CN104045111A - Artificial rutile preparation method - Google Patents
Artificial rutile preparation method Download PDFInfo
- Publication number
- CN104045111A CN104045111A CN201310534032.5A CN201310534032A CN104045111A CN 104045111 A CN104045111 A CN 104045111A CN 201310534032 A CN201310534032 A CN 201310534032A CN 104045111 A CN104045111 A CN 104045111A
- Authority
- CN
- China
- Prior art keywords
- leaching
- acid
- weight
- fluidizing
- titanium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
An artificial rutile preparation method comprises the following steps: 1, extracting oxidation and reduction treatment modified titanium-containing material by a heated acid in a fluidized manner; 2, filtering the slurry obtained in step 1 to obtain a solid and a mother liquor; and 3, washing the solid obtained in step 2, and calcining to obtain artificial rutile, wherein the titanium-containing material is ilmenite concentrate and/or titanium slag. The method adopting a fluidizing technology to prepare the artificial rutile has the advantages of continuous production, high automation degree, stable product quality and low production cost.
Description
Technical field
The present invention relates to chemical metallurgy technical field, be specifically related to a kind of method of preparing artificial rutile.
Background technology
Titanium dioxide formal name used at school titanium dioxide (TiO
2) there is best opacity, whiteness and luminance brightness, be considered at present the different white pigment of best performance in the world.Titanium dioxide is widely used in the fields such as coating, plastics, papermaking, printing-ink, chemical fibre, rubber, pottery, makeup, food and medicine.The technique of producing at present titanium dioxide is mainly two kinds of sulfuric acid process and chlorination processs.
The method of sulfuric acid process preparing titanium dioxide is low to ingredient requirement, therefore, containing the Flos Bombacis Malabarici ilmenite concentrate of high calcium and high magnesium and take its acid-dissolved titanium slag of smelting acquisition for raw material be sulfate process titanium dioxide be suitable raw material.
Chlorination process generates titanium tetrachloride with the rich titanium material such as ilmenite concentrate, titanium slag, artificial rutile or natural rutile and chlorine reaction, through rectification and purification, obtains raw material essence titanium tetrachloride.Then by gaseous oxidation, after speed is cold, through gas solid separation, obtain titanium dioxide, or adopt metallic reducing to prepare Sponge Titanium, prepare titanium alloy today.Due to the method for preparing titanium white through chlorination process powder possess skills advanced person, the advantage such as productivity effect is good, environment-friendly advantage is large, technical process is short, level of automation is high and throughput is large.But chlorination process requires highly to raw material, often needs to adopt titanium slag or artificial rutile.
The Panxi Diqu of China has abundant titanium resource, but its calcium-magnesium content is higher, is difficult to produce as chlorination process the raw material of the high-end titaniums such as titanium white, titanium sponge.For obtaining, can need to carry out modification to this type of raw material for the raw material of chlorination process, to remove calcium contained in raw material, magnesium, in chlorination process, generate the impurity of low melting point with chlorine reaction.
At present, both at home and abroad titanium ore is carried out to modification and have to prepare the method for artificial rutile defects such as producing discontinuous, level of automation is not high, unstable product quality and production cost height.
Summary of the invention
The object of this invention is to provide a kind of method of preparing artificial rutile, the method adopts fluidization technology to prepare artificial rutile, have advantages of produce continuously, level of automation is high, constant product quality and production cost low.
To achieve these goals, the invention provides a kind of method of preparing artificial rutile, the method comprises the following steps:
(1) will with the acid after heating, in fluidised mode, leach by the titaniferous material being oxidized and reduce after processing modification;
(2) by the slurries filtration of gained after leaching in step (1), obtain solid formation and mother liquor;
(3) gained solid formation in step (2) is calcined after washing, obtained artificial rutile;
Wherein, titaniferous material is ilmenite concentrate and/or titanium slag.
The method of preparing artificial rutile provided by the invention have advantages of produce continuously, level of automation is high, constant product quality and production cost low.
Other features and advantages of the present invention partly in detail are described the embodiment subsequently.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
The Leaching reaction time of the present invention refers in material enters the reaction zone of Leaching reaction tower and starts timing, finishes timing when described reaction mass is started to filter.
The invention provides a kind of method of preparing artificial rutile, the method comprises the following steps:
(1) will with the acid after heating, in fluidised mode, leach by the titaniferous material being oxidized and reduce after processing modification;
(2) by the slurries filtration of gained after leaching in step (1), obtain solid formation and mother liquor;
(3) gained solid formation in step (2) is calcined after washing, obtained artificial rutile;
Wherein, titaniferous material is ilmenite concentrate and/or titanium slag.
In the present invention, described titaniferous material is ilmenite concentrate and/or titanium slag, and the titaniferous material after described modification refers to ilmenite concentrate and/or titanium slag by being oxidized and reducing the material obtaining after processing.
