ORIGINAL RESEARCH ARTICLE

Development of a Redox Microtitration Method

for the Determination of Metallic Iron Content
in Reduced Micron-Sized Iron Ore Concentrate
Particles
YUXIANG CHENG, ZHONGJIE SHEN, YIRU YANG, QINFENG LIANG,
and HAIFENG LIU

The determination of the metallic iron content in the reduced iron ore concentrates is essential
to evaluate the reduction efficiency in the process metallurgy field. In this study, a redox
microtitration method was developed to determine the metallic iron content in the reduced
micron-sized iron ore concentrate particles. The effects of the dissolving time, dissolving
temperature, and the concentration of the FeCl3 solution as a reagent were investigated to
achieve an optimized titration condition. The results showed that the temperature for the
maximum solubility of the metallic iron content needed to be controlled below 25 C. A
stable metallic iron content highly close to the standard value was measured when the
dissolution time exceeded 40 minutes. The FeCl3 concentration of more than 100 g/L was
suitable for dissolving the total metallic iron. Highly purified commercial standard iron powders
were used to validate the developed method with good agreements between the measured data
and standard value. Finally, this method was used to determine the metallic iron content in the
reduced iron ore concentrate particle compared to the conventional titration method (standard
test method). The relative error was lower than 3.0 pct, which proved that this method was
accurate and reliable.

https://doi.org/10.1007/s11663-022-02435-3
 The Minerals, Metals & Materials Society and ASM International 2022

I. INTRODUCTION technology uses iron ore concentrate to react with

gaseous reducing agents, and its operating temperature
MASSIVE greenhouse gas emissions from the iron- is higher than the melting temperatures of products such
making and steelmaking industries have been attracted as FeO and slag.[9] Therefore, using iron ore concentrate
worldwide attention for decades, which account for in the direct reduction ironmaking technology can
about 33.8 pct annual emission and 5.0 pct world remove the sintering and coking procedures and further
amount.[1,2] In order to solve this issue, several new reduce CO2 emission,[10] providing a great potential for
ironmaking technologies, such as HYL process,[3] carbon neutrality in the future.
MIDREX process,[4] FINMET,[5] and Circored,[6] using However, the reduction degree and metallization rate
iron ore pellet or iron ore concentrate as solid materials of the iron ore concentrate were significantly affected by
and operate at low temperature,[7] have been developed the gas atmosphere, particle size, material type (e.g.,
to shorten the process and reduce the emission of CO2. hematite and magnetite), and reduction tempera-
A new flash ironmaking technology was developed by ture.[11–13] Elzohiery et al.[12] studied the reduction
Sohn et al.[8] at the University of Utah to produce iron characteristics of magnetite concentrates in the H2
at high temperatures, potentially reducing energy con- atmosphere. The results showed that the reduction
sumption and emissions. The flash ironmaking degree was inversely proportional to the particle size
from 1623 K to 1873 K and increased from 50 to 80 pct
when the particle size was reduced from 53 to 20 lm.
Fan et al.[13] investigated the reduction kinetics of
YUXIANG CHENG, ZHONGJIE SHEN, YIRU YANG, magnetite concentrate particles in H2/CO mixtures. It
QINFENG LIANG, and HAIFENG LIU are with the Shanghai was found that the magnetite particles tended to fuse
Engineering Research Center of Coal Gasification, East China and melt at temperatures above 1350 C changing the
University of Science and Technology, P. O. Box 272, Shanghai reduction mechanism. An enhanced synergistic effect
200237, P.R. China. Contact e-mail: [email protected]
Manuscript submitted September 11, 2021; accepted January 7, 2022. was found in H2/CO mixtures via computational fluid
Article published online January 31, 2022. dynamics simulation and experimental method. Xing

