1、Designation: D6501 09Standard 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 Good Laboratory Practices in Laborato-ries Engaged in Sampling and Analysis of WaterD4375 Practice for Basic Statistics in Committee D19 onWaterD5810 Guide for Spiking into Aqueous SamplesD5847 Practice for Writing Quality Control Specificationsfor St
8、andard Test Methods for Water AnalysisE275 Practice for Describing and Measuring Performanceof Ultraviolet 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
9、phosphonate, na group of organophosphorus com-pounds typically used for mineral scale and corrosion control,as cleaning agents, dispersants, and chelants.3.2.1.1 DiscussionTypical phosphonate compounds in-clude, but are not limited to, the following phosphonic acid andtheir neutralized salts: Aminot
10、ri(methylenephosphonic acid),1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-tetra (methylenephosphonic acid), hexamethylenediaminetetra(methylenephosphonic acid), and diethylenetriaminepenta(methylenephosphonic acid).4. Summary of Test Method4.1 Phosphonate materials are converted to ort
11、hophosphateby potassium 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 f
12、or the determination 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 ab
13、ility to measure lowphosphonate concentration and not upon performance criteria.Phosphonate concentrations as low as 0.16 mg/L have been1This test method is under the jurisdiction of ASTM Committee D19 on Waterand is the direct responsibility of Subcommittee D19.05 on Inorganic Constituentsin Water.
14、Current edition approved Oct. 1, 2009. Published October 2009. Originallyapproved in 1999. Last previous edition approved in 2004 as D650104. DOI:10.1520/D6501-09.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book
15、 of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.1*A Summary of Changes section appears at the end of this standard.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.shown effective i
16、n carbonate scale treatment. This test methodenables the measurement of sub-mg/L phosphonate concentra-tion in brines containing interfering elements.5.2 The procedure includes measuring total (see 12.3.8) andfree orthophosphate (see 12.4.3) ions and the difference inconcentration is the phosphonate
17、 concentration. The samplecould 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 t
18、he procedure (see 9.1.2) 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
19、toprecipitate when produced 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
20、pH below 2.6.3 Glassware 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
21、(Autoclave)3.7.2 Spectrophotometer4, for 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 Dispenser5, 20-m
22、L capacity, 2.13E 0.88 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
23、 0.13987Conclusions: All 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(brin
24、e) 0.59405Critical F(lab) 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-Fac
25、tor Without ReplicationSummary 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
26、8 6.33 0.79125 0.01978Column 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 098TABLE X1.3 Statistical Details and Analysis of Variance fo
27、r 3 mg/L SamplesBrinesLaboratory 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
28、2.71 8.12 2.706667 0.005774 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 identif
29、ied as outliers (outside 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 0.15852
30、5 14 0.011323Total 7.302 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 differen
31、t laboratories at the 95 % 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.
32、023333Column 1 8 19.65 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 23D6501
33、 099SUMMARY OF CHANGESCommittee D19 has identified the location of selected changes to this standard since the last issue (D650104)that may impact the use of this standard. (Approved October 1, 2009.)(1) The SI statement was added to Section 1.(2) D1192 was removed from Sections 2 and 10.1.(3) Reage
34、nt references were added to Sections 8, 9, 10, 11, and12.(4) Section 16.3.4 was modified.ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentionedin this standard. Users of this standard are expressly advised that determination o
35、f the validity of any such patent rights, and the riskof 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 andif not revised, either reapproved or withdrawn.
36、 Your comments are invited either for revision of this standard or for additional standardsand should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of theresponsible technical committee, which you may attend. If you feel that your comm
37、ents have not received a fair hearing you shouldmake 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
38、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 serviceastm.org (e-mail); or through the ASTM website(www.astm.org).TABLE X1.4 Statistical Details for the 0.8-mg/L Samples After the Removal of OutliersNOTE 1T
39、hese 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 0.9 0.9 2.7 0.9000 0.0000D 0.7 0.7 0.7 2.1 0.7000 0.0000 NoE 0.88
40、 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 0.0758TABLE X1.5 Statistical Details for the 3 mg/L Samples After the Removal of Outl
41、iersNOTE 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 0910