Under preferable case, in the step (1) of the method for the invention, the titaniferous material after modification can obtain by following steps: (a) by titaniferous material through 850 ℃ of-1200 ℃ of high temperature oxidation process; (b), in reducing atmosphere, the titaniferous material after oxide treatment is carried out to modified with reduction processing under 650 ℃ of-900 ℃ of conditions.To processing operation of the present invention, there is no particular limitation, can process for the conventional working method of using in this area.
In the present invention, to ilmenite concentrate or titanium slag, adopt oxide treatment can make the titanium formation in ilmenite concentrate or titanium slag be insoluble to sour titanium oxide, to it, adopt reduction to process to increase the leaching effect of impurity wherein, obtain ilmenite concentrate or titanium slag after modification.
Wherein, described in above-mentioned steps (a), high temperature oxidation process can adopt coal gas, Sweet natural gas or coal to carry out oxide treatment as thermal source, and titaniferous material is become as being insoluble to sour material, preferably uses coke-oven gas as thermal source.The reducing medium in above-mentioned steps (b), the titaniferous material after oxide treatment being reduced can adopt coal gas or hydrogen.Oxidation-reduction modification can adopt fluidization processing or rotary kiln mode to process, and preferably uses fluidization pattern to carry out the modification of ilmenite concentrate or titanium slag.
Under preferable case, in the step (1) of the method for the invention, the gross weight of ilmenite concentrate of take is benchmark, contains the TiO of 40-50 % by weight in described ilmenite concentrate
2, 25-35 % by weight T[Fe], the FeO of 20-30 % by weight is, the Fe of 1-10 % by weight
2o
3, 0.1-5 % by weight Al
2o
3, the MgO of 1-10 % by weight is, the SiO of 1-10 % by weight
2caO with 0.1-5 % by weight.The gross weight of titanium slag of take is benchmark, contains the TiO of 65-80 % by weight in described titanium slag
2, 5-15 % by weight T[Fe], the FeO of 1-10 % by weight is, the Fe of 0.001-1 % by weight
2o
3, 0.1-5 % by weight Al
2o
3, the MgO of 0.1-10 % by weight is, the SiO of 1-10 % by weight
2caO with 0.1-5 % by weight.
Under preferable case, in the step (1) of the method for the invention, the process of described leaching comprises: the acid after heating is formed to Fluidizing Leaching bed, then the titaniferous material after modification is added in described Fluidizing Leaching bed and carries out Leaching reaction.Impurity in titaniferous material is leached Ore Leaching, the proportion of titaniferous material reduces, just added the material of fluidized-bed in the bottom of fluidized-bed, prolongation with extraction time, the material that foreign matter content reduces moves on progressively, by controlling the fluidizing velocity of fluidized-bed, the material that completes Leaching reaction is discharged reactor with leach liquor in the lump overflow.
In the present invention, to the mode that adds of the titaniferous material after described modification, there is no particular limitation, the mode that preferably employing adds continuously.
Under preferable case, in the step (1) of the method for the invention, the concentration of described acid is 8-50 % by weight.
Under preferable case, in the step (1) of the method for the invention, described acid is mineral acid, and described mineral acid is selected from one or more in hydrochloric acid, sulfuric acid, titanium dioxide hydrolysis spent acid and nitric acid, is preferably hydrochloric acid.
Especially, the industrial waste acid that contains sulfuric acid, hydrochloric acid or nitric acid producing in industrial production can be applied to, in the inventive method, particularly contain the titanium white waste acid of sulfuric acid equally.
The titaniferous material of the process modification of using during Leaching reaction, because feedstock property changes, titanium in raw material can form not the material reacting with acid, by using mineral acid to adopt Fluidizing Leaching reaction to carry out acidleach to the titaniferous material after modification, the impurity such as calcium magnesium in material are leached, can realize continuous leaching operation, cost is low, and the artificial rutile quality index preparing is stable.
Under preferable case, in the step (1) of the method for the invention, the sour temperature after heating is 70-90 ℃.In the present invention, preferably by controlling steam flow in leaching system acid is heated to the temperature needing.
Under preferable case, in the step (1) of the method for the invention, the titaniferous material after modification adds in described Fluidizing Leaching bed and forms after stable fluidized, and controlling Leaching reaction temperature is 95-120 ℃, and the Leaching reaction time is 6-10 hour.In the present invention, preferably by controlling steam flow in leaching system to control the temperature of Leaching reaction.
Under preferable case, in the step (3) of the method for the invention, the temperature of calcining is 400-600 ℃, and the time of calcining is 30-100 minute.
Method of the present invention can also comprise that directly allocating a mother liquor part for gained in step (2) into acid enters the use of Fluidizing Leaching bed internal recycle.Under preferable case, the mother liquor that filters gained is formed to regenerating acid after manipulation of regeneration, and regenerating acid is cycled to used in leaching process.
