwide using both the manual and automated apparatus. Information on the type of samples and their average flash point are in the research report. The precision data for other sample types in Procedure B is not known to have been developed in accordance with RR:D02–1007.11 NOTE-Procedure B was not tested in the 1991 interlaboratory program. 5.16- Keywords automated flash point; automated Pensky-Martens closed cup; flammability; flash point; Pensky-Martens closed cup 10 Supporting data (the results of the 1991 interlaboratory cooperative test program) have been filed at ASTM International Headquarters and may be obtained. by requesting Research Report RR: S15–1008. Supporting data have been filed at ASTM International Headquarters and may be obtained by requesting Research Report RR: D02–1 A1. APPARATUS SPECIFICATIONS A1.1 A typical assembly of the apparatus, gas heated, is shown in Fig. A1.1. The apparatus shall consist of a test cup, cover, and stove conforming to the following requirements: A1.1.1 Cup—The cup shall be of brass, or other nonrustingmetal of equivalent heat conductivity, and shall conform to thedimensional requirements in Fig. A1.2. The Lid asseA1. APPARATUS SPECIFICATIONS.

A1.1 A typical assembly of the apparatus, gas heated, is shown in Fig. A1.1. The apparatus shall consist of a test cup,cover, and stove conforming to the following requirements:

 

45  

.

 

46  

(fiGA1.2) (FiG A1.3)

-

 

47  

equipped with devices for locating the position of the cup in the stove. handle attached to the flange of the cup is a desirable accessory. The handle shall not be so heavy as to tip over the empty cup.A1.1.2 Cover: A1.1.2.1 Cover Proper—The cover shown in Fig. A1.3 shall be of brass (A1.1.1) and shall have a rim projecting downward almost to the flange of the cup. The rim shall fit the outside of the cup with a clearance not exceeding 0.36 mm(0.014 in.) on the diameter. There shall be a locating or locking device, or both, engaging with a corresponding device on the cup. The four openings in the cover, A, B, C, and D, are shown in Fig. A1.3. The upper edge of the cup shall be in close contact with the inner face of the cover throughout its circumference. A1.1.2.2 Shutter—The cover shall be equipped with a brass shutter (Fig. A1.1 and Fig. A1.4), approximately 2.4 mm (3⁄32 in.) thick, operating on the plane of the upper surface of the cover. The shutter shall be so shaped and mounted that it rotates on the axis of the horizontal center of the,cover,between,two,stops,so,pla openings A, B, and C in the cover are completely closed, and when in the other extreme position, these openings are completely opened. The mechanism operating the shutter should be of the spring type and constructed so that when at rest the shutter shall exactly close the three openings. When operated to the other extreme, the three cover openings shall be exactly open and the tip of the exposure tube shall be fully depressed.A1.1.2.3 Flame-Ignition Device—The flame-ignition device (Fig. A1.4) shall have a tip with an opening 0.69 to 0.79 mm (0.027 to 0.031 in.) in diameter. This tip shall be made preferably of stainless steel, although it may be fabricated of other suitable metals. The flame-exposure device shall be equipped with an operating mechanism which, when the shutter is in the open position, depresses the tip so that the center of the orifice is between the planes of the under and upper urfaces of the cover proper at a point on a radius passing through the center of the larger opening A (Fig. A1.3). An electric ignitor is also suitable. The electric ignitors shall be of the electric resistance (hot-wire) type and shall position the heated section of the ignitor in the aperture of the test cover in the same manner as the gas flame device.

 

48  

A1.1.2.4 Pilot Flame—A pilot flame shall be provided for automatic relighting of the exposure flame. A bead 4 mm (5⁄32 in.) in diameter can be mounted on the cover so that theced, that when in one extr

1The tip of the pilot flame shall have an opening the same size as the tip

 

49  

of the flame exposure device (0.69 to 0.79 mm (0.027 to 0.031 in.) in diameter). A1.1.2.5 Stirring Device—The cover shall be equipped with a stirring device (Fig. A1.4) mounted in the center of the cover and carrying two 2-bladed metal propellers. In Fig. A1.4 lower propeller is designated by the letters L, M, and N. This propeller shall measure approximately 38 mm from tip to tip,with each of its two blades 8 mm in width with a pitch of 45°.The upper propeller is designated by the letters A, C, and G. This propeller measures approximately 19 mm, tip to tip, each of its two blades is also 8 mm in width with a pitch of 45°. Both propellers are located on the stirrer shaft in such a manner that,when viewed from the bottom of the stirrer, the blades of one propeller are at 0 and 180° while the blades of the other propeller are at 90 and 270°. A stirrer shaft may be coupled to the motor by a flexible shaft or a suitable arrangement of pulleys. A1.1.2.6 Stove—Heat shall be supplied to the cup by means of a properly designed stove which is equivalent to an air bath. The stove shall consist of an air bath and a top plate on which the flange of the cup rests. A1.1.2.7 Air Bath—The air bath shall have a cylindrical interior and shall conform to the dimensional requirements in Fig. A1.1. The air bath may be either a flame or electrically heated metal casting (A1.1.2.8), or an electric-resistance element (A1.1.2.9). In either case, the air bath must be suitable for use at the temperatures to which it will be subjected without deformation. A1.1.2.8 Heater, Flame or Electric—If the heating element is a flame or an electric heater, it shall be so designed and used that the temperatures of the bottom and the walls are approximately the same. In order that the air bath internal surfaces should be at a uniform temperature, it should not be less than 6.4 mm (1⁄4 in.) in thickness unless the heating element is designed to give equal heat flux densities over all the wall and bottom surfaces. A1.1.2.9 Heater, Electric Resistance—If the heater is of the electric resistance type, it shall be constructed so that all parts of the interior surface are heated uniformly. The wall and bottom of the air bath shall

 

50  

not be less than 6.4 mm (1⁄4 in.) in thickness unless the resistance heating elements are distributed over at least 80 % of the wall and all the bottom of the air bath.A heater having such a distribution of the heating elements positioned at least 4.0 mm (5⁄32 in.) away from the internal surface of the heating unit can be used in conjunction with a minimum thickness of 1.58 mm (1⁄16 in.) for the wall and bottom of the air bath. A1.1.2.10 Top Plate—The top plate shall be of metal, and shall be mounted with an air gap between it and the air bath. It may be attached to the air bath by means of three screws and spacing bushings. The bushings should be of proper thickness to define an air gap of 4.8 mm (3⁄16 in.), and they shall be not more than 9.5 mm (3⁄8 in.) in diameter. A2. MANUFACTURING STANDARDIZATION OF THERMOMETER AND FERRULE A2.1 The low-range thermometer, which conforms also to the pecification for the cup thermometer in the tag closed tester (Test Method D 56) and which frequently is fitted with a metal ferrule intended to fit the collar on the cover of the tag flash tester, can be supplemented by an adapter to be used in the larger diameter collar of the Pensky-Martens apparatus. Differences in dimensions of these collars, which do not affect test results, are a source of unnecessary trouble to manufacturers and suppliers of instruments, as well as to users. A2.2 Dimensional requirements are Conformity to these requirements is not mandatory, but is desirable to users as well as suppliers of Pensky-Martens testers. A4.1 Certified Reference Material (CRM)—CRM is a stable, pure (99 + mole % purity) hydrocarbon or other stable petroleum product with a method-specific flash point established by a method-specific erlaboratory study following ASTM RR:D02-1007 guidelines11 or ISO Guide 34 and 35. A4.1.1 Values of the flash point corrected for barometric pressure for some reference materials and their typical limits are given in Table 4.112 (see Note A4.1). Suppliers of CRMs will provide certificates ating the method-specific flash point for each material of the current production batch. Calculation of the limits for these other CRMs can be

 

51  

determined from the reproducibility value of these test methods, reduced by interlaboratory effect and then multiplied by 0.7. See Research Report RR:S15-1008.10 NOTE—Materials, purities, flash point values, and limits stated in Table A4.1 were developed in an ASTM interlaboratory program to determine suitability of use for verification fluids in flash point test methods. Other materials, purities, flash point values, and limits can be suitable when produced according to the practices of ASTM RR:D02- 1007 or ISO Guides 34 and 35. Certificates of performance of such materials should be consulted before use, as the flashpoint value will vary dependent on the composition of each CRM batch. A4.2 Secondary Working Standard (SWS)—SWS is a stable, pure (99 + mole % purity) hydrocarbon, or other petroleum product whose composition is known to remain appreciably stable. A4.2.1 Establish the mean flash point and the statistical control limits (3s) for the SWS using standard statistical techniques 5.17-APPENDIXES (Nonmandatory Information) X1. FLASH POINT MASKING PHENOMENON X1.1 A condition during flash point testing can occur with certain mixtures whereby the nonflammable component of the sample tends to inert the vapor space above the liquid, thus preventing a flash. Under this condition, the flash point of the material is masked resulting in the reporting of incorrect high . X1.2 This flash point masking phenomenon most frequently occurs with ignitable liquids that contain certain halogenated hydrocarbons such as dichloromethane (methylene chloride) and trichloroethylene. X1.3 Under this condition, no distinct flash as defined in 3.1.3 of these test methods is observed. Instead a significant enlargement of the test flame and a change in the color of the test flame from blue to yellow-orange laminar flame is observed. X1.4 Under this condition, continued heating and testing for flash point at temperatures above ambient temperature,have resulted in significant

