CN104045111B - A kind of method preparing artificial rutile - Google Patents
A kind of method preparing artificial rutile Download PDFInfo
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- CN104045111B CN104045111B CN201310534032.5A CN201310534032A CN104045111B CN 104045111 B CN104045111 B CN 104045111B CN 201310534032 A CN201310534032 A CN 201310534032A CN 104045111 B CN104045111 B CN 104045111B
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Abstract
Prepare a method for artificial rutile, the method comprises the following steps: the acid after being heated by oxidation and the modified titaniferous material of reduction treatment is leached in fluidised mode by (1); (2) by leaching the slurries filtration of rear gained in step (1), solid formation and mother liquor is obtained; (3) gained solid formation in step (2) is calcined after washing, obtain artificial rutile; Wherein, titaniferous material is ilmenite concentrate and/or titanium slag.The method adopts fluidization technology to prepare artificial rutile, have produce continuously, level of automation is high, constant product quality and the low advantage of production cost.
Description
Technical field
The present invention relates to chemical metallurgy technical field, be specifically related to a kind of method 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 to the white pigment that best performance is different in the world at present.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 current production titanium dioxide is mainly sulfuric acid process and chlorination process two kinds.
The method of sulfuric acid process preparing titanium dioxide is low to ingredient requirement, therefore, containing high calcium and high magnesium Flos Bombacis Malabarici ilmenite concentrate and with its for raw material smelt the acid-dissolved titanium slag obtained be sulfate process titanium dioxide be Suitable base.
Chlorination process generates titanium tetrachloride with the rich titanium material such as ilmenite concentrate, titanium slag, artificial rutile or natural rutile and chlorine reaction, obtains raw material refined titanic chloride through rectification and purification.Then by gaseous oxidation, after speed is cold, obtain titanium dioxide through gas solid separation, or adopt metallic reducing to prepare Sponge Titanium, prepare titanium alloy today.Method due to preparing titanium white through chlorination process powder possesses 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 the requirement of chlorination process to raw material is high, often titanium slag or artificial rutile need be adopted.
The Panxi Diqu of China has abundant titanium resource, but its calcium-magnesium content is higher, is difficult to be used as the raw material that chlorination process produces the high-end titanium such as titanium white, titanium sponge.Need to carry out modification to this type of raw material for obtaining the raw material that can be used for chlorination process, to remove calcium contained in raw material, magnesium generates the impurity of low melting point with chlorine reaction in chlorination process.
At present, carry out modification to titanium ore both at home and abroad to exist with the method preparing artificial rutile and produce the defects such as discontinuous, level of automation is not high, unstable product quality and production cost are high.
Summary of the invention
The object of this invention is to provide a kind of method preparing artificial rutile, the method adopts fluidization technology to prepare artificial rutile, have produce continuously, level of automation is high, constant product quality and the low advantage of production cost.
To achieve these goals, the invention provides a kind of method preparing artificial rutile, the method comprises the following steps:
(1) acid after being heated by oxidation and the modified titaniferous material of reduction treatment is leached in fluidised mode;
(2) by leaching the slurries filtration of rear gained in step (1), solid formation and mother liquor is obtained;
(3) gained solid formation in step (2) is calcined after washing, obtain artificial rutile;
Wherein, titaniferous material is ilmenite concentrate and/or titanium slag.
The method preparing artificial rutile provided by the invention have produce continuously, level of automation is high, constant product quality and the low advantage of production cost.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The Leaching reaction time of the present invention refers to timing from the reaction zone that material enters Leaching reaction tower, terminates timing to when being started to filter by described reaction mass.
The invention provides a kind of method preparing artificial rutile, the method comprises the following steps:
(1) acid after being heated by oxidation and the modified titaniferous material of reduction treatment is leached in fluidised mode;
(2) by leaching the slurries filtration of rear gained in step (1), solid formation and mother liquor is obtained;
(3) gained solid formation in step (2) is calcined after washing, obtain 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 described modified titaniferous material refers to the material by obtaining after oxidation and reduction treatment by ilmenite concentrate and/or titanium slag.
