CN114084902B - Method for preparing titanium chloride slag from titanium concentrate - Google Patents
Method for preparing titanium chloride slag from titanium concentrate Download PDFInfo
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- CN114084902B CN114084902B CN202111114703.3A CN202111114703A CN114084902B CN 114084902 B CN114084902 B CN 114084902B CN 202111114703 A CN202111114703 A CN 202111114703A CN 114084902 B CN114084902 B CN 114084902B
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- 239000002893 slag Substances 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 50
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 title claims abstract description 48
- 239000010936 titanium Substances 0.000 title claims abstract description 45
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 45
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000012141 concentrate Substances 0.000 title claims abstract description 23
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000003723 Smelting Methods 0.000 claims abstract description 26
- 239000002253 acid Substances 0.000 claims abstract description 23
- 238000000498 ball milling Methods 0.000 claims abstract description 23
- 238000002386 leaching Methods 0.000 claims abstract description 22
- 239000012535 impurity Substances 0.000 claims abstract description 19
- 238000001354 calcination Methods 0.000 claims abstract description 17
- 238000007885 magnetic separation Methods 0.000 claims abstract description 17
- 238000005469 granulation Methods 0.000 claims abstract description 5
- 230000003179 granulation Effects 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 230000001590 oxidative effect Effects 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000003638 chemical reducing agent Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 15
- 229910052742 iron Inorganic materials 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- 235000010215 titanium dioxide Nutrition 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000003245 coal Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 230000033116 oxidation-reduction process Effects 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004375 Dextrin Substances 0.000 claims description 2
- 229920001353 Dextrin Polymers 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000010426 asphalt Substances 0.000 claims description 2
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 235000019425 dextrin Nutrition 0.000 claims description 2
- 239000000295 fuel oil Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000004021 humic acid Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000002006 petroleum coke Substances 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 abstract description 21
- 238000009835 boiling Methods 0.000 abstract description 15
- 239000011575 calcium Substances 0.000 abstract description 8
- 229910052791 calcium Inorganic materials 0.000 abstract description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011777 magnesium Substances 0.000 abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000005415 magnetization Effects 0.000 abstract description 4
- 238000005272 metallurgy Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 32
- 229910010413 TiO 2 Inorganic materials 0.000 description 16
- 229910052681 coesite Inorganic materials 0.000 description 16
- 229910052906 cristobalite Inorganic materials 0.000 description 16
- 239000002994 raw material Substances 0.000 description 16
- 239000000377 silicon dioxide Substances 0.000 description 16
- 229910052682 stishovite Inorganic materials 0.000 description 16
- 229910052905 tridymite Inorganic materials 0.000 description 16
- 229920002472 Starch Polymers 0.000 description 8
- 239000000571 coke Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000005453 pelletization Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 239000008107 starch Substances 0.000 description 8
- 235000019698 starch Nutrition 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229960002089 ferrous chloride Drugs 0.000 description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000805 Pig iron Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000007131 hydrochloric acid regeneration reaction Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/02—Halides of titanium
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for preparing titanium chloride slag from titanium concentrate, and relates to the technical field of chemical metallurgy. The method mainly comprises the steps of obtaining slag through magnetization roasting, ball milling, wet magnetic separation, granulation and smelting, and obtaining titanium chloride slag through sequentially carrying out oxidation roasting, reduction roasting, pressurized acid leaching and calcination on the slag. The method combines magnetizing roasting, desilication and decalcification and titanium chloride slag upgrading technologies to prepare the low-calcium-magnesium high-grade titanium chloride slag product suitable for large-scale boiling chlorination. The method can effectively reduce the impurity (especially calcium and magnesium) content in the titanium chloride slag prepared from ilmenite, and the prepared titanium chloride slag has the purity of more than 90 percent and has good impurity removal effect.
Description
Technical Field
The invention relates to the technical field of chemical metallurgy, in particular to a method for preparing titanium chloride slag from titanium concentrate.
