CN1952188A - Process for separation and production of titanium-rich materials from titanium-containing blast furnace slag - Google Patents
Process for separation and production of titanium-rich materials from titanium-containing blast furnace slag Download PDFInfo
- Publication number
- CN1952188A CN1952188A CNA2006101342603A CN200610134260A CN1952188A CN 1952188 A CN1952188 A CN 1952188A CN A2006101342603 A CNA2006101342603 A CN A2006101342603A CN 200610134260 A CN200610134260 A CN 200610134260A CN 1952188 A CN1952188 A CN 1952188A
- Authority
- CN
- China
- Prior art keywords
- slag
- titanium
- blast furnace
- temperature
- uhligite
- 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
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
A method for separating titanium from the slag containing titanium component, contains the following three steps: heating the slag in the slag tank, adding additives at the same time or after that, blowing oxidizing gases into the tank, stirring the slag constantly, causing titanium components selectively to enrich in perovskite phase, then controlling cooling rate for the slag cooling to room temperature, perovskite phase selectively growing up, finally, crushing the cooling condensate residue grinding and ore dressing perovskite to obtain titanium-rich material, magnetic-separating iron magnetic beads deposited on the metal slag to obtain vanadiferous iron. The process is reasonably designed with practical equipment easy to operate and can make use of the own energy of the slag to regulate the slag temperature, promote oxidation reaction in the slag, has high thermal efficiency, facilitate the promotion of selective enrichment of various titanium scattered in the phase of titanium for the deposition of ironic beads entrained in the slag, and is profit to the realization of comprehensive utilization of titanium, vanadium resources, and is easy for industrial production, is energy-saving and pollution-free.
Description
Technical field
The present invention relates to a kind of treatment process that reclaims titanium component from titanium-containing blast furnace slag, the energy that particularly a kind of energy that makes full use of slag self and slag oxidation discharge is regulated the slag temperature, promote the carrying out of slag oxidizing reaction, to be scattered in the titanium component selective enrichment of various titaniferous in mutually, make the metallic iron drop deposition of carrying secretly in the slag, the comprehensive utilization of realization titanium resource, the method of the rich titanium material of separation of produced from titanium-containing blast furnace slag of energy suitability for industrialized production, this method is particularly useful for the blast furnace slag that titanium oxide content is 15-30%.
Background technology
As everyone knows, vanadium titano-magnetite is that China contains one of abundant many metals mineral intergrowth, iron content 30-45% wherein, TiO
26-15%.This mineral composition complexity, disseminated grain size is thin, directly adopts the method for ore dressing separation of iron and titanium, poor effect.(iron concentrate grade is TFe52.84%, TiO to adopt at present beneficiation method to obtain the iron ore concentrate of grade 55-60%Fe
212.81%), can realize that slag-iron separates though smelt in blast furnace, most of titaniferous oxide compound is then deposited slag mutually with very tiny the tax with the dispersive state mutually, becomes to contain 15-25%TiO
2High-titanium blast furnace slag.At present, domestic scientific worker has carried out number of research projects in order to extract the valuable element titanium from titanium-containing blast furnace slag, and the technical scheme of formation can be divided into following three classes:
The first kind: wet chemistry method with acid, the direct enrichment uhligite of alkali technology, mainly contains sulfuric acid process and produces TiO
2Technology, NaOH produce TiO
2Technology.
