API MPMS 10.7-2002 Manual of Petroleum Measurement Standards Chapter 10 Sediment and Water Section 7 Standard Test Method for Water in Crude Oils by Potentiometric Karl Fischer Tit.pdf

1、Manual of PetroleumMeasurement StandardsChapter 10Sediment and WaterSection 7Standard Test Method for Water in Crude Oils by Potentiometric Karl Fischer TitrationSECOND EDITION, DECEMBER 2002REAFFIRMED, MAY 2011Manual of PetroleumMeasurement StandardsChapter 10Sediment and WaterSection 7Standard Tes

2、t Method for Water in Crude Oils by Potentiometric Karl Fischer TitrationMeasurement CoordinationSECOND EDITION, DECEMBER 2002REAFFIRMED, MAY 2011SPECIAL NOTESAPI publications necessarily address problems of a general nature. With respect to partic-ular circumstances, local, state, and federal laws

3、and regulations should be reviewed.API is not undertaking to meet the duties of employers, manufacturers, or suppliers towarn and properly train and equip their employees, and others exposed, concerning healthand safety risks and precautions, nor undertaking their obligations under local, state, or

4、fed-eral laws.Information concerning safety and health risks and proper precautions with respect to par-ticular materials and conditions should be obtained from the employer, the manufacturer orsupplier of that material, or the material safety data sheet.Nothing contained in any API publication is t

5、o be construed as granting any right, byimplication or otherwise, for the manufacture, sale, or use of any method, apparatus, or prod-uct covered by letters patent. Neither should anything contained in the publication be con-strued as insuring anyone against liability for infringement of letters pat

6、ent.Generally, API standards are reviewed and revised, reaffirmed, or withdrawn at least everyfive years. Sometimes a one-time extension of up to two years will be added to this reviewcycle. This publication will no longer be in effect five years after its publication date as anoperative API standar

7、d or, where an extension has been granted, upon republication. Statusof the publication can be ascertained from the API Measurement Coordination Departmenttelephone (202) 682-8000. A catalog of API publications and materials is published annu-ally and updated quarterly by API, 1220 L Street, N.W., W

8、ashington, D.C. 20005.This document was produced under API standardization procedures that ensure appropri-ate notification and participation in the developmental process and is designated as an APIstandard. Questions concerning the interpretation of the content of this standard or com-ments and que

9、stions concerning the procedures under which this standard was developedshould be directed in writing to the standardization manager, American Petroleum Institute,1220 L Street, N.W., Washington, D.C. 20005. Requests for permission to reproduce ortranslate all or any part of the material published h

10、erein should also be addressed to the gen-eral manager.API standards are published to facilitate the broad availability of proven, sound engineer-ing and operating practices. These standards are not intended to obviate the need for apply-ing sound engineering judgment regarding when and where these

11、standards should beutilized. The formulation and publication of API standards is not intended in any way toinhibit anyone from using any other practices.Any manufacturer marking equipment or materials in conformance with the markingrequirements of an API standard is solely responsible for complying

12、with all the applicablerequirements of that standard. API does not represent, warrant, or guarantee that such prod-ucts do in fact conform to the applicable API standard.All rights reserved. No part of this work may be reproduced, stored in a retrieval system, or transmitted by any means, electronic

13、, mechanical, photocopying, recording, or otherwise, without prior written permission from the publisher. Contact the Publisher, API Publishing Services, 1220 L Street, N.W., Washington, D.C. 20005.Copyright 2002 American Petroleum InstituteFOREWORDAPI publications may be used by anyone desiring to

14、do so. Every effort has been made bythe Institute to assure the accuracy and reliability of the data contained in them; however, theInstitute makes no representation, warranty, or guarantee in connection with this publicationand hereby expressly disclaims any liability or responsibility for loss or

15、damage resultingfrom its use or for the violation of any federal, state, or municipal regulation with which thispublication may conflict.Suggested revisions are invited and should be submitted to the standardization manager,American Petroleum Institute, 1220 L Street, N.W., Washington, D.C. 20005.ii

16、iCONTENTSPage1 SCOPE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 REFERENCED DOCUMENTS. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 SUMMARY OF TEST METHOD . . . . . . . . .

17、. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 SIGNIFICANCE AND USE. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15 INTERFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

18、. 16 APPARATUS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27 REAGENTS AND MATERIALS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28 SAMPLING AND TEST SAMPLES. . . . . . . . . . . . . . . . . .