Background
The titanium industry mainly develops the end products such as titanium white of a chloride process, high-end special titanium white and the like, accelerates the development of sponge titanium, metallic titanium, titanium materials and the like, and actively develops military and civil titanium alloy materials and deep-processing products such as aerospace, ships, medical use and the like. Compared with the sulfuric acid process titanium dioxide process, the chloridizing process titanium dioxide process has no ferrous sulfate production, the solid waste is reduced by 20-50%, the product quality advancement and stability are higher, and the application is wider. Only the clean and environment-friendly titanium white production process by the chloride process is greatly promoted to replace the traditional titanium white production process by the sulfuric acid process, resources can be better saved, and the environment-friendly pollution problem is solved.
The main flow process equipment for producing titanium pigment by the chlorination method has higher requirements on raw materials, particularly the impurity content in the raw materials, and the impurity content in the raw materials, particularly the calcium and magnesium content can influence the chlorination process, so that the requirements on the impurity content are more severe, and CaO and MgO are less than or equal to 0.15 percent. The Sichuan Panxi area has 90% of titanium ore in China, but the ilmenite in the area has compact structure, and the obtained titanium concentrate has low titanium grade and high calcium and magnesium content, so the ilmenite is directly used for the sulfuric acid method titanium white, and a very small part of ilmenite is used for upgrading the titanium-rich material. The titanium ore is used for upgrading the titanium-rich material, and meanwhile, the titanium ore has the defects of small production scale, low grade, poor quality, high cost and the like, and the titanium ore is difficult to realize by means of the traditional technology to produce high-quality titanium chloride slag with the content of more than 90 percent. Therefore, the independent research and development of titanium chloride slag potential meeting the production of titanium dioxide by a chloride process through technical innovation is necessary. At present, the preparation of titanium-rich materials for the chlorination process by reduction smelting-titanium slag upgrading is one of the important directions of efficient utilization of titanium resources, and many enterprises and scientific institutions have started to research high-calcium magnesium ilmenite in China or directly prepare titanium chloride slag products suitable for boiling chlorination by upgrading titanium slag.
Chinese patent document CN107399758A discloses a method for preparing synthetic rutile from high titanium slag, which prepares the rutile raw material capable of meeting the requirements of a chlorination process by crushing the high titanium slag, performing alkaline leaching impurity removal, modifying roasting, acid leaching slag removal, calcining and the like. The method in the patent has good upgrading effect on titanium slag with high grade and low impurity content, and has poor upgrading effect on producing titanium slag by directly using ilmenite with high calcium and magnesium. In the modified roasting stage, the addition of sodium carbonate can cause sintering phenomenon of a roasting product, and the requirements on roasting equipment are relatively high.
The Chinese patent document CN104828864A also discloses a preparation method of the synthetic rutile, which comprises the steps of reduction roasting, pressure leaching, roasting and hydrochloric acid regeneration, thus obtaining the synthetic rutile which meets the production process requirements of the chlorination method. The hydrochloric acid used in the method is used for directly leaching the ilmenite subjected to the modification by compression and reduction, a large amount of ferrous chloride can be generated, and the utilization value is relatively low.
At present, most of the prior art is to prepare the synthetic rutile by modifying ilmenite and then leaching with hydrochloric acid, and the method has the advantages of simple equipment and relatively short flow, but can produce a large amount of ferrous chloride, high treatment cost and low utilization value. Thus, there is a need to develop and improve a new process for the preparation of titanium chloride slag.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a method for preparing titanium chloride slag from titanium concentrate, which aims to solve the problems of small production scale, low grade, poor quality, high cost and the like in the existing technology of upgrading the titanium chloride slag by using titanium ore. The method of the invention is formed by continuously improving and optimizing the preparation process. The method combines magnetization roasting, desilication decalcification and titanium chloride slag upgrading technologies, improves the grade of the titanium chloride slag to more than 90%, and ensures that the granularity and the impurity content meet the requirements of a chlorination method.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
a method for preparing titanium chloride slag from titanium concentrate, comprising the following steps:
(a) Magnetizing roasting and ball milling: ball milling ilmenite obtained by oxidizing and roasting the titanium concentrate at 600-800 ℃ into fine-powder ilmenite;
(b) Wet magnetic separation and granulation: carrying out wet magnetic separation on the fine-powder ilmenite, and granulating the separated magnetic ilmenite;
(c) Smelting: smelting the granulated ilmenite at 1500-1600 ℃ and separating to obtain furnace slag;
(d) And (3) oxidation-reduction roasting: sequentially carrying out oxidizing roasting and reducing roasting on the slag to obtain modified slag;
(e) Pressurized acid leaching: carrying out pressurized acid leaching impurity removal reaction on the modified slag and inorganic acid, washing and drying to obtain acid leaching impurity removal slag;
(f) Calcining the obtained acid leaching impurity-removing slag at 900-1000 ℃ to obtain the titanium chloride slag.