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 53B, APRIL 2022—807

et al.[14] found that the metallic iron could be easily solution was titrated by potassium dichromate (0.01667
enwrapped in the liquid product as wüstite, and this mol/L). The determination range of the metallic iron
process was highly dependent of the reaction tempera- content was above 50 pct. From Table I, a 0.1g solid
ture. The interfacial chemical reaction on the liquid reduced iron sample or more is typically required by the
surface became the rate-controlling step, which affected standard test methods. The kinetics of single-particle
the reduction degree and metallic iron content in the iron concentrates are extremely important for studying
product. This phenomenon was frequently found during the reduction properties of iron concentrates. However,
the reduction process of iron ore concentrates at high it is challenging to quantify the metallic iron content or
temperature,[11–14] resulting in difficulties to the mea- reduction degree of the reduction products of single-par-
surement of the reduction degree and metallization rate. ticle iron concentrates by the conventional redox
Thus, a highly accurate determination of the reduction method due to the sample mass and experimental
degree and metallization rate is critical to evaluate the apparatus limitations. In order to determine the metallic
reduction efficiency. iron content of a small amount or even a single iron ore
The metallization rate is the ratio of the metallic iron concentrate particle, the current redox titration method
content to the total iron content in the reduced sample. is not suitable, and a new microtitration method is
Generally, redox titration method,[15,16] atomic absorp- needed.
tion spectroscopy (AAS),[17] and inductive coupled Generally, FeCl3 solution was usually used to dissolve
plasma emission spectrometer (ICP)[18] were used to the metallic iron, and the valence state of iron (III) was
determine the content of iron or other iron valence reduced to Fe2+ as shown in Reaction [1].
states in tested samples. Table I lists the information for
different standard test methods to determine the total 2Fe3þ (l) + Fe0 (s) = 3Fe2þ (l) ½1
iron or metallic iron contents. ISO-5416[19] used a Compared with other reagents used as dissolution
bromine-methanol solution with a concentration of 50 reagents for metallic iron such as HgCl2, CuSO4, and
mL/L as a dissolution reagent for dissolving the iron. PbCl2, FeCl3 solution reacts with metallic iron more
The mass of the experimental material was 0.5 g. After accurately.[24] One advantage is that using FeCl3 disso-
dissolution, the solution was titrated with potassium lution does not require adding acid and mercury-con-
dichromate solution (0.01667 mol/L). However, the taining solutions, which is environmental-friendly and
removal of bromine and methanol in this method was convenient for the subsequent experimental waste dis-
complicated and requires extra use of a mercury-con- posal. After dissolution, the Fe2+ content can be
taining reagent (Mercury(II) chloride solution, 50 g/L). determined by three methods that were abovemen-
The range for determining the metallic iron content was tioned.[15–18] However, Fe3+ as an interfering ion will
from 15 to 95 pct. The latest international standard for affect the measurement of metallic iron content for the
the determination of the metallic iron content is AAS method.[25] ICP can only measure the total iron
ISO-16878-2016.[20] Based on the standard test method content in solution,[26] and the addition of high concen-
ISO-16878,[20] a 35 mL ferric chloride solution with a tration FeCl3 solution makes it impossible to quantify
concentration of 250 g/L was used to dissolve a 0.2 g the Fe2+ content dissolved from the sample. Therefore,
sample. Then, Fe2+ is titrated by potassium dichromate the redox method is an efficient and accurate way to
solution (0.01667 mol/L) using a sodium diphenylamine determine Fe2+ in the solution and further calculate the
sulfonate indicator. The determination range of the metallic iron content in the reduced samples.
metallic iron content is 57.5 to 90.5 pct. Both ASTM This study developed a redox microtitration method
and JIS have relevant standards for determining the to determine the metallic iron content in the reduced
total iron content in the iron ore.[21,22] Total iron refers micro-scale iron ore concentrate particles. The effects of
to all valence forms (Fe0, Fe2+, and Fe3+) of iron in the dissolving time, dissolving temperature, and reagent
iron ore. No ASTM and JIS standard test methods for concentration on the solubility of the metallic iron and
determining the metallic iron content for iron ores have the titration result were investigated. Highly purified
been defined. The conventional method used in the commercial standard iron powders (Fe, Fe2O3, and
manuscript was GB/T 38812.2-2020 from China.[23] In Fe3O4) were used to simulate the partially reduced iron
this standard test method, 40 mL of ferric chloride ore particles with different reduction degrees and met-
solution with a concentration of 100 g/L was used to allization rate were titrated to validate the developed
dissolve 0.1 g of the sample. After that, the Fe2+ in the method. Errors of all redox microtitration experiments

Table I. Information for Different Standard Test Methods

Standard Measurement Items Sample Mass (g) Dissolution Reagent Titration Reagent
[19]
ISO-5416 metallic iron 0.5 Br2-CH3OH K2Cr2O7
ISO-16878[20] metallic iron 0.2 FeCl3 K2Cr2O7
ASTM E246-2001[21] total iron 0.5 HCl, H2SO4 K2Cr2O7
JIS M8212-2005[22] total iron 0.4 Na2CO3, Na2O2 K2Cr2O7
GB/T 38812.2-2020[23] metallic iron 0.1 FeCl3 K2Cr2O7