In " research that titanium white is produced in the hydrolysis of complicated sulfate liquor system " as " Hunan non-ferrous metal " (1991 the 12nd (3) P30) report, disclose with sulfuric acid process processing steel climbing high slag and produced titanium white, the percent hydrolysis of titanium is 95.18%, makes the titanium dioxide that meets national standard.In " steel climbing high slag extracts the research of titanium dioxide and scandium oxide " of " steel vanadium titanium " (1999 the 20th (4) phase P35) report, disclosing with concentration is that 93% the vitriol oil is at 220 ℃ of left and right sides acidolysis titanium-containing blast furnace slags.In " approach of Panzhihua Iron blast furnace slag comprehensive utilization " of " mineral products comprehensive utilization " (1997 the 6th phase P21) report, disclose, made titanium white with useless vitriol oil solid phase method acidolysis titanium-containing blast furnace slag.In " the slag titanium separation test of high-titanium blast furnace slag " of " steel vanadium titanium " (1999 the 20th (4) phase P35) report, disclose, handled steel climbing high slag with NaOH and carry out the isolating technology of slag titanium 1200 ℃～1300 ℃ temperature ranges.In " Kunming University of Science and Technology " (Ph D dissertation in 2002) record " climbing uhligite beneficiation test research in the skill flower blast furnace slag ", technological minerals characteristic to uhligite in the steel climbing high slag is studied, and having studied the floatation separating technology of blast furnace slag uhligite, the result shows, TiO in the ilmenite concentrate
2Content is 43.01%, and the rate of recovery of titanium is 29.89%, and the productive rate of concentrate is 15.63%.But still contain 18.69% TiO in the mine tailing
2
It is that temperature is low that above-mentioned wet chemistry method is carried the titanium technological advantage, and easy to operate, technology is simple; No matter but be sulfuric acid process, or the salt acid system carries titanium, all has the problem that spent acid is difficult to utilize after the hydrolysis, also can cause secondary pollution; And the wet chemistry method treatment scale is less, can not solve the handling problem of 3,000,000 tons of titanium-containing blast furnace slags of annual output.
Second class: the master alloy technology, mainly adopt silicothermic process reduction+electrosmelting ferro-silico-titanium technology.In " vanadium titanium " 1993 (5) phase P51 " comprehensive utilization of blast furnace titanium slag (I) ", disclose direct employing and contained TiO
224.18% steel climbing high slag is tested, obtains to contain 27.08%Ti, and 31.05%Si, the ferro-silico-titanium of 20.20%Fe, titanium recovery rate are 76.70%.Though this method can be utilized part titanium in the titanium-containing blast furnace slag, current consumption is bigger, and cost is higher, and treatment scale is limited.
The 3rd class: carbonization, chlorination technique, mainly adopt high temperature cabonization-low temperature chlorination to produce TiCl
4Technology, high temperature cabonization-carbide slag sorting titanium carbide technology.This technology contents is reported in " the steel climbing high slag melting and reducing carbonization TiO of " steel vanadium titanium " (1994 the 15th (2) phase P17) respectively
2Pilot-plant test research ", the patent No. is in " experimental study that the employing steel climbing high slag is produced titanium carbide " of " method of preparing titanic chloride using carbon-containing slag ", " mineral products comprehensive utilization " (1997 (6) phase P34) of CN87107488.5.
Wherein in the patent of " method of preparing titanic chloride using carbon-containing slag ", introduced the carbonization blast furnace slag 400 ℃～550 ℃ following chlorinations, continuous charging continuous pulp discharge in fluidized-bed, the chlorination rate of titanium is greater than 85%, TiO in the chloride residue of discharge
2Content is 3.35%, and the chlorination rate of calcium can be less than 7%, and the chlorination rate of magnesium can be less than 5%.In " adopt steel climbing high slag produce titanium carbide experimental study ", disclose in electric furnace the reduction blast furnace slag and produced carbide slag, adopted the method sorting titanium carbide of ore dressing then.At the 24kVA electric arc furnace blast furnace slag has been carried out carbonization test, so that produce the required carbide slag of beneficiation test.Carried out the titanium carbide sorting afterwards.Test has two kinds of sorting flow processs, and the result is respectively: low intensity magnetic separation-high intensity magnetic separation-10% hydrochloric acid leaches flow process, obtains TiO
2Content is 60.79% concentrate, and the productive rate of concentrate is 13.94%, and mine tailing contains TiO
2Be 4.15%, productive rate is 44.91%; Elder generation's leaching-back magnetic dressing process, obtaining comprehensive grade is 64.93%TiO
2Concentrate, productive rate is 31.11%.Such carbonization, chlorination technique, the rate of recovery of titanium is higher, but the processing condition harshness, treatment capacity is limited, and the muriate residue of a large amount of by-products is difficult to digestion, serious environment pollution.