The method of the invention firstly adopts magnetization roasting to increase the magnetism of ilmenite (namely, the ferroilmenite is obtained), then carries out desilication and decalcification on the ilmenite through ball milling and wet magnetic separation, namely, carries out impurity removal pretreatment on the ilmenite, and then carries out upgrading on the prepared chloridized primary slag through oxidation reduction, acid leaching and the like, thereby improving the impurity removal rate, especially the calcium removal rate, simultaneously obtaining the iron which can be taken out through smelting, and improving the iron utilization value in the ilmenite. The method is quite suitable for preparing titanium chloride slag products suitable for large-scale boiling chlorination by high-calcium magnesium ilmenite, and is easy to realize industrial production.
In one embodiment, in the step (d), the oxidizing roasting is performed at 800-1000 ℃ under an oxygen atmosphere for 1-2 hours; and/or; the condition of the reduction roasting is that the reduction roasting is carried out for 1-2 hours at 700-900 ℃ under the reducing atmosphere. Specifically, the aerobic atmosphere is air or an oxygen atmosphere.
In one embodiment, the time of the oxidative calcination in step (a) is from 1 to 2 hours; the smelting time in the step (c) is 6-10 h; the calcination time in the step (f) is 1-2 h.
In one embodiment, the ball milling comprises mechanical ball milling; ball milling to obtain fine powder with particle size not greater than 325 mesh, and accounting for 80% by weight. And (3) performing mechanical ball milling on ilmenite pre-oxidized by magnetizing roasting, and obtaining fine-powder ilmenite after ball milling.
In one embodiment, the magnetic field strength of the wet magnetic separation is 2000 to 4000 gauss. Carrying out wet magnetic separation on the fine-powder ilmenite obtained by ball milling, separating magnetic ilmenite from nonmagnetic ilmenite, and drying.
In one embodiment, the magnetic ilmenite resulting from the magnetic separation is granulated; the granulating is carried out by adding a binder; preferably, the binder comprises one or more of starch, sodium chloride, cellulose, asphalt, heavy oil, dextrin, humic acid and the like; more preferably, the binder is added in an amount of 2 to 5wt%.
In one embodiment, the ilmenite with a grain size of not less than 160 mesh is 90% or more by weight.
In one embodiment, in step (d), the reducing agent used in the reduction roasting is one or two of coal, gas, hydrogen and petroleum coke.
In one embodiment, in step (e), the acid leaching impurity removal time is from 3 to 5 hours; the liquid-solid ratio of the inorganic acid to the modified slag is 5-10: 1, a step of; the drying temperature is 100-110 ℃, and the drying time is 1-2 h.
In one embodiment, in step (e), the mineral acid has a concentration of 10 to 30wt%; the pressurized acid leaching is carried out at 120-180 ℃.
In one embodiment, the pressure of the pressurized acid leaching is from 0.20 to 0.8MPa.
In one embodiment, in step (e), the inorganic acid is one or more of industrial hydrochloric acid, sulfuric acid, nitric acid, and titanium white waste acid.
In one embodiment, the composition of the titanium concentrate comprises: tiO 2: 40-50 wt%; TFe (total or total iron): 25-30wt%; caO:0.8 to 2.0 weight percent; mgO:3 to 6 weight percent; siO 2: 2 to 6 weight percent.
