1、Designation: D 3764 06e1An American National StandardStandard Practice forValidation of the Performance of Process Stream AnalyzerSystems1This standard is issued under the fixed designation D 3764; the number immediately following the designation indicates the year oforiginal adoption or, in the cas
2、e of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon (e) indicates an editorial change since the last revision or reapproval.e1NOTEUpdated Fig. 5 editorially in November 2006.INTRODUCTIONOperation of a process stream analyzer s
3、ystem typically involves four sequential activities.(1) Analyzer CalibrationWhen an analyzer is initially installed, or after major maintenance hasbeen performed, diagnostic testing is performed to demonstrate that the analyzer meets themanufacturers specifications and historical performance standar
4、ds.These diagnostic tests may requirethat the analyzer be adjusted so as to provide predetermined output levels for certain referencematerials. (2) CorrelationOnce the diagnostic testing is completed, process stream samples areanalyzed using the analyzer system. For application where the process ana
5、lyzer system results arerequired to agree with results produced from an independent (primary) test method (PTM), amathematical function is derived that relates the analyzer results to the primary test method results(PTMR). The application of this mathematical function to an analyzer result produces
6、a predictedprimary test method result (PPTMR). (3) Probationary ValidationAfter the correlation relation-ship between the analyzer results and primary test method results has been established, a probationaryvalidation is performed using an independent but limited set of materials that were not part
7、of thecorrelation activity. This probationary validation is intended to demonstrate that the PPTMRs agreewith the PTMRs to within user-specified requirements for the analyzer system application. (4) Gen-eral and Continual ValidationAfter an adequate amount of PPTMRs and PTMRs have beenaccrued on mat
8、erials that were not part of the correlation activity, a comprehensive statisticalassessment is performed to demonstrate that the PPTMRs agree with the PTMRs to within thetolerances established from the correlation activities. Subsequent to a successful general validation,quality assurance control c
9、hart monitoring of the differences between PPTMR and PTMR is conductedduring normal operation of the process analyzer system to demonstrate that the agreement between thePPTMRs and PTMRs established in the General Validation is maintained. This practice deals with thethird and fourth of these activi
10、ties.1. Scope1.1 This practice describes procedures and methodologiesbased on the statistical principles of Practice D 6708 to validatewhether the degree of agreement between the results producedby a total analyzer system (or its subsystem), versus the resultsproduced by an independent test method t
11、hat purports tomeasure the same property, meets user-specified requirements.This is a performance-based validation, to be conducted usinga set of materials that are not used a priori in the developmentof any correlation between the two measurement systems underinvestigation. A result from the indepe
12、ndent test method isherein referred to as a Primary Test Method Result (PTMR).1.2 This practice assumes any correlation necessary tomitigate systemic biases between the analyzer system and PTMhave been applied to the analyzer results.1.3 This practice requires that both the primary methodagainst whi
13、ch the analyzer is compared to, and the analyzersystem under investigation, are in statistical control. Practicesdescribed in Practice D 6299 should be used to ensure thiscondition is met.1.4 This practice applies if the process stream analyzersystem and the primary test method are based on the same
14、measurement principle(s), or, if the process stream analyzer1This practice is under the jurisdiction of ASTM Committee D02 on PetroleumProducts and Lubricants and is the direct responsibility of Subcommittee D02.25 onPerformance Assessment and Validation of Process Stream Analyzer Systems forPetrole
15、um and Petroleum Products.Current edition approved July 1, 2006. Published August 2006. Originallyapproved in 1980. Last previous edition approved in 2001 as D 376401.1Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.system uses a dire
16、ct and well-understood measurement prin-ciple that is similar to the measurement principle of the primarytest method. This practice also applies if the process streamanalyzer system uses a different measurement technology fromthe primary test method, provided that the calibration protocolfor the dir
17、ect output of the analyzer does not require use of thePTMRs (see Case 1 in Note 1).1.5 This practice does not apply if the process streamanalyzer system utilizes an indirect or mathematically modeledmeasurement principle such as chemometric or multivariateanalysis techniques where PTMRs are required
