1、Designation: D 6501 04Standard Test Method forPhosphonate in Brines1This standard is issued under the fixed designation D 6501; 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 indi
2、cates the year of last reapproval. Asuperscript epsilon (e) 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
3、This 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 analyticalski
4、ll.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 This standard does not purport to address all of thesafety concerns, if any, associated
5、 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. For specific hazardstatements, see 9.1.3.2. Referenced Documents2.1 ASTM Standards:2D 1129 Terminology Re
6、lating to WaterD 1192 Specification for Equipment for Sampling Waterand Steam in Closed ConduitsD 1193 Specification for Reagent WaterD 2777 Practice for Determination of Precision and Bias ofApplicable Test Methods of Committee D-19 on WaterD 3370 Practices for Sampling Water from Closed ConduitsD
7、3856 Guide for Good Laboratory Practices in Laborato-ries Engaged in Sampling and Analysis of WaterD 4375 Terminology for Basic Statistics in Committee D19on WaterD 5810 Guide for Spiking into Aqueous SamplesD 5847 Practice for Writing Quality Control Specificationsfor Standard Test Methods for Wate
8、r AnalysisE 275 Practice for Describing and Measuring Performanceof Ultraviolet, Visible, and Near Infrared Spectrophotom-eters3. Terminology3.1 DefinitionsFor definitions of terms used in this testmethod, refer to Terminology D 1129.3.2 Definitions of Terms Specific to This Standard:3.2.1 phosphona
9、te, na group of organophosphorus com-pounds typically used for mineral scale and corrosion control,as cleaning agents, dispersants, and chelants. Typical phospho-nate compounds include, but are not limited to, the followingphosphonic acid and their neutralized salts: Aminotri(methyl-enephosphonic ac
10、id), 1-hydroxyethylidene-1,1-diphosphonicacid, ethylenediaminetetra (methylenephosphonic acid), hex-amethylenediaminetetra (methylenephosphonic acid), and di-ethylenetriaminepenta (methylenephosphonic acid).4. Summary of Test Method4.1 Phosphonate materials are converted to orthophosphateby potassiu
11、m 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 o
12、f 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 lowph
13、osphonate 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.1This test method i
14、s 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 1, 2004. Published April 2004. Originallyapproved in 1999. Last previous edition approved in 1999 as D 650199.2For reference
15、d ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at serviceastm.org. For Annual Book 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.Copyrigh
16、t ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.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 concentration. The samplecould contain orth
17、ophosphate 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 9.1.2) eliminate this inte
18、rfer-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 produced brines reach new
19、 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 Glassware must be cleaned wit
20、h 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)3.7.2 Spectrophotometer4, for mea
21、surement 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 E 275.7.3 Bottle Top Liquid Dispenser5, 20-mL capacity, 2.13E 0.88 0.76 0.84 2.48 0.826
22、67 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: All values from labora
23、tory 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(lab) 92.315Critical F(
24、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 ReplicationSummary Count Sum Av
25、erage 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 0.01978Column 3 8 6.44 0.805
26、 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 23D6501048TABLE X1.3 Statistical Details and Analysis of Variance for 3 mg/L SamplesBrinesLaboratory 1 2 3 Lab S
27、um 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 0.005774 Yes, remove data
28、 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 (outside of 95 % upper and l
29、ower confidence limitsand T value, extreme mean tested, that exceeds the critical value (see Practice D 277798).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 7.302 23F (lab) 89.39915
30、F(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 95 % confidence level
31、.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 2.45625 0.279427Colu
32、mn 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 23D6501049SUMMARY OF CHANGESCommittee D19 has iden
33、tified the location of selected changes to this standard since the last issue (D 650199)that may impact the use of this standard.(1) Section 8.2 was modified to use Type 1 water.(2) Sections 15 Quality Control and 16 Precision and Bias werechanged to Section 15 Precision and Bias and 16 QualityContr
34、ol.Section 15.7 was added to the Precision and Bias.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 of the validity of any such patent rig
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36、 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 comments have not received a fair hearing
37、 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 multiple copies) of this standard may
38、 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 1These are the values at 0.8 mg/L after
39、 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 0.76 0.84 2.48 0.8267 0.0611G 0.95 0
40、.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 OutliersNOTE 1Data for 3 mg/L after outli
41、ers 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 0.2889D65010410