19、 . . . . . . . . . . . . . . . . . . . . . 29 CALIBRATION AND STANDARDIZATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310 PROCEDURE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 311 CALCULATIONS. . . . . . . . .

20、. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 312 PRECISION AND BIAS. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4ANNEX A1 HOMOGENIZATION EFFICIENCY OF UNKNOWN MIXERS . . . . . 4ANNEX A2 APPARATUS . . .

21、. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5FiguresA2.1 Apparatus for Determination of Water by Karl Fischer Reagent. . . . . . . . . . . . . . 5A2.2 Electrode . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

22、 . . . . . . . . . 6Tables1 Test Sample% Water Content Based on Sample Size . . . . . . . . . . . . . . . . . . . . 32 Precision Intervals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4vDesignation: D 4377 00e1Designation: Manual of Petroleum Me

23、asurement Standards (MPMS), Chapter 10.7Designation: 356/99An American National StandardStandard Test Method forWater in Crude Oils by Potentiometric Karl Fischer Titration1This standard is issued under the fixed designation D 4377; the number immediately following the designation indicates the year

24、 oforiginal adoption or, in the case 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.This standard has been approved for use by agencies of the Departme

25、nt of Defense.e1NOTEFootnote 1 and the Referenced Documents were corrected editorially to comply with the ASTM-API joint standardcontract in October 2002.1. Scope1.1 This test method covers the determination of water inthe range from 0.02 to 2 % in crude oils. Mercaptan and sulfide(Sor H2S) sulfur a

26、re known to interfere with this test method(see Section 5).1.2 This test method is intended for use with standard KarlFischer reagent or pyridine-free Karl Fischer reagents.1.3 The values stated in SI units are to be regarded as thestandard.1.4 This standard does not purport to address all of thesaf

27、ety concerns, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety and health practices and determine the applica-bility of regulatory limitations prior to use. Specific precau-tionary statements are given in Section 7.2. Referenced D

28、ocuments2.1 ASTM Standards:D 1193 Specification for Reagent Water2D 4006 Test Method for Water in Crude Oil by Distillation(API MPMS Chapter 10.2)3D 4057 Practice for Manual Sampling of Petroleum andPetroleum Products (API MPMS Chapter 8.1)3D 4177 Practice for Automatic Sampling of Petroleum andPetr

29、oleum Products (API MPMS Chapter 8.2)3E 203 Test Method for Water Using Volumetric Karl FischerReagent42.2 API Standards:5MPMS Chapter 8.1 Manual Sampling of Petroleum andPetroleum Products (ASTM Practice D 4057)MPMS Chapter 8.2 Automatic Sampling of Petroleum andPetroleum Products (ASTM Practice D

30、4177)MPMS Chapter 10.2 Determination of Water in Crude Oilby Distillation (ASTM Test Method D 4006)3. Summary of Test Method3.1 After homogenizing the crude oil with a mixer, analiquot of the crude, in a mixed solvent, is titrated to anelectrometric end-point using Karl Fischer reagent.4. Significan

31、ce and Use4.1 A knowledge of the water content of crude oil isimportant in the refining, purchase, sale, or transfer of crudeoils.5. Interferences5.1 A number of substances and class of compounds asso-ciated with condensation or oxidation-reduction reactions in-terfere in the determination of water

32、by Karl Fischer. In crudeoils, the most common interferences are mercaptans andsulfides. At levels of less than 500 g/g (ppm) (as sulfur) theinterference from these compounds is insignificant. For moreinformation on substances that interfere in the determination ofwater using the (Karl Fischer reage

33、nt) titration method see TestMethod E 203.1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products and Lubricants and the API Committee on Petroleum Measure-ment, and is the direct responsibility of Subcommittee D02.02/COMQ, the jointASTM-API Committee on Static Petrole

34、um Measurement.Current edition approved Aug. 10, 2000. Published October 2000. Originallypublished as D 437784. Last previous edition D 437793a.2Annual Book of ASTM Standards, Vol 11.01.3Annual Book of ASTM Standards, Vol 05.02.4Annual Book of ASTM Standards, Vol 15.05.5Published as Manual of Petrol

35、eum Measurement Standards. Available from theAmerican Petroleum Institute (API), 1220 L St., NW, Washington, DC 20005-4070.1 6. Apparatus6.1 Karl Fischer Apparatus, using electrometric end-point.A suggested assembly of the apparatus is described in AnnexA2.6.1.1 Presently there is available on the m