18、 for the chemo-metric or multivariate model development. Users should referto Practice D 6122 for detailed validation procedures for thesetypes of analyzer systems (see Case 2 in Note 1).NOTE 1For example, for the measurement of benzene in sparkignition fuels, comparison of a Mid-Infrared process an
19、alyzer systembased on Test Method D 6277 to a Test Method D 3606 gas chromatog-raphy primary test method would be considered Case 1, and this practicewould apply. For each sample, the Mid-Infrared spectrum is convertedinto a single analyzer result using methodology (Test Method D 6277) thatis indepe
20、ndent of the primary test method (Test Method D 3606).However, when the same analyzer uses a multivariate model to correlatethe measured Mid-Infrared spectrum to Test Method D 3606 referencevalues using the methodology of Practice E 1655, it is considered Case 2and Practice D 6122 applies. In this c
21、ase 2 example, the direct output ofthe analyzer is the spectrum, and the conversion of this multivariate outputto an analyzer result require use of Practice D 6122, hence it is notindependent of the primary test method.1.6 Performance Validation is conducted by calculating theprecision and bias of t
22、he differences between results from theanalyzer system (or subsystem) after the application of anynecessary correlation, (such results are herein referred to asPredicted Primary Test Method Results (PPTMRs), versus thePTMRs for the same sample set. Results used in the calculationare for samples that
23、 are not used in the development of thecorrelation. The calculated precision and bias are statisticallycompared to user-specified requirements for the analyzersystem application.1.6.1 For analyzers used in product release or productquality certification applications, the precision and bias re-quirem
24、ent for the degree of agreement are typically based onthe site or published precision of the Primary Test Method.NOTE 2In most applications of this type, the PTM is the specification-cited test method.1.6.2 This practice does not describe procedures for estab-lishing precision and bias requirements
25、for analyzer systemapplications. Such requirements must be based on the critical-ity of the results to the intended business application and oncontractual and regulatory requirements. The user must estab-lish precision and bias requirements prior to initiating thevalidation procedures described here
26、in.1.7 Two procedures for validation are described: the linesample procedure and the validation reference material (VRM)injection procedure.1.8 Only the analyzer system or subsystem downstream ofthe VRM injection point or the line sample extraction point isbeing validated by this practice.1.9 The li
27、ne sample procedure is limited to applicationswhere material can be safely withdrawn from the samplingpoint of the analyzer unit without significantly altering theproperty of interest.1.10 Validation information obtained in the application ofthis practice is applicable only to the type and property
28、rangeof the materials used to perform the validation.1.11 Two types of validation are described: General Valida-tion, and Level Specific Validation. These are typically con-ducted at installation or after major maintenance once thesystem mechanical fitness-for-use has been established.1.11.1 General
29、 Validation is based on the statistical prin-ciples and methodology of Practice D 6708. In most cases,General Validation is preferred, but may not always be possibleif the variation in validation materials is insufficient. GeneralValidation will validate analyzer operation over a wider oper-ating ra
30、nge than Level Specific Validation.1.11.2 When the variation in available validation materialsis insufficient to satisfy the requirements of Practice D 6708,aLevel Specific Validation is done to validate analyzer operationover a limited range.1.11.3 The validation outcome are considered valid onlywi
31、thin the range covered by the validation material Data fromseveral different Validations (general or level-specific) canpotentially be combined for use in a General Validation.1.12 Procedures for the continual validation of systemperformance are described. These procedures are typicallyapplied at a
32、frequency commensurate with the criticality of theapplication.1.13 This practice does not address procedures for diagnos-ing causes of validation failure.1.14 This standard does not purport to address all of thesafety concerns, if any, associated with its use. It is theresponsibility of the user of
33、this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use.2. Referenced Documents2.1 ASTM Standards:2D 1265 Practice for Sampling Liquefied Petroleum (LP)Gases, Manual MethodD 3606 Test Method for Determination of Benz