Under preferable case, in the step (1) of the method for the invention, modified titaniferous material can be obtained by following steps: (a) by titaniferous material through 850 DEG C of-1200 DEG C of high temperature oxidation process; B titaniferous material after oxide treatment, in reducing atmosphere, is carried out modified with reduction process by () under 650 DEG C of-900 DEG C of conditions.To process operation of the present invention, there is no particular limitation, can be the conventional working method process used in this area.
In the present invention, adopt oxide treatment that the titanium in ilmenite concentrate or titanium slag can be made to form the titanium oxide being insoluble to acid to ilmenite concentrate or titanium slag, adopt reduction treatment to increase the leaching effect of impurity wherein to it, obtain modified ilmenite concentrate or titanium slag.
Wherein, high temperature oxidation process described in above-mentioned steps (a) can adopt coal gas, Sweet natural gas or coal to carry out oxide treatment as thermal source, titaniferous material is turned into and is insoluble to sour material, preferably uses coke-oven gas as thermal source.Coal gas or hydrogen can be adopted to the reducing medium that the titaniferous material after oxide treatment reduces in above-mentioned steps (b).Oxidation-reduction modification can adopt fluidization process 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, with the gross weight of ilmenite concentrate for benchmark, the TiO containing 40-50 % by weight in described ilmenite concentrate
2, the T [Fe] of 25-35 % by weight, FeO, 1-10 % by weight of 20-30 % by weight Fe
2o
3, 0.1-5 % by weight Al
2o
3, 1-10 % by weight the SiO of MgO, 1-10 % by weight
2with the CaO of 0.1-5 % by weight.With the gross weight of titanium slag for benchmark, the TiO containing 65-80 % by weight in described titanium slag
2, the T [Fe] of 5-15 % by weight, FeO, 0.001-1 % by weight of 1-10 % by weight Fe
2o
3, 0.1-5 % by weight Al
2o
3, 0.1-10 % by weight the SiO of MgO, 1-10 % by weight
2with the CaO of 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 Fluidizing Leaching bed, is then added in described Fluidizing Leaching bed by modified titaniferous material and carry out Leaching reaction.Impurity in titaniferous material is leached Ore Leaching, the proportion of titaniferous material reduces, just add the bottom of material at fluidized-bed of fluidized-bed, with the prolongation of extraction time, foreign matter content reduce material progressively on move, by controlling the fluidizing velocity of fluidized-bed, the material completing Leaching reaction discharges reactor with leach liquor in the lump overflow.
In the present invention, to the feed postition of described modified titaniferous material, there is no particular limitation, the mode that preferred 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, described mineral acid be selected from hydrochloric acid, sulfuric acid, titanium dioxide hydrolysis spent acid and nitric acid one or more, be preferably hydrochloric acid.
Especially, the industrial waste acid containing sulfuric acid, hydrochloric acid or nitric acid produced in industrial production can be applied in the inventive method equally, the titanium white waste acid particularly containing sulfuric acid.
The titaniferous material through modification used during Leaching reaction, because feedstock property changes, titanium in raw material can form the material do not reacted with acid, Fluidizing Leaching reaction is adopted to carry out acidleach to modified titaniferous material by using mineral acid, the impurity such as the calcium magnesium in material are leached, can realize continuous leaching operation, cost is low, and the artificial rutile quality index prepared is stablized.
Under preferable case, in the step (1) of the method for the invention, the temperature of the acid after heating is 70-90 DEG C.In the present invention, preferably by the steam flow controlled in leaching system acid to be heated to the temperature of needs.
Under preferable case, in the step (1) of the method for the invention, titaniferous material after modification adds in described Fluidizing Leaching bed and after forming stable fluidized, controlling Leaching reaction temperature is 95-120 DEG C, and the Leaching reaction time is 6-10 hour.In the present invention, preferably by the steam flow controlled 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 DEG C, and the time of calcining is 30-100 minute.