808—VOLUME 53B, APRIL 2022 METALLURGICAL AND MATERIALS TRANSACTIONS B

 Table II. Chemical Compositions of the Materials Used in This Study (Wt. Pct)

Samples Total Fe Fe2O3 Fe3O4 Si Mg Ca Al Heavy Metals

Sample A 99.9 — — — — — — 0.01
Sample B 99 — — — — — — £ 0.005
Sample C 98 — — — — — — £ 0.15
Sample D 65.01 — — 1.91 0.50 0.59 0.272 —
Fe2O3 69.73 99 — — — — — £ 0.01
Fe3O4 71.69 — 99 — — — — £ 0.01

were analyzed. The reduction degrees of different

reduced iron ore concentrate particles were measured
by the developed redox microtitration method. The
results were compared with the measured value of the
conventional titration method.

II. EXPERIMENT
A. Materials
Six materials, including three commercial iron pow-
ders (denoted as Sample A, Sample B, and Sample C),
Fe2O3 powder, Fe3O4 powder, and iron ore concentrate
(Sample D), were used in this study. The chemical
compositions of all samples used in this study are given
in Table II. The particle sizes for samples A, B, and C
are 150 lm, 48 lm, and 38 lm, respectively, manufac-
Fig. 1—The schematic diagram of the experimental apparatus for
tured by Shanghai Macklin Biochemical Co., Ltd., reduced iron sample preparation.
China. According to the information from the vendor,
the purities of three commercial iron powders were 99.9,
99, and 98 pct, respectively. Moreover, Sample A is an
analytical reagent. Fe2O3 and Fe3O4 powders (purity 99 degrees were denoted as Sample D1 to D4, respectively.
pct, Shanghai Macklin Biochemical Co., Ltd., China) After reduction, H2 was shifted to N2 to cool down the
were used to mix with sample A to simulate the partially sample and prevent re-oxidization. The reduced sample
reduced iron ore concentrates with different reduction was collected after the furnace was cooled down.
degrees. Sample D was hematite powder (provided by The developed redox microtitration method used
Baoshan Iron & Steel Co., Ltd, China) with a particle different reagents in this study. H2SO4 (> 96.0 vol pct
size range of 43 to 50 lm. Shanghai Hushi Chemical Co., Ltd) was mixed with
The real reduced or partially reduced iron ore H3PO4 (> 85.0 vol pct, Shanghai Macklin Biochemical
concentrate samples were prepared in the high-temper- Co., Ltd) to prepare the H2SO4–H3PO4 mixed acid. The
ature tube furnace. The experimental apparatus is volume mixing ratios of H2SO4, H3PO4, and water were
shown in Figure 1, including gas cylinders, controlling 15:15:70. FeCl3 solution reagent (100 g/L) was prepared
system, heating furnace, gas transportation system, and with dissolving 10 g FeCl3 powder (‡ 99.9 wt pct purity,
sample basket (u25mm 9 40mm). The heating furnace Meryer (Shanghai) Chemical Technology Co., Ltd.,
consists of a reaction tube (u48 mm 9 1100 mm), China) in the deionized water (100 mL). Fe(NH4)2Æ(-
heating elements, and insulation layer inside the metal SO4)2Æ6H2O solution reagent (40 g/L) was prepared with
shell. The reduction reaction is carried out at atmo- dissolving 40 g Fe(NH4)2Æ(SO4)2Æ6H2O (99.5 wt pct
spheric pressure. Sample D was placed in the basket purity, Shanghai Aladdin Biochemical Technology Co.,
with one particle thickness inside the tube furnace. The Ltd, China.) into sulfuric acid and diluted to 1000 mL
tube furnace was heated up to 850 C at a heating rate of with deionized water. K2Cr2O7 standard solution (con-
10 C/min. The flow rate of N2 was set to 600 mL/min centration c(1/6K2Cr2O7) = 0.1000 mol/L) was pre-
before the reduction experiment to remove air. Then, the pared with dissolving 4.9036 g K2Cr2O7 (‡ 99.8 wt pct,
sample basket was put down to the center of the tube Sinopharm Chemical Reagent Co., Ltd., China) in the
furnace. Meantime, H2 with a 600 mL/min flowrate was deionized water (1000 mL). Sodium dipheny-
introduced into the furnace after the temperature lamine-4-sulfonate (C12H10NNaO3S) indicator solution
stabilized. To get the reduced or partially reduced (4 g/L) was prepared with dissolving 0.4 g
samples, H2 was introduced within different time periods C12H10NNaO3S (‡ 97.0 pct, Shanghai Macklin Bio-
(e.g., 12, 15, 20, and 30 minutes). Four reduced or chemical Co., Ltd) in 100 mL of Na2CO3 solution (2 g/
partially reduced samples with different reduction L) into deionized water.