In a specific embodiment, the titanium concentrate is a Panzhihua titanium concentrate. The titanium slag produced by ilmenite in Panzhihua area has high calcium and magnesium content and is not suitable for being used as a raw material for boiling chlorination. The invention has more excellent impurity removing effect on ilmenite (Panzhihua titanium concentrate) from Sichuan Panxi area.
The beneficial effects are that:
(1) Aiming at the characteristics of high-calcium magnesium ilmenite, the magnetizing roasting, desilication decalcification and titanium chloride slag upgrading technology is adopted, so that the impurity removal rate can be effectively improved, the grade of titanium chloride slag is improved, and low-calcium magnesium high-grade titanium chloride slag products suitable for large-scale boiling chlorination are prepared;
(2) According to the preparation method of the titanium chloride slag, the ilmenite is subjected to decalcification pretreatment by adopting magnetization roasting, so that the calcium in the high-calcium magnesium ilmenite can be reduced to about 0.2% from about 1.0% and the magnesium is reduced to about 2.0% from about 5.0% and the subsequent difficulty in removing impurities from the titanium chloride slag is greatly reduced;
(3) The non-magnetic ore which is magnetically separated out in the invention can be used as a raw material of a sulfuric acid method, pig iron which is separated in the process of smelting and chloridizing primary slag can be directly sold, a large amount of ferrous chloride can not be generated, acid can be recycled in the acid leaching process, the utilization value of titanium and iron in the ore is improved in the whole process, and no waste side is basically generated;
(4) The preparation method of the titanium chloride slag has simple equipment and easy operation, and can realize large-scale industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is a process flow diagram of preparing titanium chloride slag from ilmenite, which is provided by the embodiment of the invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
Putting a certain titanium concentrate (TiO 246.83 wt％、TFe27.68 wt％、CaO 1.46wt％、 MgO3.5 wt％,SiO2 3.39.39 wt%) of Panzhihua into a fluidized bed, oxidizing and roasting for 2 hours at 680 ℃ under an air atmosphere, ball-milling for 10 minutes, performing wet magnetic separation at 3000GS strength, and adding starch into the obtained magnetic ore to perform granulation (pelletizing); adding the pelletization sample and the reducing agent diced coke directly into a smelting furnace, smelting for 8 hours at 1550 ℃, and then separating slag from iron to obtain slag; crushing the slag, putting the crushed slag into a rotary kiln, oxidizing the slag for 1h at 900 ℃ in an air atmosphere, and reducing the slag in the rotary kiln for 1h at 800 ℃ by taking coal as a reducing agent to obtain modified slag; mixing the modified slag and 21% hydrochloric acid according to a liquid-solid ratio of 1:5, reacting at 120 ℃ for 6 hours, washing and drying, and calcining at 1000 ℃ for 1 hour to obtain titanium chloride slag, wherein the main composition of the titanium chloride slag is TiO 2 90.21wt％、TFe0.78wt％、CaO 0.20wt％、 MgO1.13wt％、SiO2 0.98.98 wt% and meets the index requirement of boiling chlorination on raw materials. Fig. 1 is a process flow diagram of preparing titanium chloride slag from ilmenite, which is provided by the embodiment of the invention.
Example 2:
Adding a certain titanium concentrate (TiO 246.83 wt％、TFe 27.68wt％、CaO 1.46wt％、 MgO3.5 wt％,SiO2 3.39.39 wt%) of Panzhihua into a fluidized bed, oxidizing for 1h at 750 ℃ under air atmosphere, ball-milling for 15min, performing wet magnetic separation under 4000GS strength, and adding starch into the obtained magnetic ore for granulating; adding the pelletization sample and the reducing agent diced coke directly into a smelting furnace, smelting for 6 hours at 1550 ℃, and then separating slag from iron to obtain slag; adding the slag into a rotary kiln, oxidizing for 1h at 950 ℃ in air atmosphere, and reducing for 1h at 850 ℃ in the rotary kiln by taking coal as a reducing agent to obtain modified slag; mixing the modified slag and 21% hydrochloric acid according to a liquid-solid ratio of 1:8, reacting for 2 hours at 180 ℃, washing and drying, and calcining for 1 hour at 1000 ℃ to obtain titanium chloride slag, wherein the titanium chloride slag mainly comprises TiO 291.93wt％、TFe0.32wt％、CaO 0.18wt％、MgO0.94wt％、SiO2 of 1.05wt% and meets the index requirement of boiling chlorination on raw materials.
