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In principle rock (primary ore) and placer (secondary mineral) it can be used for the production method of powdery titanium sulfate. However, the composition of the titanium complex of iron ore, Causes and its ore type, intergrowth relevant, even within the same ilmenite deposits, also due to weathering, different degrees of alteration, the use of a different effect. Therefore, choosing ilmenite is the primary task of producing high quality products. Pay special attention to the following points when selecting ilmenite.
a. The grade of titanium dioxide is the first factor to consider when selecting ilmenite, which directly affects the yield and cost of the plant. The grade of titanium dioxide is too low, not only to increase the consumption of minerals, but also to consume more sulfuric acid. Due to the low content of titanium dioxide, the non-titanium impurities in the ore are high, making the precipitation and purification process in production complicated and difficult. The titanium dioxide content should not be lower than 47%. However, the titania content is too high (above 60%), the difficulty of the acid solution increases, the high titania content usually ilmenite (particularly secondary mineral) generally contain small amounts of rutile, rutile insoluble in sulfuric acid, and finally precipitate When it is drained together with the waste, the acid hydrolysis rate is lowered.
b. The grade of titanium dioxide is mainly related to the economic and consumption quota and the ratio of FeO/Fe 2 O 3 in ilmenite directly affects the operation and safety of acid hydrolysis. Because 1 mol of Fe 2 O 3 reacts with sulfuric acid to generate 20 KJ more heat than 1 mol of FeO and sulfuric acid, the ilmenite with high Fe 2 O 3 content has a large heat release, a strong reaction, and a pan accident. Iron slag and sulfuric acid are consumed more during leaching and reduction. A domestic factory once calculated that for every 1% increase in Fe 2 O 3 content, the value of sulfuric acid and iron powder consumed per ton of ilmenite is 9.85 yuan (1998 price).
c. Controlling the content of harmful impurities in ilmenite is one of the key factors to improve product quality (whiteness, color reduction). Since some impurities in ilmenite are difficult to remove by general beneficiation methods, producers of titanium dioxide should pay attention to controlling the content of harmful impurities in the ore. These harmful impurities are mainly transition metal elements such as chromium , cobalt , manganese , vanadium , lead , copper , antimony , tin , antimony and rare earth elements. The above-mentioned elements generally present in the form of oxides, arsenic compounds, sulfide and phosphate in ilmenite, sulfates become an acid solution and dissolving titanium into the solution, typically by gravitational settling method can not be completely removed, Upon hydrolysis, they precipitate and adsorb to the surface of the hydrated titanium dioxide, and finally become an oxide upon calcination to develop color. For example, when the content of Cr 2 O 3 exceeds 1.5 mg/kg, the product is light yellow, and when the content of V 2 O 5 exceeds 70 mg/kg, the hue of the product can be grayed out. Cr and Ni are recognized as the most easily produced except iron. The harmful impurities of photosensitive phenomenon, the content of Pb and Cu are strictly regulated in the production of metallurgical and capacitor titanium dioxide. The high Nb content is not suitable for the production of titanium dioxide for enamel, and the reaction of Nb 2 O 5 and Sb 2 O 3 will be produced. The yellow phase, other Mn, Pb, Co, etc. should not be too high.
d. A1 2 O 3 , SiO 2 , MgO, CaO, S, P and other non-metallic impurities have little effect on the whiteness of the product, but they form during acid hydrolysis (especially SiO 2 and A1 2 O 3 colloid, seriously affecting the sedimentation and purification of titanium sulfate solution, to product quality and yield lead to undesirable consequences .CaO and MgO content is too high, the formation of a precipitate during acid hydrolysis huge volume of calcium sulfate and magnesium sulfate, sedimentation effect sludge recovery effects and titanium solution. high sulfur content will corrode apparatus, when an acid solution is generated toxic gas hydrogen sulphide, sulfur, phosphorus content will be too high and the welding of titanium white enamel caused by poor The effect of sulfur is that the weld welded out of the electrode has hot brittleness, and the opposite of phosphorus will cause cold brittleness of the weld.
In order to produce high quality titanium dioxide, the content of impurities in ilmenite should not exceed the following range.
Fe 2 O 3 <13%, Cr 2 O 3 <0.03%, MnO<1.5%, Nb 2 O 5 <0.2%, V 2 O 5 <0.5%, S<0.2%, A1 2 O 3 <1%, SiO 2 <1%, P 2 O 5 <0.025%, and rutile <0.5%.
The above impurity content can be determined by conventional chemical analysis or spectral analysis. Mines that usually have red and yellow phases with obvious mud sand are certainly not good mines. In addition, by judging the content of impurities other than iron and titanium oxide, the quality of ilmenite can also be identified. In general, when TiO 2 % + FeO% + Fe 2 O 3 % ≥ 94% in ilmenite The acid hydrolysis and precipitation operations generally do not have major problems. Of course, the rutile content in the ore should also be considered. For chlorinated titanium dioxide, a high vanadium content cannot be used because the vanadium chloride is not easily separated during distillation of titanium tetrachloride.
Different grades and different quality ilmenite should be treated differently when using them. Do not use the same process in the same way. Sometimes different types of mines should be used according to the indicators. [next]
The mine where foreign sulfate process titanium dioxide plant by generally divided into low TiO 2 content a.TiO 2 content of 71% to 85% of acid-soluble titanium slag (typically of South African slag of acid-soluble high TiO 2 content, Canada , Norway's lower); b. Acid-soluble titanium slag and ilmenite ore (TiO 2 content 60% ~ 70%); c. Ordinary ilmenite (TiO 2 content 45% ~ 59%). The type of ore used in the sulfuric acid titanium dioxide factory in China belongs to category c. Table 1 shows the proportion of mine types in the world titanium dioxide plant (excluding China).
