1、Designation: D8150 17Standard Test Method forDetermination of Organic Chloride Content in Crude Oil byDistillation Followed by Detection Using Combustion IonChromatography1This standard is issued under the fixed designation D8150; the number immediately following the designation indicates the year o
2、foriginal adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method covers the determination of organicchlori
3、de (above 1 g/g organically-bound chlorine) in crudeoils, using distillation and combustion ion chromatography.1.2 This test method involves the distillation of crude oiltest specimens to obtain a naphtha fraction prior to chloridedetermination. The chloride content of the naphtha fraction ofthe who
4、le crude oil can thereby be obtained. See Section 5regarding potential interferences.1.3 The test procedure covers the determination of organicchloride in the washed naphtha fraction of crude oil bycombustion ion chromatography. Other halides can be deter-mined but are not included in the precision
5、statement of the testmethod.1.4 The values stated in SI units are to be regarded asstandard. The preferred concentration units are micrograms ofchloride per gram of sample.1.4.1 ExceptionThe values given in parentheses are forinformation only.1.5 WarningMercury has been designated by many regu-lator
6、y agencies as a hazardous material that can cause centralnervous system, kidney and liver damage. Mercury, or itsvapor, may be hazardous to health and corrosive to materials.Caution should be taken when handling mercury and mercurycontaining products. See the applicable product MaterialSafety Data S
7、heet (MSDS) for details and EPAs websitehttp:/www.epa.gov/mercury/faq.htmfor additional informa-tion. Users should be aware that selling mercury and/ormercury containing products into your state or country may beprohibited by law.1.6 This standard does not purport to address all of thesafety concern
8、s, if any, associated with its use. It is theresponsibility of the user of this standard to establish appro-priate safety, health, and environmental practices and deter-mine the applicability of regulatory limitations prior to use.1.7 This international standard was developed in accor-dance with int
9、ernationally recognized principles on standard-ization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recom-mendations issued by the World Trade Organization TechnicalBarriers to Trade (TBT) Committee.2. Referenced Documents2.1 ASTM Standards:2D86
10、 Test Method for Distillation of Petroleum Products andLiquid Fuels at Atmospheric PressureD1193 Specification for Reagent WaterD1298 Test Method for Density, Relative Density, or APIGravity of Crude Petroleum and Liquid Petroleum Prod-ucts by Hydrometer MethodD4052 Test Method for Density, Relative
11、 Density, and APIGravity of Liquids by Digital Density MeterD4057 Practice for Manual Sampling of Petroleum andPetroleum ProductsD4177 Practice for Automatic Sampling of Petroleum andPetroleum ProductsD4929 Test Method for Determination of Organic ChlorideContent in Crude OilD6299 Practice for Apply
12、ing Statistical Quality Assuranceand Control Charting Techniques to Evaluate AnalyticalMeasurement System PerformanceD6300 Practice for Determination of Precision and BiasData for Use in Test Methods for Petroleum Products andLubricantsD6708 Practice for Statistical Assessment and Improvementof Expe
13、cted Agreement Between Two Test Methods thatPurport to Measure the Same Property of a MaterialE288 Specification for Laboratory Glass Volumetric FlasksE969 Specification for Glass Volumetric (Transfer) Pipets1This test method is under the jurisdiction of ASTM Committee D02 onPetroleum Products, Liqu
14、id Fuels, and Lubricants and is the direct responsibility ofSubcommittee D02.03 on Elemental Analysis.Current edition approved Oct. 1, 2017. Published November 2017. DOI:10.1520/D8150-17.2For referenced ASTM standards, visit the ASTM website, www.astm.org, orcontact ASTM Customer Service at servicea
15、stm.org. For Annual Book of ASTMStandards volume information, refer to the standards Document Summary page onthe ASTM website.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United StatesThis international standard was developed in accordance with
16、internationally recognized principles on standardization established in the Decision on Principles for theDevelopment of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.13. Summary of Test Method3.1 DistillationA
17、crude oil distillation is performed toobtain the naphtha cut at 204 C (400 F). The distillationmethod was adapted from Test Method D86 for the distillationof petroleum products as well as Test Method D4929 fordetermination of organic chloride content in crude oil. Thenaphtha cut is washed with caust
18、ic, repeatedly when necessary,until all hydrogen sulfide is removed. The naphtha cut, free ofhydrogen sulfide, is then washed with water, repeatedly whennecessary, to remove inorganic halides (chlorides).3.2 Detection Using Combustion Ion ChromatographyAsample of known weight or volume is placed int
19、o a sample boatand introduced at a controlled rate into a high temperaturecombustion tube. There, the sample is combusted in an oxygenrich pyrohydrolytic environment. The gaseous by-products ofthe combusted sample are trapped in an absorption mediumwhere the hydrogen halides (HX) formed during combu
20、stiondisassociate into their respective ions, X-while the sulfuroxides (SOX) formed are further oxidized to SO42-in thepresence of an oxidizing agent.An aliquot of known volume ofthe absorbing solution is then automatically injected into an ionchromatograph (IC) by means of a sample injection valve.
