Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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METHOD FOR CONVERTING AND SEPARATING VANADIUM,
TITANIUM, AND IRON FROM VANADIUM-TITANIUM-IRON
CONCENTRATE
TECHNICAL FIELD
The present invention relates to the field of comprehensive utilization of
metallurgical
technology and mineral resources, in particular, to a method for converting
and separating the
vanadium, the titanium, and the iron from the vanadium-titanium-iron
concentrate in one step.
BACKGROUND
Around the world, nowadays, the methods of utilizing the vanadium-titanium-
iron
concentrate are as below. (1) The process of blast furnace-converter can only
extract the iron
and a part of vanadium, while the titanium enters the blast furnace slag and
cannot be
effectively and economically recovered and utilized. A large amount of blast
furnace titanium
slag that is additionally produced causes a huge drain of titanium resources
and serious
environmental pollution. (2) In the process of rotary hearth furnace-
electrical furnace, the
vanadium-bearing titano-magnetite is firstly pre-reduced in a rotary hearth
furnace, and then is
melted and separated by the electrical furnace, such that hot metal and the
titanium enriched
slag are obtained. However, the location of vanadium is hard to control, and
the utilization rate
of the vanadium is not high. Also, the mineral phase of the melting-separated
titanium slag is
stable, and has a compact structure. There is no mature process to deal with
melting-separated
titanium slag at present. Only a small amount of melting-separated titanium
slag is used as a
raw material to produce titanium dioxide pigment in sulfate process. (3)The
process of direct
reduction and grinding beneficiation achieves the separation of iron and
vanadium-titanium,
and obtains iron powder and vanadium-titanium enriched slag. The vanadium-
titanium
enriched slag is further subjected to the process of sodium salt roasting. The
vanadium is
extracted by water leaching. The vanadium solution and the titanium enriched
slag are
obtained. (4) In the process which firstly extracts the vanadium, the vanadium-
titanium-iron
concentrate firstly is subjected to
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the process of sodium salt roasting and water leaching extraction of vanadium.
Next, the
iron making proccss with the blast furnace or the non-blast furnace is
conducted. After the
vanadium extraction, since the content of residual sodium is high, the smooth
conduction
of the process of iron making is negatively affected. Also, the obtained
titanium slag still
cannot be utilized as in above processes. Moreover, these processes require
conducting two
or three high-temperature steps to achieve the effective separation of the
iron, the
vanadium, and the titanium. There are defects of a long process, a high
investment, a high
cost, serious pollution, and a low comprehensive utilization degree. In view
of the above,
no matter what kind of usage is conducted, the recovering and utilization of
the iron, the
vanadium, and the titanium from the vanadium-bearing titano-magnetite cannot
be
achieved simultaneously, which causes a waste of resources. The present
invention
provides a new method for converting and separating the vanadium, the
titanium, and the
iron from the vanadium-titanium-iron concentrate in one step. An efficient and
clean
recovery of the vanadium, the titanium, and the iron is achieved. The method
has the
significant advantages of the short process, low investment, low production
cost, reduced
environmental pollution, the efficiency of comprehensive recovery, and has a
wide
application prospect.
SUMMARY
Regarding the defects of the existing processes that include two or three
steps to make
comprehensive utilization of the vanadium-tit9nium-iron concentrate, the
present invention
develops a method for converting and separating vanadium, titanium, and iron
from
vanadium-titanium-iron concentrate in one step. Meanwhile, the method has the
significant
advantages of reduced environmental pollution, high comprehensive recovery
rate, and has
a wide application prospect.
The method for converting and separating vanadium, titanium, and iron from the
vanadium-titanium-iron concentrate in one step provided by the present
invention includes
the following steps.
(1)The vanadium-titanium-iron concentrate is mixed with an addition agent and
a
reducing agent. Roasting is conducted for 0.5-4 hours at the temperature of
1100-1400 C,
so that the vanadium-containing pig iron and the vanadium titanium enriched
slag are
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achieved, wherein the ratio by weight is vanadium-titanium-iron concentrate:
addition
agent: reducing agent-- 100: (40-80): (20-50).
(2) The vanadium titanium enriched slag obtained in the step (1) is leached in
water
and filtered, and thereby the vanadium-containing solution and the titanium
slag are
obtained.
The method according to claim 1 is characterized in that the vanadium-titanium-
iron
concentrate in the step (1) can be any type of vanadium-titanium-iron
concentrate known
in the art. The major compositions include the iron with a total mass fraction
of 30%-60%,
V205 with a mass fraction of 0.15%-5.0%, and TiO2 with a mass fraction of 5%-
35%.