36、arket commercialKarl Fischer titration assemblies, some of which automaticallystop the titration at the end-point. Instructions for operation ofthese devices are provided by the manufacturer and notdescribed herein. This test method is not intended for use withcoulometric Karl Fischer titrators.6.2

37、Mixer, to homogenize the crude sample.6.2.1 Non-Aerating, High-Speed, Shear Mixer,6capable ofmeeting the homogenization efficiency test described in AnnexA1. The sample size is limited to that suggested by themanufacturer for the size of the probe.6.3 Syringes:6.3.1 Samples and base liquid are most

38、easily added to thetitration vessel by means of accurate glass syringes with LUERfittings and hypodermic needles of suitable length. The boresof the needles used should be kept as small as possible, butlarge enough to avoid problems arising from back pressure/blocking whilst sampling. Suggested syri

39、nge sizes are asfollows:6.3.1.1 Syringe, 10 L, with a needle long enough to dipbelow the surface of the base solution in the cell during thestandardization procedure (see Section 9).6.3.1.2 Syringes, 2.5 mL, 5 mL, and 10 mL for crude oilsamples (see Section 10).6.3.1.3 Syringe, 20 mL or larger for s

40、ample solvent.7. Reagents and Materials7.1 Purity of ReagentsReagent grade chemicals shall beused in all tests. Unless otherwise indicated, it is intended thatall reagents shall conform to the specifications of the Commit-tee on Analytical Reagents of the American Chemical Society,where such specifi

41、cations are available.7Other grades may beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of the determination.7.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean reagent w

42、ater as definedby Type IV of Specification D 1193.7.3 1-Ethylpiperidine (99 + percent). (WarningIrritant.Flammable.)7.4 Karl Fischer Reagents, Standard reagent containingpyridine (7.4.1) or pyridine-free reagent (7.4.2).7.4.1 Karl Fischer Reagent Ethylene Glycol MonomethylEther Solution, stabilized,

43、 containing pyridine, (1 mL = 5 mgof water)Fresh Karl Fischer reagent must be used. Must beused with solvent in 7.6.1. (WarningCombustible. Harmfulif swallowed, inhaled, or absorbed through the skin.)7.4.2 Pyridine-Free Karl Fischer (one-component) reagentdiluted with xyleneDilute three parts pyridi

44、ne-free KarlFischer (one-component) reagent8(1 mL = 5 mg water) to 1part xylene. Fresh Karl Fischer reagent must be used.(WarningSee 7.4.1) Must be used with solvent in 7.6.2.7.5 Methanol (anhydrous), Maximum 0.1 % water but pref-erably less than 0.05 % water. (WarningFlammable. Vaporharmful. May be

45、 fatal or cause blindness if swallowed orinhaled. Cannot be made nonpoisonous.)7.6 Sample SolventUse 7.6.1 for standard Karl Fischerreagent containing pyridine and 7.6.2 for pyridine-free KarlFischer reagent.7.6.1 Sample SolventMix 40 mL of 1-ethylpiperidine, 20mL of methanol, and 40 mL of Karl Fisc

46、her reagent in asealable glass bottle. Allow this mixture to sit overnight beforeadding 200 mL of xylene. Additional methanol may berequired in some cases for the proper function of the elec-trodes. (Warningsee 7.3.)7.6.2 Sample Solvent for Pyridine-Free ReagentsMix 3parts chloroform to 1 part pyrid

47、ine-free solvent using solventpart of two-component reagent8(contains SO2and odorlessamine dissolved in methanol) and store in a sealable glassbottle. An evaluation of a number of crude oils has demon-strated that xylene can be substituted for chloroform with noapparent change in accuracy of this te

48、st method. (WarningFlammable. Vapor harmful.) (Also, see 7.4.1.)7.7 Xylene, reagent grade. Less than 0.05 % water.7.8 Chloroform, reagent grade. (WarningHarmful if in-haled or swallowed. Carcinogen (animal positive). Skin andeye irritant. May produce toxic vapors if burned.8. Sampling and Test Sampl

49、es8.1 Sampling, is defined as all the steps required to obtain analiquot representative of the contents of any pipe, tank, or othersystem, and to place the sample into the laboratory testcontainer. The laboratory test container and sample volumeshall be of sufficient dimensions and volume to allow mixing asdescribed in 8.1.2.1.8.1.1 Laboratory SampleOnly representative samples ob-tained as specified in Practice D 4057 (API MPMS Chapter8.1) and Practice D 4177 (API MPMS Chapter 8.2) sh