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 53B, APRIL 2022—809

B. Experimental Method endpoint. The addition volume (V) of the K2Cr2O7
The experimental procedure of the redox microti- standard solution was achieved. Each redox titration
tration method developed in this study is shown in experiment with effects of the dissolving time, dissolv-
Figure 2(a). About 1.00 mg solid sample was fully ing temperature, and reagent concentration was
dissolved in the FeCl3 solution in a test tube and repeated five times.
vibrated on a vortex mixer (HT-200 Shanghai HUXI In addition, the blank test experiment was carried out,
Industrial Co., Ltd., China) with a vibration frequency and the procedure is shown in Figure 2(b). The blank
of 200 rpm. To prevent the oxidation of divalent iron test experiment was to reduce the error from the external
ions by oxygen in the solution or in the air, the effects of the operator, water, purity of reagent, and
deoxygenated water was used to prepare the FeCl3 cleanliness of instruments. 20 lL FeCl3 solution was
solution, and N2 was continuously blown into the test pipetted in the Durham tube without adding any solid
tube during the dissolution process. Then, a 20 lL sample, as the blank sample. Then, 10 lL Ammonium
liquid from the dissolved solution was pipetted into a iron (II) sulfate (Fe(NH4)2Æ(SO4)2Æ6H2O) solution was
Durham tube via a high precision micropipette (0.5 to added to the 20 lL FeCl3 solution, followed by 10 lL
10 lL, Eppendorf (Shanghai) International Trade Co. H2SO4–H3PO4 mixed acid. 1 mL sodium dipheny-
Ltd., China). 1 mL sodium diphenylamine-4-sulfonate lamine-4-sulfonate (C12H10NNaO3S) indicator solution
(C12H10NNaO3S) indicator solution was diluted to 100 was diluted to 100 mL, and then 10 lL of the diluted
mL, and then 10 lL of the diluted indicator solution indicator solution was added to the blank test solution.
was added to the titration solution. Meantime, 10 lL After that, the K2Cr2O7 standard solution was titrated
H2SO4–H3PO4 mixed acid was added. The aim of until the color of the solution shifted to purple and
adding H3PO4 in the titration process was to reduce stabilized. The first titrated dosage of K2Cr2O7 was
the potential of the Fe3+/Fe2+ pair before the recorded as titration volume (V1). Then, 10 ll Fe(N-
stoichiometric point.[27] Thus, the titration jump range H4)2Æ(SO4)2Æ6H2O solution was added to this solution
was enlarged and included inside the color-changing until the purple missed. The solution was titrated with
range for reducing the error. The color did not change K2Cr2O7 standard solution until it changed to a
when the dosage of the adding mixed acid was below stabilized purple liquid. The secondary titrated volume
10 lL. Finally, K2Cr2O7 standard solution was titrated of K2Cr2O7 was noted as V2. The blank value (V0) was
until the solution was stable as purple for the calculated via the difference of V1 and V2.

Fig. 2—The diagram of the procedure of the developed redox microtitration method in this study. (a) Redox microtitration method; (b) Blank
test.