 

52  

burning of the ignitable vapor outside the test cup, often above the test flame. This can be a potential fire hazard if not recognized. X1.5 It is recommended that if this condition is encountered during the flash point testing of these type of materials,testing should be discontinued. X1.6 Further commentaries regarding flash point test andflammability of mixtures can be found in Test Method E 502. 12 Supporting data have been filed at ASTM International Headquarters and may be obtained by requesting Research Report RR: S15–1010. 13 Manual on Presentation of Data and Control Chart Analysis, ASTM MNL, 6th ed., ASTM International, W. Conshohocken, 1990. X2. FLASH POINT TEST AND FLAMMABILITY OF IXTURES X2.1 While the flash point can be used to indicate the flammability of liquid materials for certain end uses, flash point does not represent the minimum temperature at which a material can evolve flammable vapors. X2.2 There are instances with pure materials where the absence of a flash point does not ensure freedom from flammability. Included in this category are materials that require large diameters for flash propagation, such as trichloroethylene. This material will not propagate a flame in apparatus the size of a flash point tester, however, its vapors are flammable and will burn when ignited in apparatus of adequate size. X2.3 When a liquid contains flammable and nonflammable components, there are cases where this liquid can evolve flammable vapors under certain conditions and yet will not exhibit a close-cup flash point. This phenomenon is noted when a nonflammable component is sufficiently volatile and present in sufficient quantity to inert the vapor space of the closed cup, thus preventing a flash. In addition, there are certain instances where an appreciable quantity of the nonflammable component will be present in the vapor, and the material will exhibit no flash point. X2.4 Liquids containing a highly volatile nonflammable component or impurity, which exhibit no flash point because of the influence of the nonflammable material, may form flammable mixtures if totally flash vaporized in air in the proper proportions.

 

53  

Section6 : Standard Test Method for Water in Petroleum Products and Bituminous Materials by Distillation This standard is issued under the fixed designation D95; the number immediately following the designation indicates the year of original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A superscript epsilon (´) indicates an editorial change since the last revision or reapproval. This standard has been approved for use by agencies of the Department of Defense. 6.1- Scope This test method covers the determination of water in the range from 0 to 25 % volume in petroleum products, tars,and other bituminous materials by the distillation method. Volatile water-soluble material, if present, may be measuredas water. The specific products considered during the development of this test method are listed in Table 1. For bituminous emulsions refer to Test Method D244. For crude oils, refer to Test Method D4006 10.2. With some types of oil, satisfactory results may be obtained from Test Method D1796 . The values stated in SI units are to be regarded as the standard. The values in parentheses are for information only. This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. For specific hazard statements 6.2- Terminology Definitions:bituminous material, n—in petroleum technology, a black or dark-colored very viscous liquid or semi-solid composed principally

 

54  

of high molecular weight condensed aromatic,or naphthenic compounds, or both. This test method is under the jurisdiction of ASTM Committee D02 on Petroleum Products and Lubricants and the API Committee onPetroleum Measurement,and is the direct responsibility of Subcommittee 02.02.0B /COMQ, the joint ASTM-API Committee on Sampling, Sediment, Water.Current edition approved May 1, 2010. Published May 2010. Originally approved in 1921. Last previous edition approved in 2005 as D95–05. DOI:10.1520/D0095-05R10. For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at ervice@astm.org. For Annual Book of ASTM Standards volume information, refer to the standard’s Document Summary page on the ASTM website. Published as Manual of Petroleum Measurement Standards. Available from American Petroleum Institute (API), 1220 L. St., NW,Washington, DC 20005-4070,http://www.api.org.. 6.3 Summary of Test Method. The material to be tested is heated under reflux with a water-immiscible solvent, which co-distills with the water in the sample. Condensed solvent and water are continuously separated in a trap, the water settling in the graduated section of the trap and the solvent returning to the still. 6.4 -Significance and Use. A knowledge of the water content of petroleum products is important in the refining, purchase, sale, and transfer of products. The amount of water as determined by this test method (to the nearest 0.05 or 0.1 volume %, depending on the trap size used) may be used to correct the volume involved in the custody transfer of petroleum products and bituminous materials. The allowable amount of water may be specified in contracts. 6.5 - Solvent-Carrier Liquid. Asolvent-carrier liquid appropriate to the material being tested (see Table 1) shall be used.

 

55  

Aromatic Solvent—The following aromatic solvents are acceptable: Industrial Grade Xylene—(Warning—Flammable. Vapor harmful.) Ablend of 20 volume % industrial grade toluene and 80 volume % industrial grade xylene. (Warning—Flammable. Vapor harmful.) Petroleum Naphtha or Coal Tar Naphtha, free of water, yielding not more than 5% distillates at 125°C (257°F) and not less than 20% at 160°C (320°F) and with a relative density (specific gravity) not lower than 0.8545 at 15.56/15.56°C (60/60°F). (Warning—Extremely flammable. Harmful if inhaled. Vapors may cause fire.)Petroleum Distillate Solvent—A petroleum distillate solvent, 5% boiling between 90 and 100°C (194 and 212°F)and 90% distilling below 210°C (410°F), shall be used. Percent may be determined by mass or by volume. (Warning Flammable. Vapor harmful.) volatile spirits solvents are acceptable: Petroleum Spirit, with a boiling range from 100 to 120°C (Warning—Flammable. Vapor harmful.) Iso-octane, of 95% purity or better. Warning—Extremely flammable. Harmful if inhaled. Vapors may cause fire.)Solvent Blank—The water content of the solvent shall be determined by distilling an equivalent amount of the same solvent used for the test sample in the distillation apparatus to the nearest scale division and used to correct the volume of

water in the trap. 6.6- Apparatus General—The apparatus comprises a glass or metal still, a heater, a reflux condenser, and a graduated glass trap.

 

56  

The still, trap, and condenser may be connected by any suitable method that produces a leakproof joint. Preferred connections are ground joints for glass and O-rings for metal to glass. Typical assemblies are illustrated in Fig. 1, Fig. 2, and Fig. 3.The stills and traps should be chosen to cover the range of materials and water contents expected. On assembly, care shall be taken to prevent the joints from freezing or sticking. Always apply a very thin film of stopcock grease to prevent the glassware joints from seizing. Still—A glass or metal vessel with a short neck and suitable joint for accommodating the reflux tube of the trap shall be used. Vessels of 500, 1000, and 2000-mL nominal capacity have proved satisfactory. Heater—Asuitable gas burner or electric heater may be used with the glass still. A gas ring burner with ports on the inside circumference shall be used with the metal still. The gas ring burner shall be of such dimensions that it may be moved up and down the vessel when testing materials that are likely to foam or solidify in the still. Glassware—Dimensions and descriptions of typical glassware for use in this test method are provided in Specification Instead of standardizing on a particular apparatus pecification with respect to dimensions and style, a given apparatus will be deemed satisfactory when accurate results are obtained by the standard addition technique

 

57  

Type of Solvent-Carrier Liquid Material to be Tested Aromatic asphalt, tar, coal tar, water gas tar, road tar, cut-back bitumin, liquid asphalt, tar acid Petroleum distillate road oil, fuel oil, lubricating oil, petroleum sulfonates Volatile spirits lubricating grease Copyright by ASTM Int'l (all rights reserved); Sun Nov 7

 

58  

23:36:39 EST 2010,Downloaded/printed by King Mongkut Univ of Tech N. Bangkok pursuant to License Agreement. No further reproductions authorized. 6.7-Sampling Sampling is defined as all steps required to obtain an aliquot of the contents of any pipe, tank, or other system and to place the sample into the laboratory test container. Only representative samples obtained as specified in Practices D4057 shall be used for this test method. The size of the test portion should be based on the expected water content of the sample, such that the water yield does not exceed the capacity of the trap (unless a trap with a stopcock is used permitting excess water to be withdrawn into a graduated cylinder). Practice D5854 contains information on sampling and homogenization efficiency of unknown mixers. This test method should not be followed without strict adherence to Practice D5854 6.8-Verification The accuracy of the graduation marks on the trap shall be certified or verified, using only national or international standards, such as National Institute of Standards and Technology (NIST)4 traceable equipment. Verification shall be with a traceable 5 mL Micro Burette or Micro Pipette, readable to the nearest 0.01 mL. In styles A, B, C, and D, mL through 1.0 mL) in the conical portion of the tube shall be verified. Thereafter, each major subdivision (that is, 2.0 mL,3.0 mL, 4.0 mL, and up to the total volume of the trap) shall be verified. In styles E and F, as specified in Table 2, each major subdivision (0.1 mL, 1.0 mL, 2.0 mL, 4.0 mL, and 5.0 mL in the case of Style E; 0.05 mL, 0.5 mL, 1.0 mL, 1.5 mL, and 2.0 9.2 The entire glassware assembly shall be verified prior to first use and at a regular frequency thereafter as follows. Put 400 mL of dry (0.02 % water maximum) xylene or the solvent to be utilized in the analysis of unknown samples into the apparatus When complete malfunction resulting from vapor leaks, too rapid boiling,