Under preferable case, the fluidizing reactor using in method of the present invention, the pipeline that stores sour equipment and use all adopt anticorrosion material to make.The leaching tower that the materials such as the fluidizing reactor using in the method for the invention especially, and the sour equipment of storage are glass-lined steel steel, the acidproof film of steel lining and acid-resistant porcelain are made; The acid-proof corrosion pipeline that the materials such as the pipeline using is glass reinforced plastic, steel lining tetrafluoroethylene glass-lined steel are made.
A preferred embodiment of the invention, by titaniferous material through 850 ℃ of-1200 ℃ of high temperature oxidation process; In reducing atmosphere, titaniferous material after oxide treatment is carried out to modified with reduction processing under 650 ℃ of-900 ℃ of conditions, obtain ilmenite concentrate or the titanium slag material of modification, use the acid that acid proof pump is the leaching of 8-50 % by weight by concentration to pump in leaching tower, form Fluidizing Leaching bed; Leach acid and use graphite heat exchanger to heat, control steam flow leaching acid is heated to 70-90 ℃; Through ilmenite concentrate or the titanium slag material of modification, directly and continuously add in Fluidizing Leaching tower, control the sour flow pumping into, make titaniferous material in leaching tower in fluidized state; Controlling Leaching reaction temperature is 95-120 ℃, and the Leaching reaction time is 6-10 hour.The material that process leaches, due to the variation of proportion, drains into and leaches in slurry tank with leach liquor; Slurry is carried out after solid-liquid separation, and solid formation is calcined and within 30-100 minute, is obtained artificial rutile product under 400-600 ℃ of condition, and the spent acid of generation enters leaching system and is recycled after regenerating unit manipulation of regeneration.
Below will describe the present invention by embodiment.The raw material using in following examples is in case of no particular description all from being purchased.
Embodiment 1
After being oxidized under 960 ℃ of conditions, it is standby that the ilmenite concentrate of processing 820 ℃ of reduction is put into leaching feed bin.In complex acid groove, use concentrated hydrochloric acid and water, the hydrochloric acid soln that is mixed with acid concentration and is 22 % by weight is standby, the acid preparing is pumped in Fluidizing Leaching circulation groove, use acid proof pump that leaching acid is pumped in Fluidizing Leaching reaction tower, at the leaching operation initial stage, leaching acid enters in Fluidizing Leaching reaction tower process uses graphite heat exchanger to heat, control steam flow leaching acid is heated to 80 ℃, form Fluidizing Leaching bed; Open Modified Titanium concentrate feed bin baiting valve, by controlling the baiting valve aperture under feed bin, control Modified Titanium concentrate feeding quantity according to 1.5 tons of/hour continuous chargings, the ilmenite concentrate after modification directly adds Fluidizing Leaching reaction tower reaction zone, by regulate pump discharge valve to control leaching sour flow, is 8m
3/ h, make titaniferous material in leaching tower in fluidized state; After whole fluidized-bed is stable, controlling steam flow makes in Leaching reaction district temperature-stable at 105 ± 5 ℃, along with Leaching reaction carries out, the material having reacted overflows Leaching reaction tower with leaching acid, the solution that leaching completes is through filtration treatment, and after filtering, solid formation is through washing, calcine at 500 ℃ the artificial rutile product obtaining for 80 minutes containing titanium dioxide; Filter the spent acid part producing and after regenerating unit manipulation of regeneration, enter leaching system recycle.Solution after another part filters is back in circulation groove, recycles as leaching acid with the leaching acid newly adding.
According to aforesaid method, produce 72 hours continuously, the content that detects titanium dioxide in the artificial rutile product obtaining is 90.11～90.63 % by weight.
Comparative example 1
After being oxidized under 960 ℃ of conditions, it is standby that the ilmenite concentrate of processing 820 ℃ of reduction is put into leaching feed bin.
In complex acid groove, use concentrated hydrochloric acid and water, be mixed with the hydrochloric acid soln that acid concentration is 22 % by weight, and be heated to 80 ℃ with graphite heat exchanger, standby.
Open Modified Titanium concentrate feed bin baiting valve, to the ilmenite concentrate and the 24m that add 7.0 tons of modifications in Leaching reaction tower reaction zone
3above-mentioned standby leaching acid, be uniformly mixed post-heating, make in Leaching reaction district temperature-stable at 105 ± 5 ℃, in leaching process, constantly stir, Leaching reaction carried out after 8 hours, by reaction mass cooling-sedimentation, then solid formation is carried out to filtration treatment, after filtering, solid formation is through washing, calcine at 500 ℃ the artificial rutile product obtaining for 80 minutes containing titanium dioxide 84.01 % by weight.
According to above-mentioned identical method, prepare five batches of artificial rutile products again, detect respectively the content of titanium dioxide wherein, result is as shown in table 1 below.