= In the method according to the present invention, the addition agent of
step (1) is one
item or a mixture of more than one items selected from a group consisting of
sodium
carbonate, sodium hydroxide, sodium sulfate, sodium chloride, sodium borate,
and sodium
bicarbonate.
In the method according to the present invention, the reducing agent of the
step (1) is
one item or a mixture of more than one items selected from a group consisting
of
anthracite, bituminous coal, brown coal, and coke.
In the method according to the present invention, the vanadium-containing pig
iron in
the step (1) has an iron mass fraction of 90%-99%, and a vanadium mass
fraction of
0.05%4%.
The method according to the present invention, preferably, the leaching liquid-
solid
mass ratio in the step (2) is 1:1-5:1, and the leaching temperature is 30-100
C, and the
leaching time is 0.5-4 hours.
The technical processes in the prior art need to conduct two or even three
high-
temperature steps to achieve the separation of vanadium, titanium, and iron.
Specifically,
the process of blast furnace-converter can only extract the iron and a part of
vanadium,
while the titanium enters the blast furnace slag and cannot be effectively and
economically
recovered. In the process of the direct reduction-electric furnace, the
whereabouts of
vanadium is hard to control, and the titanium slag is hard to be utilized.
There are problems
of long process and low recovery rate of the valuable components.
The technical features of the present invention are as below. By the new
process of
sodium salt roasting and reduction coupling, a new system of low-temperature
smelting
multiphase reaction separation is constructed. The reduction of iron, the
sodiumizing of
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vanadium, and the melting separation process of the vanadium titanium enriched
slag and the
iron is achieved in one step. Three products, i.e., vanadium-containing pig
iron, vanadium-
containing solution, and titanium slag are produced. A new, efficient, and
economical process
of comprehensive utilization of vanadium-titanium-iron concentrate is created.
Compared with
the traditional "blast furnace-converter" or "direct reduction-melting
separation/grinding
beneficiation" processes, the present invention has the significant advantages
of a short
process, a low investment, a low production cost, little environmental
pollution, and a high
comprehensive recovery rate. A new technology of efficient and comprehensive
utilization of
vanadium-titanium-iron mineral resources is provided, which has a wide
application prospect.
According to an aspect of the invention, there is provided a method for
converting and
separating vanadium, titanium, and iron from vanadium-titanium-iron
concentrate, comprising:
(1) Mixing the vanadium-titanium-iron concentrate with an addition agent
containing sodium
element and a reducing agent, conducting roasting, so that vanadium-contained
containing pig
iron and vanadium titanium enriched slag are obtained, wherein a ratio by
weight is vanadium-
titanium-iron concentrate: addition agent containing sodium element: reducing
agent = 100:
(40-80): (20-50); (2) Leaching the vanadium titanium enriched slag obtained in
the step (1) in
water, conducting filtering, such that a vanadium-containing solution and a
titanium slag are
obtained.
The specific advantages of the present invention are as below.
(1) The present invention provides a new method for converting and separating
vanadium,
titanium, and iron from vanadium-titanium-iron concentrate in one step,
avoiding problems of
repeated high-temperature roasting, a high cost, and a serious pollution in
the traditional
smelting process of the vanadium-bearing titano-magnetite.
(2) The present invention provides a new method for converting and separating
vanadium,
titanium, and iron from the vanadium-titanium-iron concentrate in one step.
The recovery rates
of the iron, the vanadium, and the titanium are high. The iron is produced as
vanadium-
containing pig iron which has a high additional value, and the obtained
titanium slag has good
acid soluble ability.
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BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is the process flow chart of the method for converting and separating
vanadium,
titanium, and iron from vanadium-titanium-iron concentrate in one step of the
present
invention.
DETAILED DESCRIPTION
Further description of the present invention in conjunction with specific
embodiments
will be described as below.
