Tiêu chuẩn iso 04689 3 2017

© ISO 2017 Iron ores — Determination of sulfur content — Part 3 Combustion/infrared method Minerais de fer — Dosage du soufre — Partie 3 Méthode par combustion et infrarouge INTERNATIONAL STANDARD ISO[.]

Iron ores — Determination ofsulfur

Part 3:

Mine ais de fe — Dosage du sour —

Partie 3: Méth de p r comb stion et infraro ge

T ir d edition

2 17-0

Reference n mb r

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© ISO 2017, P blshed in Sw itz rlan

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written permis ion Permis ion c n be req esed from either ISO at the ad r es below or ISO’s member bod y in the c u try of

F reword i v

Introduction v

1 Sc ope 1

2 Nor mati ve r eferenc es 1

3 Terms an definitions 1

4 Principle 2

5 Re g ents 2

6 A pparatus 2

7 S mpl n and samples 5

7.1 L b ratory sample 5

7.2 Pr eparation of pr edried tes samples 5

8 Proc ed re .5

8.1 Numbe of dete minations 5

8.2 Tes p rtion 5

8.3 Blan tes and che k tes 5

8.4 Dete mination

6 8.5 Pr eparation of calbration g raph 6

9 Ex pres io of r esults 7

9.1 Calculation of sulfur content

7 9.2 General tr eatment of r esult 7

9.2.1 Repeatabi ty an pe mis ible toleranc 7

9.2.2 Dete mination of analytical r esult 7

9.2.3 Betwe n-la oratoriesprecision 8

9.2.4 Che k for truenes 8

9.2.5 C lculation of final r esult 9

10 Test rep r t 9

A nne x A (normative) Flowshe t of the pr oc edure for the ac c eptanc e of anal ytical values for test samples 11

A nne x B (informative)Deri vation of r epe tabiity and permis ible toleranc e eq ations

12 A nne x C (informative) Pr ecisio data o tained by inter national anal ytical tr ial 13

Biblog raphy 14

ISO (he Int ernational Org nization for Stan ardization) is a worldwidefede ation of national s an ards

b dies (ISO membe b dies) The work of pr p ring Int ernational Stan ards is normaly car ied out

through ISO t ech ical committ ees Each membe b dy int er st ed in a subje t for w hich a t ech ical

committ ee has be n es a lshed has the right t o be r pr sent ed on that committ ee Int ernational

org nizations, g ove nmental an non-g ove nmental, in laison with ISO, also take part in the work

ISO cola orat es closely with the Int ernational Ele trot ech ical C mmis ion (IEC) on al matt ers of

ele trot ech ical s an ardization

The proc d r s used t o develo this document an those int en ed for it furthe maint enanc ar

desc ibed in the ISO/IEC Dir ctives, Part 1 In p rticular the dife ent a pro al c it eria ne ded for the

dife ent ty es of ISO document should be not ed This document was draft ed in ac ordanc with the

edit orial rules of the ISO/IEC Dir ctives, Part 2 ( e www iso org dir ctives)

A tt ention is drawn t o the p s ibi ity that some of the element of this document ma be the subje t of

p t ent right ISO shal not be held r sponsible for identifying any or al such p t ent right Detais of

any p t ent right identified d ring the develo ment of the document wi be in the Introd ction an / r

on the ISO ls of p t ent de larations r c ived ( e www iso org p t ent )

Any trade name used in this document is information given for the convenienc of use s an does not

cons itut e an en orsement

F or an ex lanation on the v lu tary natur of s an ards, the meaning of ISO spe if ic t erms an

ex r s ions r lat ed t o conformity as es ment, as wel as information a out ISO’ s adhe enc t o the

World Trade Org nization (WTO) principles in the Te hnical Bar ie s t o Trade (TBT) se the folowing

URL: www iso org iso / for word html

This document was pr p r d b Te h ical C mmitt ee ISO/TC 1 2, Iro or a d dir c t r duc ed iro ,

Subcommitt ee SC2, Chemic al a alys i s

This third edition canc ls and r plac s the se ond edition (ISO 46 9-3:2 1 ), of w hich it cons itut es a

minor r vision, with the folowing chang es:

— “0,0 1 %” has be n inse t ed befor “ ulfur” in 5.1;

— in 6.7:

