1、 IS0 3837 93 W 4853903 0669299 663 9 INTERNATIONAL STANDARD IS0 3837:1993 TECHNICAL CORRIGENDUM 2 Published 1996-07-1 5 Liquid petroleum products - Determination of hydrocarbon types - Fluorescent indicator adsorption method TECHNICAL CORRIGENDUM 2 Produits ptroliers liquides - Dtermination des grou
2、pes dhydrocarbures - Mthode par adsorption en prsence dindicateurs fluorescents RECTIFICATIF TECHNIQUE 2 Technical corrigendum 2 to International Standard IS0 3837:1993 was prepared by Technical Committee ISOPC 28, Petroleum products and lubricants. Page 5 Replace the text of note 10 with the follow
3、ing text: Improper packing of the gel, or incomplete elution of the hydrocarbon by propan-2-01, may lead to erroneous re- sults. With precision-bore columns, where at least 500 mm of total length of the several zones is required for satisfactory analysis, this criterion of total length is an indicat
4、or of incomplete elution. With standard wall tubing, this criterion is not strictly applicable since the inside diameter is not the same in all columns. For samples containing more than 20 %(V/Vl of material boiling above 204 OC, elution may be improved by the use of 3-methylbutan-1-01 in place of t
5、he propan-2-01. , ICs 75.080 Ref. No. IS0 3837:1993/Cor.2:1996(E) I Descriptors: petroleum products, liquids, chemical analysis, determination of content, hydrocarbons. O IS01996 Printed in Switzerland , I IS0 3837 93 W Y851903 0565383 669 W INTERNATIONAL STANDARD IS0 3837:1993 TECHNICAL CORRIGENDUM
6、 1 Published 1994-07-15 INTERNATIONAL OROANUATION FOR STANDARDIUTION* MWYHAPOAHM OPTAHHJAUHR no CTAHMPTH3AUHH. ORGANISATION INTERNATIONALE DE NORMALISATION Liquid petroleum products - Determination of hydrocarbon types - Fluorescent indicator adsorption method TECHNICAL CORRIGENDUM 1 Produits ptroli
7、ers liquides - Dtermination des groupes dhydrocarbures - Mthode par adsorption en prsence dindicateurs fluorescents RECTIFICATIF TECHNIQUE 7 Technical corrigendum 1 to International Standard IS0 3837:1993 was prepared by Technical Committee ISOTTC 28, Petroleum products and lubricants. Page 7 Clause
8、 1, NOTE 4 Replace the present text with the following: “The precision statement of this test method has not been determined with oxygenated fuels. This method may or may not apply to automotive gasolines containing lead anti-knock mixtures.“ Clause 2 Add: IS0 3170:1988, Petroleum liquids - Manual s
9、ampling. Clause 7 Replace “. given in IS0 3171.“ with “. given in IS0 3170 or IS0 3171.“ UDC 665.6-404:543.54:661.715 Ref. No. IS0 3837:1993/Cor.l:1994(E) Descriptors: petroleum products, liquids, chemical analysis, determination of content, hydrocarbons. 0 IS01994 Printed in Switzerland IS0 3837 93
10、 4851903 0551918 755 I NTERNAT I O NAL STANDARD IS0 3837 First edition 1993-1 2-1 5 Liquid petroleum products - Determination of hydrocarbon types - Fluorescent indicator adsorption method Produits ptroliers liquides - Dtermination des groupes dhydrocarbures - Mthode par adsorption en prsence dindic
11、ateurs fluorescents Reference number IS0 3837:1993(E) IS0 3837 93 H 4853903 055Ll19 693 IS0 3837:1993(E) Foreword IS0 (the International Organization for Standardization) is a worldwide federation of national standards bodies (IS0 member bodies). The work of preparing International Standards is norm
12、ally carried out through IS0 technical committees. Each member body interested in a subject for which a technical committee has been established has the right to be represented on that committee. International organizations, governmental and non-governmental, in liaison with ISO, also take part in t
13、he work. IS0 collaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization. Draft International Standards adopted by the technical committees are circulated to the member bodies for voting. Publication as an International Standard re
14、quires approval by at least 75 % of the member bodies casting a vote. International Standard IS0 3837 was prepared by Technical Committee ISO/TC 28, Petroleum products and lubricants. Annex A of this International Standard is for information only. 0 IS0 1993 All rights reserved. No part of this publ
15、ication may be reproduced or utilized in any form or by any means, electronic or mechanical, including photocopying and microfilm, without per- mission in writing from the publisher. International Organization for Standardization Case Postale 56 CH-121 1 Genve 20 Switzerland Printed in Switzerland I
16、I IS0 3837 93 4851903 0553920 303 = IS0 3837: 1993 (E) Introduction The determination of the total volume percent % (VrV of saturates, olefins and aromatics in petroleum fractions is important in characterizing the quality of petroleum fractions as gasoline blending components and as feeds to cataly
17、tic reforming processes, and in characterizing petroleum fractions and products from catalytic reforming and from thermal and catalytic cracking as blending components for motor and aviation fuels. This information is also important as a measure of the quality of aviation turbine fuels. . 111 INTERN
18、ATIONAL STANDARD IS0 3837:1993(E) Liquid petroleum products - Determination of hydrocarbon types - Fluorescent indicator adsorption method WARNING - This standard may involve hazardous materials, operations and equipment. This standard does not purport to address all of the safety problems associate
19、d with its use. It is the responsibility of the user of this standard to consult and establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. coho1 desorbent. Other oxygenated compounds must be individually verified. When samples conta