 

59  

inaccuracies in calibration of the trap, or ingress of extraneous moisture. Eliminate these factors before repeating the verification. 6.9- Procedure The precision of this test method will be affected by water droplets adhering to surfaces in the apparatus and therefore not settling into the water trap to be measured. To minimize the problem, all apparatus must be cleaned chemically at least daily to remove surface films and debris, which hinder free drainage of water in the test apparatus. More frequent cleaning is recommended if the nature of samples being run causes persistent contamination. Measure a suitable amount of sample to an accuracy of 6 1% and transfer it to the still. Measure ordinary liquid samples in a graduated cylinder of an appropriate size. Rinse the material adhering to the cylinder with one 50-mL and two 25-mL portions of the solvent-carrier liquid cylinder thoroughly after the sample transfer and each rinsing. Weigh solid or viscous materials directly into the still and add 100 mL of the selected solvent-carrier liquid. In cases of material with a low-water content when large samples must be used, a solvent-carrier liquid volume in excess of 100 mL may be necessary. Glass beads or other boiling aids may be added, if necessary, to reduce bumping. Assemble the components of the apparatus, accordance with the expected water content of the sample and making all connections vapor and liquid tight. If a metal still with a removable cover is used, insert a gasket of heavy paper,moistened with solvent, between the still body and the cover. The condenser tube and trap must be chemically clean to ensure free drainage of water into the bottom of the trap. Insert a loose cotton plug in the top of the condenser to prevent condensation of atmospheric moisture inside it. Circulate cold water through the jacket of the ondenser. Apply heat to the still, adjusting the rate of boiling so that condensed distillate discharges from the condenser at the rate of two to five drops

 

60  

per second. If the metal still is used,start heating with the ring burner about 76 mm (3 in.) above the bottom of the still and gradually lower the burner as the distillation proceeds. Continue distillation until no water is National Institute of Standards and Technology (NIST), Copyright by ASTM Int'l (all rights reserved); Sun Nov 7 23:36:39 EST 2010.Downloaded/printed by King Mongkut Univ of Tech N. Bangkok pursuant to License Agreement. No further reproductions authorized.

 

61  

 

62  

Copyright by ASTM Int'l (all rights reserved); Sun Nov 7 23:36:39 EST 2010 Downloaded/printed by King Mongkut Univ of Tech N. Bangkok pursuant to License Agreement. No further reproductions authorized. visible in any part of the apparatus except in the trap and the volume of water in the trap remains constant for 5 min. If there is a persistent ring of water in the condenser tube, carefully increase the rate of distillation or cut off the condenser water for a few minutes. When the evolution of water is complete, allow the trap and contents to cool to room temperature. Dislodge any drops of water adhering to the sides of the trap with a glass or polytetrafluoroethylene (PTFE) rod or other suitable means and transfer them to the water layer. Read the volume of the water in the trap to the nearest scale division. A solvent blank shall be established, 6.10-Calculation Calculate the water in the sample, as weight or volume percent, in accordance with the basis on which the sample was taken, as follows: Water, % (V/V) =~Volume in water trap, mL! 2 ~Water in solvent blank, mL!Volume in test sample, mL 3 100 Water, % (V/m) =~Volume of water in trap, mL! 2 ~Water in solvent blank, mL!Mass of test sample, g 3 100

 

63  

6.11-Report Report the results as the water content to the nearest 0.05% if the 2-mL receiver has been used and to the nearest 0.1% if the 10-mL or 25-mL receiver has been used and to the nearest subdivision if a 5-mL receiver has been used with a 100-mL or 100-g sample. 6.12- Precision and Bias Precision—The criteria described in 13.1.1 and 13.1.2 should be used to judge the acceptability of results when using the 10 or 25-mL traps. The precision when using the 2-mL trap or a 5–mL trap has not been established. Practice D6300 was not used in obtaining precision data. Repeatability—The difference between successive test results, obtained by the same operator with the same apparatus under constant operating conditions on identical test material, would, in the long run, in the normal and correct Reproducibility—The difference between two single and independent test results obtained by different operators working in different laboratories on identical test material,would, in the long run, in the normal and correct operation of the test method, exceed the values in Table 4 in only one case in twenty. Bias—As there is no accepted reference material suitable for determining bias for the procedure described in this test method for measuring water in petroleum products and bituminous materials by distillation, no statement about bias is made. 6.13- Keywords bituminous materials; distillation; petroleum products;solvent carrier liquid; water by distillation; water content Copyright by ASTM Int'l (all rights reserved); Sun Nov 7 23:36:39 EST 2010 Downloaded/printed by King Mongkut Univ of Tech N. Bangkok pursuant to License Agreement. No further reproductions authorized.

 

64  

ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned in this standard. Sectio.7-Distillation of Petroleum Products at Reduced Pressure1 This standard is issued under the fixed designation D 1160; the number immediately following the designation indicates the year of original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A superscript epsilon (e) indicates an editorial change since the last revision or reapproval. This standard has been approved for use by agencies of the Department of Defense. 7.1- Scope This test method covers the determination, at reduced pressures, of the range of boiling points for petroleum products that can be partially or completely vaporized at a maximum liquid temperature of 400°C. Both a manual method and an automatic method are specified. In cases of dispute, the referee test method is the manual test method at a mutually agreed upon pressure. The values stated in SI units are to be regarded as the standard. The values in parentheses are for information only. This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. For specific hazard statements. atmospheric equivalent temperature (AET)—the temperature converted from the measured vapor temperature using Eq A7.1. The AET is the expected distillate temperature if the distillation was performed at atmospheric pressure and there was no thermal decomposition. end point (EP) or final boiling point (FBP)—the maximum vapor temperature reached during the test. initial boiling point (IBP)—the vapor temperature that is measured at the instant the first drop of condensate falls from the lower end of the condenser section drip tip. Discussion—When a chain is attached to the drip tip the first drop will form and run down the chain. In automatic apparatus, the first drop detection device shall be located as near to the lower end of the drip tip as practical.

 

65  

spillover point—the highest point of the lower internal junction of the distillation column and the condensing section of the vacuum-jacketed column assembly. 7.2- Summary of Test Method The sample is distilled at an accurately controlled pressure between 0.13 and 6.7 kPa (1 and 50 mm Hg) under conditions that are designed to provide approximately one theoretical plate fractionation. Data are obtained from which the initial boiling point, the final boiling point, and a distillation curve relating volume percent distilled and atmospheric equivalent boiling point temperature can be prepared. 7.3- Summary of Test Method This test method is used for the determination of the distillation characteristics of petroleum products and fractions that may decompose if distilled at atmospheric pressure. This boiling range, obtained at conditions designed to obtain approximately one theoretical plate fractionation, can be used in engineering calculations to design distillation equipment, to prepare appropriate blends for industrial purposes, to determine compliance with regulatory rules, to determine the suitability of the product as feed to a refining process, or for a host of other purposes. This test method is under the jurisdiction of ASTM Committee D02 on Petroleum Products and Lubricants and is the direct responsibility of ubcommittee D02.08 on Volatility. Current edition approved June 10, 2003. Published August 2003. Originally approved in 1951. Last previous edition approved in 2002 as D 1160–02a. . Copyright by ASTM Int'l (all rights reserved);Reproduction authorized per License Agreement with Genevieve PONS (GECIL Process); Wed Nov 3 07:09:49 EST 2004 The boiling range is directly related to viscosity, vapor pressure, heating value, average molecular weight, and many other chemical, physical, and mechanical properties. Any of these properties can be the determining factor in the suitability of the product in its intended application. Petroleum product specifications often include distillation limits based on data by this test method. Many engineering design correlations have been developed on data by this test method. These correlative methods are used extensively in current engineering practice.