Embodiment 1
100 parts of 1 # vanadium-titanium-iron concentrate, 40 parts of sodium
carbonate, and
parts of anthracite are well mixed. Then, the mixture is kept for 3 hours in a
muffle furnace
at temperature of 1200 C. Vanadium-containing pig iron and vanadium titanium
enriched slag
are obtained. The vanadium titanium enriched slag is crushed and finely
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grounded, and is leached for 2 hours under the condition of 30 C and a liquid-
solid mass
ratio of 2:1. Filtering is conducted, after which the vanadium-containing
solution and the
titanium enriched slag are obtained. The chemical compositions of the vanadium-
titanium-
iron concentrate are shown in table 1. The separating results of the vanadium-
containing
pig iron, the vanadium-containing solution, and the titanium enriched slag are
shown in
table 2. The iron grade of the obtained vanadium-containing pig iron is
97.62%, and the
recovery rate is up to 99.40%. The concentration of the vanadium-containing
solution
V205 is 3.2 g/L, and the recovery rate of vanadium is 70.46%. The TiO2 grade
of the
titanium enriched slag is 35.67%, and the recovery rate of titanium is 99.77%.
The
conversion and separation of iron, vanadium, and titanium from vanadium-
titanium-iron
concentrate are well achieved.
Embodiment 2
100 parts of 2 # vanadium-titanium-iron concentrate, 60 parts of sodium
bicarbonate
and 30 parts of coke are well mixed. Then, the mixture is kept for 4 hours in
a muffle
furnace at temperature of 1100 C. The vanadium-containing pig iron and
vanadium
titanium enriched slag are obtained. The vanadium titanium enriched slag is
crushed and
finely grounded, and is leached for 2 hours under the condition of 30 C and a
liquid-solid
mass ratio of 1:1. Filtering is conducted, after which the vanadium-containing
solution and
the titanium enriched slag are obtained. The chemical compositions of vanadium-
titanium-
iron concentrate are shown in table 1. The separating results of the vanadium-
containing
pig iron, the vanadium-containing solution, and the titanium enriched slag are
shown in
table 2. The iron grade of the obtained vanadium-containing pig iron is
95.38%, and the
recovery rate is up to 98.71%. The concentration of the vanadium-containing
solution
V205 is 5.2 g/L, and the recovery rate of vanadium is 90.50%. The TiO2 grade
of the
titanium enriched slag is 42.67%, and the recovery rate of titanium is 99.54%.
The
conversion and separation of iron, vanadium, and titanium from vanadium-
titanium-iron
concentrate are well achieved.
Embodiment 3
100 parts of 3 # vanadium-titanium-iron concentrate, 70 parts of sodium
sulfate, and
40 parts of bituminous coal are well mixed. Then, the mixture is kept for half
an hour in a
muffle furnace at temperature of 1300 C. Vanadium-containing pig iron and
vanadium
titanium enriched slag are obtained. The vanadium titanium enriched slag is
crushed and
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finely grounded, and is leached for half an hour under the condition of 100 C
and a liquid-
solid mass ratio of 4:1. Filtering is conducted, after which the vanadium-
containing
solution and the titanium enriched slag are obtained. The chemical
compositions of
vanadium-titanium-iron concentrate are shown in table 1. The separating
results of the
vanadium-containing pig iron, the vanadium-containing solution, and the
titanium enriched
slag are shown in table 2. The iron grade of the obtained vanadium-containing
pig iron is
96.54%, and the recovery rate is up to 99.10%. The concentration of the
vanadium-
containing solution V205 is 4.5 g/L, and the recovery rate of vanadium is
88.56%. The
TiO2 grade of the titanium enriched material is 39.52%, and the recovery rate
of titanium is
99.61%. The conversion and separation of iron, vanadium, and titanium from
vanadium-
titanium-iron concentrate are well achieved.
Embodiment 4
100 parts of 4 # vanadium-titanium-iron concentrate, 80 parts of mixture of
sodium
carbonate and sodium sulfate (mol(Na2CO3/NaC1)=1:1), and 40 parts of brown
coal are
well mixed. Then, the mixture is kept for 2 hours in a muffle furnace at
temperature of
1400 C. Vanadium-containing pig iron and vanadium titanium enriched slag are
obtained.
The vanadium titanium enriched slag is crushed and finely grounded, and is
leached for 1
hour under the condition of 90 C and a liquid-solid mass ratio of 3:1.
Filtering is
conducted, after which the vanadium-containing solution and the titanium
enriched slag are
obtained. The chemical compositions of vanadium-titanium-iron concentrate are
shown in
table 1. The separating results of the vanadium-containing pig iron, the
vanadium-
containing solution, and the titanium enriched slag are shown in table 2. The
iron grade of
the obtained vanadium-containing pig iron is 97.38%, and the recovery rate is
up to
99.85%. The concentration of the vanadium-containing solution V205 is 2.8 g/L,
and the
recovery rate of vanadium is 80.30%. The TiO2 grade of the titanium enriched
slag is
46.69%, and the recovery rate of titanium is 99.74%. The conversion and
separation of
iron, vanadium, and titanium from vanadium-titanium-iron concentrate are well
achieved.