Table 1
| Batch | The % by weight of titanium dioxide |
| First | 86.72 |
| Second batch | 85.21 |
| The 3rd batch | 85.69 |
| The 4th batch | 87.86 |
| The 5th batch | 85.78 |
Result from embodiment 1 and comparative example 1 can be found out, the stable content that utilizes method provided by the invention to produce continuously titanium dioxide in the rutile product obtaining for 72 hours is 90.11～90.63 % by weight, and the content of titanium dioxide is as shown in table 1 in the rutile product of the different batches of producing according to the method described in comparative example 1, difference is larger.Therefore the quality product that the rutile quality product of, utilizing method production provided by the invention to obtain obviously obtains compared with method described in comparative example 1 is high and stable.
Embodiment 2
After being oxidized under 1010 ℃ of conditions, it is standby that the ilmenite concentrate of processing 860 ℃ of reduction is put into leaching feed bin.In complex acid groove, use the vitriol oil and water, the sulphuric acid soln that is mixed with acid concentration and is 21 % by weight is standby, the acid preparing is pumped in Fluidizing Leaching circulation groove, use acid proof pump that leaching acid is pumped in Fluidizing Leaching reaction tower, at the leaching operation initial stage, leaching acid enters in Fluidizing Leaching reaction tower process uses graphite heat exchanger to heat, control steam flow leaching acid is heated to 70 ℃, form Fluidizing Leaching bed; Open Modified Titanium concentrate feed bin baiting valve, by controlling the baiting valve aperture under feed bin, control Modified Titanium concentrate feeding quantity according to 1.5 tons of/hour continuous chargings, Modified Titanium concentrate directly adds Fluidizing Leaching reaction tower reaction zone, by regulate pump discharge valve to control leaching sour flow, is 7.5m
3/ h, make titaniferous material in leaching tower in fluidized state; After whole fluidized-bed is stable, controlling steam flow makes in Leaching reaction district temperature-stable at 115 ± 5 ℃, carrying out along with Leaching reaction, the material having reacted overflows Leaching reaction tower with leaching acid, the solution that leaching completes is through filtration treatment, and after filtering, solid formation is through washing, calcine at 550 ℃ the artificial rutile product obtaining for 100 minutes containing titanium dioxide; Filter the spent acid part producing and after regenerating unit manipulation of regeneration, enter leaching system recycle.Solution after another part filters is back in circulation groove, recycles as leaching acid with the leaching acid newly adding.
According to aforesaid method, produce 72 hours continuously, the content that detects titanium dioxide in the artificial rutile product obtaining is 90.89～91.44 % by weight, constant product quality.
Embodiment 3
After being oxidized under 970 ℃ of conditions, it is standby that the ilmenite concentrate of processing 830 ℃ of reduction is put into leaching feed bin.In complex acid groove, use the vitriol oil and water, the sulphuric acid soln that is mixed with acid concentration and is 43 % by weight is standby, the acid preparing is pumped in Fluidizing Leaching circulation groove, use acid proof pump that leaching acid is pumped in Fluidizing Leaching reaction tower, at the leaching operation initial stage, leaching acid enters in Fluidizing Leaching reaction tower process uses graphite heat exchanger to heat, control steam flow leaching acid is heated to 90 ℃, form Fluidizing Leaching bed; Open Modified Titanium concentrate feed bin baiting valve, by controlling the baiting valve aperture under feed bin, control Modified Titanium concentrate feeding quantity according to 1.5 tons of/hour continuous chargings, Modified Titanium concentrate directly adds Fluidizing Leaching reaction tower reaction zone, by regulate pump discharge valve to control leaching sour flow, is 8m
3/ h, make titaniferous material in leaching tower in fluidized state; After whole fluidized-bed is stable, controlling steam flow makes in Leaching reaction district temperature-stable at 100 ± 5 ℃, carrying out along with Leaching reaction, the material having reacted overflows Leaching reaction tower with leaching acid, the solution that leaching completes is through filtration treatment, and after filtering, solid formation is through washing, calcine at 400 ℃ the artificial rutile product obtaining for 80 minutes containing titanium dioxide; Filter the spent acid part producing and after regenerating unit manipulation of regeneration, enter leaching system recycle.Solution after another part filters is back in circulation groove, recycles as leaching acid with the leaching acid newly adding.
According to aforesaid method, produce 72 hours continuously, the content that detects titanium dioxide in the artificial rutile product obtaining is 90.21～90.51 % by weight, constant product quality.