Although above-mentioned all kinds of processing scheme is technical feasible, but because of only limiting to laboratory stage, reasons such as so its separation efficiency is low, treatment capacity is little, contaminate environment, long flow path, the big benefit of investment are low, finally fail on technical scale, to realize from titanium-containing blast furnace slag, recycling the target of titanium, so far there are more than 3,000 ten thousand tons of titanium-containing blast furnace slags still to be deposited in the slag field, and still increase at present with annual 3000000 tons scale.Handle as untimely, then both wasted and contain titanium resource, pollute surrounding environment again.
At the problem that exists in the above-mentioned titanium-containing blast furnace slag recycling process, the inventor was in " method of separating titanium component from titanium-contained slag " of CN 98 1 14444.6 in the patent No. once, disclosed a kind of titanium slag is sent into fusion in the smelting furnace, added CaO, SiO simultaneously
2, Al
2O
3, MgO, FeO
xEtc. metallurgical waste, adjust slag and form, keep oxygen partial pressure 10
-6-1atm, make in the slag to disperse to compose and be stored in the titanium of various titaniums in mutually and optionally be enriched to the uhligite phase, and in process of cooling subsequently, adding additive promotes uhligite to grow up mutually and alligatoring, cooling at last is after broken, ore grinding, gravity treatment dump mine tailing in conjunction with flotation, the separation method that uhligite is separated.Although this method has had characteristics such as treatment capacity is big, flow process short, pollution-free, but still has following shortcoming:
1, adopt common slag ladle, heat insulation effect is poor, and rate of cooling is difficult to control, can not effectively utilize titaniferous blast furnace slag self physics heat fully, exists energy consumption big, the problem that production cost is high.
2, adopt adding FeO
xWait the oxygen position of regulating slag, oxidization time is long, weak effect, needs to replenish a large amount of physics heat, production cost height.The slag temperature is lower than 1400 ℃, and the slag relative viscosity is big, and the enrichment of uhligite and the weak effect of growing up are unfavorable for that slag iron separates, and can't reclaim the metallic iron of carrying secretly of 6-8% in the slag.
Summary of the invention
The purpose of this invention is to provide a kind of from titanium-containing blast furnace slag the method for the rich titanium material of separation of produced, this process design is reasonable, the equipment practicality is easy to operate, the energy that can make full use of slag self is regulated the slag temperature, promote the carrying out of oxidizing reaction in the slag, the slag oxidation discharges a large amount of heats, the thermo-efficiency height, be convenient to promote to be scattered in the titanium component selective enrichment of various titaniferous in mutually, make the metallic iron microballon deposition of carrying secretly in the slag, help realizing titanium, vanadium resource comprehensive utilization, be easy to suitability for industrialized production, energy-conservation and non-environmental-pollution.