 

66  

7.4-Apparatus The vacuum distillation apparatus, shown schematically in Fig. 1, consists in part of the components described below plus others that appear in Fig. 1 but are not specified, either as to design or performance. Some of these parts are not essential for obtaining satisfactory results from the tests but are desirable components of the assembly for the purpose of promoting the efficient use of the apparatus and ease of its operation. Both manual and automatic versions of the apparatus must conform to the following requirements. Additional requirements for the automatic apparatus can be found in Annex A9. Distillation Flask, of 500-mL capacity, made of borosilicate glass or of quartz conforming to the dimensions given in Fig. 2 or Fig. 3, and having a heating mantle with insulating top. These dimensions can vary slightly by manufacturer, and are not considered critical dimensions, with the exception of the position of the end of the temperature sensing probe, and the inner diameter of the connection to the distillation column not being less than the inner diameter of the distillation column. The use of the thermowell can be replaced by an encased temperature probe and the second side neck is present on commercially available flasks used in this test method. Vacuum-Jacketed Column Assembly, of borosilicate glass, consisting of a distilling head and an associated condenser section as illustrated in the lettered drawing, Fig. 4 and Table 1. The head shall be enclosed in a completely silvered glass vacuum jacket with a permanent vacuum of less than 10−5 Pa (10−7 mm Hg) (Note 1). The attached condenser section shall be enclosed in water jackets as illustrated and have an adapter at the top for connection to the vacuum source. A light drip-chain shall hang from the drip tip of the condenser to a point 5 mm below the 10-mL mark of the receiver as shown in Fig. 5. Alternatively, instead of the metal drip-chain,a metal trough may be used to channel the distillate to the wall of the receiver. This trough may either be attached to the condenser drip tip as shown in Fig. 5 or it may also be located in the neck of the receiver. There is no simple method to determine the vacuum in the jacket once it is completely sealed. A Tesla coil can be used, but the spark can actually create a pinhole in a weak spot in the jacket. Even the slightest pinhole or crack not readily detectable by sight alone will negate the vacuum in the jacket.

 

67  

 

68  

 

69  

 

70  

FIG.4vacum Jacket column o 400°C and have a response time of less than 200 s as described in Annex A2. The location of the vapor temperature sensor is extremely critical. As shown in Fig. 6, the vapor temperature measuring device shall be centered in the upper

 

71  

portion of the distillation column with the top of the sensing tip 3 6 1 mm below the spillover point The vapor temperature measuring device can consist of different configurations depending if it is a platinum resistance in glass or metal, or if it is a thermocouple in glass or metal. Figs. 7 and 8 show the proper positioning of these two types in relation to the spillover point. In glass platinum resistance devices the top of the spiral winding is the top of the sensing tip, in thermocouples it is the top of the thermocouple junction, in metal jacketed devices it is 1 6 1 mm above the bottom of the device.An alignment procedure is described in Appendix X1. The vapor temperature measuring device shall be mounted through a compression ring type seal mounted on the top of the glass temperature sensor/vacuum adapter or fused into a ground taper joint matched to the distillation column. In some distillation apparatus configurations, the vacuum adapter at the top of the distillation column can be omitted. In these cases, the position of the vapor temperature measuring device shall be adjusted accordingly. The boiler temperature measuring device may be either a thermocouple or PRT and shall also be calibrated as above. Receiver of borosilicate glass, conforming to the dimensions shown. If the receiver is part of an automatic unit and is mounted in a thermostatted chamber, the jacket is not required. (Warning—The glass parts of the apparatus are subjected to severe thermal conditions and, to lessen the chances of failure during a test, only equipment shown to be strain-free under polarized light should be used.) Vacuum Gage, capable of measuring absolute pressures with an accuracy of 0.01 kPa in the range below 1 kPa absolute and with an accuracy of 1 % above this pressure. The McLeod gage can achieve this accuracy when properly used, ,but a mercury manometer will permit this accuracy only down to a pressure of about 1 kPa and then only when read with a good cathetometer (an instrument based on a telescope mounted on a vernier scale to determine levels very accurately). An electronic gage such as the Baratron is satisfactory when calibrated from a McLeod gage but must be rechecked periodically as described in Annex A3. A suitable pressure calibration setup is illustrated in Fig. A3.1. Vacuum gages based on hot wires, radiation, or conductivity detectors are not recommended. NOTE 2—Suitable instruments for measuring the pressure of the system during the test are the tensimeter or an electronic pressure gage, provided the output is traceable to a primary gage, such as the non-tilting McLeod gage. Connect the vacuum gage to the side tube of the temperature sensor/vacuum adapter of the distillation column (preferred location) or to the side tube of the sensor/vacuum adapter of the condenser when assembling the apparatus.

 

72  

Connections shall be as short in length as possible and have an inside diameter not less than 8 mm. Pressure Regulating System, capable of maintaining the pressure of the system constant within 0.01 kPa at pressures of 1 kPa absolute and below and within 1 % of the absolute pressure at 1 kPa or higher. Suitable equipment for this purpose is described in Annex A4. Connect the pressure regulating TABLE 1 Vacuum-Jacketed Column Assembly Dimensions These dimensions are for guidance for verifying the appropriate construction of the assembly. The actual dimensions used by glassmakers vary to some extent, and the dimensions they use to construct the assembly are not easily obtained after the assembly is fused together. Those dimensions noted as critical shall be adhered to within the tolerance listed. The dimensions listed in this chart have been gathered from users of the various manufactured manual and automatic apparatus who participated in the interlaboratory program to produce the precision for this test method. Important—Further study will progress to produce a set of dimensions which will be more restrictive in range of dimension, since it is believed that the current wide variance in dimensions has resulted in precision for this test method to be significantly high. The target dimensions for this assembly and other components of the apparatus are expected to be available within the next year, with implementation expected to occur after five years of initial revised test method publication date.

 

73  

(Table.1) Component Critical DimensionsA Notes A no 265 6 10 . . .B yes 99 6 4 Spillover point ,C yes 85 6 3 Internal measurement difficult, used by

 

74  

manufacturer for assembly. Dimension is where center of angled inner tube intersects with the inner wall of the vertical column D (OD) no 64.5 6 2 . . . E no 14/23 or 19/38 Tapered ground joint – femaleB F no 35/25 Spherical ground joint – maleB G no 35 6 10 This area to be covered by the insulating top of the heating mantle H (ID) yes 24.7 6 1.2 Use of 28 mm OD tubing achieves this dimension I no 2 − 12 Window allows observation of boil-up rate and column cleanliness, but also allows detrimental heat loss J no 60 6 20 . . K no 12 6 7 . . .L (OD) no 8 Minimum, cooling medium connections M yes 230 6 13 This dimension determines condensed vapor run down time and affects temperature/recovery results N (OD) no 38 6 2 . . .O yes 140 6 20 This dimension affects vapor condensing efficiency which influences temperature/recovery results P (ID) yes 18.7 6 1.1 Use of 22 mm OD tubing achieves this dimension Q yes 60 6 2° . . .R no not applicable Connection to vacuum system; any suitable means is allowed S no not applicable Extension above condensing section; must maintain minimum or greater internal diameter of condensing section T (ID) yes 18.7 6 1.1 Use of 22 mm OD tubing achieves this dimension U yes 140 6 5 This dimension affects vapor condensing efficiency which influences temperature/recovery results V no not applicable Extensions on the upper and lower portions of the condensing section vary by manufacturer and have no influence on the test W no 12 6 7 . . . X yes 50 6 8 . . . Y yes 30 6 7 Distance to end of drip tip A All dimensions are in millimetres. B Ground glass joints from different sources may have one of a number of diameter to length ratios. For purposes of this test method, any are suitable, and in some instances, the diameter itself is not critical. However, it is critical that the male and female parts of each joint are from the same series to avoid recession or protuberance. Copyright by ASTM Int'l (all rights reserved);Reproduction authorized per License Agreement with Genevieve PONS (GECIL Process); Wed Nov 3 07:09:49 EST 2004,

 

75  

 

76  

 

77  

 

78  

 

79  

• range of operating pressures. A vacuum adapter is used to connect the source to the top of the condenser (Fig. 1) with tubing of 8 mm ID or larger and as short as practical. A single stage pump of at least 850 L/min (30 cfm) capacity at 100 kPa is suitable as a vacuum source, but a double stage pump of similar or better capacity is recommended if distillations are to be performed below 0.5 kPa. Surge tanks of at least 5 L capacity are recommended to reduce pressure fluctuations. Cold Traps: Cold trap mounted between the top of the condenser and the vacuum source to recover the light boiling components in the distillate that are not condensed in the condenser section.

 

80  

This trap shall be cooled with a coolant capable of maintaining the temperature of the trap below − 40°C. Liquid nitrogen is commonly used for this purpose. (Warning—If there is a large air leak in the system and liquid nitrogen is used as the coolant, it is possible to condense air (oxygen) in the trap. If hydrocarbons are also present in the trap, a fire or explosion can result when the trap is warmed up Cold trap mounted between the temperature sensor/vacuum adapter and the vacuum gage to protect the gage from contamination by low boiling components in the distillate. Low Pressure Air or Carbon Dioxide Source to cool the flask and heater at the end of the distillation. FIG. 8 Thermocouple Temperature Measuring Device NOTE—Jacket is not required for automatic units when receiver is placed in thermostatted chamber. If jacket is used, connections should not interfere with reading of graduations. Copyright by ASTM Int'l (all rights reserved); Reproduction authorized per License Agreement with Genevieve PONS (GECIL Process); Wed Nov 3 07:09:49 EST 2004. Low Pressure Nitrogen Source to release the vacuum in the system. Safety Screen or Safety Enclosure that adequately shields the operator from the distillation apparatus in the event of mishap. Reinforced glass, 6 mm thick clear plexiglass, or a clear material of equivalent strength is recommended. Coolant Circulating System, capable of supplying coolant to the receiver and condenser system, at a temperature controlled within 63°C in the range between 30 and 80°C. For automatic units where the receiver is mounted in a thermostatted chamber, the coolant circulating system has to be capable of supplying coolant to the condenser system only. 7.5- Reagents and Materials n-Tetradecane—Reagent grade conforming to the specifications of the Committee on Analytical Reagents of the American Chemical Society.6 ASTM Cetane Reference Fuel (n-Hexadecane), conforming to the specification in Test Method D 613. Silicone Grease—High vacuum silicone grease specially manufactured for the use in high vacuum applications. Silicone Oil, certified by the manufacturer to be applicable for prolonged use at temperatures above 350°C. Toluene—Technical grade. Cyclohexane—Technical grade.

