1、Designation: D6501 15Standard Test Method forPhosphonate in Brines1This standard is issued under the fixed designation D6501; the number immediately following the designation indicates the year oforiginal adoption or, in the case of revision, the year of last revision. A number in parentheses indica
2、tes the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope*1.1 This test method covers the colorimetric determinationof phosphonate (PNA) in brines from gas and oil productionoperations in the range from 0.1 to 5 mg/L.1.2 Thi
3、s phosphonate method is intended for use to analyzelow concentration of phosphonate in brine containing interfer-ing elements. This test method is most useful for analyzingphosphonate at 0.1 to 1 mg/L range in brines with interferingelements; however, it requires personnel with good analyticalskill.
4、1.3 This test method has been used successfully withreagent water and both field and synthetic brine. It is the usersresponsibility to ensure the validity of this test method forwaters of untested matrices.1.4 The values stated in SI units are to be regarded asstandard. No other units of measurement
5、 are included in thisstandard.1.5 This standard does not purport to address all of thesafety 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 limitation
6、s prior to use. For specific hazardstatements, see 9.1.3.2. Referenced Documents2.1 ASTM Standards:2D1129 Terminology Relating to WaterD1193 Specification for Reagent WaterD2777 Practice for Determination of Precision and Bias ofApplicable Test Methods of Committee D19 on WaterD3370 Practices for Sa
7、mpling Water from Closed ConduitsD3856 Guide for Management Systems in LaboratoriesEngaged in Analysis of WaterD4375 Practice for Basic Statistics in Committee D19 onWaterD5810 Guide for Spiking into Aqueous SamplesD5847 Practice for Writing Quality Control Specificationsfor Standard Test Methods fo
8、r Water AnalysisE275 Practice for Describing and Measuring Performance ofUltraviolet and Visible Spectrophotometers3. Terminology3.1 DefinitionsFor definitions of terms used in this testmethod, refer to Terminology D1129.3.2 Definitions of Terms Specific to This Standard:3.2.1 phosphonate, na group
9、of organophosphorus com-pounds typically used for mineral scale and corrosion control,as cleaning agents, dispersants, and chelants.3.2.1.1 DiscussionTypical phosphonate compoundsinclude, but are not limited to, the following phosphonic acidand their neutralized salts: Aminotri(methylenephosphonicac
10、id), 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenedi-aminetetra (methylenephosphonic acid), hexamethylenedi-aminetetra (methylenephosphonic acid), and diethylenetri-aminepenta (methylenephosphonic acid).4. Summary of Test Method4.1 Phosphonate materials are converted to orthophosphateby potass
11、ium persulfate digestion. The orthophosphate is thenreacted with ammonium molybdate to form a phosphomolyb-date complex. The complex is extracted with a methyl isobutylketone/cyclohexane mixture and measured colorimetrically.5. Significance and Use5.1 This test method is useful for the determination
12、 of tracelevel phosphonate residues in brines. Chemical treatmentwhich contain phosphonates are used as mineral scale andcorrosion inhibitors in gas and oil drilling and productionoperations; and other industrial applications. Often, the deci-sion for treatment is based on the ability to measure low
13、phosphonate concentration and not upon performance criteria.Phosphonate concentrations as low as 0.16 mg/L have beenshown effective in carbonate scale treatment. This test methodenables the measurement of sub-mg/L phosphonate concentra-tion in brines containing interfering elements.5.2 The procedure
14、 includes measuring total (see 12.3.8) andfree orthophosphate (see 12.4.3) ions and the difference in1This test method is under the jurisdiction of ASTM Committee D19 on Waterand is the direct responsibility of Subcommittee D19.05 on Inorganic Constituentsin Water.Current edition approved March 15,