21、 Thehalide and sulfate anions are separated on the anion separationcolumn of the IC. The conductivity of the eluent is reducedwith an anion suppression device prior to the ion chromato-graphs conductivity detector, where the anions of interest aremeasured. Quantification of the chlorine in the origi
22、nal com-busted sample is achieved by first calibrating the system witha series of standards containing known amounts of chlorine andthen analyzing unknown samples under the same conditions asthe standards. The combined system of pyrohydrolytic com-bustion followed by ion chromatographic detection is
23、 referredto as Combustion Ion Chromatography (CIC).4. Significance and Use4.1 Organic chlorides do not occur naturally in crude oil.When present, they result from contamination in some manner,such as disposal of chlorinated solvent used in many dewaxingpipeline or other equipment operations.4.1.1 Un
24、contaminated crude oil will contain no detectableorganic chloride, and most refineries can handle very smallamounts without deleterious effects.4.1.1.1 Most trade contracts specify that no organic chlorideis present in the crude oil.4.1.2 Several pipelines have set specification limits less than1 g/
25、g organic chlorides in the whole crude, and less than 5g/g in the light naphtha, based on the yield of naphtha being20 % of the original sample.4.1.2.1 To ensure less than 1 g/g organic chloride in thecrude oil, the amount measured in the naphtha fraction shall beless than 1/f (where f is the naphth
26、a fraction calculated with Eq1). For example, a crude oil sample with 1 g/g of organicchloride but a 10 % yield of naphtha would create a naphthacontaining 10 g/g organic chloride. Further, a crude contain-ing 1 g/g of organic chloride but a 40 % yield of naphthawould create a naphtha containing 2.5
27、 g/g organic chloride.Due to the difference in naphtha yields, the impact on refiningoperations can be significantly different.4.1.2.2 Since crude oil deposits worldwide exhibit differentyields of naphtha, the working range of detection for thismethod shall cover a broad range, possibly as high as 5
28、0 g/gin a naphtha fraction.4.1.3 Organic chloride present in the crude oil (for example,methylene chloride, perchloroethylene, etc.) is usually distilledinto the naphtha fraction. Some compounds break down duringfractionation and produce hydrochloric acid, which has acorrosive effect. Some compounds
29、 survive fractionation andare destroyed during hydro-treating (desulfurization of thenaphtha).4.2 Other halides can also be used for dewaxing crude oil; insuch cases, any organic halides will have similar impact on therefining operations as the organic chlorides.4.3 Organic chloride species are pote
30、ntially damaging torefinery processes. Hydrochloric acid can be produced inhydro- treating or reforming reactors and the acid accumulatesin condensing regions of the refinery. Unexpected concentra-tions of organic chlorides cannot be effectively neutralized anddamage can result. Organic chlorides ar
31、e not known to benaturally present in crude oils and usually result from cleaningoperations at producing sites, pipelines, or tanks. It is importantfor the oil industry to have common methods available for thedetermination of organic chlorides in crude oil, particularlywhen transfer of custody is in
32、volved.5. Interferences5.1 Detection Using Combustion Ion ChromatographySubstances that co-elute with the anions of interest willinterfere. A high concentration of one anion can interfere withother constituents if their retention times are close enough toaffect the resolution of their peak.6. Purity
33、 of Reagents6.1 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 specifications are available.3Othe
34、r grades can beused, provided it is first ascertained that the reagent is ofsufficiently high purity to permit its use without lessening theaccuracy of the determination.6.2 Purity of WaterUnless otherwise indicated, referencesto water shall be understood to mean reagent water as definedby Type I of
35、 Specification D1193.DISTILLATION AND CLEANUP PROCEDURE7. Apparatus7.1 Round-Bottom Boiling Flask, borosilicate, 1 L, singleshort neck with 24/40 outer ground-glass joint.3Reagent Chemicals, American Chemical Society Specifications, AmericanChemical Society, Washington, DC. For suggestions on the te