 

81  

7.6- Sample and Sampling Requirements Sampling shall be done in accordance with Practices D 4057 or D 4177. It is assumed that a 4- to 8-L sample,representative of a shipment or of a plant operation, is received by the laboratory and that this sample is to be used for a series of tests and analyses. An aliquot portion slightly in excess of 200 mL will be required for this test method. The aliquot used for this test shall be moisture-free. If there is evidence of moisture (drops on the vessel wall, a liquid layer on the bottom of the container, use the procedure given in Annex A6, paragraph A6.1, to dehydrate a sufficient quantity of sample to provide the 200-mL charge to the distillation flask. Determine the density of the oil sample at the temperature of the receiver by means of a hydrometer by Practice D 1298, by means of a digital density meter by Test Method D 4052, and by using either the mathematical subroutines or tables of Guide D 1250, or a combination thereof. If the sample is not to be tested immediately upon receipt, store at ambient temperature or below. If the sample is received in a plastic container, it shall be transferred to a container made out of glass or of metal prior to storage. The sample shall be completely liquid before charging.If crystals are visible, the sample shall be heated to a temperature that permits the crystals to dissolve. The sample must then be stirred vigorously for 5 to 15 min, depending on the sample size, viscosity, and other factors, to ensure uniformity. If solids are still visible above 70°C, these particles are .probably inorganic in nature and not part of the distillable portion of the sample. Remove most of these solids by filtering or decanting the sample. There are several substances, such as visbroken residues and high melting point waxes, that will not be completely fluid at 70°C. These solids and semi-solids should not be removed since they are part of the hydrocarbon feed. 7.7-Preparation, Calibration, and Quantification of Apparatus Calibrate the temperature sensors and associated signal conditioning and processing device as a unit in accordance with Annex A1. Check the operation of the pressure regulating system as described in Annex A4. Clean and dry the glass parts and relubricate the joints.Silicone high-vacuum grease can be used but no more than is necessary to give a uniform film on the ground glass surfaces.An excess of grease can cause leaks and can contribute to foaming at startup.9.4 Assemble the empty apparatus and conduct a leak test as described in A3.3.2.

 

82  

Check the total apparatus using either of the two reagents described in 7.1 and 7.2 and in accordance with Annex A5. 7.8 Procedure Determine when the temperature sensor was last calibrated.Recalibrate according to Annex A1 if more time has elapsed than that specified in Annex A1. Set the temperature of the condenser coolant to at least 30°C below the lowest vapor temperature to be observed in the test. A suitable coolant temperature for distillation of many materials is 60°C. From the density of the sample determine the weight,to the nearest 0.1 g, equivalent to 200 mL of the sample at the temperature of the receiver. Weigh this quantity of oil into the distillation flask. Lubricate the spherical joints of the distillation apparatus with a suitable grease certain that the surfaces of the joints are clean before applying the grease, and use only the minimum quantity required. Connect the flask to the lower spherical joint of the distilling head, place the heater under the flask, put the top mantle in place and connect the rest of the apparatus using spring clamps to secure the joints. Silicone high-vacuum grease has been used for this purpose. An excess of this lubricant applied to the flask joint can cause the sample to foam during distillation. Place a few drops of silicone oil in the bottom of the thermowell of the flask and insert the temperature sensor to the bottom. The sensor can be secured with a wad of glass wool at the top of the thermowell. Start the vacuum pump and observe the flask contents for signs of foaming. If the sample foams, allow the pressure on the apparatus to increase slightly until the foaming subsides. Reagent Chemicals, American Chemical Society Specifications, American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed by the American Chemical Society, see Annual Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville, Apply gentle heat to assist the removal of dissolved gas. For general directions for suppression of excessive foaming of the sample,. Evacuate the apparatus until the pressure reaches the level prescribed for the distillation Failure to reach the distillation pressure, or the presence of a steady increase in pressure in the apparatus with the pump blocked off, is evidence of significant leakage into the system. Bring the system to atmospheric condition using a nitrogen bleed and relubricate all joints. If this does not result in a vacuum-tight system, examine other parts of the system for leaks.

 

83  

The most commonly prescribed pressure is 1.3 kPa (10 mm Hg). For heavy products with a substantial fraction boiling above 500°C, an operating pressure of 0.13 kPa (1 mm Hg) or 0.26 kPa (2 mm Hg) is generally specified. After the desired pressure level has been attained, turn on the heater and apply heat as rapidly as possible to the flask,without causing undue foaming of the sample. As soon as vapor or refluxing liquid appears at the neck of the flask, adjust the rate of heating so that the distillate is recovered at a uniformrate of 6 to 8 mL/min It is extremely difficult to achieve the desired rate at the very beginning of the distillation, but this rate should be attainable after the first 10 % of the distillate has been recovered. Record the vapor temperature, time, and the pressure at each of the following volume percentage fractions of the charge collected in the receiver: IBP, 5, 10, 20, 30, 40, 50, 60,70, 80, 90, 95, and at the end point. If the liquid temperature reaches 400°C, or if the vapor reaches a maximum temperature before the end point is observed, record the vapor temperature reading and the total volume recovered at the time the distillation is discontinued. When a product is tested for conformity with a given specification, record all requested observations, whether or not they are listed above. The maximum vapor temperature will result either from complete distillation of the oil or from the onset of cracking. If a sudden increase in pressure is observed, coupled with the formation of white vapors and a drop in the vapor temperature, the material being distilled is showing significant cracking. Discontinue the distillation immediately and record the fact on the run sheet. If necessary, rerun the distillation with a fresh sample at lower operating pressure. Lower the flask heater 5 to 10 cm and cool the flask and heater with a gentle stream of air or, preferably, with a stream of carbon dioxide. Repressure the contents of the still with dry nitrogen (Warning—Repressuring the contents of the still with air while it contains hot oil vapors can result in fire or explosion.) if it is necessary to dismantle the apparatus before it has cooled below 200°C. Carbon dioxide can also be used for repressuring, provided liquid nitrogen traps are not in use. (Warning—In addition to other precautions, it is recommended to discontinue the distillation at a maximum vapor temperature of 350°C. Operating the distillation flask at temperatures above 350°C for prolonged periods at pressures below 1 kPa may also result in thermal deformation of the In this case, discard the flask after use. Alternatively, use a quartz flask gentle stream of carbon dioxide is preferred to cool the flask to prevent fire in the event the flask cracks during the test or during the cooling cycle.

 

84  

Bring the temperature of the cold trap mounted before the vacuum source back to ambient temperature. Recover,measure, and record the volume of the light products collected in the trap. Remove the receiver and replace with another. Remove the flask and replace with another flask filled with a cleaning solvent. Run a distillation at atmospheric pressure to clean the unit. At the end of this cleaning run,remove the flask and receiver and blow a gentle stream of air or nitrogen to dry the unit. Toluene or cyclohexane can be used as cleaning solvent. 7.9-Calculations and Report Convert the recorded vapor temperature readings to Atmospheric Equivalent Temperatures (AET) using the equations. Report the AET to the nearest degree Celsius corresponding to the volumetric percentages of liquid recovered in the receiver. Report also the identity of the sample, the density (measured in 8.3), the total amount of liquid distillate recovered in the receiver and in the cold trap before the vacuum source, any unusual occurrence such as foaming or burping,together with the measures that were taken to correct the problem. 7.10- Precision and Bias Precision—The precision of this test method was generated from data obtained in a 1983 cooperative interlaboratory program with nine laboratories participating and eight samples being run. In this program, one laboratory used an automatic vacuum distillation analyzer and the results obtained with this equipment have been included in the data used to generate this precision statement. The precision of this test method is as follows: Repeatability—The difference between two test results,in degrees Celsius, obtained by the same operator with the same apparatus under constant operating conditions on aterials would, in the long run, in the normal and correct operation of this test method, exceed the values indicated in Table 2 in only 1 case in 20. Reproducibility—The difference between two single and independent results in degrees Celsius, obtained by different operators working in different laboratories on identical test material would, in the long run, in the normal and correct operation of this test method, exceed the values indicated in Table 2 in only 1 case in 20. In Table 2, the rate of change in degrees Celsius (AET) per percentage of liquid volume recovered is shown as C/V %. At any point between the 10 and the 90 % point this value is assumed to be equal to the average value of C/V % of the two data points that bracket the point in question. In no case shall the span of these two points be more than 20 % recovered.