15、2015. Published April 2015. Originallyapproved in 1999. Last previous edition approved in 2009 as D6501 09. DOI:10.1520/D6501-15.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book of ASTMStandards volume informati
16、on, refer to the standards Document Summary page onthe ASTM website.*A Summary of Changes section appears at the end of this standardCopyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States1concentration is the phosphonate concentration. The s
17、amplecould contain orthophosphate naturally, or from decompositionof the phosphonate during processing or well treatment or fromtreating compounds containing molecular dehydrated phos-phates.6. Interferences6.1 Sulfide interferes in this test method, but techniquesdescribed in the procedure (see 9.1
18、.2) eliminate this interfer-ence. Concentrations less than 1000 mg/L copper (Cu+2) andsilica (SiO2/SiO32/Si+4); and less than 200 mg/L of iron(Fe+2/Fe+3) can be tolerated.6.2 Produced brines can contain high concentrations ofdissolved solids. Some of these dissolved solids tend toprecipitate when pr
19、oduced brines reach new equilibria atatmospheric temperature and pressure. Phosphonate will co-precipitate or adsorb onto these newly formed solids andbecome unavailable for analysis. This problem can be mini-mized by acidifying the brine sample on-site with hydrochloricacid to pH below 2.6.3 Glassw
20、are must be cleaned with phosphate free deter-gent and rinsed with 0.1 N hydrochloric acid to remove allresidual phosphate or phosphonate.6.4 The standard addition method in 12.6 is recommendedfor brine with high matrix interference.7. Apparatus7.1 Pressure Cooker or Sterilizer (Autoclave).37.2 Spec
21、trophotometer,4for measurement above 650 nmwith 4-cm light path cells. A longer light path will yield acorresponding higher sensitivity (see 12.5.1). Spectrophotom-eter practices prescribed in this test method shall conform toPractice E275.7.3 Bottle Top Liquid Dispenser,520-mL capacity, 2.13E 0.88
22、0.76 0.84 2.48 0.82667 0.0611G 0.95 0.95 0.94 2.84 0.94667 0.00577 Yes, remove data from Lab hH 0.48 0.5 0.48 1.46 0.48667 0.01155I 0.83 0.85 0.83 2.51 0.83667 0.01155Brine sum 6.41 6.33 6.44 19.18Brine mean 0.80125 0.79125 0.805Brine std 0.14865 0.14066 0.14928Mean 0.79917Std 0.13987Conclusions: Al
23、l values from laboratory h were identified as outliers (outside of 95 % upper and lower confidencelimits.Anova Table Sourceof VarianceSum of SquaresDegrees ofFreedomMeanSquaresLabs 0.43965 7 0.06281Brine 0.00081 2 0.0004Error 0.00952 14 0.00068Total 0.44998F (lab) 92.315F(brine) 0.59405Critical F(la
24、b) 92.315Critical F(brine) 0.59405Conclusion: The are no significant differences between results in different brines at the 95 % confidence level.Conclusion: The are significant differences between results from different laboratories at the 95 % confidence level.Anova: Two-Factor Without Replication
25、Summary Count Sum Average VarianceRow 1 3 2.57 0.85667 0.00083Row 2 3 2.52 0.84 0.0003Row 3 3 2.7 0.9 0Row 4 3 2.1 0.7 1.1E-16Row 5 3 2.48 0.82667 0.00373Row 6 3 2.84 0.94667 3.3E-05Row 7 3 1.46 0.48667 0.00013Row 8 3 2.51 0.83667 0.00013Column 1 8 6.41 0.80125 0.0221Column 2 8 6.33 0.79125 0.01978C
26、olumn 3 8 6.44 0.805 0.02229AnovaSource of Variation SS df MS F P-Value F critRows 0.43965 7 0.06281 92.315 1.2E-10 2.7642Columns 0.00081 2 0.0004 0.59405 0.56542 3.73889Error 0.00952 14 0.00068Total 0.44998 23D6501 159TABLE X1.3 Statistical Details and Analysis of Variance for 3 mg/L SamplesBrinesL
27、aboratory 1 2 3 Lab Sum Lab Mean Lab Std Outlier mean test ? =A 1.34 0.99 1.12 3.45 1.15 0.176918 Xbar = 2.415000B 2.58 2.6 2.56 7.74 2.58 0.02 S mean = 0.5808860C 2.8 2.8 2.7 8.3 2.766667 0.057735D 333930Xbar 1.15/S mean=2.1782.13E 2.46 2.13 2.55 7.14 2.38 0.221133G 2.71 2.7 2.71 8.12 2.706667 0.00
28、5774 Yes, remove data from Lab aH 2.06 2.05 2.1 6.21 2.07 0.026458I 2.7 2.5 2.8 8 2.666667 0.152753Brine sum 19.65 18.77 19.54 57.96Brine mean 2.45625 2.34625 2.4425Brine std 0.528608 0.634754 0.593795Mean 2.415Std 0.563452Conclusions: All values from laboratory a were identified as outliers (outsid