Method of the present invention can also comprise directly to be allocated acid into and enters Fluidizing Leaching bed internal recycle and use by a mother liquor part for gained in step (2).Under preferable case, the mother liquor filtering gained is formed regenerating acid after manipulation of regeneration, and regenerating acid is cycled to used in leaching process.
Under preferable case, the fluidizing reactor used in method of the present invention, the equipment of storage acid and the pipeline of use all adopt anticorrosion material to make.Especially, the leaching tower that the materials such as the fluidizing reactor used in the method for the invention and the equipment storing acid are glass-lined steel steel, the acidproof film of steel lining and acid-resistant porcelain make; The acid-proof corrosion pipeline that the materials such as the pipeline used is glass reinforced plastic, steel lining tetrafluoroethylene glass-lined steel make.
A preferred embodiment of the invention, by titaniferous material through 850 DEG C of-1200 DEG C of high temperature oxidation process; In reducing atmosphere, titaniferous material after oxide treatment is carried out modified with reduction process under 650 DEG C of-900 DEG C of conditions, obtain ilmenite concentrate or the titanium slag material of modification, use acid proof pump the acid that concentration is the leaching of 8-50 % by weight to be pumped into and leach in tower, form Fluidizing Leaching bed; Leaching acid uses graphite heat exchanger to heat, and controls steam flow and leaching acid is heated to 70-90 DEG C; Through the ilmenite concentrate of modification or titanium slag material directly and add in Fluidizing Leaching tower continuously, control the sour flow pumped into, make titaniferous material be in fluidized state in leaching tower; Controlling Leaching reaction temperature is 95-120 DEG C, and the Leaching reaction time is 6-10 hour.Pass through the change of material due to proportion of leaching, drain into leach liquor and leach in slurry tank; After slurry is carried out solid-liquid separation, solid formation is calcined and is obtained artificial rutile product in 30-100 minute under 400-600 DEG C of condition, and the spent acid of generation enters leaching system and is recycled after regenerating unit manipulation of regeneration.
Below will be described the present invention by embodiment.The raw material used in following examples is in case of no particular description all from being purchased.
Embodiment 1
After being oxidized under 960 DEG C of conditions, put into leaching feed bin at the ilmenite concentrate of 820 DEG C of reduction treatments for subsequent use.In complex acid groove, use concentrated hydrochloric acid and water, be mixed with acid concentration be 22 % by weight hydrochloric acid soln for subsequent use, the acid prepared is pumped in Fluidizing Leaching circulation groove, use acid proof pump to pump in Fluidizing Leaching reaction tower by leaching acid, at the leaching operation initial stage, leaching acid enters in Fluidizing Leaching reaction tower process and uses graphite heat exchanger to heat, control steam flow and leaching acid is heated to 80 DEG C, 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 ilmenite concentrate directly adds Fluidizing Leaching reaction tower reaction zone, and leaching sour flow by regulating pump discharge Valve controlling is 8m
3/ h, makes titaniferous material be in fluidized state in leaching tower; After whole fluidized-bed is stable, controlling steam flow to make in Leaching reaction district temperature-stable at 105 ± 5 DEG C, along with Leaching reaction carries out, the material reacted overflows Leaching reaction tower with leaching acid, the solution leached is through filtration treatment, and after filtering, through washing, at 500 DEG C, calcining obtains the artificial rutile product containing titanium dioxide for 80 minutes to solid formation; Filter the spent acid part produced and enter leaching system recycle after regenerating unit manipulation of regeneration.Solution return after another part filters, in circulation groove, recycles as leaching acid with the leaching acid newly added.
According to aforesaid method continuous seepage 72 hours, the content detecting titanium dioxide in the artificial rutile product obtained was 90.11 ~ 90.63 % by weight.
Comparative example 1
After being oxidized under 960 DEG C of conditions, put into leaching feed bin at the ilmenite concentrate of 820 DEG C of reduction treatments for subsequent use.