 

85  

Supporting data have been filed at ASTM International Headquarters and may be obtained by requesting Research Report RR: D02–1206. Copyright by ASTM Int'l (all rights reserved);Reproduction authorized per License Agreement with Genevieve PONS (GECIL Process); Wed Nov 3 07:09:49 EST 2004,An exception is the 5 % point where the span shall be not more than 10 %. See Annex A8 for an example.

 

86  

7.11-Keywords atmospheric equivalent temperature (AET); boiling range; distillation; vacuum distillation ANNEXES (Mandatory Information) A1. PRACTICE FOR CALIBRATION OF TEMPERATURE SENSORS A1.1 Principle—This section of the annex deals with the basic calibration of the vapor temperature sensor against primary temperature standards as recommended by the National Institute for Science and Technology (NIST) in order to avoid the problems associated with the use of secondary temperature references. It can also be used for the calibration of other temperature sensors. A1.2 Sensors should be calibrated over the full range of emperatures at the time of first use and whenever the sensor or its associated instrument is repaired or rviced. Sensors used in vapor temperature service should be checked monthly at one or more temperatures. A1.3 Calibrate the sensors with their associated Instruments y recording the temperatures of the freezing points of water and of the selected pure metals and metal blends listed in A1.6.A1.4 Apparatus—A suitable apparatus is shown in Fig. A1.1. For the freezing point of water, a Dewar flask filled with at least 50 % crushed ice in water may be substituted. A1.5 Procedure: A1.5.1 For sensors that are mounted loosely in a thermowell, place enough silicone oil or other inert liquid in the bottom of the well so as to make good physical contact between the sensor and the tip of the well. Those sensors that are fused into good contact with the tip of the well may be calibrated as is.A1.5.2 Place about 0.3 mL of silicone oil in the bottom of the thermowell of the melting point bath and insert the sensors to be calibrated. The oil must cover the tips..

 

87  

teau of constant temperature for at least 1 min, the temperature of the recorded plateau is accepted as the calibration temperature. A1.5.5 Apply a correction to be added to the reading, if necessary, to give the correct temperature. A chart may be drawn of correction versus temperature for interpolation. In the case of automated instruments, the correction must be built into the record and must be adjustable. A1.5.6 If the freezing plateau is too short, it can be increased by applying some heat during the cooling cycle. Be aware of the possibility that the metal bath can become contaminated or too oxidized. In this case, replace the metal.

 

88  

A1.6 Reagents and Materials: A1.6.1 Distilled Water—Reagent grade as defined by Type III of Specification D 1193, freezing point 0.0°C. A1.6.2 Metals Blend of Sn 50 wt %, Pb 32 wt %, Cd 18 wt %—Freezing point 145.0°C. A1.6.3 Sn—100 %, freezing point 231.9°C. A1.6.4 Pb—100 %, freezing point 327.4°C. A2. PRACTICE FOR DETERMINATION OF TEMPERATURE RESPONSE TIME A2.1 Scope—This practice is for the determination of the temperature response time based on the rate of cooling of the sensor under prescribed conditions. A2.2 Significance and Use—This practice is performed to ensure that the sensor is able to respond sufficiently rapidly to changes in temperature that no significant error due to lag is introduced in a rapidly rising temperature curve. A2.2.1 The importance of this test is greatest under the lowest pressure conditions when the heat content of the vapors is minimal. A2.3 Procedure: A2.3.1 Arrange a 1-L beaker of water on a hot plate with a glass thermowell supported vertically in the water. Maintain e temperature of the water at 90 6 5°C. A2.3.2 Connect the sensor to a suitable instrument preferably having a digital readout with a readability to 0.1°C.Alternatively, connect the sensor to a strip chart recorder of suitable range that will allow interpolation to 0.1°C. Set the chart speed to at least 30 cm/h for ease of reading.A2.3.3 Insert the sensor into a hole in the center of one side of a cardboard cube box of about 30 cm in each dimension. The sensor should be held in place by friction fit of the joint in the hole. Record the temperature in the box when it becomes stable. A2.3.4 Remove the sensor and insert it into the thermowell in the beaker of water. After the sensor has reached a temperature of 80°C, remove it and immediately insert it into the hole in the box. A2.3.5 Observe with a stopwatch, or record on the stripchart,the time interval required by the sensor to cool from 30°C above to 5°C above the temperature recorded in A2.3.3. A2.3.6 A time interval in excess of 200 s is not acceptable. A3. PRACTICE FOR CALIBRATION OF VACUUM GAGES A3.1 Principle—The calibration of vacuum sensors is based upon the use of the McLeod gage, which is the only practical primary gage suitable for this pressure range. NOTE A3.1—The general principles of construction of McLeod gages are well-established. The dimensions and tolerances of a gage that, when properly employed, fulfills the requirements of 6.1.5 for the pressure range from 0.1 to 5 kPa are: capillary length of 200 6 5 mm, capillary diameter of 2.7 mm (known to

 

89  

0.002 mm), bulk volume + capillary volume, 10.5 6 ,0.5 mL (known to 0.05 mL). This gage is best used by adjusting the mercury level in the system pressure arm to a point opposite the closed end of the capillary tube. The system pressure is calculated by means of the following equation:P 5 Kbh 2 /~V 2 bh! (A3.1) where: K = 133.32. This is a dimensioned conversion factor to convert mm to N/m2, P = system pressure, Pa, b = volume of capillary per unit of length expressed as mL/mm,h = length of capillary left unfilled by mercury, mm, and V = combined volume of bulb and capillary, mL.This equation includes the correction term required when the system pressure is an appreciable fraction of the length of the capillary left unfilled with mercury. A requirement for the successful operation of this gage to measure system pressures in the range from 100 Pa to 200 Pa (0.75 mm Hg to 1.5 mm Hg) is the determination of the length of capillary left unfilled with mercury with an accuracy of 0.2 mm. At pressures from 0.2 to 2 kPa (1.5 to 15 mm Hg), a precision in this measurement of 0.5 mm is sufficient. A3.2 Apparatus—A suitable test setup is shown in Fig.A3.1. It must be capable of maintaining pressures that are steady within 1 % of the required pressure at pressures of 1 kPa and higher and within 0.01 kPa at pressures below 1 kPa. A3.2.1 The McLeod gage, when used as the standard, must have been baked out hot and empty at a pressure below 0.01 kPa before refilling with clean mercury and thereafter be protected from exposure to moisture such as that from mospheric air. The use of two McLeod gages of different pressure Copyright by ASTM Int'l (all rights reserved);Reproduction authorized per License Agreement

 

90  

ith Genevieve PONS (GECIL Process); Wed Nov 3 07:09:49 EST

A3.3.1 Set up a test manifold such as that shown in Fig.A3.1. A3.3.2 Ensure that the test manifold is leak-free and can be maintained at a steady pressure at the required level. A suitable leak test is to pump down to a pressure below 0.1 kPa and isolate the pump. Observe the pressure inside the unit for at least 1 min. If the pressure rises no more than 0.01 kPa in that period, the pparatus is considered acceptable. A3.3.3 Connect the primary vacuum gage(s) and the gage(s) to be calibrated. Adjust the pressure to the required level for the test and run a final leak test as above. A3.3.4 Read and record the pressures indicated by all the gages as nearly simultaneously as possible. A3.3.5 Repeat the above procedure at the pressure levels 0.13, 1.3, and 6.7 kPa (1, 10, and 50 mm Hg). A3.3.6 Make up a chart of corrections to be added at each pressure level for each gage tested. This can be used for interpolation when necessary.

 

91  

A4. PRESSURE REGULATING SYSTEM A4.1 The following is suggested as a satisfactory example of a pressure regulating system: A low-efficiency, highcapacity vacuum pump is connected to one of two surge tanks,each having a capacity of 10 to 20 L and arranged in series. solenoid valve or other type regulator is installed in the connection between the tanks so that the first tank is maintained at pump pressure and the second one at the pressure of the distillation apparatus.A4.1.1 With some apparatus it is desirable to have a slight bleed to the second tank that will cause the controls to operate at regular intervals in order to provide smooth operation.However, experience has shown that the bleed shall be held at an absolute minimum in order to prevent loss of vapors through the manometer connection at the top of the column. A4.1.2 Connecting lines from the second tank to the vacuum distillation apparatus shall be as short in length and as large in diameter as possible. A minimum internal diameter of 12 mm is suggested. A4.1.3 For multiple still arrangements, it is possible to use a large pump and a large low-pressure surge tank. Several smaller tanks operating at the pressures of the various distillations can be attached to the large low-pressure surge tank with individual pressure regulators. Other arrangements can be used, provided the pressure is maintained constant within the limits specified in 6.1.7. NOTE A4.1—If a solenoid valve or other electrically operated regulator is used, a suitable manostat is required for activation of the regulating device. Many such manostats are described in the literature or are available from laboratory supply houses. As an alternative for the separate manostat and solenoid, a Cartesian Manostat can be used. This device is capable of maintaining the system pressure within the specified limits down to a pressure of about 1 kPa. A5. APPARATUS CHECK WITH REAGENT FUEL A5.1 Check the assembled apparatus, including the previously calibrated pressure measuring and temperature sensor and associated instrumentation, to indicate proper assembly and operating control. Conduct the test procedure as described at the test pressure in connection with a specific sample or at two or more pressures in connection with general checks of the equipment, using n-hexadecane or n-tetradecane. A5.1.1 If n-hexadecane is used, the average of distillation temperatures obtained in the 10 % to 90 % range, inclusive, should conform with the data in Table A5.1.