29、e of 95 % upper and lower confidence limitsand T value, extreme mean tested, that exceeds the critical value (see Practice D277798).Anova Table Source ofVarianceSum SquaresDegrees ofFreedomMeanSquaresLabs 7.086 7 1.012286 1.55E-10Brine 0.057475 2 0.028737 0.114685Error 0.158525 14 0.011323Total 7.30
30、2 23F (lab) 89.39915F(brine) 2.537928Critical F(lab) 2.764196Critical F(brine) 3.73889Conclusion: There are no significant differences between results with different brines at the 95 % confidence level.Conclusion: There are significant differences between results from different laboratories at the 9
31、5 % confidence level.Anova: Two-Factor Without ReplicationSummary Count Sum Average VarianceRow 1 3 3.45 1.15 0.0313Row 2 3 7.74 2.58 0.0004Row 3 3 8.3 2.766667 0.003333Row4 3930Row 5 3 7.14 2.38 0.0489Row 6 3 8.12 2.706667 3.33E-05Row 7 3 6.21 2.07 0.0007Row 8 3 8 2.666667 0.023333Column 1 8 19.65
32、2.45625 0.279427Column 2 8 18.77 2.34625 0.402913Column 3 8 19.54 2.4425 0.352593AnovaSource of Variation SS df MS F P-Value F critRows 7.086 7 1.012286 89.39915 1.55E-10 2.764196Columns 0.057475 2 0.028737 2.537928 0.114685 3.73889Error 0.158525 14 0.011323Total 7.302 23TABLE X1.4 Statistical Detai
33、ls for the 0.8-mg/L Samples After the Removal of OutliersNOTE 1These are the values at 0.8 mg/L after the removal of the outliers.BrinesLaboratory 1 2 3 Lab Sum Lab Mean Lab Std Outlier Single Value ? =A 0.84 0.84 0.89 2.57 0.8567 0.0289B 0.83 0.83 0.86 2.52 0.8400 0.0173 Xbar 0.7/S =1.902.73C 0.9 0
34、.9 0.9 2.7 0.9000 0.0000D 0.7 0.7 0.7 2.1 0.7000 0.0000 NoE 0.88 0.76 0.84 2.48 0.8267 0.0611G 0.95 0.95 0.94 2.84 0.9467 0.0058I 0.83 0.85 0.83 2.51 0.8367 0.0115Brine sum 5.93 5.83 5.96 17.72Brine mean 0.8471 0.8329 0.8514Brine std 0.0783 0.0832 0.0767Mean 0.8438 So 0.0268Std 0.0758D6501 1510SUMMA
35、RY OF CHANGESCommittee D19 has identified the location of selected changes to this standard since the last issue (D6501 09) that may impact the use of this standard. (Approved Apr. 1, 2015.)(1) Added Note 1. (2) Revised 11.3, 12.2.3, and 15.7.ASTM International takes no position respecting the valid
36、ity of any patent rights asserted in connection with any item mentionedin this standard. Users of this standard are expressly advised that determination of the validity of any such patent rights, and the riskof infringement of such rights, are entirely their own responsibility.This standard is subje
37、ct to revision at any time by the responsible technical committee and must be reviewed every five years andif not revised, either reapproved or withdrawn. Your comments are invited either for revision of this standard or for additional standardsand should be addressed to ASTM International Headquart
38、ers. Your comments will receive careful consideration at a meeting of theresponsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing you shouldmake your views known to the ASTM Committee on Standards, at the address shown below.This standard
39、 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 aboveaddress or at 610-832-9585 (phone), 610-832-9555 (fax), or servic
40、eastm.org (e-mail); or through the ASTM website(www.astm.org). Permission rights to photocopy the standard may also be secured from the Copyright Clearance Center, 222Rosewood Drive, Danvers, MA 01923, Tel: (978) 646-2600; http:/ X1.5 Statistical Details for the 3 mg/L Samples After the Removal of O
41、utliersNOTE 1Data for 3 mg/L after outliers have been removed.BrinesLaboratory 1 2 3 Lab Sum Lab Mean Lab Std Outlier Single Value ? =B 2.58 2.6 2.56 7.74 2.5800 0.0200 Xbar 2.05/S =1.892.73C 2.8 2.8 2.7 8.3 2.7667 0.0577D 3 3 3 9 3.0000 0.0000 NoE 2.46 2.13 2.55 7.14 2.3800 0.2211G 2.71 2.7 2.71 8.12 2.7067 0.0058H 2.06 2.05 2.1 6.21 2.0700 0.0265I 2.7 2.5 2.8 8 2.6667 0.1528Brine sum 18.31 17.78 18.42 54.51Brine mean 2.6157 2.5400 2.6314Brine std 0.2978 0.3460 0.2797Mean 2.5957 So 0.1047Std 0.2889D6501 1511