20、ining oxygenated blending components are analyzed, the hydrocarbon type results can be reported on an oxygenate-free basis or, when the oxygenate content is known, the results can be cor- rected to a total-sample basis. 1 Scope This International Standard specifies a fluorescent in- dicator adsorpti
21、on method for the determination of hydrocarbon types over the concentration ranges from o/o to 99 (vm hydrocarbnsl 6 Samples containing darkcoloured components that in- Oi3 % (vm to 55 ?4 (vm lefinsi and % (vm to 95 % (Vm saturated hydrocarbons in petroleum frac- tions that distill below 31 5 OC. te
22、rfere with reading the chromatographic bands cannot be analyzed. Restrictions inherent in the method and the determi- nation of precision may limit its application as noted. 2 Normative references NOTES 1 This method may apply to concentrations outside these ranges, but the precision has not been de
23、termined. 2 This test method is intended for use with full boiling range products. Cooperative data have established that the precision statement does not apply to petroleum fractions with narrow boiling ranges near the 315 “C limit. Such samples are not eluted properly, and results are erratic. 3 T
24、he applicability of this test method to products derived from fossil fuels other than petroleurn, such as coal, shale or tar sands, has not been determined and the precision statement does not apply to such products. The following standards contain provisions which, through reference in this text, c
25、onstitute provisions of this International Standard. At the time of publi- cation, the editions indicated were valid. All standards are subject to revision, and parties to agreements based on this International Standard are encouraged to investigate the possibility of applying the most re- cent edit
26、ions of the standards indicated below. Members of IEC and IS0 maintain registers of cur- rently valid International Standards. IS0 756-1 :1981, Propan-2-01 for industrial use - Methods of test - Part 1: General. 4 The precision of this test method has not been deter- mined with oxygenated fuels and
27、thus does not apply to automotive gasolines containing lead anti-knock mixtures. IS0 31 71 :1988, Petroleum liquids - Automatic pipe- line sampling. ASTM D 3663-84, Test method for surface area of cataysts. 5 The oxygenated blending components methanol, ethanol. methvl tert-butvl ether. ten-amvl met
28、hvl ether and ethyl ten-butyl ether do not interface with the determi- nation of hydrocarbon types at concentrations normally ASTM D 4815-89, Test method for analysis of CI to found in commercial petroleum blends. These oxygenated C, alcohols and MTBE in gasoline by gas compounds are not detected si
29、nce they elute wit6 the al- chromotograph y. l IS0 3837 93 = Y851903 0551922 L8b IS0 3837:1993(E) 3 Definitions the analyzer outlet. The column tip attached to the 1212 socket shall have a 2 mm inside diameter. Clama For the purposes of this International Standard, the following definitions apply. t
30、he ball and socket together and ensure that the tip does not tend to slide from a position in a direct line with the analyzer section during the packing and sub- 3.1 saturates: Volume percent % (VIV) of alkanes plus cycloalkanes. sequent use Of the column. For convenience, adsorption columns with st
31、andard wall tubing, as shown on the left in figure 1, may be lyzer section, it is necessary to select tubing of uni- 3.2 Olefins: Volume percent % Of used. When using standard wall tubing for the ana- plus cycloalkenes plus some alkadienes. 3.3 aromatics: Volume percent % (V/v) of con- densed monocy
32、clic and polycyclic aromatic hydro- carbons plus aromatic olefinic hydrocarbons, some dienes, compounds containing sulfur and nitrogen, or higher-boiling oxygenated compounds (excluding those listed in Note 5). 4 Principle Approximately 0,75 ml of sample is introduced into a special glass adsorption
33、 column packed with activated silica gel. A small layer of the silica gel contains a mixture of fluorescent dyes. When all the sample has been adsorbed onto the gel, alcohol is added to desorb the sample down the column. The hydro- carbons are separated, according to their adsorption affinities, int
34、o aromatics, olefins and saturates. The fluorescent dyes are also separated selectively with the hydrocarbon types, and render the boundaries of the aromatic, olefin and saturate zones visible under ultraviolet light. The volume percentage % (VIV) of each hydrocarbon type is calculated from the leng
35、th of each zone in the column. NOTE 7 Errors leading to high saturate values and low aromatic and low olefin values can result if the sample contains C, or lighter hydrocarbons, or more than 5 % C, hydrocarbons, or more than 10 % C, and C5 hydrocarbons. Such samples should be depentanized as specifi
36、ed in ANSI/ASTM D2001 (see annex A). 5 Apparatus 5.1 Adsorption columns, either with precision bore tubing, as shown on the right in figurel, made of glass and consisting of a charger section with a capillary neck, a separator section, and an analyzer section; or with standard wall tubing, as shown
37、on the left in figure 1. The inside diameter of the analyzer section for the precision bore tubing shall be 1,60 mm to 1,65 mm and an approximately 100 mm thread of mercury shall not vary by more than 0,3 mm in any part of the ana- lyzer section. In glass-sealing the various sections to each other,
38、long-taper connections shall be made in- stead of shouldered connections. Support the silica gel with a small piece of glass wool located between the ball socket of the 12/2 spherical joint and covering form bore and to provide- a leakproof connection between the separator and the analyzer sections.