 

92  

FIG. A3.1 Calibration of Vacuum Gages TABLE A5.1 Distillation Temperatures of Reference Compounds

Copyright by ASTM Int'l (all rights reserved); Reproduction authorized per License Agreement with Genevieve PONS (GECIL Process); Wed Nov 3 07:09:49 EST 2004 A5.1.2 For pressures over 0.1 kPa not given in Table A5.1, the range of average temperatures shall not deviate by more than 1.5°C from a temperature, t, given by:t 5 @1831.316/~6.14438 2 log P!# 2 154.53 (A5.1)where P is in kPa, and t is in °C, or t 5 @1831.316/~7.01944 2 log P!# 2 154.53 (A5.2) where P is in mm Hg, and t is in °C. A5.1.3 If n-tetradecane is used, the average of distillation temperatures obtained in the 10 % to 90 % range, inclusive,should conform with the data in Table A5.1. A5.1.4 For pressures over 0.1 kPa not given in Table A5.1,and if n-tetradecane is used, the range of average temperatures shall not deviate by more than 1.5°C from a temperature, t14,given by: t14 5 @1747.452/~6.1471 2 log P!# 2 168.44 (A5.3) where P is in kPa, and t is in °C, or t14 5 @1747.452/~7.02216 2 log P!# 2 168.44 (A5.4) where P is in mm Hg, and t is in °C.

 

93  

A6. SAMPLE DEHYDRATION AND FOAMING SUPPRESSION A6.1 Dehydration of Sample—The following is suggested as a convenient means of dehydrating samples to be subjected to this distillation test. Heat 300 mL of the sample to 80°C, add 10 to 15 g of 8- to 12-mesh fused calcium chloride (CaCl2), and stir vigorously for 10 to 15 min. Allow the mixture to cool without stirring, and remove the oil layer by decantation. A6.2 Suppression of Foaming and Bumping of the Sample:A6.2.1 The tendency of samples to bump or foam excessively is frequently a serious obstacle to the successful distillation of petroleum products under vacuum. In some cases, this is due to the presence of water or dissolved gases, but many samples foam even when apparently free from these contaminants.There is no unanimity of opinion concerning the best way to reduce excessive foaming to manageable proportions.The following methods are offered solely as examples of means that have been employed successfully for that purpose. A6.2.2 Degassing—The procedure described in 10.6 is intended to promote degassing. Slow rates of pressure reduction or temperature increase, or both, for the oil in the flask are important factors in achieving success by this means. Another technique for degassing is to filter the sample under vacuum before weighing. A6.2.3 Application of Steel Wool—Separate about 10 g of a folded pad of median-grade steel wool. Unfold, and separate into 8 to 10 long, loose strands. Push each strand separately nto the bulk of the flask. Avoid packing tightly or forming large void spaces. Fill the upper half of the bulb with steel wool, but do not allow any strand to protrude more than 6 mm into the neck of the flask. Alternatively, take 0.5 to 0.6 g of Grade 2 steel wool, roll into five balls, each approximately 8 to 10 mm in diameter, and drop into the flask. A6.2.4 Boiling Chips—These consist of broken pieces of porcelain drying plates or broken alundum thimbles that are dropped into the flask before starting a distillation. Hengar granules of the plain type, as used in Kjeldahl nitrogen determinations, are also used in the same way (Note A6.1). NOTE A6.1—The use of anti-bumping aids can affect the distillation curve. Their use should therefore be limited to cases where they are absolutely needed to perform the distillation. A6.2.5 Silicone Fluids—The addition of one or two drops of silicone fluid8 (350 cSt) to the sample in the flask is effective in the suppression of foam in many cases. However, analytical tests run on the products from this test method can be biased by the presence of these fluids, so the report shall make note of their use. A6.2.6 Flask Preparation—Some laboratories have treated the inside of the flask, prior to use for distillation, in order to provide an active ebullition surface. Methods used for this purpose include: boiling 100 mL of 33 % sodium hydroxide

 

94  

solution for 15 to 20 min, etching of the inside of the flask bottom with hydrofluoric acid fumes, and the infusion of fine carborundum or fritted glass to the inside of the flask bottom. A7. PRACTICE FOR CONVERTING OBSERVED VAPOR TEMPERATURES TO ATMOSPHERIC EQ UIVALENT TEMPERATURES (AET) A7.1 Scope A7.1.1 This practice is for conversion of the actual distillation temperature obtained at sub-ambient pressure to atmospheric equivalent temperature (AET) corresponding to the 8 The sole source of supply of Dow Corning Silicone Fluid No. 200 known to the committee at this time is Dow Corning. If you are aware of alternative suppliers,please provide this information to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the responsible technical committee,1 which you may attend.Copyright by ASTM Int'l (all rights reserved);Reproduction authorized per License Agreement with Genevieve PONS (GECIL Process); Wed Nov 3 07:09:49 EST 2004 equivalent boiling point at atmospheric pressure, 101.3 kPa (760 mm Hg), by means of equations derived by Maxwell and Bonnell.9 A7.2 Significance and Use A7.2.1 Final data on atmospheric equivalent temperatures are to be obtained by computation. A7.3 Calculation A7.3.1 Convert observed vapor temperature to atmospheric equivalent temperature using Eq A7.1 ; AET 5;48.1A @1/~T 1 273.1!# 1 0.3861A – 0.00051606 – 273.1 (A7.1) where:AET = atmospheric equivalent temperature, °C, and T = observed vapor temperature, °C. A7.3.1.1 Calculate A using Eq A7.2 or Eq A7.3:A 5 5.143222 – 0.972546 log10 P 2579.329 – 95.76 log10 P (A7.2) where:P = operating pressure, kPa, (operating pressure $0.266 kPa), or A 5 5.994295 – 0.972546 log10 P 2663.129 – 95.76 log10 P (A7.3) where: P = operating pressure, mm Hg (operating pressure $2 mm Hg). A7.3.1.2 If the operating pressure < 0.266 kPa (< 2 mm Hg), calculate A using Eq A7.4 or Eq A7.5:A 5 5.897249 – 0.987672 log10 P 2962.909 – 43.00 log10 P (A7.4) where: P = operating pressure, kPa, or A 5 6.761559 – 0.987672 log10 P 3000.538 – 43.00 log10 P (A7.5) where: P = operating pressure, mm Hg.

 

95  

A7.3.2 The equations are correct only for specimens that have a Watson K-factor of 12.0 6 0.2. The K-factor shall be assumed to be 12 and any effect of K-factor ignored unless there is mutual agreement to the contrary. A7.3.3 If correction is required, calculate the K-factor using Eq A7.6:K 5=3 1.8~B 1 273.1!D (A7.6) where: B = mean average boiling point, °C, and D = relative density at 15.6/15.6°C. A7.3.3.1 By custom, either the mid-point vapor temperature of the specimen or the mid-point of a gas chromatographic distillation of the specimen can be used for the mean average boiling point. In either case the method must be specified. A7.3.3.2 An estimate of the K-factor can be made using Fig. A7.1. A7.3.4 Calculate the correction to be applied to the AET using Eq A7.7: t 5 –1.4@K – 12#Flog10SPa PoDG (A7.7) where: t = correction, °C, Pa = atmospheric pressure, kPa (mm Hg), and Po = observed pressure, kPa (mm Hg). A7.3.4.1 An estimate of the correction can be made using Fig. A7.2. 9 Maxwell and Bonnell, Industrial Engineering Chemistry, Vol 49, 1957, p. 1187. FIG. A7.1 Watson Characterization Factor of Petroleum Fractions Copyright by ASTM Int'l (all rights reserved); Reproduction authorized per License Agreement with Genevieve PONS (GECIL Process); Wed Nov 3 07:09:49 EST 2004 A8. EXAMPLE OF PRECISION CALCULATIONS

 

96  

A8.1 Procedure A8.1.1 For a given percentage recovered from a distillation at a given pressure (0.13 or 1.3 kPa), calculate the change in temperature per volume percent recovered {°C(AET)/V %}. A8.1.2 Look up the desired precision (repeatability or reproducibility) from Table 2. Use linear interpolation to find the precision when °C(AET)/V % is not a whole number. A8.2 Example—Desired result: reproducibility of 30 % recovered, 0.13 kPa (1 mm Hg), °C: AET (°C) 40 % 443 AET (°C) 30 % 427 AET (°C) 20 % 409 °C/V % = (443 − 409)/(40 − 20) = 34/20 = 1.7,From Table 2, Reproducibility, 0.13 kPa (1 mm Hg); recovery between 5 and 50 % (inclusive): °C/V % of 1.5 = 13 °C/V % of 2.0 = 16