810—VOLUME 53B, APRIL 2022 METALLURGICAL AND MATERIALS TRANSACTIONS B

 The reaction of K2Cr2O7 with Fe2+ is shown in metallic iron content in the sample was fully dissolved
Eq. [2]. The amount of Fe2+ can be deduced from the into FeCl3 solution. When the temperature was higher
amount of K2Cr2O7, while the amount of Fe0 was equal than the room temperature (25 C), the dissolution
to 1/3 Fe2+ concentrate, based on Eq. [1]. The metallic degree of the iron in the FeCl3 solution, which was
iron content of the raw material is derived from the ratio assumed to the reduction degree, was reduced to 91 and
of the mass of Fe0 to the mass of the raw material, and 90 pct at 40 C and 60 C, respectively. Therefore,
the calculation formula is shown in Eq. [3]. increasing the temperature has a negative effect on the
þ
dissolution of the metallic iron in FeCl3 solution. At 40
6Fe2þ + Cr2 O2
7 + 14H = 6Fe
3þ
+ 2Cr3þ + 7H2 O C and 60 C, the amount of Fe3+ was reduced,
½2 resulting in less iron dissolved in the FeCl3 solution. In
addition, with combined analyses of bar graph and
images in Figure 3, solutions at 4 C and 25 C were
clean without any precipitates. In comparison, turbid
c  ðV  V 0 Þ  M  f liquid solutions were displayed at 40 C and 60 C,
WFe ¼  100 ½3
3m indicating that the iron (III) hydroxide formed in the
where WFe is the metallic iron content, f is the volume liquid. FeCl3 is a strong electrolyte that undergoes a
ratio of the dissolved solution to the volume of the complex series of reactions in water. Related reactions
titrating solution. In this study, the volume ratio (f) is are shown from Eqs. [4] through [6]. The DH was calculated
set to 50. c is 1/6 of the concentration of the K2Cr2O7 by FactSage 7.2 software.[28]
standard solution (mol/L), c = 0.1000 mol/L. V is the
Fe3þ + H2 O $ FeOH2þ + Hþ DH ¼ 43:17 kJ=mol
volume of the K2Cr2O7 standard solution consumed
by the titration with Fe2+ (L), and V0 is the volume ½4
of K2Cr2O7 standard solution calculated from the
blank test experiment, namely V0 = V1–V2. M is the
atomic mass of Fe (M= 55.85 g/mol), ‘‘3’’ is the fac- Fe3þ + 2H2 O $ Fe(OH)þ þ
2 + 2H DH
tor that the molar ratio of Fe2+ to Fe0, and m is the ¼ 182:16 kJ=mol ½5
mass of the raw sample (g).

III. RESULTS AND DISCUSSION Fe3þ + 3H2 O $ Fe(OH)3ðaqÞ + 3Hþ DH

¼ 237:87 kJ=mol ½6
A. Effect of Dissolving Temperature
In order to investigate the effect of dissolution All three reactions were endothermic, and the increas-
temperature, experiments were conducted at different ing temperature of the solution would cause the reaction
temperatures (e.g., 4 C, 25 C, 40 C, and 60 C). The move towards the right side. In the FeCl3 solution, the
dissolution time was set to 3 hours. The experimental hydrolyzed iron ion (III) polymerized to iron (III)
results the used the microtitration method to determine hydroxide when the temperature increased,[29] the con-
the iron concentration in the solution is shown in centrate of Fe3+ in the solution decreased and hence it
Figure 3. The metallic iron contents denoted as WFe and was difficult to completely dissolve Fe0 from the sample
measured by the redox microtitration method at 4 C to the solution, based on Eq. [1]. Therefore, all iron
and 25 C were both 98 pct. This indicated that the powder and reduced samples were dissolved at the set
temperature of 4 C to study other effects on the redox
microtitration method.

B. Effect of Dissolving Time

The dissolution degree of the iron ore sample in the
FeCl3 solution that affected by the dissolution time will
finally change the determination of the metallic iron
content of the iron ore concentrate. The metallic iron
contents of Samples A and D3 were measured at the
different dissolving time periods from 10 to 100 minutes
in this study. The operating temperature was set to 4 C,
based on the results in Figure 3. The effect of the
dissolving time on the determination of the metallic iron
content is shown in Figure 4. Results showed that the
metallic iron content of both tested samples increased
with the increasing dissolving time when the time was
less than 40 minutes. The measured metallic iron content
reached the maximum value when the dissolving time
Fig. 3—Effect of the dissolution temperature on the determination of was 40 minutes. When the dissolving time was more
iron content.

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 53B, APRIL 2022—811

 100 65 7

90 60 6

80 5
55

WFe (wt.%)

pH value
WFe (wt.%)

70 4
50
60 WFe of sample
3
45 pH of the solution
50 2
Sample A 40
Sample D3 1
40
35 0
30 50 75 100 125 150
0 10 20 30 40 50 60 70 80 90 100
Dissolving time (min) FeCl3 concentration(g/L)

Fig. 4—Effect of dissolving time on the determination of metallic Fig. 5—Effect of FeCl3 concentration and pH value on the metallic
iron content via redox microtitration method. iron content tested from the redox microtitration method.