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 carry out being heated to 80 DEG C with graphite heat exchanger, for subsequent use.
Open Modified Titanium concentrate feed bin baiting valve, in Leaching reaction tower reaction zone, add ilmenite concentrate and the 24m of 7.0 tons of modifications
3leaching acid above-mentioned for subsequent use, be uniformly mixed post-heating, to make in Leaching reaction district temperature-stable at 105 ± 5 DEG C, constantly stir in leaching process, after Leaching reaction carries out 8 hours, by reaction mass cooling-sedimentation, then carry out filtration treatment to solid formation, after filtering, through washing, at 500 DEG C, calcining obtains the artificial rutile product containing titanium dioxide 84.01 % by weight for 80 minutes to solid formation.
Prepare five batches of artificial rutile products again according to above-mentioned identical method, detect the content of titanium dioxide wherein respectively, result is as shown in table 1 below.
Table 1
| Batch | % by weight of titanium dioxide |
| First | 86.72 |
| Second batch | 85.21 |
| 3rd batch | 85.69 |
| 4th batch | 87.86 |
| 5th batch | 85.78 |
Result as can be seen from embodiment 1 and comparative example 1, in the rutile product utilizing method continuous seepage provided by the invention to obtain for 72 hours, the stable content of titanium dioxide is 90.11 ~ 90.63 % by weight, and as shown in table 1 according to the content of titanium dioxide in the rutile product of the different batches of the method production described in comparative example 1, difference is larger.Therefore, the quality product that the rutile quality product utilizing method provided by the invention to produce to obtain obviously obtains compared with method described in comparative example 1 is high and stable.
Embodiment 2
After being oxidized under 1010 DEG C of conditions, put into leaching feed bin at the ilmenite concentrate of 860 DEG C of reduction treatments for subsequent use.In complex acid groove, use the vitriol oil and water, be mixed with acid concentration be 21 % by weight sulphuric acid soln for subsequent use, the acid prepared is pumped in Fluidizing Leaching circulation groove, use acid proof pump to pump in Fluidizing Leaching reaction tower by leaching acid, at the leaching operation initial stage, leaching acid enters in Fluidizing Leaching reaction tower process and uses graphite heat exchanger to heat, control steam flow and leaching acid is heated to 70 DEG C, 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, and leaching sour flow by regulating pump discharge Valve controlling is 7.5m
3/ h, makes titaniferous material be in fluidized state in leaching tower; After whole fluidized-bed is stable, controlling steam flow to make in Leaching reaction district temperature-stable at 115 ± 5 DEG C, along with the carrying out of Leaching reaction, the material reacted overflows Leaching reaction tower with leaching acid, the solution leached is through filtration treatment, and after filtering, through washing, at 550 DEG C, calcining obtains the artificial rutile product containing titanium dioxide for 100 minutes to solid formation; Filter the spent acid part produced and enter leaching system recycle after regenerating unit manipulation of regeneration.Solution return after another part filters, in circulation groove, recycles as leaching acid with the leaching acid newly added.
According to aforesaid method continuous seepage 72 hours, the content detecting titanium dioxide in the artificial rutile product obtained was 90.89 ~ 91.44 % by weight, constant product quality.
Embodiment 3
After being oxidized under 970 DEG C of conditions, put into leaching feed bin at the ilmenite concentrate of 830 DEG C of reduction treatments for subsequent use.In complex acid groove, use the vitriol oil and water, be mixed with acid concentration be 43 % by weight sulphuric acid soln for subsequent use, the acid prepared is pumped in Fluidizing Leaching circulation groove, use acid proof pump to pump in Fluidizing Leaching reaction tower by leaching acid, at the leaching operation initial stage, leaching acid enters in Fluidizing Leaching reaction tower process and uses graphite heat exchanger to heat, control steam flow and leaching acid is heated to 90 DEG C, 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, and leaching sour flow by regulating pump discharge Valve controlling is 8m
3/ h, makes titaniferous material be in fluidized state in leaching tower; After whole fluidized-bed is stable, controlling steam flow to make in Leaching reaction district temperature-stable at 100 ± 5 DEG C, along with the carrying out of Leaching reaction, the material reacted overflows Leaching reaction tower with leaching acid, the solution leached is through filtration treatment, and after filtering, through washing, at 400 DEG C, calcining obtains the artificial rutile product containing titanium dioxide for 80 minutes to solid formation; Filter the spent acid part produced and enter leaching system recycle after regenerating unit manipulation of regeneration.Solution return after another part filters, in circulation groove, recycles as leaching acid with the leaching acid newly added.