Embodiment 4
After being oxidized under 950 ℃ of conditions, it is standby that the Flos Bombacis Malabarici ilmenite concentrate titanium slag of processing 850 ℃ of reduction is put into leaching feed bin.In complex acid groove, use concentrated nitric acid and water, the salpeter solution that is mixed with acid concentration and is 50 % by weight is standby, the acid preparing is pumped in Fluidizing Leaching circulation groove, use acid proof pump that leaching acid is pumped in Fluidizing Leaching reaction tower, at the leaching operation initial stage, leaching acid enters in Fluidizing Leaching reaction tower process uses graphite heat exchanger to heat, control steam flow leaching acid is heated to 75 ℃, form Fluidizing Leaching bed; Open Modified Titanium concentrate feed bin baiting valve, by controlling the baiting valve aperture under feed bin, control Modified Titanium concentrate feeding quantity according to 1.5 tons of/hour continuous chargings, Modified Titanium concentrate directly adds Fluidizing Leaching reaction tower reaction zone, by regulate pump discharge valve to control leaching sour flow, is 7.5m
3/ h, make titaniferous material in leaching tower in fluidized state; After whole fluidized-bed is stable, controlling steam flow makes in Leaching reaction district temperature-stable at 100 ± 5 ℃, carrying out along with Leaching reaction, the material having reacted overflows Leaching reaction tower with leaching acid, the solution that leaching completes is through filtration treatment, and after filtering, solid formation is through washing, calcine at 450 ℃ the artificial rutile product obtaining for 90 minutes containing titanium dioxide; Filter the spent acid part producing and after regenerating unit manipulation of regeneration, enter leaching system recycle.Solution after another part filters is back in circulation groove, recycles as leaching acid with the leaching acid newly adding.
According to aforesaid method, produce 72 hours continuously, the content that detects titanium dioxide in the artificial rutile product obtaining is 90.06～90.48 % by weight, constant product quality.
Embodiment 5
After being oxidized under 990 ℃ of conditions, it is standby that the ilmenite concentrate of processing 860 ℃ of reduction is put into leaching feed bin.In complex acid groove, use concentrated hydrochloric acid and water, the hydrochloric acid soln that is mixed with acid concentration and is 8 % by weight is standby, the acid preparing is pumped in Fluidizing Leaching circulation groove, use acid proof pump that leaching acid is pumped in Fluidizing Leaching reaction tower, at the leaching operation initial stage, leaching acid enters in Fluidizing Leaching reaction tower process uses graphite heat exchanger to heat, control steam flow leaching acid is heated to 85 ℃, form Fluidizing Leaching bed; Open Modified Titanium concentrate feed bin baiting valve, by controlling the baiting valve aperture under feed bin, control Modified Titanium concentrate feeding quantity according to 1.5 tons of/hour continuous chargings, Modified Titanium concentrate directly adds Fluidizing Leaching reaction tower reaction zone, by regulate pump discharge valve to control leaching sour flow, is 8.5m
3/ h, make titaniferous material in leaching tower in fluidized state; After whole fluidized-bed is stable, controlling steam flow makes in Leaching reaction district temperature-stable at 105 ± 5 ℃, carrying out along with Leaching reaction, the material having reacted overflows Leaching reaction tower with leaching acid, the solution that leaching completes is through filtration treatment, and after filtering, solid formation is through washing, calcine at 500 ℃ the artificial rutile product obtaining for 50 minutes containing titanium dioxide; Filter the spent acid part producing and after regenerating unit manipulation of regeneration, enter leaching system recycle.Solution after another part filters is back in circulation groove, recycles as leaching acid with the leaching acid newly adding.
According to aforesaid method, produce 72 hours continuously, the content that detects titanium dioxide in the artificial rutile product obtaining is 90.37～90.59 % by weight, constant product quality.
Embodiment 6
After being oxidized under 960 ℃ of conditions, it is standby that the ilmenite concentrate of processing 820 ℃ of reduction is put into leaching feed bin.In complex acid groove, use concentrated nitric acid and water, the salpeter solution that is mixed with acid concentration and is 42 % by weight is standby, the acid preparing is pumped in Fluidizing Leaching circulation groove, use acid proof pump that leaching acid is pumped in Fluidizing Leaching reaction tower, at the leaching operation initial stage, leaching acid enters in Fluidizing Leaching reaction tower process uses graphite heat exchanger to heat, control steam flow leaching acid is heated to 85 ℃, form Fluidizing Leaching bed; Open Modified Titanium concentrate feed bin baiting valve, by controlling the baiting valve aperture under feed bin, control Modified Titanium concentrate feeding quantity according to 1.5 tons of/hour continuous chargings, Modified Titanium concentrate directly adds Fluidizing Leaching reaction tower reaction zone, by regulate pump discharge valve to control leaching sour flow, is 6.5m
3/ h, make titaniferous material in leaching tower in fluidized state; After whole fluidized-bed is stable, controlling steam flow makes in Leaching reaction district temperature-stable at 110 ± 5 ℃, carrying out along with Leaching reaction, the material having reacted overflows Leaching reaction tower with leaching acid, the solution that leaching completes is through filtration treatment, and after filtering, solid formation is through washing, calcine at 600 ℃ the artificial rutile product obtaining for 30 minutes containing titanium dioxide; Filter the spent acid part producing and after regenerating unit manipulation of regeneration, enter leaching system recycle.Solution after another part filters is back in circulation groove, recycles as leaching acid with the leaching acid newly adding.
According to aforesaid method, produce 72 hours continuously, the content that detects titanium dioxide in the artificial rutile product obtaining is 91.09～91.35 % by weight, constant product quality.