— un e “Combus ion c ucible” , “Length ” has be n chang ed t o “ Height” ;

— un e “Combus ion c ucible” , out er diamet er has be n chang ed from “1 mm” t o “ 26 mm” ;

— un e “Combus ion c ucible” , in e diamet er has be n chang ed from “ 26 mm”t o “1 mm” ;

— “0,2g” has be n ad ed aft er “ ulfur” in 8.2;

— F ormula (7) an the r lev nt desc iptions in 9.2.4 ha e be n modif ied t o harmoniz this clause

ac os al s an ards for w hich ISO/TC 1 2 SC 2 is r sp nsible

A l s of al p rt in theISO 46 9 se ies can be fou d on the ISO websit e

ISO 46 9- 2 was originaly publshed as ISO 46 0:1 86 Unde a p l cy of rationalzation of then mbe ing

sy st em used in ISO/TC 1 2, it has be n de ided t o r -designat e ISO 46 0:1 8 as ISO 46 9- 2 It was

furthe de ided t o introd c a combus ion/infrar d method, n mbe ed ISO 468 -3, i.e this document

When next r vised, ISO 46 9:1 8 wi l be r -designat ed as ISO 46 9-1

Iron ores — Determination ofsulfur content —

Part 3:

WARNING — This document may inv lve hazardo s materials, o eratio s, and equipment This

document d es not p rp rt to ad res al of the safety pro lems as ociated with its use It is the

respo sibi ity of the use of this document to establsh appro riate he lth and safety practices

and determine the applcabiity of re ulatory lmitations prior to use

This document spe if ies a combus ion/infrar d method, using a high-fr q ency in uction furnac , for

the det ermination of the sulfur cont ent of iron or s

This method is a plca le t o sulfur cont ent betwe n 0,00 % (mas fraction) and 0,2 % (mas

fraction) in natural iron or s, iron or conc ntrat es an a glome at es, inclu ing sint er prod ct The

method is not a pl ca le t o iron or s containing mor than 1,0 % (mas fraction) of combined wat er

The a p ratus, of w hich the metal f ilt er is eq ip ed with a heating devic , can be a pled t o iron or s

containing les than 3,0 % (mas fraction) of combined wat er

2 Normati ve r eferences

The folowing document ar r fe r d t o in the t ext in such a wa that some or al of their cont ent

cons itut es r q ir ment of this document F or dat ed r fe enc s, only the edition cit ed a ples F or

un at ed r fe enc s, the lat es edition of the r fe enc d document ( inclu ing any amen ment ) a ples

ISO 648, L b rator y glas swar — Sin le-v lume pipet es

ISO 1 42, L b rator y glas swar — One -mark v lumetric flask s

ISO 2 9 , Iro or s — Dete min tio o h grosc opic moi s tur in a aly tic al s amples — Grav imetric, Karl

Fi s che a d mas s-os s meth ds

ISO 3 8 , Iro or s — S mpln a d s ample pr p ratio proc edur s

ISO 7764, Iro or s — Prep ratio o pr dried tes t s amples fr chemic al a alys i s

ISO Guide 3 , R efe enc e mate ial s — G ene al a d s tati s tic al princ iples fr c ertific atio

3 Terms and definitions

No t erms an def initions ar lst ed in this document

ISO an IEC maintain t erminolo ical data ases for use in s an ardization at the folowing ad r s es:

— IECEle tro edia: a aia le at ht p:/ www ele tro edia org

— ISO Onlne brow sing plat orm:a ai a le at ht p:/ www iso org o p

4 Principle

The sample is mix ed with a flux containing iron, tin and tungst en an heat ed in a high-fr q ency

in uction furnac , using o y g en as a sup orting fuel an car ie g s

The ev lved sulfur dio ide is car ied b o y g en int o the c l of an infrar d det ect or, w he e the

a sorption scale is r ad

During analy sis, use only r ag ent of r co niz d analytical grade, an only dis i led wat er or wat er of

eq iv lent purity

5.1 Metalic iron, particle siz 0,2mm to 1,2 mm containing les than 0,0 1% sulfur

5.2 Mag nesium perchlorate, Mg (ClO

4)