According to aforesaid method continuous seepage 72 hours, the content detecting titanium dioxide in the artificial rutile product obtained was 90.21 ~ 90.51 % by weight, constant product quality.
Embodiment 4
After being oxidized under 950 DEG C of conditions, put into leaching feed bin at the Flos Bombacis Malabarici ilmenite concentrate titanium slag of 850 DEG C of reduction treatments for subsequent use.In complex acid groove, use concentrated nitric acid and water, be mixed with acid concentration be 50 % by weight salpeter solution for subsequent use, the acid prepared is pumped in Fluidizing Leaching circulation groove, use acid proof pump to pump in Fluidizing Leaching reaction tower by leaching acid, at the leaching operation initial stage, leaching acid enters in Fluidizing Leaching reaction tower process and uses graphite heat exchanger to heat, control steam flow and leaching acid is heated to 75 DEG C, 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, and leaching sour flow by regulating pump discharge Valve controlling is 7.5m
3/ h, makes titaniferous material be in fluidized state in leaching tower; After whole fluidized-bed is stable, controlling steam flow to make in Leaching reaction district temperature-stable at 100 ± 5 DEG C, along with the carrying out of Leaching reaction, the material reacted overflows Leaching reaction tower with leaching acid, the solution leached is through filtration treatment, and after filtering, through washing, at 450 DEG C, calcining obtains the artificial rutile product containing titanium dioxide for 90 minutes to solid formation; Filter the spent acid part produced and enter leaching system recycle after regenerating unit manipulation of regeneration.Solution return after another part filters, in circulation groove, recycles as leaching acid with the leaching acid newly added.
According to aforesaid method continuous seepage 72 hours, the content detecting titanium dioxide in the artificial rutile product obtained was 90.06 ~ 90.48 % by weight, constant product quality.
Embodiment 5
After being oxidized under 990 DEG C of conditions, put into leaching feed bin at the ilmenite concentrate of 860 DEG C of reduction treatments for subsequent use.In complex acid groove, use concentrated hydrochloric acid and water, be mixed with acid concentration be 8 % by weight hydrochloric acid soln for subsequent use, the acid prepared is pumped in Fluidizing Leaching circulation groove, use acid proof pump to pump in Fluidizing Leaching reaction tower by leaching acid, at the leaching operation initial stage, leaching acid enters in Fluidizing Leaching reaction tower process and uses graphite heat exchanger to heat, control steam flow and leaching acid is heated to 85 DEG C, 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, and leaching sour flow by regulating pump discharge Valve controlling is 8.5m
3/ h, makes titaniferous material be in fluidized state in leaching tower; After whole fluidized-bed is stable, controlling steam flow to make in Leaching reaction district temperature-stable at 105 ± 5 DEG C, along with the carrying out of Leaching reaction, the material reacted overflows Leaching reaction tower with leaching acid, the solution leached is through filtration treatment, and after filtering, through washing, at 500 DEG C, calcining obtains the artificial rutile product containing titanium dioxide for 50 minutes to solid formation; Filter the spent acid part produced and enter leaching system recycle after regenerating unit manipulation of regeneration.Solution return after another part filters, in circulation groove, recycles as leaching acid with the leaching acid newly added.
According to aforesaid method continuous seepage 72 hours, the content detecting titanium dioxide in the artificial rutile product obtained was 90.37 ~ 90.59 % by weight, constant product quality.