Embodiment 7
After being oxidized under 960 ℃ of conditions, it is standby that the ilmenite concentrate of processing 820 ℃ of reduction is put into leaching feed bin.In complex acid groove, use titanium dioxide hydrolysis spent acid and water, the titanium dioxide hydrolysis waste acid liquor that is mixed with acid concentration and is 23 % by weight is standby, the acid preparing is pumped in Fluidizing Leaching circulation groove, use acid proof pump that leaching acid is pumped in Fluidizing Leaching reaction tower, at the leaching operation initial stage, leaching acid enters in Fluidizing Leaching reaction tower process uses graphite heat exchanger to heat, control steam flow leaching acid is heated to 78 ℃, form Fluidizing Leaching bed; Open Modified Titanium concentrate feed bin baiting valve, by controlling the baiting valve aperture under feed bin, control Modified Titanium concentrate feeding quantity according to 1.5 tons of/hour continuous chargings, Modified Titanium concentrate directly adds Fluidizing Leaching reaction tower reaction zone, by regulate pump discharge valve to control leaching sour flow, is 8m
3/ h, make titaniferous material in leaching tower in fluidized state; After whole fluidized-bed is stable, controlling steam flow makes in Leaching reaction district temperature-stable at 105 ± 5 ℃, carrying out along with Leaching reaction, the material having reacted overflows Leaching reaction tower with leaching acid, the solution that leaching completes is through filtration treatment, and after filtering, solid formation is through washing, calcine at 480 ℃ the artificial rutile product obtaining for 50 minutes containing titanium dioxide; Filter the spent acid part producing and be back in circulation groove, recycle as leaching acid with the leaching acid newly adding; Solution after another part filters enters leaching system recycle after regenerating unit manipulation of regeneration.
According to aforesaid method, produce 72 hours continuously, the content that detects titanium dioxide in the artificial rutile product obtaining is 89.04～89.37 % by weight, constant product quality.
Embodiment 8
After being oxidized under 960 ℃ of conditions, it is standby that the ilmenite concentrate of processing 820 ℃ of reduction is put into leaching feed bin.In complex acid groove, use the vitriol oil and water, the sulphuric acid soln that is mixed with acid concentration and is 10 % by weight is standby, the acid preparing is pumped in Fluidizing Leaching circulation groove, use acid proof pump that leaching acid is pumped in Fluidizing Leaching reaction tower, at the leaching operation initial stage, leaching acid enters in Fluidizing Leaching reaction tower process uses graphite heat exchanger to heat, control steam flow leaching acid is heated to 90 ℃, form Fluidizing Leaching bed; Open Modified Titanium concentrate feed bin baiting valve, by controlling the baiting valve aperture under feed bin, control Modified Titanium concentrate feeding quantity according to 1.5 tons of/hour continuous chargings, Modified Titanium concentrate directly adds Fluidizing Leaching reaction tower reaction zone, by regulate pump discharge valve to control leaching sour flow, is 8m
3/ h, make titaniferous material in leaching tower in fluidized state; After whole fluidized-bed is stable, controlling steam flow makes in Leaching reaction district temperature-stable at 105 ± 5 ℃, carrying out along with Leaching reaction, the material having reacted overflows Leaching reaction tower with leaching acid, the solution that leaching completes is through filtration treatment, and after filtering, solid formation is through washing, calcine at 560 ℃ the artificial rutile product obtaining for 60 minutes containing titanium dioxide; Filter the spent acid part producing and after regenerating unit manipulation of regeneration, enter leaching system recycle.Solution after another part filters is back in circulation groove, recycles as leaching acid with the leaching acid newly adding.
According to aforesaid method, produce 72 hours continuously, the content that detects titanium dioxide in the artificial rutile product obtaining is 90.28～90.64 % by weight, constant product quality.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, between various embodiment of the present invention, also can carry out arbitrary combination, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a method of preparing artificial rutile, is characterized in that, the method comprises the following steps:
(1) will with the acid after heating, in fluidised mode, leach by the titaniferous material being oxidized and reduce after processing modification;
(2) by the slurries filtration of gained after leaching in step (1), obtain solid formation and mother liquor;
(3) gained solid formation in step (2) is calcined after washing, obtained artificial rutile;
Wherein, titaniferous material is ilmenite concentrate and/or titanium slag.
2. method according to claim 1, wherein, in step (1), the titaniferous material after modification obtains by following steps: (a) by titaniferous material through 850 ℃ of-1200 ℃ of high temperature oxidation process; (b), in reducing atmosphere, the titaniferous material after oxide treatment is carried out to modified with reduction processing under 650 ℃ of-900 ℃ of conditions.