100 3.0
This study
than 40 minutes, the determined metallic iron content Conventional method
98 97.70
was stable. Therefore, the minimum dissolving time for 2.5
98
96
the dissolution of all iron in a 1.00 mg solid sample was

Relative error (%)

suggested to be more than 40 minutes. In this study, to 95.32 2.0
WFe (wt.%) 96 95
completely dissolve the iron, all subsequent experiments
94.13 1.5
adopted the dissolution time to 60 minutes.
94
1.0
C. Effect of FeCl3 Concentration
92
In this study, FeCl3 solution is the reagent used to 0.5
dissolve metallic iron in the solid samples. The effect of
FeCl3 concentration (e.g., 50, 75, 100, 125, and 150 g/L) 90 0.0
50 100 150
on the determination of metallic iron content was
studied using Sample D3, and the results are given in FeCl3 concentration (g/L)
Figure 5. With the increasing concentration of FeCl3
solution but below 100 g/L, the measured metallic iron Fig. 6—Comparison of the measured metallic iron content under
content increased. When the FeCl3 concentration was different FeCl3 concentrations between the conventional titration
higher than 100 g/L, the determined metallic iron method and redox microtitration method in this study.
content was stable at a high value. For the Reactions
(4) through (6), Fe3+ hydrolysis reaction makes the influence of the acidity on the dissolution process, the
solution acidic, and the pH value of the FeCl3 solution concentration of FeCl3 solution should be more than
decreases with increasing the FeCl3 concentration. The 100 g/L.
pH values of different concentrations of FeCl3 solutions The experimental results under different FeCl3 con-
are shown in Figure 5. Theoretically, H+ in the solution centrations (50, 100, 150 g/L) were compared between
may react with the iron in the sample and bias the the conventional titration method[15,16] and the redox
measurement. However, the pH value of the solution microtitration method developed in this study, which
should not be adjusted because pH adjusters, such as are given in Figure 6. The conventional titration method
NaOH and acid, can react with Fe3+ or metallic iron was carried out according to the standard test method
and make the measurement inaccurate.[30] From Fig- GB/T 38812.2-2020,[23] as shown in Table I. The
ure 5, the pH value of the solution was close to 1.0 experimental procedure was to dissolve 0.1 g of sample
regardless of the experimental concentration range, in 40 ml of FeCl3 solution (100 g/L) and then titrate
indicating the influence of the pH value on the results using K2Cr2O7 solution (c = 0.1000 mol/L) with a
can be ignored. A low concentration of FeCl3 in the burette. Five repeated experiments were performed for
solution will cause an incomplete dissolution of the each data point to assess the error. The relative error is
metallic iron and affect the determination and results shown on the right y-axis. The relative error in Figure 6
with errors. When FeCl3 was dissolved in water, various refers to the ratio of the difference between the conven-
iron complexes (e.g., FeOH2+, Fe(OH)2+, and Fe(O- tional titration method and microtitration method to the
H)3(aq)) formed, thus it needed a particular concentra- measured data of the conventional titration method.
tion that higher than the critical value to dissolve total Results showed that the mean determined metallic iron
Fe0 in the sample completely. Therefore, to ensure the content from the developed redox microtitration
complete dissolution of metallic iron and minimize the method at three concentrations were 95, 96, and 98

812—VOLUME 53B, APRIL 2022 METALLURGICAL AND MATERIALS TRANSACTIONS B

pct, respectively. The experimental results measured by (Sample A). The simulation sample was then titrated to
the conventional titration method were 94.12, 95.31, and determine the metallic iron content and compared with
97.70 pct, respectively. The relative error decreased the actual value of the metallic iron content, and the
when the FeCl3 concentration increased from 50 to 150 measured results are shown in Figure 8. The results
g/L, and the minimum error value was about 0.3 pct. showed that the measured values matched well with the
This result also proved that a high FeCl3 concentration actual values in the simulation samples. Similarly, the
benefitted the dissolution of the metallic iron. The relative error was calculated for each experiment con-
results of the microtitration method developed in this dition. For the method developed in this study, errors
study are in good agreement with the conventional may arise from the titration process, including losses
method. during the pipetting of the solution and the judgment of
the titration endpoint. The errors were all within 5 pct,
and it was found that with the increasing metallic iron
D. Method Validation
content the error reduced obviously, proving that this
Experiments for the determination of the metallic iron method is suitable for the determination of the metallic
content in the standard samples (Samples A, B, and C) iron content to calculate the reduction degrees of iron
were carried out to validate the accuracy of the redox ore concentrates.
microtitration method. The determined metallic iron
contents measured by the redox microtitration method
were 99, 98, and 99 pct, respectively, with error bars E. Measurement of Reduced Iron Ore Concentrates
shown in Figure 7. Compared to the iron contents in The metallic iron contents of reduced real iron ore
three standard samples (99.9, 99, and 98 pct), the concentrate samples at different reduced time periods
relative errors were 1.4, 0.86, and 0.61 pct. In this (Samples D1 to D4) were measured by the redox
section, the error was defined as the ratio of the absolute microtitration method. The blank test data (V1, V2,
value of the difference between the measured value and V0) and the K2Cr2O7 standard solution dosage (V) for
the theoretical value to the theoretical value. The both methods are presented in Tables III and IV. The
maximum error was less than 3.0 pct for the five standard deviations (SD) of the titration volumes of the
repeated experiments using the microtitration method in K2Cr2O7 standard solution for the both methods are
this study. The relative standard deviations (RSD) were shown in Table IV. Each experiment was repeated five
0.86, 0.83, and 0.68 pct, respectively, indicating that the times. The dosage of K2Cr2O7 standard solution in the
results from the developed redox microtitration method conventional method was much higher than that of the
were close to the standard value. microtitration method of this study, due to the different
During the reduction process of iron ore concentra- solution volume. However, the standard deviation of the
tion, the evolution of the reduction degree is a crucial microtitration method was lower than the results of the
parameter to study the kinetic characteristics. In this conventional method. This indicated that the stability of
study, samples of mixing iron powder (Fe) with Fe2O3 the measurement results of the developed method was
or Fe3O4 were prepared to simulate the reduced or better than the conventional method.
partially reduced iron ore concentrates with different The results of the determination of the metallic iron
reduction degrees. The mixed samples were prepared by content in the real reduced iron ore concentrate samples
adding different weight percentages of Fe2O3 or Fe3O4 are given in Figure 9. Results showed that the mean
into the high purity commercial reduced iron powder metallic iron contents of Samples D1 to D4 were 22, 43,
60, and 83 pct, respectively. The experimental results
measured from the conventional titration method were
100.0
99.9 Measured
99.5 Standard 100
Fe + Fe2O3
99.0 80 Fe + Fe3O4
WFe (wt.%)