The object of the present invention is achieved like this: this method adopts following three steps:
1. titanium component selective enrichment:
Utilize insulation slag ladle splendid attire titanium-containing blast furnace slag, feed incendivity gas heating slag then in slag ladle, control slag temperature adds additive at 1400-1450 ℃ in slag ladle, and additive therefor is for containing CaO or CaF
2In a kind of or both mixture, the consumption of additive is 1%～5% of a slag gross weight, when adding additive or afterwards, the oxidizing gas of jetting in slag makes slag at a middle or low price titanylization the time, the slag oxidation discharges a large amount of heats, the slag temperature raises, and gas constantly stirs slag, the influence of the oxidated property of the ratio of oxidization time and titanium-containing blast furnace slag gas flow, to be controlled at minute: gram=1: 10～50 is advisable, and the dividing potential drop of oxygen is controlled at 1-10 in the oxidizing gas
2In the kPa scope, make be scattered in the slag titanium component of various titaniferous in mutually optionally be enriched in uhligite mutually in, the metallic iron microballon that is mingled with in the slag takes place to assemble and grow up;
2. the uhligite phase selectivity is grown up:
Through step 1 make titanium component in 1450-1400 ℃ of temperature range, optionally be enriched in uhligite mutually after, slag cooling is grown up the uhligite phase selectivity; Control slag speed of cooling is cooled to room temperature in 0.5-5 ℃/min scope; Meanwhile, the metallic iron microballon that is mingled with in the slag takes place to assemble and grow up, and the iron microballon finally is deposited on the slag ladle bottom;
3. the uhligite phase selectivity is separated:
Crust block after step 1 handled with 2, through broken, levigate, adopt beneficiation method with the uhligite phase selectivity in the crust block separate, obtain containing 40-45%TiO
2Rich titanium material, meanwhile, the metallic iron microballon that adopts magnetic selection method will be deposited in the crust block of slag ladle bottom is separated, and contains higher vanadium in the metallic iron, can be used as pig iron containing vanadium and uses.
In the chemical constitution of described slag, titanyl compound content is 15-30%.
The isolating method of described ore dressing is with through enrichment and the crust block of growing up after handling, through broken, levigate be+150 orders～-300 orders to granularity after, usefulness gravity treatment, flotation, or gravity treatment is separated out with the uhligite in the crust block in conjunction with the integrated processes of flotation, obtains TiO
2The rich titanium material that grade is higher.
Described insulation slag ladle is inside and outside tank body bilayer structure, and the slag ladle top is provided with insulation cover, fills heat-insulating material between the inside and outside tank body perisporium.
Because process design of the present invention is reasonable, adopt the multiple technologies measure in the integrated conduct method of one, act synergistically, so be easy to realize the rich titanium material of separation of produced from titanium-containing blast furnace slag.This integrated conduct method at first adopts insulation skill wood, carries out the slag modification in having the bilayer structure slag ladle of heat insulation function, and equipment is practical simple, easy handling; Adopt temperature adjustment skill wood then, in slag, spray into incendivity gas, make full use of the bigger physics latent heat of blast furnace slag self capacity and discharge a large amount of heat energy, the utilization efficiency of heat energy height by combustion reactions, can make the slag temperature be elevated to 1400-1450 ℃, reach the condition that winding-up requires; Adopt additive skill wood and winding-up skill wood again, when promptly in slag, adding additive or afterwards, the oxidizing gas of in slag, jetting, slag middle or low price titanyl is turned to be the high price titanium, adjust the thing phase composite of slag, control the trend and the pattern (shown in Fig. 2-6) that contain titanium component in the slag, thereby, finally obtain TiO for adopting the isolating method of ore dressing to realize that uhligite separates with the gangue phase selectivity
2The higher rich titanium material of grade creates favorable conditions.In addition, in the slag oxidising process, because improve the oxygen position, and Ti in the slag (C, N) oxidation disappears, viscosity is reduced, simultaneously, go back ortho states material generation exothermic oxidation reaction in the slag, this not only makes the slag temperature raise, promote the carrying out of chemical reaction in the slag, and oxidation can make and is scattered in the titanium component selective enrichment of various titaniferous in mutually in the slag to the uhligite phase and grow up.When jetting oxidation, because the slag temperature raises, viscosity reduces and the air-flow stirring action, slag is kept in motion, the probability of iron microballon collision increases, and promotes the metallic iron microballon of carrying secretly in the slag to assemble, grow up, and is deposited on the slag ladle bottom, slag-iron is separated, produce beyond thought heavy iron effect, and obtained pig iron containing vanadium, realized the comprehensive utilization of titanium, vanadium resource.The detection of titanium-containing blast furnace slag after the inventive method comprehensive treating process learns that the chemical constitution of concentrate and tailings is as shown in table 1:
Table 1
| Product | TiO 2 | CaO | MgO | FeOx | Al 2O 3+SiO 2 |
| Concentrate | 35-45 | 30-35 | 8-9 | 3-5 | 18-6 |
| Mine tailing | 8-11 | 15-25 | 8-10 | 7-10 | 60-40 |
Description of drawings
Below in conjunction with accompanying drawing the present invention is further described.