3. method according to claim 1 and 2, wherein, in step (1), the gross weight of ilmenite concentrate of take is benchmark, contains the TiO of 40-50 % by weight in described ilmenite concentrate
2, 25-35 % by weight T[Fe], the FeO of 20-30 % by weight is, the Fe of 1-10 % by weight
2o
3, 0.1-5 % by weight Al
2o
3, the MgO of 1-10 % by weight is, the SiO of 1-10 % by weight
2caO with 0.1-5 % by weight;
The gross weight of titanium slag of take is benchmark, contains the TiO of 65-80 % by weight in described titanium slag
2, 5-15 % by weight T[Fe], the FeO of 1-10 % by weight is, the Fe of 0.001-1 % by weight
2o
3, 0.1-5 % by weight Al
2o
3, the MgO of 0.1-10 % by weight is, the SiO of 1-10 % by weight
2caO with 0.1-5 % by weight.
4. method according to claim 1, wherein, in step (1), the process of described leaching comprises: the acid after heating is formed to Fluidizing Leaching bed, then the titaniferous material after modification is added in described Fluidizing Leaching bed and carries out Leaching reaction.
5. according to the method described in claim 1 or 4, wherein, in step (1), the concentration of described acid is 8-50 % by weight.
6. according to the method described in claim 1 or 4, wherein, in step (1), described acid is mineral acid, and described mineral acid is selected from one or more in hydrochloric acid, sulfuric acid, titanium dioxide hydrolysis spent acid and nitric acid, is preferably hydrochloric acid.
7. according to the method described in claim 1 or 4, wherein, in step (1), the sour temperature after heating is 70-90 ℃.
8. method according to claim 4, wherein, in step (1), the titaniferous material after modification adds in described Fluidizing Leaching bed and forms after stable fluidized, and controlling Leaching reaction temperature is 95-120 ℃, and the Leaching reaction time is 6-10 hour.
9. method according to claim 1, wherein, in step (3), the temperature of calcining is 400-600 ℃, the time of calcining is 30-100 minute.
10. method according to claim 1, wherein, the method also comprises: the mother liquor that filters gained in step (2) is formed to regenerating acid through manipulation of regeneration, and regenerating acid is cycled to used in to leaching process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310534032.5A CN104045111B (en) | 2013-11-01 | 2013-11-01 | A kind of method preparing artificial rutile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310534032.5A CN104045111B (en) | 2013-11-01 | 2013-11-01 | A kind of method preparing artificial rutile |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104045111A true CN104045111A (en) | 2014-09-17 |
| CN104045111B CN104045111B (en) | 2016-02-03 |
Family
ID=51498568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310534032.5A Active CN104045111B (en) | 2013-11-01 | 2013-11-01 | A kind of method preparing artificial rutile |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104045111B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107955885A (en) * | 2017-11-21 | 2018-04-24 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of preparation method of modified ilmenite concentrate |
| US10287176B2 (en) | 2014-07-08 | 2019-05-14 | Avertana Limited | Extraction of products from titanium-bearing minerals |
| CN110606471A (en) * | 2019-09-18 | 2019-12-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for comprehensively utilizing low-temperature chlorination tail gas |
| CN110629045A (en) * | 2019-10-31 | 2019-12-31 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing titanium-rich material for boiling chlorination from high-calcium magnesium and low-grade titanium slag |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5885324A (en) * | 1996-07-26 | 1999-03-23 | Tiomin Resources, Inc. | Method for the production of synthetic rutile |
| US6306195B1 (en) * | 2000-03-24 | 2001-10-23 | Council Of Scientific And Industiral Research | Process for the preparation of high grade synthetic rutile and pig iron |
| CN101851004A (en) * | 2010-06-25 | 2010-10-06 | 长沙矿冶研究院 | Method for producing artificial rutile by using residual slope accumulated ilmenite |
| CN101935065A (en) * | 2010-09-09 | 2011-01-05 | 中南大学 | Method for preparing artificial rutile from rock ore type titanium concentrate with high calcium and manganese content serving as raw material |
| CN102745743A (en) * | 2012-08-08 | 2012-10-24 | 长沙矿冶研究院有限责任公司 | Method for preparing artificial rutile by titanium slags |
| CN102786082A (en) * | 2012-04-09 | 2012-11-21 | 中国科学院过程工程研究所 | Method for preparing artificial rutile |
| WO2013100963A1 (en) * | 2011-12-28 | 2013-07-04 | Zhigang Zak Fang | Production of titanium dioxide pigments |
-
2013
- 2013-11-01 CN CN201310534032.5A patent/CN104045111B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5885324A (en) * | 1996-07-26 | 1999-03-23 | Tiomin Resources, Inc. | Method for the production of synthetic rutile |
| US6306195B1 (en) * | 2000-03-24 | 2001-10-23 | Council Of Scientific And Industiral Research | Process for the preparation of high grade synthetic rutile and pig iron |