99 99 99
Actual value
98.5 60
WFe (wt.%)

Error = ±5 %
98.0 40
98 98

97.5 20

97.0 0
A B C 0 20 40 60 80 100
Sample Fe/(Fe+M), M=Fe2O3 or Fe3O4 (wt.%)

Fig. 7—Comparison of the result of the microtitration method with Fig. 8—Comparison of the metallic iron content measured by the
the standard sample. microtitration method with actual iron content.

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 53B, APRIL 2022—813

 Table III. Blank Test Data for Both Microtitration Method and Conventional Titration Method

Method Number V1 (mL) V2 (mL) V0 (mL) Average of V0 (mL)

-3 -3 -3
This Study 1 10.3 9 10 10.2 9 10 0.1 9 10 0.1 9 10-3
2 10.2 9 10-3 10.1 9 10-3 0.1 9 10-3
3 10.3 9 10-3 10.2 9 10-3 0.1 9 10-3
4 9.9 9 10-3 9.8 9 10-3 0.1 9 10-3
5 10.0 9 10-3 9.9 9 10-3 0.1 9 10-3
Conventional Method 1 10.53 10.16 0.37 0.37
2 11.23 10.78 0.45
3 10.38 10.13 0.25
4 10.79 10.41 0.38
5 11.14 10.72 0.42

Table IV. Dosages (V) of the K2Cr2O7 Standard Solution for Both Microtitration Method and Conventional Titration Method

V (mL)
Average of V
Method Sample Weight(g) 1 2 3 4 5 SD (mL)
This Study D1 0.00100 2.5 9 10-3 2.5 9 10-3 2.4 9 10-3, 2.6 9 10-3 2.5 9 10-3 0.070 2.5 9 10-3
D2 0.00100 4.7 9 10-3 4.8 9 10-3 4.7 9 10-3 4.7 9 10-3 4.7 9 10-3 0.045 4.7 9 10-3
D3 0.00100 6.6 9 10-3 6.5 9 10-3 6.5 9 10-3 6.5 9 10-3 6.5 9 10-3 0.045 6.5 9 10-3
D4 0.00100 9.0 9 10-3 8.9 9 10-3 9.0 9 10-3 9.0 9 10-3 9.0 9 10-3 0.045 9.0 9 10-3
Conventional D1 0.1000 11.89 12.48 12.27 12.58 11.84 0.3364 12.21
Method D2 0.1000 23.41 24.11 23.68 23.04 24.43 0.5512 23.74
D3 0.1000 32.91 33.55 33.66 33.16 32.85 0.3671 33.23
D4 0.1000 43.96 44.22 44.04 43.84 42.90 0.5174 43.79

100 10 conventional method. Therefore, the developed redox

microtitration method can be used to determine the
90 This study 9
83 80.82 metallic iron content in the micron-sized iron concen-
Conventional method
80 8 trates with various reduction degrees.
Relative error
Relative error (%)