Example 3:
Adding a certain titanium concentrate (TiO 246.83 wt％、TFe27.68 wt％、CaO 1.46wt％、 MgO3.5 wt％,SiO2 3.39.39 wt%) of Panzhihua into a fluidized bed, oxidizing for 1.5h at 730 ℃ under air atmosphere, ball-milling for 10min, performing wet magnetic separation at 3000GS strength, adding starch into the obtained magnetic ore, and granulating; adding the pelletization sample and the reducing agent diced coke directly into a smelting furnace, smelting for 9 hours at 1550 ℃, and then separating slag from iron to obtain slag; adding the slag into a rotary kiln, oxidizing for 1h at 800 ℃ in air atmosphere, and reducing for 1h at 750 ℃ in the rotary kiln by taking coal as a reducing agent to obtain modified slag; mixing the modified slag and 21% hydrochloric acid according to a liquid-solid ratio of 1:6, reacting for 2 hours at 150 ℃, washing and drying, and calcining for 2 hours at 1000 ℃ to obtain titanium chloride slag, wherein the main composition TiO 290.75wt％、TFe0.90wt％、CaO 0.18wt％、MgO1.09wt％,SiO2 0.86.86 wt% meets the index requirement of boiling chlorination on raw materials.
Example 4:
Adding a certain titanium concentrate (TiO 246.71 wt％、TFe 32.53wt％、CaO 1.34wt％、 MgO3.92 wt％,SiO2 3.92.92 wt%) of Yunnan ore into a fluidized bed, oxidizing for 1.5h at 730 ℃ under an air atmosphere, performing ball milling for 10min, performing wet magnetic separation at 3000GS strength, and adding starch into the obtained magnetic ore for granulating; adding the pelletization sample and the reducing agent diced coke directly into a smelting furnace, smelting for 9 hours at 1550 ℃, and then separating slag from iron to obtain slag; adding the slag into a rotary kiln, oxidizing for 1h at 800 ℃ in air atmosphere, and reducing for 1h at 750 ℃ in the rotary kiln by taking coal as a reducing agent to obtain modified slag; mixing the modified slag and 21% hydrochloric acid according to a liquid-solid ratio of 1:6, reacting at 150 ℃ for 2 hours, washing with water, drying, and calcining at 1000 ℃ for 2 hours to obtain titanium chloride slag, wherein the main composition TiO 291.05wt％、TFe 1.0wt％、CaO 0.15wt％、MgO1.15 wt％,SiO2 1.15.15 wt% meets the index requirement of boiling chlorination on raw materials.
Example 5:
Adding domestic titanium concentrate (TiO 245.68wt％、TFe32.26wt％、CaO 0.98wt％、MgO 4.64wt％,SiO2 2.16.16 wt%) selected by a certain company into a fluidized bed, oxidizing for 1.5h at 730 ℃ under air atmosphere, ball-milling for 10min, performing wet magnetic separation at 3000GS strength, adding starch into the obtained magnetic ore, and granulating; adding the pelletization sample and the reducing agent diced coke directly into a smelting furnace, smelting for 9 hours at 1550 ℃, and then separating slag from iron to obtain slag; putting the slag into a rotary kiln, oxidizing for 1h at 800 ℃ in an air atmosphere, and reducing for 1h at 750 ℃ in the rotary kiln by taking coal as a reducing agent to obtain modified slag; mixing the modified slag and 21% hydrochloric acid according to a liquid-solid ratio of 1:6, reacting for 2 hours at 150 ℃, washing and drying, and calcining for 2 hours at 1000 ℃ to obtain titanium chloride slag, wherein the main composition of the titanium chloride slag is TiO 2 90.88wt％、TFe0.95 wt％、CaO 0.14wt％、MgO1.23 wt％, SiO2 0.92.92 wt%, and the titanium chloride slag meets the index requirement of boiling chlorination on raw materials.