| CN101851004A (en) * | 2010-06-25 | 2010-10-06 | 长沙矿冶研究院 | Method for producing artificial rutile by using residual slope accumulated ilmenite |
| CN101935065A (en) * | 2010-09-09 | 2011-01-05 | 中南大学 | Method for preparing artificial rutile from rock ore type titanium concentrate with high calcium and manganese content serving as raw material |
| WO2013100963A1 (en) * | 2011-12-28 | 2013-07-04 | Zhigang Zak Fang | Production of titanium dioxide pigments |
| CN102786082A (en) * | 2012-04-09 | 2012-11-21 | 中国科学院过程工程研究所 | Method for preparing artificial rutile |
| CN102745743A (en) * | 2012-08-08 | 2012-10-24 | 长沙矿冶研究院有限责任公司 | Method for preparing artificial rutile by titanium slags |
Non-Patent Citations (3)
| Title |
|---|
| 孙朝晖: "攀枝花钛铁矿精矿制备高品质富钛料的比较", 《矿产保护与利用》, no. 6, 31 December 2007 (2007-12-31) * |
| 欧阳红勇等: "微波场中钛铁矿的升温曲线及流态化浸出行为研究", 《矿冶工程》, vol. 30, no. 1, 28 February 2010 (2010-02-28) * |
| 欧阳红勇等: "电炉钛渣制备高品位人造金红石的试验研究", 《矿冶工程》, vol. 31, no. 6, 31 December 2011 (2011-12-31) * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10287176B2 (en) | 2014-07-08 | 2019-05-14 | Avertana Limited | Extraction of products from titanium-bearing minerals |
| US10294117B2 (en) | 2014-07-08 | 2019-05-21 | Avertana Limited | Extraction of products from titanium-bearing minerals |
| US10407316B2 (en) | 2014-07-08 | 2019-09-10 | Avertana Limited | Extraction of products from titanium-bearing minerals |
| CN107955885A (en) * | 2017-11-21 | 2018-04-24 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of preparation method of modified ilmenite concentrate |
| CN110606471A (en) * | 2019-09-18 | 2019-12-24 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for comprehensively utilizing low-temperature chlorination tail gas |
| CN110629045A (en) * | 2019-10-31 | 2019-12-31 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing titanium-rich material for boiling chlorination from high-calcium magnesium and low-grade titanium slag |
| CN110629045B (en) * | 2019-10-31 | 2021-11-09 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing titanium-rich material for boiling chlorination from high-calcium magnesium and low-grade titanium slag |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104045111B (en) | 2016-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103130279B (en) | A kind of method of chlorination production high purity vanadic anhydride | |
| CN102745743B (en) | Method for preparing artificial rutile by titanium slags | |
| CN101967563B (en) | Method for wet-process vanadium extraction by using vanadium- and titanium-containing converter slag | |
| CN101215005A (en) | Method for producing vanadium pentoxide by utilizing vanadium slag | |
| CN103265069B (en) | A kind of method preparing rutile titanium dioxide | |
| CN104045111B (en) | A kind of method preparing artificial rutile | |
| CN106241868B (en) | A kind of titanium dioxide and preparation method thereof | |
| CN103966424A (en) | Method for extracting vanadium from vanadium slag through blank roasting | |
| US3071439A (en) | Method for the preparation of titanium hydrate | |
| CN101367546B (en) | Method for preparing titanium liquid and method for preparing titanium dioxide | |
| CN109467123A (en) | A kind of artificial rutile mether liquor comprehensive resource utilizes method | |
| CN108299863A (en) | A kind of clean preparation method of titanium white | |
| CN101555036A (en) | Method for extracting TiO 2 and SiO 2 in blast furnace slag | |
| CN104098136A (en) | Titanium dioxide production method | |
| CN101851004B (en) | Method for producing artificial rutile by using residual slope accumulated ilmenite | |
| CN1244498C (en) | Manufacture of high grade artificial rutile from low grade primary greporite | |
| CN107267766A (en) | A kind of method of Selective Separation vanadium, titanium, iron from modified vanadium slag | |
| CN107043128A (en) | A kind of method that iron salt solutions lixiviation process prepares synthetic rutile | |
| CN104071835A (en) | Preparation method of titanium dioxide | |
| CN102161505A (en) | Recycling preparation process of potassium fluotitanate | |
| CN103922423A (en) | Method of improving vanadium slag grade by utilizing titanium white waste acid | |
| CN110484712A (en) | A kind of prereduction-electric furnace depth reduction-fluoride process comprehensive utilization of V-Ti magnetite technique | |
| CN104609472B (en) | A kind of titanium tetrachloride refines the method except vanadium mud produces vanadic anhydride | |
| CN112390295A (en) | Method for utilizing artificial rutile mother liquor | |
| CN105271390A (en) | Fine-fraction artificial rutile granulation binding agent and use method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230404 Address after: 617067 Guaziping, East District, Panzhihua City, Sichuan Province Patentee after: PANGANG GROUP MINING Co.,Ltd. Address before: 617000 Taoyuan street, East District, Panzhihua, Sichuan Province, No. 90 Patentee before: PANGANG GROUP PANZHIHUA IRON & STEEL RESEARCH INSTITUTE Co.,Ltd. |
|
| TR01 | Transfer of patent right |