Embodiment 6
After being oxidized under 960 DEG C of conditions, put into leaching feed bin at the ilmenite concentrate of 820 DEG C of reduction treatments for subsequent use.In complex acid groove, use concentrated nitric acid and water, be mixed with acid concentration be 42 % by weight salpeter solution for subsequent use, the acid prepared is pumped in Fluidizing Leaching circulation groove, use acid proof pump to pump in Fluidizing Leaching reaction tower by leaching acid, at the leaching operation initial stage, leaching acid enters in Fluidizing Leaching reaction tower process and uses graphite heat exchanger to heat, control steam flow and leaching acid is heated to 85 DEG C, 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, and leaching sour flow by regulating pump discharge Valve controlling is 6.5m
3/ h, makes titaniferous material be in fluidized state in leaching tower; After whole fluidized-bed is stable, controlling steam flow to make in Leaching reaction district temperature-stable at 110 ± 5 DEG C, along with the carrying out of Leaching reaction, the material reacted overflows Leaching reaction tower with leaching acid, the solution leached is through filtration treatment, and after filtering, through washing, at 600 DEG C, calcining obtains the artificial rutile product containing titanium dioxide for 30 minutes to solid formation; Filter the spent acid part produced and enter leaching system recycle after regenerating unit manipulation of regeneration.Solution return after another part filters, in circulation groove, recycles as leaching acid with the leaching acid newly added.
According to aforesaid method continuous seepage 72 hours, the content detecting titanium dioxide in the artificial rutile product obtained was 91.09 ~ 91.35 % by weight, constant product quality.
Embodiment 7
After being oxidized under 960 DEG C of conditions, put into leaching feed bin at the ilmenite concentrate of 820 DEG C of reduction treatments for subsequent use.In complex acid groove, use titanium dioxide hydrolysis spent acid and water, be mixed with acid concentration be 23 % by weight titanium dioxide hydrolysis waste acid liquor for subsequent use, the acid prepared is pumped in Fluidizing Leaching circulation groove, use acid proof pump to pump in Fluidizing Leaching reaction tower by leaching acid, at the leaching operation initial stage, leaching acid enters in Fluidizing Leaching reaction tower process and uses graphite heat exchanger to heat, control steam flow and leaching acid is heated to 78 DEG C, 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, and leaching sour flow by regulating pump discharge Valve controlling is 8m
3/ h, makes titaniferous material be in fluidized state in leaching tower; After whole fluidized-bed is stable, controlling steam flow to make in Leaching reaction district temperature-stable at 105 ± 5 DEG C, along with the carrying out of Leaching reaction, the material reacted overflows Leaching reaction tower with leaching acid, the solution leached is through filtration treatment, and after filtering, through washing, at 480 DEG C, calcining obtains the artificial rutile product containing titanium dioxide for 50 minutes to solid formation; Filtering the spent acid part produced is back in circulation groove, recycles as leaching acid with the leaching acid newly added; Solution after another part filters enters leaching system recycle after regenerating unit manipulation of regeneration.
According to aforesaid method continuous seepage 72 hours, the content detecting titanium dioxide in the artificial rutile product obtained was 89.04 ~ 89.37 % by weight, constant product quality.
Embodiment 8
After being oxidized under 960 DEG C of conditions, put into leaching feed bin at the ilmenite concentrate of 820 DEG C of reduction treatments for subsequent use.In complex acid groove, use the vitriol oil and water, be mixed with acid concentration be 10 % by weight sulphuric acid soln for subsequent use, the acid prepared is pumped in Fluidizing Leaching circulation groove, use acid proof pump to pump in Fluidizing Leaching reaction tower by leaching acid, at the leaching operation initial stage, leaching acid enters in Fluidizing Leaching reaction tower process and uses graphite heat exchanger to heat, control steam flow and leaching acid is heated to 90 DEG C, 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, and leaching sour flow by regulating pump discharge Valve controlling is 8m
3/ h, makes titaniferous material be in fluidized state in leaching tower; After whole fluidized-bed is stable, controlling steam flow to make in Leaching reaction district temperature-stable at 105 ± 5 DEG C, along with the carrying out of Leaching reaction, the material reacted overflows Leaching reaction tower with leaching acid, the solution leached is through filtration treatment, and after filtering, through washing, at 560 DEG C, calcining obtains the artificial rutile product containing titanium dioxide for 60 minutes to solid formation; Filter the spent acid part produced and enter leaching system recycle after regenerating unit manipulation of regeneration.Solution return after another part filters, in circulation groove, recycles as leaching acid with the leaching acid newly added.