2, an ydrous, fr ee flowing , p rticle siz 0,5 mm to 2 mm

5.3 Ir on(I I ox ide, containing les than 0,0 3% sulfur

5.4 Metal ic tin, p rticle siz 0,2 mm to 1,2 mm, containing les than 0,0 1 % sulfur

5.5 Metal ic tung sten, p rticle siz 0,2 mm to 1,2 mm containing les than 0,00 % sulfur

5.6 Sodium h ydrox ide c oated siica, p r ticle siz 0,5 mm to 2 mm

5.7 Sodium h ydrox ide, particle siz 0,5mm to 2 mm

5.8 Standar d sulfur solutio , pr ep r ed as folows

Dry 8 g of p tas ium sulfate [purity > 9 , 99 % (mas fra ction)] to cons ant mas at 1 5 °C to 1 0 °C an

co l in a desic ator Weigh the dried mas es ofp tas ium sulfate spe ified in Ta le 1 an dis olve ea ch

p rtion in w ater C ol, trans e each p rtion to sep rate v lumetric flasks an diute to v lume with w ater

Table 1 — Sulfur standard solution (cal bratio series)

Solution no Mas of p tas ium sulfat e

Ordinary la orat ory a p ratus, inclu ing one-mark pipett es an one-mark v lumetric flasks complying

with the spe if ications of ISO 648 and ISO 1 42, r spe tively, as wel as the folowing S e Figur 1

6.1 Ox yg en suppl y

6.2 A bsorptio tower, containing soda-asbes os (5.6) or sodium hydr oxide (5.7)

6.3 Dr ying tower, containing mag nesium per chlorate (5.2)

6.4 High-frequency induction furnac e, ha ving a heating ind ction coi (height 3 mm to 5 mm, 4 to

6.7 Tin capsule.

The folowing dimensionsma be used as guidelnes

6.8 Metal fi ter

6.9 Dust trap, containing glas wo l

6.10 Detector for infr ar ed absor ption, an example of which is show n in Fig ure 2

6.11 Micro-pipete, ca acity 1 0μl, ac ur ate to 1 μl

7 Sampl ng and samples

7.1 Laboratory sample

F or analy sis, use a la orat ory sample of − 0 μm p rticle siz w hich has be n taken an pr p r d

in ac ordanc with ISO 3 8 In the case of or s ha ing significant cont ent of combined wat er or

o idiza le compou ds, use a p rticle siz of − 6 μm

NOTE A guideline on signif icant contents of combined water an o idiza le compou ds is incorporated in

ISO 77 64

7.2 Preparation of predried test samples

Thoroughly mix the la orat ory sample an , taking multiple inc ement , extract a t es sample in

such a manne that it is r pr sentative of the entir cont ent of the containe Dry the t es sample at

1 5 °C ± 2°C as spe ified in ISO 7764 This isthe pr dried t es sample

F or or s ha ing signif icant cont ent of combined wat er or o idiza le comp u ds, an air-eq i ibrat ed

t es sample shal be pr p r d in ac ordanc with ISO 2 96

8.1 Number of deter minations

Car y out the analy sis at leas in d plcat e in ac ordanc with An ex A, in epen ently, on one pr dried

t es sample

NOTE T e e pres ion “in epen ently” me ns that the secon an an subseq ent result are not afected

by the previous result s) F or this particular analytical method, this con ition implies that the repetition of the

proced re is car ied out either by the same operat or at a diferent ime or by a diferent operat or, inclu ing in

either case, ap ropriat e recalibration

8.2 Test por tion

Taking seve al inc ement , weigh t o the near s 0,0 0 2 g, a pro imat ely 0,5 g of the pr dried t es

sample o tained in ac ordanc with 7.2 F or samples containing in ex ces of 0,1 % (mas fraction),

sulfur 0,2 g should be taken

The t es p rtion should be taken and weighed q ickly t o avoid r -a sorption of mois ur

8.3 Blank test and check test

In each ru , one blank t es an one analysis of a c rtif ied r fe enc mat erial of the same ty e of or shal

be car ied out in p ralel with the analy sis of the or sample( ) u de the same con itions A pr dried

t es sample of thec rtified r fe enc mat erial shal be pr p r d as spe ified in 7.2