70 7
60 61.16
WFe (wt.%)

60 6
50 5 IV. CONCLUSION
43 43.49
40 4 In this study, a redox microtitration method was
30 3 developed to determine the metallic iron content in the
22 22.04 micron-sized iron ore concentrate particles. Factors that
20 2
affect the accuracy of the determination of the metallic
10 1 iron content were considered and studied, including the
0 0 dissolving time, dissolving temperature, and FeCl3
D1 D2 D3 D4 solution concentration. The dissolving temperature
Sample below the room temperature (25 C) was found to be
suitable for the determination of the metallic iron
Fig. 9—The measured metallic iron content in the reduced iron ore content. When the dissolving time exceeds 40 min, a
concentrates with different reduction degrees by microtitration stable content of the metallic iron close to the standard
method and conventional titration method.
value was measured. For the FeCl3 solution concentra-
tion, more than 100 g/L was proved to be suitable for
the complete dissolution of the metallic iron. In addi-
22.04, 43.49, 61.16, and 80.82 pct, respectively. Accord- tion, the comparative experiment via testing commercial
ing to the relative error shown on the right y-axis, it can standard iron powders of high purity validated the
be seen that the relative error between the conventional developed method of this study, and the error was below
method and developed method of this study were less 3.0 pct. The measured data of the reduced or partially
than 3 pct. The error below 3 pct is the post-exper- reduced iron ore concentrates showed good agreement
imental statistics but not a critical error. This value was with the conventional titration method results. The
obtained by comparing the average experimental data relative error was lower than 5.0 pct, indicating that this
obtained from five repeated experiments with the method is reliable. This redox microtitration method

814—VOLUME 53B, APRIL 2022 METALLURGICAL AND MATERIALS TRANSACTIONS B

provides to measure minute amount of the metallic iron 10. H.Y. Sohn: Metals., 2020, vol. 10, p. 54.
content in the micron-sized iron concentrate particle, 11. D. Spreitzer and J. Schenk: Steel Res. Int., 2019, vol. 90, p.
1900108.
and the dosages of reagents are significantly reduced 12. M. Elzohiery, D. Fan, Y. Mohassab, and H.Y. Sohn: Ironmak.
compared to conventional titration methods. Steelmak., 2021, vol. 48, pp. 485–92.
13. D. Fan, M. Elzohiery, Y. Mohassab, and H.Y. Sohn: Ironmak.
Steelmak., 2021, vol. 48, pp. 1064–75.
14. L.Y. Xing, Y.X. Qu, C.S. Wang, L. Shao, and Z.S. Zou: Metall.
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ACKNOWLEDGMENTS 15. H.J. Hu, Y. Tang, H.S. Ying, M.H. Wang, P.Y. Wan, and X.J.
Yang: Talanta., 2014, vol. 125, pp. 425–31.
This study was supported by the National Natural 16. V.S. Sastri: Talanta., 1978, vol. 25, pp. 702–04.
17. H.M. Morcali: J. Min. Metall., 2016, vol. 52, pp. 151–55.
Science Foundation of China (Grant No.21908063), 18. S.C. Wilschefski and M.R. Baxter: Clin. Biochem. Rev., 2019, vol.
the Shanghai Pujiang Program (21PJ1402300), the 40, pp. 115–33.
Fundamental Research Funds of the Central Universi- 19. ISO: Direct Reduced Iron—Determination of Metallic Iron—
ties (JKB01211715), the Chinese Postdoctoral Science Bromine-Methanol Titrimetric Method (ISO No 5416), Interna-
Foundation (2021TQ0108), and the Open Research tional Organization for Standardization, 2006.
20. ISO: Iron Ores—Determination of Metallic Iron Content—
Fund of State Key Laboratory of Multiphase Com- Iron(III) Chloride Titrimetric Method (ISO No 16878), Interna-
plex Systems (No. MPCS-2021-D-07). tional Organization for Standardization, 2016.
21. ASTM: Standard Test Methods for Determination of Iron ores and
Related Materials by Dichromate Titration (ASTM E 246-01),
American Society of Testing Materials, 2005.
CONFLICT OF INTEREST 22. JIS: Iron Ores—Determination of Total Iron Content (JIS M
8212), Japanese Industrial Standards Committee, 2005.
On behalf of all authors, the corresponding author 23. GB/T: Direct reduced iron—Determination of Metallic Iron—The
states that there is no conflict of interest. Potassium Dichromate Titrimetric Method After Decomposition by
Ferric Chloride (GB/T No 38812.2), Standardization Adminis-
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