According to aforesaid method continuous seepage 72 hours, the content detecting titanium dioxide in the artificial rutile product obtained was 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 characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, 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 (6)
1. prepare a method for artificial rutile, it is characterized in that, the method comprises the following steps:
(1) acid after being heated by oxidation and the modified titaniferous material of reduction treatment is leached in fluidised mode, the process of described leaching comprises: the acid after heating is formed Fluidizing Leaching bed, then modified titaniferous material is added in described Fluidizing Leaching bed and carry out Leaching reaction, the temperature of the acid after described heating is 70-90 DEG C, wherein, modified titaniferous material is obtained by following steps: (a) by titaniferous material through 850 DEG C of-1200 DEG C of high temperature oxidation process; B titaniferous material after oxide treatment, in reducing atmosphere, is carried out modified with reduction process by () under 650 DEG C of-900 DEG C of conditions;
(2) by leaching the slurries filtration of rear gained in step (1), solid formation and mother liquor is obtained;
(3) calcined after washing by gained solid formation in step (2), obtain artificial rutile, wherein, the temperature of calcining is 400-600 DEG C, and the time of calcining is 30-100 minute;
Wherein, titaniferous material is ilmenite concentrate, with the gross weight of ilmenite concentrate for benchmark, and the TiO containing 40-50 % by weight in described ilmenite concentrate
2, the T [Fe] of 25-35 % by weight, FeO, 1-10 % by weight of 20-30 % by weight Fe
2o
3, 0.1-5 % by weight Al
2o
3, 1-10 % by weight the SiO of MgO, 1-10 % by weight
2with the CaO of 0.1-5 % by weight.
2. method according to claim 1, wherein, in step (1), the concentration of described acid is 8-50 % by weight.
3. method according to claim 1, wherein, in step (1), described acid is mineral acid, described mineral acid be selected from hydrochloric acid, sulfuric acid, titanium dioxide hydrolysis spent acid and nitric acid one or more.
4. method according to claim 3, wherein, described acid is hydrochloric acid.
5. method according to claim 1, wherein, in step (1), titaniferous material after modification to add in described Fluidizing Leaching bed and after forming stable fluidized, controlling Leaching reaction temperature is 95-120 DEG C, and the Leaching reaction time is 6-10 hour.
6. method according to claim 1, wherein, the method also comprises: the mother liquor filtering gained in step (2) is formed regenerating acid through manipulation of regeneration, and regenerating acid is cycled to used in leaching process.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310534032.5A CN104045111B (en) | 2013-11-01 | 2013-11-01 | A kind of method preparing artificial rutile |
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|---|---|---|---|
| CN201310534032.5A CN104045111B (en) | 2013-11-01 | 2013-11-01 | A kind of method preparing artificial rutile |
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| Publication Number | Publication Date |
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| CN104045111A CN104045111A (en) | 2014-09-17 |
| CN104045111B true CN104045111B (en) | 2016-02-03 |
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| CA2182123C (en) * | 1996-07-26 | 1999-10-05 | Graham F. Balderson | 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 |
| CN101851004B (en) * | 2010-06-25 | 2012-02-29 | 长沙矿冶研究院 | Method for producing artificial rutile by using residual slope accumulated ilmenite |
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| CN102745743B (en) * | 2012-08-08 | 2014-07-23 | 长沙矿冶研究院有限责任公司 | Method for preparing artificial rutile by titanium slags |
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