34、ene andToluene in Finished Motor and Aviation Gasoline by GasChromatographyD 4057 Practice for Manual Sampling of Petroleum andPetroleum ProductsD 4177 Practice for Automatic Sampling of Petroleum andPetroleum ProductsD 5842 Practice for Sampling and Handling of Fuels forVolatility MeasurementD 6122
35、 Practice for Validation of the Performance of Mul-tivariate Process Infrared SpectrophotometersD 6277 Test Method for Determination of Benzene in2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards
36、 volume information, refer to the standards Document Summary page onthe ASTM website.D376406e12Spark-Ignition Engine Fuels Using Mid Infrared Spectros-copyD 6299 Practice for Applying Statistical Quality AssuranceTechniques to Evaluate Analytical Measurement SystemPerformanceD 6708 Practice for Stat
37、istical Assessment and Improve-ment of Expected Agreement Between Two Test Methodsthat Purport to Measure the Same Property of a MaterialE 456 Terminology Relating to Quality and StatisticsE 1655 Practices for Infrared Multivariate QuantitativeAnalysisF 307 Practice for Sampling Pressurized Gas for
38、GasAnaly-sis2.2 ASTM Adjuncts:Software Program CompTM, adjunct to Practice D 670833. Terminology3.1 Definitions:3.1.1 accepted reference value (ARV), na value thatserves as an agreed-upon reference for comparison, and whichis derived as: (1) a theoretical or established value, based onscientific pri
39、nciples, (2) an assigned or certified value, based onexperimental work of some national or international organiza-tion, or (3) a consensus or certified value, based on collabora-tive experimental work under the auspices of a scientific orengineering group. E 4563.1.2 cross-method reproducibility (RX
40、Y), na quantitativeexpression of the random error associated with the differencebetween two results obtained by different operators usingdifferent apparatus and applying the two methods X and Y,respectively, each obtaining a single result on an identical testsample, when the methods have been assess
41、ed and an appro-priate bias-correction has been applied in accordance with thispractice; it is defined as the 95 % confidence limit for thedifference between two such single and independent results.D 67083.1.2.1 DiscussionWithin the context of this practice, RXYis interpreted to be the 95 % confiden
42、ce limit for the predictiondeviation between any single Primary Test Method Result(PTMR) and the Predicted Primary Test Method Result(PPTMR) produced by the analyzer system that is deemedacceptable on the assumption that both the analyzer system andprimary test method are in statistical control, and
43、 that thecorrelation relationship applied to the analyzer results toproduce the PPTMR is fit-for-purpose.3.1.3 precision, nthe closeness of agreement betweenindependent test results obtained under stipulated conditions.E 4563.1.4 repeatability conditions, nconditions where inde-pendent test results
44、are obtained with the same method onidentical test items in the same laboratory by the same operatorusing the same equipment within short intervals of time.E 4563.1.5 reproducibility conditions, nconditions where testresults are obtained with the same method on identical testitems in different labor
45、atories with different operators usingdifferent equipment. E 4563.1.6 site precision conditions, nconditions under whichtest results are obtained by one or more operators in a singlesite location practicing the same test method on a singlemeasurement system using test specimens taken at randomfrom t
46、he same sample of material, over an extended period oftime spanning at least a 15 day interval. D 62993.1.6.1 DiscussionA measurement system may comprisemultiple instruments being used for the same test method.3.1.7 site precision, n2.77 times the standard deviation ofresults obtained under site pre
47、cision conditions. D 62993.2 Definitions of Terms Specific to This Standard:3.2.1 Analyzer System Items:3.2.1.1 analyzer output, na signal (pneumatic, electrical,or digital), proportional to the property being measured that issuitable for readout or control instrumentation external to theanalyzer sy
48、stem.3.2.1.2 analyzer system result, nthe measured propertyreading, in the accepted property measurement units, that isdisplayed by the analyzer unit readout instrumentation ortransmitted to end user of the analyzer system.3.2.1.3 analyzer unit, nthe instrumental equipment nec-essary to automaticall
49、y measure the physical or chemicalproperty of a process or product stream sample using either anintermittent or a continuous technique.3.2.1.4 analyzer unit repeatability, n2.77 times the stan-dard deviation of results obtained from repetitive analysis ofthe same material directly injected into the analyzer unit underrepeatability conditions.3.2.1.5 continuous analyzer unit, nan analyzer that mea-sures the property value of a process or product stream on acontinuous basis and dynamically displays the instantaneouslyupdated analyzer output.3.2.1.6 intermittent ana