Embodiment 5
100 parts of 5 # vanadium-titanium-iron concentrate, 50 parts of sodium
hydroxide,
and 30 parts of anthracite are well mixed. Then, the mixture is kept for 1
hour in a muffle
furnace at temperature of 1250 C. The vanadium-containing pig iron and the
vanadium
titanium enriched slag are obtained. The vanadium titanium enriched slag is
crushed and
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finely grounded, and is leached for 3 hours under the condition of 70 C and a
liquid-solid
mass ratio of 5:1. Filtering is conducted, after which the vanadium-containing
solution and
the titanium enriched slag are obtained. The chemical composition of vanadium-
titanium-
iron concentrate are shown in table 1. The separating result of the vanadium-
containing pig
iron, the vanadium-containing solution, and the titanium enriched slag are
shown in table
2. The iron grade of the obtained vanadium-containing pig iron is 97.02%, and
the
recovery rate is up to 98.60%. The concentration of the vanadium-containing
solution
V205 is 4.1 g/L, and the recovery rate of vanadium is 86.22%. The TiO2 grade
of the
titanium enriched material is 48.12%, and the recovery rate of titanium is
99.73%. The
conversion and separation of iron, vanadium, and titanium from vanadium-
titanium-iron
concentrate are well achieved.
Embodiment 6
100 parts of 6 # vanadium-titanium-iron concentrate, 70 parts of a mixture of
sodium
carbonate and sodium chloride (mol(Na2CO3/1\faC1)=1:1), and 30 parts of coke
are well
mixed. Then, the mixture is kept for 2 hours in a muffle furnace at
temperature of 1300 C.
The vanadium-containing pig iron and the vanadium titanium enriched slag are
obtained.
The vanadium titanium enriched slag is crushed and finely grounded, and is
leached for 1
hour under the condition of 90 C and a liquid-solid mass ratio of 4:1.
Filtering is
conducted, after which the vanadium-containing solution and the titanium
enriched slag are
obtained. The chemical composition of vanadium-titanium-iron concentrate are
shown in
table 1. The separating results of the vanadium-containing pig iron, the
vanadium-
containing solution, and the titanium enriched slag are shown in table 2. The
iron grade of
the obtained vanadium-containing pig iron is 98.12%, and the recovery rate is
up to
99.85%. The concentration of the vanadium-containing solution V205 is 4.7 g/L,
and the
recovery rate of vanadium is 83.40%. The TiO2 grade of the titanium enriched
slag is
40.67%, and the recovery rate of titanium is 99.01%. The conversion and
separation of
iron, vanadium and titanium from vanadium-titanium-iron concentrate are well
achieved.
Embodiment 7
100 parts of 7 # vanadium-titanium-iron concentrate, 65 parts of a mixture of
sodium
carbonate and sodium borate (mol(Na2CO3/ Na2B407)=7:3), and 20 parts of coke
are well
mixed. Then, the mixture is kept for 3 hours in a muffle furnace at
temperature of 1150 C.
The vanadium-containing pig iron and the vanadium titanium enriched slag are
obtained.
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The vanadium titanium enriched slag is crushed and finely grounded, and is
leached for 4
hour under the condition of 100 C and a liquid-solid mass ratio of 3:L
Filtering is
conducted, after which the vanadium-containing solution and the titanium
enriched slag are
obtained. The chemical composition of vanadium-titanium-iron concentrate are
shown in
table 1. The separating results of the vanadium-containing pig iron, the
vanadium-
containing solution, and the titanium enriched slag are shown in table 2. The
iron grade of
the obtained vanadium-containing pig iron is 91.28%, and - the recovery rate
is up to
92.68%. The concentration of the vanadium-containing solution V205 is 8.5 g/L,
and the
recovery rate of vanadium is 89.45%. The TiO2 grade of the titanium enriched
slag is
39.85%, and the recovery rate of titanium is 99.47%. The conversion and
separation of
iron, vanadium and titanium from vanadium-titanium-iron concentrate are well
achieved.