Comparative example 1:
directly ball-milling titanium concentrate (TiO 246.83wt％、TFe 27.68wt％、CaO 1.46wt％、 MgO3.5 wt％,SiO2 3.39.39 wt%) of Panzhihua for 10min, then wet-process magnetic-separating under the condition of 3000GS strength, adding starch into the obtained magnetic ore, granulating; adding the pelletization sample and the reducing agent diced coke directly into a smelting furnace, smelting for 9 hours at 1550 ℃, and then separating slag from iron to obtain slag; adding the slag into a rotary kiln, oxidizing for 1h at 800 ℃ in an air atmosphere, and reducing for 1h at 750 ℃ in the rotary kiln by taking coal as a reducing agent to obtain modified slag; mixing the modified slag and 21% hydrochloric acid according to a liquid-solid ratio of 1:6, reacting for 2 hours at 150 ℃, washing and drying, and calcining for 2 hours at 1000 ℃ to obtain titanium chloride slag, wherein the main composition of the titanium chloride slag is TiO 286.75 wt％、TFe 1.52wt％、CaO 2.40wt％、 MgO4.54 wt％,SiO2 3.54.54 wt% which does not meet the index requirement of boiling chlorination on raw materials.
Comparative example 2:
Adding Panzhihua titanium concentrate (TiO 246.83 wt％、TFe 27.68wt％、CaO 1.46wt％、 MgO3.5 wt％,SiO2 3.39.39 wt%) into a fluidized bed, oxidizing for 2h at 680 ℃ in air atmosphere, directly carrying out magnetic separation at 3000GS strength, adding the obtained magnetic ore and reducer diced coke into a smelting furnace, smelting for 8h at 1550 ℃, and carrying out slag-iron separation to obtain slag; adding the slag into a rotary kiln, oxidizing for 1h at 900 ℃ in an air atmosphere, and reducing for 1h at 800 ℃ in the rotary kiln by taking coal as a reducing agent to obtain modified slag; mixing the modified slag and 21% hydrochloric acid according to a liquid-solid ratio of 1:5, reacting for 6 hours at 120 ℃, washing and drying, and calcining for 1 hour at 1000 ℃ to obtain titanium chloride slag, wherein the titanium chloride slag mainly comprises TiO 288.98 wt％、TFe 1.85wt％、CaO 0.84wt％、MgO2.28 wt％,SiO2 2.46.46 wt% and does not meet the index requirement of boiling chlorination on raw materials.
Comparative example 3:
Adding a certain titanium concentrate (TiO 246.83 wt％、TFe27.68 wt％、CaO 1.46wt％、 MgO3.5 wt％,SiO2 3.39.39 wt%) of Panzhihua into a fluidized bed, oxidizing for 2 hours at 680 ℃ under air atmosphere, ball-milling for 10 minutes, performing wet magnetic separation at 3000GS strength, adding starch into the obtained magnetic ore, and granulating; adding the pelletization sample and the reducing agent diced coke directly into a smelting furnace, smelting for 8 hours at 1550 ℃, and then separating slag from iron to obtain slag; mixing the slag and 21% hydrochloric acid according to a liquid-solid ratio of 1:5, reacting at 120 ℃ for 6 hours, washing with water, drying, and calcining at 1000 ℃ for 1 hour to obtain titanium chloride slag, wherein the main composition of the titanium chloride slag is TiO 288.98 wt％、TFe 1.54wt％、CaO 0.35wt％、 MgO1.79 wt％、SiO2, and the titanium chloride slag does not meet the index requirement of boiling chlorination on raw materials.