Table 1 Types of mines used in the world titanium dioxide factory
Types of
Mineral source and grade
Number of factories
Total capacity /%
Remarks
Sulfuric acid method
Class a
Class b
Class c
Acid soluble titanium slag
TiO 2 , 71%~85%
Titanium slag + ilmenite
TiO 2 , 60%~70%
Ilmenite
TiO 2 , 45%~59%
12
7
44
48
twenty two
9
17
There are 5 100kt factories
Chlorination
Class a
Class b
Class c
Rutile mine
TiO 2 , 90%~85%
South African high titanium slag mixed mine
TiO 2 , 85%~89%
Titanium slag and low grade titanium ore
TiO 2 , 60%~84%
14
5
4
52
twenty four
8
20
Such as the Kronos factory
DuPont
Table 2 shows the ilmenite standards formulated by the Ministry of Metallurgy of China.
Table 2 Ilmenite (mineral) concentrate YB-835-87
grade
TiO 2 /%>
Impurity content </%
CaO+MgO
P
First level
one type
Second class
52
50
0.5
0.5
0.025
0.025
Secondary
Third level
Level four
Five levels
50
49
49
48
0.5
0.6
0.6
1.0
0.030
0.040
0.050
0.070
Note: Titanium concentrate containing iron rutile has TiO 2 >57%, (CaO+MgO)<0.6%, P<0.045% as the first grade product.
grade
TiO 2 /%>
Impurity content </%
P
Fe 2 O 3
First level
one type
Second class
50
50
0.02
0.02
10
13
Secondary
one type
Second class
49
49
0.02
0.025
10
13
Note: Products with TiO 2 content >52%, P<0.025% and Fe2O3<10% in concentrates are used as first-grade products.
The above table in the table is the ilmenite specification for the production of synthetic rutile, titanium-iron alloy, high-titanium slag, electric welding rod, etc.; the following table shows the specifications of titanium concentrate for the production of titanium dioxide.
The above standards of the Ministry of Metallurgy refer to sand mines (secondary mines), and rock mines (primary mines) such as Panzhihua are not included here. [next]
The chemical composition of ilmenite commonly used abroad is shown in Table 3.
Table 3 Chemical composition of titanium ore by origin /%
ingredient
India MK
Quilon, India
Sri
Lanka
Australian University
Lia
Malay
West Asia
Norway
Titanium
slag
Ishihara artificial
Rutile
Natural rutile AMA
TiO 2
54.7
59.6
53.6
54.4
51.7
43.9
70.4
96.1
86.4
FeO
21.6
9.5
18.9
19.6
38.5
36.0
13.4
Fe 2 O 3
19.5
24.6
23.3
20.2
3.77
11.1
1.70
0.25
SiO 2
0.84
0.70
1.48
0.86
1.00
3.28
4.92
0.50
0.56
Al 2 O 3
0.70
1.32
0.58
1.05
1.56
0.85
5.08
0.46
0.17
MgO
0.98
0.78
0.85
0.21
0.21
3.69
5.07
0.07
0.04
CaO
0.09
0.06
0.12
0.06
0.18
0.95
0.01
0.05
Cr 2 O 3
0.07
0.16
0.09
0.04
0.02
0.03
0.11
0.15
0.15
MnO
0.43
0.48
0.95
1.55
3.15
0.33
0.26
0.03
0.41
V 2 O 5
0.17
0.20
0.19
0.15
0.04
0.20
0.40
0.20
0.61
P 2 O 5
0.07
0.14
0.07
0.06
0.09
0.12
0.04
0.17
0.02
Table 4 shows the impurity elements in the commonly used ilmenite in China.
Table 4 Impurity components of domestic commonly used ilmenite/(mg/kg)
element
Hainan
Panzhihua
Yunnan
Guangxi
element
Hainan
Panzhihua
Yunnan
Guangxi
Al
0.32%
0.65%
0.31%
0.44%
Na
159
633
128
720
Ba
18.2
8.0
17.0
19.3
Nb
320
50.9
302
661
Be
5.69
5.99
5.76
Ni
5.99
26.9
188
10.5
Ca
560
0.81%
179
0.22%
P
299
167
154
173
Cd
2.99
2.10
2.99
2.80
Pb
80.9
29.9
83.9
344.9
Cr
83.9
26.9
647
88.4
Sc
29.9
42.0
56.9
37.2
Cu
Sr
3.29
23.9
3.00
11.7
Li
5.09
5.09
6.89
5.01
V
935
446
2200
919.8
Mg
0.14%
4.03%
1.39%
0.13%
Zn
291
101
331
317
Mn
1.35%
0.48%
0.56%
1.52%
Ce
110
48
188
130
Mo
5.99
1.79
7.49
6.42
Zr
1.5%
The above data is for reference only, because the ilmenite analysis data between different batches of the same mine has different points in different mines in the same mine.
The Panzhihua Mine has a low TiO 2 content of about 47.5%, a high sulfur content of 0.1% to 0.2%, and a high calcium and magnesium content, but other impurities that are harmful to whiteness are less. The TiO 2 content of Yunnan ore is generally 48.5%~49%, and the TiO 2 content of Hainan Mine is generally 49%~50% and contains a little rutile.