 

97  

Therefore: 13 + (0.2/0.5)(16 − 13) = 14.2, rounded = 14°C. FIG. A7.2 Boiling Point Corrections for K-Factor Copyright by ASTM Int'l (all rights reserved);Reproduction authorized per License Agreement with Genevieve PONS (GECIL Process); Wed Nov 3 07:09:49 EST 2004 A9. DISTILLATION OF PETROLEUM PRODUCTS AT REDUCED PRESSURE (AUTOMATIC) A9.1 Scope—This test method covers the determination by automatic equipment, at reduced pressures, of the range of boiling points for petroleum products that can be partially or completely vaporized at a maximum liquid temperature of 400°C. A9.2 Summary of Test Method—The sample is distilled in an automatic distillation apparatus that duplicates the distillation conditions described in the manual procedure. Data are obtained from which the initial boiling point (IBP), the final boiling point (FBP), and a distillation curve of atmospheric equivalent temperature (AET) versus volume can be obtained. A9.3 Apparatus—The automatic apparatus should be designed to include the components as described in 6.1. Additional parts not specified can be included by the manufacturer that are not essential for obtaining satisfactory results but are desirable components to the assembly for the purpose of promoting efficient use of the apparatus and ease of operation. A9.3.1 Level Follower/Recording Mechanism for the measurement of the volume of liquid recovered in the receiver. The system shall have a resolution of 0.1 mL with an accuracy of 61 mL. The calibration of the assembly should be confirmed according to the manufacturer’s instructions. A9.3.2 Vacuum Gage, capable of measuring the absolute pressure with an accuracy of 610 Pa (60.08 mm Hg) at 1 kPa (7.5 mm) and below. The vacuum gage is usually an electronic pressure measuring system. An accuracy of 61 % of the observed reading is required in the range above 1 kPa.Electronic diaphragm gages are capable of achieving this level of accuracy, but they must be properly calibrated and rechecked periodically, as described in Annex A3. A9.3.3 Receiver Chamber Temperature Control System, capable of controlling the receiver temperature between 32°C and 78°C. A9.4 Sample and Sample Requirements—Sample and sampling requirements are described in Section 8. A9.5 Preparation of Apparatus—The instrument is prepared in accordance with the manufacturer’s instructions.

 

98  

A9.6 Procedure A9.6.1 Set the temperature of the condenser coolant to at least 30°C below the lowest vapor temperature to be observed in the test.Atemperature near 60°C has been found satisfactory for most charges. A9.6.2 Determine the density of the sample at the temperature of the receiver by means of a hydrometer by Test Method D 1298, by means of a digital density meter using Test Method D 4052, or by using either the mathematical subroutines or tables of Guide D 1250, or a combination thereof. A9.6.3 From the density of the sample, determine the weight, to the nearest 0.1 g, equivalent to 200 mL of the sample at the temperature of the receiver. Weigh this quantity of oil into the distillation flask. A9.6.4 Lubricate the spherical joints of the distillation apparatus with a suitable grease. Connect the flask to the lower spherical joint of the distilling head, place the heater under the flask, put the top mantle in place, and connect the rest of the apparatus using spring clamps to secure the joints. A9.6.5 Insert the temperature sensor into the thermowell of the flask. A9.6.6 Set the operating pressure to the prescribed value for the distillation 3). The pressure should be automatically reduced in stages to prevent foaming of the sample. A9.6.7 Set the initial heat rate to the desired value. The apparatus should have the capability to adjust heat input so that the distillate recovered is at a uniform rate of 6 to 8 mL/min. A9.6.8 After ensuring that the apparatus controls are set according to the manufacturer’s instructions, initiate the distillation. A9.6.9 The apparatus will automatically record the initial boiling point, final boiling point, percent volumes recovered with corresponding actual temperatures, and distillation rates.Actual temperatures recorded are automatically converted to Atmospheric Equivalent Temperatures (AET) using software supplied by the manufacturer. This conversion should be based on (Eq A7.1). A9.6.10 If the liquid temperature reaches 400°C, or if the vapor temperature reaches a maximum before the end point is observed, the distillation equipment shall switch off and terminate the distillation. The apparatus shall automatically record the vapor temperature and total volume percent recovered at the time the distillation is discontinued. A9.6.11 Upon completion of the distillation, the apparatus will automatically enter into a cooling cycle. After the temperature drops below a safe limit, usually 100°C, the pressure in the distillation assembly is gradually increased to atmospheric pressure. The flask and receiver can then be removed for cleaning. If it is necessary to dismantle the apparatus before the contents have cooled below 100°C, use dry nitrogen to bring the system pressure back to atmospheric pressure.

 

99  

A9.6.12 The unit is cleaned as described in 10.13. A9.6.13 Any material in the cold trap is recovered as described in 10.12. A9.7 Precision and Bias A9.7.1 The precision of the test method using automatic Test Method D 1160 equipment is being determined. A9.7.2 The bias between the manual and the automatic test method is being determined.Copyright by ASTM Int'l (all rights reserved);Reproduction authorized per License Agreement with Genevieve PONS (GECIL Process); Wed Nov 3 07:09:49 EST 2004 7.12-APPENDIX (Nonmandatory Information) X1. VAPOR TEMPERATURE MEASURING DEVICE ALIGNMENT PROCEDURE X1.1 A tool to help in determining the spillover point was made out of an approximately 3 mm rod approximately 300 mm in length. A 90° bend was made approximately 25 mm from one end. Then a 2 mm inside diameter (ID) flexible plastic tubing was placed over the end to a total distance of about 30 mm. The flexible plastic tubing is used to prevent scratching of the glassware. The length of the bend is dependent upon the ID of the distillation column.X1.2 This tool is then carefully moved up from the bottomof the distillation column until the end can protrude into the condensing arm. The tip of the bent end of the tool should then be rested on the highest point of the lower internal junction of the distillation column and the condensing section of the vacuum-jacketed column assembly. This is the spillover point. Then with a ballpoint pen make a mark on one side of the outside glass of the distillation column in line with the bottom of the tool. Repeat this step on the opposite side of the distillation column. With two straight edge rulers confirm that the distance from the top of the distillation column down to each of the two marks is equal. If they are both equal, then this is the spillover point. If they are not equal, repeat the steps described above. X1.3 Once the spillover point has been determined, then make a mark on both sides of the outside glass 3 mm 6 1 mm below the marks determined above. This is where the top of the sensing tip should be aligned. (If possible, these two sets of marks should be permanently made on the distillation column since they should not change unless repairs are made to the glassware). X1.4 While holding the distillation column such that you can see through the distillation column, insert the thermocouple which has been placed in the tapered screw cap down into the distillation column. With the tapered fitting in its normal

 

100  

operating position adjust the thermocouple (up or down) so that the top of the sensing tip is aligned with the lower of the two marks made on the outside glass. Once in the proper position tighten the screw cap. Then mark the point where the thermocouple aligns with the top of the screw cap with a permanent marker. This marking will be accurate for this particular distillation column, tapered screw cap, and thermocouple only and can be used to verify proper alignment. 7.13-SUMMARY OF CHANGES Subcommittee D02.08 has identified the location of selected changes to this standard since the last issue (D 1160-02a) that may impact the use of this standard (approved June 10, 2003).(1) Changed variable D to relative density in Eq A7.6. Subcommittee D02.08 has identified the location of selected changes to this standard since the last issue (D 1160-99) that may impact the use of this standard (approved April 10, 2002). (1) Replaced old vacuum-jacketed column figure with a new Fig. 4. (2) Created a new Table 1. ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned in this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the risk of infringement of such rights, are entirely their own responsibility.This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and if not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standards and should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the responsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you should make your views known to the ASTM Committee on Standards, at the address shown below.This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,United States. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above address or at 610-832-9585 (phone), 610-832-9555 (fax), or service@astm.org (e-mail); or through the ASTM website (www.astm.org). Copyright by ASTM Int'l (all rights reserved);Reproduction authorized per License Agreement with Genevieve PONS (GECIL Process); Wed Nov 3 07:09:49 EST 2004

 

101  

Reference 1.ISO 3104, petroleum products-transparent and opaque liquids-determination of kinematic viscosity and calculation of dynamic viscosity. 2.d56 test methods for flash point by tag closed cup tester. 3. D3941 test metod for flash point by the Equilibrium method with a closed cup apparatus . 4.IP 309 diesel and domestic heating fuels-determination of cold filter plugging point pecifications for IP standard thermometrs. 5.D1796 test method for water in crude oils by the distillation method(ASTM test method D4006). 6.D1298 test method for density , relative density or API gravity of crued petroleum and liqvids petroleum products by hydrometer method.