Fig. 1 is a kind of process flow sheet of the present invention.
Fig. 2 is the digital photograph that is deposited on the metallic iron microballon in the crust block of slag ladle bottom.
Fig. 3 (a) is the microstructure figure of former slag;
(b) be the microstructure figure of oxidization time oxidation sludge when being 2min;
(c) be the microstructure figure of oxidization time oxidation sludge when being 12min.
Fig. 4 (a) is the microstructure figure of former slag,
(b) the microstructure figure of oxidation sludge (1200kg).
Fig. 5 is the uhligite graph of a relation of the amount of separating out and grain size and oxidization time mutually.
Fig. 6 is different oxidization time slag temperature variations.
Fig. 7 is a kind of insulation slag ladle structural representation of the present invention.
Sequence number explanation among the figure: 1 outer tank body, 2 heat-insulating materials, 3 interior tank bodies, 4 loam cakes, 5 jars of mouths, 6 heat-insulating materials, 7 incendivity gas entrances.
Embodiment
Describe concrete structure of the present invention and working process in detail according to Fig. 1-7 and embodiment.This method adopts following three steps:
1. titanium component selective enrichment:
Utilize insulation slag ladle splendid attire titanium-containing blast furnace slag, feed incendivity gas heating slag then in slag ladle, control slag temperature adds additive at 1400-1450 ℃ in slag ladle, and additive therefor is for containing CaO or CaF
2In a kind of or both mixture, the consumption of additive is 1%～5% of a slag gross weight, when adding additive or afterwards, the oxidizing gas of jetting in slag makes slag at a middle or low price titanylization the time, the slag oxidation discharges a large amount of heats, the slag temperature raises, and gas constantly stirs slag, the influence of the oxidated property of the ratio of oxidization time and titanium-containing blast furnace slag gas flow, to be controlled at minute: gram=1: 10～50 is advisable, and the dividing potential drop of oxygen is controlled at 1-10 in the oxidizing gas
2In the kPa scope, make be scattered in the slag titanium component of various titaniferous in mutually optionally be enriched in uhligite mutually in, the metallic iron microballon that is mingled with in the slag takes place to assemble and grow up;
2. the uhligite phase selectivity is grown up:
Through step 1 make titanium component in 1450-1400 ℃ of temperature range, optionally be enriched in uhligite mutually after, slag cooling is grown up the uhligite phase selectivity; Control slag speed of cooling is cooled to room temperature in 0.5-5 ℃/min scope; Meanwhile, the metallic iron microballon that is mingled with in the slag takes place to assemble and grow up, and the iron microballon finally is deposited on the slag ladle bottom;
3. the uhligite phase selectivity is separated:
Crust block after step 1 handled with 2, through broken, levigate, adopt beneficiation method with the uhligite phase selectivity in the crust block separate, obtain containing 40-45%TiO
2Rich titanium material.Available it as furnace retaining material, system titanium dioxide raw material, welding electrode welding agent; Remaining poor titanium tailings can be used as cement Additive, materials for wall, pavior brick etc.Meanwhile, the metallic iron microballon that adopts magnetic selection method will be deposited in the crust block of slag ladle bottom is separated, and contains higher vanadium in the metallic iron, can be used as pig iron containing vanadium and uses.
Used titanium-containing blast furnace slag means the titanium-containing slag of directly emitting from blast furnace in the above-mentioned steps 1, and its slag temperature is generally more than 1300 ℃, and in its chemical constitution, 15-30% is advisable with titanyl compound content, also can use the titanium-containing blast furnace slag that is deposited in the slag field.
The isolating method of used ore dressing is with the crust block after the enrichment and the processing of growing up in the above-mentioned steps 3, through broken, levigate be+150 orders～-300 orders to granularity after, with gravity treatment, flotation, or gravity treatment is separated out with the uhligite in the crust block in conjunction with the integrated processes of flotation, obtains TiO
2The rich titanium material that grade is higher.