36、sting of reagents notlisted by the American Chemical Society, see Analar Standards for LaboratoryChemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeiaand National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC), Rockville,MD.D8150 1727.2 Tee Adapter, borosilicate, 75 ang
37、le side-arm, 24/40ground-glass joints.7.3 Thermometer, ASTM thermometer 2C (5 C to 300 C)or 2F, (20 F to 580 F).7.3.1 Other temperature measuring devices, such as thermo-couples or resistance thermometers, can be used when thetemperature reading obtained by these devices is determined toproduce the
38、same naphtha fraction that is obtained whenmercury-in-glass thermometers are used.7.4 Thermometer Adapter, borosilicate, 24/40 inner ground-glass joint.7.5 Liebig Condenser, borosilicate, 300 mm length, 24/40ground-glass joints.7.6 Vacuum Take-Off Adapter, borosilicate, 105 angle bend,24/40 ground-g
39、lass joints.7.7 Receiving Cylinder, borosilicate, 250 mLcapacity, 24/40outer ground-glass joint.7.8 Wire Clamps, for No. 24 ground-glass joints, stainlesssteel.7.9 Receiver Flask, for ice bath, 4 L.7.10 Copper Tubing, for heat exchanger to cool condenserwater, 6.4 mm outside diameter, 3 m length.7.1
40、1 Electric Heating Mantle, Glas-Col Series 0, 1 L size,140 W upper heating element, 380 W lower heating element,or equivalent.7.12 Variable Transformer, 2, for temperature control ofupper and lower heating elements, 120 V, 10 amps.8. Reagents and Materials8.1 Acetone, chloride-free. (WarningExtremel
41、yflammable, can cause flash fires. Health hazard.)8.2 Caustic Solution, 1 M potassium hydroxide(WarningCan cause severe burns to skin.) prepared indistilled/deionized water.8.3 Deionized Water.8.4 Filter Paper, Whatman No. 41 or equivalent.8.5 Stopcock Grease.48.6 Toluene, chloride-free. (WarningFla
42、mmable. Healthhazard.)9. Sampling9.1 Obtain a test unit in accordance with Practice D4057 orD4177. To preserve volatile components, which are in somesamples, do not uncover samples any longer than necessary.Samples should be analyzed as soon as possible, after takingfrom bulk supplies, to prevent lo
43、ss of organic chloride orcontamination due to exposure or contact with sample con-tainer. (WarningSamples that are collected at temperaturesbelow room temperature can undergo expansion and rupturethe container. For such samples, do not fill the container to thetop; leave sufficient air space above t
44、he sample to allow roomfor expansion.)9.2 If the test unit is not used immediately, then thoroughlymix in its container prior to taking a test specimen. Some testunits can require heating to ensure sample homogenization.(WarningWhen heating is required, care should be taken sothat no organic chlorid
45、e containing hydrocarbons are lost.)10. Preparation of Distillation Apparatus10.1 Clean all glassware by rinsing successively with tolu-ene and acetone. After completing the rinse, dry the glasswareusing a stream of dry nitrogen gas. Obtain and record themasses of the round-bottom flask and receivin
46、g cylinder.Assemble the glass distillation apparatus using stopcock greaseto seal all joints and wire clamps to prevent loosening of thejoints. Adjust the thermometer position within the adapter teesuch that the lower end of the capillary is level with the highestpoint on the bottom of the inner wal
47、l of the adapter tee sectionthat connects to the condenser.NOTE 1A diagram illustrating the appropriate positioning of thethermometer can be found in Test Method D86.10.2 Form the copper tubing into a coil to fit inside thereceiver flask, leaving room in the center of the flask for thereceiving cyli
48、nder. With the PVC tubing, connect one end ofthe copper coil to the water source, and connect the other endof the coil to the lower fitting of the Liebig condenser coolingjacket. Connect the upper condenser fitting to the water drain.Fill the receiver flask with an ice/water mixture, and turn on the
49、water. Maintain the temperature of the condenser below 10 C.11. Procedure11.1 Add a 500 mL crude oil test specimen to a tared roundbottom flask. Obtain and record the mass of the crude oil-filledflask to the nearest 0.1 g. Connect the flask to the distillationapparatus. Place the heating mantle around the flask, andsupport the heating mantle/flask from the bottom. Connect theheating mantle to the variacs. Turn on the variacs and start thedistillation. During the distillation, adjust the variac settings togive a distillation rate of approximately 5