The c rtif ied r fe enc mat erial should be of the same ty e as the sample t o be analy sed, an the

pro e ties of the two mat erialsshould be sufficiently simi ar t o ensur that in eithe case, no significant

chang es in the analytical proc d r wi l be ome ne es ary

Whe e the analy sis is car ied out on seve al samples at the same time, the blank v lue ma be

r pr sent ed b one t es , pro ided that the proc d r is the same an the r ag ent ar from the same

r ag ent b t les

Whe e the analy sis is car ied out on seve al samples of the same ty e of or at the same time, the

analytical v lue of one c rtif ied r fe enc mat erial ma be used

8.4 Deter mination

Conne t he furnac (6.4) with comp nent (6.1, 6.2, 6.3, 6.5, 6.8, 6 9, an 6.1 ) an swit ch on thep we

S t the con ition for heating in ac ordanc with the man factur r’ s ins ructions aft er s a i zation of

the a p ratus

Analy se a s an ardization sample as folow s

a) Adjus the r ading of the det ect or t o the sulfur cont ent of the s an ardization sample Plac the

t es p rtion in a r fract ory combus ion c ucible (6.6) an co e the t es p rtion with 0,5 g of iron

(5.1), 0,3 g t o 0,5 g of tin (5.4), an 1,0 g of tu gst en (5.5) in that orde F or 0,2g of sample, co e the

t es p rtion with 0,8 g of iron, 0,3g t o 0,5 g of tin, and 1,0 g of tu gst en in that orde

b) Inse t the c ucible int o a q artz combus ion tube (6.5) of the furnac at the c ntr p sition of the

heating in uction coi Subs itut e o y g en for air in the combus ion tube, adjus the in e pr s ur

t o the spe ified pr s ur and lo d the powe t o the heating in uction coi Contin e combus ion of

the t es p rtion unti the r ading of the det ect or does not v ry R ead out an r cord the in icat ed

v lue Swit ch of the p we an take out the c ucible

c) Aft er combus ion, the used c ucible shal be che ked t o det ermine w hethe the combus ion is

complet e or not

d) If incomplet e, the t es shal be car ied out a ain

A s andardization sample means a sample used for adjus ing the sensitivity ofa det ect or It should not

easiy deg ene at e an should be homog eneous

NOTE An ap aratus eq ip ed with a timer st ops automatical y

8.5 Preparation of cal bration g raph

De ant wat er an sulfur s an ard solution (5.8), in ac ordanc with Ta le 2, int o five tin ca sules (6.7)

Heat each ca sule g ently at 9 °C, t o drynes , an co l in a desic at or

Plac the dried ca sule in a r fract ory combus ion c ucible (6.6) an pr s the ca sule a ains the

b tt om of the c ucible Co e the ca sule with 0,5 g of iron o ide (5.3), 0,5 g of iron (5.1), an 1,0 g of

tungst en (5.5) in that orde

Tr at each c ucible as desc ibed in 8.4 Plot the r lationship betwe n the q antity of sulfur, in

mic o rams, an the net r ading

S veral CRMsma be used ins ead of sulfur s andard solutions In this case, the sulfur content of the

CRMs should cover the a plca le range of this method CRMs should be tr ated as in icated in 8.3

an 8.4

Table 2 — Alqu t of sulfur standard solutio

No of sulfur s an ard

9 Ex pres ion of r esults

9.1 Calculation of sulfur c ontent

The sulfur cont ent, w

s, is calculat ed as a pe c ntag e b mas , t o f ive de imal plac s for cont ent highe

than 0,0 % an t o six de imal plac s for cont ent lowe than 0,0 %, using F ormula 1

w

ms

(%) =

−

×14

is themas , in mic o rams, of sulfur in the blan t est ;

m is themas , in grams, of the t es portion

9.2 General treatment of results

9.2.1 Repe tabiity and permis ible toleranc e

The pr cision of thisanalytical method is ex r s ed b the folowing formulae:

NOTE A dditional information is given in An ex es B an C

is thein epen ent d plcat e lmit ;

P is thepe mis ible t ole anc betwe n la orat ories;

is thebetwe n-la orat ories s an ard deviation;

X is thesulfur cont ent, ex r s ed as a pe c ntag e b mas , of the pr dried t es sample

calculat-ed as folow s:

— within-la orat ory [F ormulae (2) an (4 )]:the arithmetic mean of the d plcat e v lues;

— betwe n-la orat ories [F ormulae (3)an (5)]: the arithmetic mean of the f inal r sult

(9.2.5) of the two la orat ories

9.2.2 Determinatio of anal ytical result