Embodiment 8
100 parts of 8 # vanadium-titanium-iron concentrate, 50 parts of a mixture of
sodium
carbonate and sodium hydroxide (mol(Na2CO3/Na0H)=1:1), and 40 parts of
anthracite are
well mixed. Then, the mixture is kept for 1.5 hours in a muffle furnace at
temperature of
1250 C. The vanadium-containing pig iron and the vanadium titanium enriched
slag are
obtained. The vanadium titanium enriched slag is crushed and finely grounded,
and is
leached for 4 hour under the condition of 90 C and a liquid-solid mass ratio
of 2.5:1.
Filtering is conducted, after which the vanadium-containing solution and the
titanium
enriched slag are obtained. The chemical composition of vanadium-titanium-iron
concentrate are shown in table 1. The separating results of the vanadium-
containing pig
iron, the vanadium-containing solution, and the titanium enriched slag are
shown in table
2. The iron grade of the obtained vanadium-containing pig iron is 97.65%, and
the
recovery rate is up to 98.15%. The concentration of the vanadium-containing
solution
V205 is 11.8 g/L, and the recovery rate of vanadium is 89.58%. The TiO2 grade
of the
titanium enriched slag is 38.74%, and the recovery rate of titanium is 99.65%.
The
conversion and separation of iron, vanadium and titanium from vanadium-
titanium-iron
concentrate are well achieved.
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Table 1 Analysis of eight vanadium-titanium-iron concentrates
in the embodiments /%
Ore
sample TFe TiO2 V205 SiO2 A1203 CaO MgO
number
1 50.28 13.12 0.53 3.07 6.17 1.04 3.77
2 37.45 28.85 1.23 12.37 2.62 6.75 0.99
3 45.38 18.58 1.52 8.66 2.56 3.27 0.88
4 55.33 8.65 0.35 4.60 4.52 2.01 0.60
30.06 32.47 1.03 14.37 3.02 6.95 ' 1.29
6 59.58 6.23 1.86 2.13 2.65 1.01 0.57
7 48.18 25.22 3.89 7.56 1.89 2.01 2.11
8 50.15 18.18 4.90 3.58 3.68 1.09 0.85
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Table 2 Reaction and separation results of the "one-step method"
of eight vanadium-titanium-iron concentrates in the embodiments
Grade/% Recover"
Ore sample
Product name
number TFe TiO2 V205 Fe
TiO2 V205
Vanadium-containing
97.62 0.20 0.21 99.40 0.23 19.35
Pig iron
Vanadium-containing
_ _ 3.2g/L - - 70.46
1 solution
Titanium enriched
0.66 35.67 0.16 0.60 99.77 10.19
slag
Vanadium-containing
95.38 0.32 0.24 98.71 0.46 5.42
Pig iron
Vanadium-containing
- - 5.2g/L - 90.50
2 solution
Titanium enriched
0.81 42.67 0.25 1.29 99.54 4.08
slag
Vanadium-containing
96.54 0.26 0.30 99.10 0.39 7.05
Pig iron
Vanadium-containing
3 4.5g/L - 88.56
solution
Titanium enriched
0.52 39.52 0.22 0.90 99.61 4.39
slag
Vanadium-containing
97.38 0.25 0.52 99.85 0.26 15.82
Pig iron
Vanadium-containing
- - 2.8g/L - - 80.30
4 solution
Titanium enriched
0.51 46.69 0.17 0.29 99.74 3.68
slag
1 Vanadium-containing
97.02 0.30 0.38 98.60 0.27 10.05
Pig iron
5
Vanadium-containing
4.1g/L - 86.22
solution
Titanium enriched
0.32 48.12 0.17 1.40 99.73 3.73
slag
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Vanadium-containing
98.12 0.10 0.20 99.85 0.09 10.05
Pig iron
Vanadium-containing
- 4.7g/L - 83.40
6 solution
Titanium enriched
0.26 40.67 0.08 0.15 99.01 6.55
slag
Vanadium-containing
91.28 0.15 0.10 92.68 0.13 2.81
Pig iron
; 7 Vanadium-containing 8.5
89.45
solution g,/L
Titanium enriched
5.68 39.85 0.38 7.32 99.87 7.74
slag
Vanadium-containing 97.65 0.10 0.75 98.15 035 5.84
Pig iron
8 Vanadium-containing 11.8 89.58
solution
Titanium enriched
0.45 38.74 0.28 1.85 99.65 4.58
slag
Moreover, the present invention may also have a variety of embodiments.
Artisans
who are familiar with the art can make various corresponding modifications and
variations
based on the disclosure of the present invention without departing from the
spirit and
substance of the present invention. However, the corresponding modifications
and
variations should belong to the protective scope of the claims of the
invention.