In summary, as can be seen from comparative examples and examples, according to the preparation method of the invention, slag is obtained by magnetizing roasting, ball milling, wet magnetic separation, granulation and smelting of high-calcium magnesia-ilmenite, and titanium chloride slag is obtained by sequentially oxidizing roasting, reducing roasting, pressurized acid leaching and calcining the slag, so that the requirements of boiling chlorination on indexes of raw materials are met; when the process steps are different from the preparation method of the invention (shown in comparative example), the prepared titanium chloride slag does not meet the index requirement of boiling chlorination on raw materials.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (8)
1. A method for preparing titanium chloride slag from titanium concentrate, which is characterized by comprising the following steps:
(a) Magnetizing roasting and ball milling: ball-milling ilmenite obtained by oxidizing and roasting the titanium concentrate at 600-800 ℃ into fine-powder ilmenite; the ball milling is carried out until the grain diameter is not more than 325 meshes of fine powder accounting for more than 80 percent by weight;
(b) Wet magnetic separation and granulation: carrying out wet magnetic separation on the fine-powder ilmenite at 3000GS strength, and granulating the separated magnetic ilmenite; the granulating is carried out by adding a binder; the binder is one or more of cellulose, asphalt, heavy oil, dextrin and humic acid; the addition amount of the binder is 2-5wt%; the ilmenite with the grain diameter of not less than 160 meshes accounts for more than 90% by weight;
(c) Smelting: smelting the granulated ilmenite at 1500-1600 ℃ and separating to obtain slag;
(d) And (3) oxidation-reduction roasting: sequentially carrying out oxidizing roasting and reducing roasting on the slag to obtain modified slag; in the step (d), the oxidizing roasting condition is that the oxidizing roasting is carried out for 1-2 hours at 800-1000 ℃ in an oxygen atmosphere; the condition of the reduction roasting is that the reduction roasting is carried out for 1-2 hours at 700-900 ℃ in a reducing atmosphere;
(e) Pressurized acid leaching: carrying out pressurized acid leaching impurity removal reaction on the modified slag and inorganic acid, washing and drying to obtain acid leaching impurity removal slag;
(f) Calcining the obtained acid leaching impurity-removing slag at 900-1000 ℃ to obtain the titanium chloride slag.
2. The method of claim 1, wherein the time of the oxidative calcination in step (a) is 1-2 hours; the smelting time in the step (c) is 6-10 hours; and (f) calcining for 1-2 hours.
3. The method of claim 1, wherein the ball milling comprises mechanical ball milling.
4. The method of claim 1, wherein the reducing agent used in the reduction roasting comprises one or two of coal, gas, hydrogen, and petroleum coke.
5. The method of claim 1, wherein in step (e), the acid leaching and impurity removal time is 3-5 hours; the liquid-solid ratio of the inorganic acid to the modified slag is 5-10: 1, a step of; the drying temperature is 100-110 ℃, and the drying time is 1-2 h.
6. The method of claim 1, wherein in step (e), the concentration of the mineral acid is 10-30 wt%; the pressurized acid leaching is carried out at the temperature of 120-180 ℃.
7. The method of claim 1, wherein in step (e), the inorganic acid comprises one or more of industrial hydrochloric acid, sulfuric acid, nitric acid, and titanium white waste acid.
8. The method according to any one of claims 1 to 7, wherein the composition of the titanium concentrate comprises: tiO 2: 40-50 wt%; TFe iron: 25-30wt%; caO: 0.8-2.0 wt%; mgO: 3-6wt% of SiO 2: 2-6wt%.
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| CN1429919A (en) * | 2002-10-18 | 2003-07-16 | 中国科学院过程工程研究所 | Method of producing titanium enriched material using titanium mineral |
| CN108910942A (en) * | 2018-10-09 | 2018-11-30 | 龙蟒佰利联集团股份有限公司 | A method of synthetic rutile is prepared by high calcium magnesium titanium slag |
| CN111534706A (en) * | 2020-05-11 | 2020-08-14 | 河南佰利联新材料有限公司 | Method for preparing titanium-rich material from Panxi titanium concentrate |
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| CN1429919A (en) * | 2002-10-18 | 2003-07-16 | 中国科学院过程工程研究所 | Method of producing titanium enriched material using titanium mineral |
| CN108910942A (en) * | 2018-10-09 | 2018-11-30 | 龙蟒佰利联集团股份有限公司 | A method of synthetic rutile is prepared by high calcium magnesium titanium slag |
| CN111534706A (en) * | 2020-05-11 | 2020-08-14 | 河南佰利联新材料有限公司 | Method for preparing titanium-rich material from Panxi titanium concentrate |
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