39、 Calibrations of standard wall tubing would be imprac- tical; however, any variations of 0,5 mm or greater, as measured by ordinary calipers, in the outside di- ameter along the tube may be taken as an indication of irregularities in the inside diameter and such tubing should not be used. Draw out o
40、ne end of the tubing selected for the analyzer section to a fine capillary to retain the gel. Connect the other end of the analyzer section to the separator section with a 30 mm length of polyvinyl tubing, making certain that the two glass sections touch. To ensure a leakproof glass-to- polyvinyl se
41、al with the analyzer section, it is necessary to heat the upper end of the analyzer section until it is just hot enough to melt the polyvinyl, then insert the upper end of the analyzer section into the poly- vinyl sleeve. Alternatively, this seal can be made by securing the polyvinyl sleeve to the a
42、nalyzer section by wrapping it tightly with soft wire. 5.2 Zone-measuring-device. The zones may be marked with glass-writing pencil and the distances measured with a metre rule, with the analyzer section lying horizontally. Alternatively, the metre rule may be fastened adjacent to the col- umn. In t
43、his case, it is convenient to have each rule fitted with four movable metal index clips (figure 1) for marking zone boundaries and measuring the length of each zone. 5.3 Ultraviolet light source, with radiation pre- dominantly at wavelength 365 nm. A convenient arrangement consists of one or two uni
44、ts 915 mm or 1 220 mm in length mounted verti- cally alongside the apparatus. Adjust to give the best fluorescence. 5.4 Electric vibrator, for vibrating the individual col- umns or for vibrating the frame supporting multiple columns. 5.5 Hypodermic syringe, of capacity 1 ml, gradu- ated to 0,Ol ml o
45、r 0,02 ml, with needle 102 mm in length, with an inside diameter of 0,7 mm to 1,2 mm. Needles of No. 18, 20 or 22 gauge are satisfactory. 2 IS0 3837 93 m 4853903 0553923 O32 m IS0 3837:1993(E) Dimensions in millimetres unless otherwise indicated C F Li C Polyvinyl tubing 1/8 in - O O N 7 Standard wa
46、ll tubing - Standard column Precision bore column Figure 1 - Adsorption columns with standard wall (left) and precision bore (right) tubing in analyzer section 3 IS0 3837 93 4853903 0553924 T5 IS0 3837:1993(E) 6 Reagents 6.1 Silica gel“, manufactured to conform to the specifications shown in table 1
47、. The surface area of the gel is determined in accordance with ASTM D 3663. Determine the pH of the silica gel by placing 59 of the gel sample in a 250 ml beaker. Add 100 ml of water and a stirring bar. Standardize the pH meter with standards of pH 4 and pH 7. Stir the slurry with the magnetic stirr
48、er for 20 min and then deter- mine the pH. Before use, dry the gel in a shallow vessel at 176 OC for 3 h. Transfer the dried gel to an airtight container while still hot, and protect it from atmospheric moisture. NOTE 8 Some batches of silica gel that otherwise meet specifications have been found to
49、 produce olefin-boundary fading. The exact reason for this phenomenon is unknown but will affect accuracy and precision. Table 1 - Silica gel specifications Surface area: 430 to 530 m2/g pH of 5 % water slurry: 5,5 to 7,O Loss on ignition at 955 OC: 4,5 to 10.0 mass % Iron as Fe203, dry basis: 50 max. mass ppm Particle size distribution Cim I Sieve number I Mass % 250 180 150 75 on 60 on 80 on 100 through 200 1 O0 95 min. 15 max. 6.2 Fluorescent indicator-dyed geP, a standard dyed gel, consisting of a mixture of recrystallized Petrol red AB4 and purified