Insulation slag ladle in the above-mentioned steps 1 can adopt the bilayer structure that is made of inside and outside tank body 3,1 as shown in Figure 7, and tank body 3 can be selected existing common slag ladle for use or select fire-resistant tank body for use in it, and tank body 1 combines outside one of its outer setting again.The slag ladle top is provided with the insulation cover 4 of a jar mouth 5, incendivity gas entrance 7, fills heat- insulating materials 2,6 between the perisporium of inside and outside tank body 3,1 and in the loam cake 4.
Embodiment 1 (according to the corresponding contents in the following embodiment of modification adjustment of claim)
Take by weighing the 200g titanium-containing blast furnace slag, its composition is 24.79%TiO
2, 20.14%CaO, 8.89%MgO, 13.86%Al
2O
3, 3.10%FeO, 5.89%MFe and 18.60%SiO
2The titanium slag that takes by weighing is contained in the slag ladle, and heat fused sprays into incendivity gas in slag, regulates the slag temperature about 1400 ℃; After homo(io)thermism, in the slag of slag ladle, add addition of C aO 4g, when adding additive (or afterwards), the air of jetting in slag, oxidization time are 5min, the branch of oxygen is pressed in 1-10
2In the kPa scope, make titanium component optionally be enriched in uhligite mutually in.Afterwards, about 30 ℃ because of oxidation raises of the temperature of slag reach 1430 ℃; 1430～1100 ℃ of temperature range inner control speed of cooling is 2 ℃/min, and furnace cooling is to room temperature, and uhligite carries out selectivity mutually and grows up.Cooled oxidation crust block is through broken, levigate, granularity+100 orders～-200 orders, and through gravity treatment, flotation dumps mine tailing, obtains containing the rich ilmenite concentrate of 38.3%TiO2.In addition, also have 8g metallic iron microballon to be deposited on the slag ladle bottom, separate obtaining pig iron containing vanadium by magnetic separation.
Take by weighing the 200g titanium-containing blast furnace slag, its composition is 24.79%TiO
2, 20.14%CaO, 8.89%MgO, 13.86%Al
2O
3, 3.10%FeO, 5.89%MFe and 18.60%SiO
2The titanium slag that takes by weighing is contained in the slag ladle, and resistive heating makes the slag fusing, sprays into incendivity gas in slag, when regulating the slag temperature to 1400C, steady temperature, bubbling air under molten state, add addition of C aO 8g simultaneously, oxidization time 5min, the branch of oxygen is pressed in 1-10
2In the kPa scope; The slag temperature is elevated to 1420 ℃ after the oxidation, lowers the temperature 2 ℃/min of speed of cooling in 1420～1100 ℃ of temperature ranges; Cooled oxidation crust block is through broken, levigate, granularity+100 orders～-200 orders, and through gravity treatment, flotation dumps mine tailing, obtains containing 40.3%TiO
2Rich ilmenite concentrate; In addition, also have 7.8g metallic iron microballon to be deposited on the slag ladle bottom, separate obtaining pig iron containing vanadium by magnetic separation.
Embodiment 3
Take by weighing the 200g titanium-containing blast furnace slag, its composition is 24.79%TiO
2, 20.14%CaO, 8.89%MgO, 3.86%Al
2O
3, 3.10%FeO, 5.89%MFe and 18.60%SiO
2The titanium slag that takes by weighing is contained in the slag ladle, and just slag fusing of resistive heating sprays into incendivity gas in slag, when regulating 1400 ℃ of slag temperature, steady temperature, aerating oxygen under molten state, add addition of C aO 8g simultaneously, oxidization time 5min, the branch of oxygen is pressed in 1-10
2In the kPa scope, the slag temperature is elevated to 1450 ℃ after the oxidation.Lower the temperature in 1450～1100 ℃ of temperature ranges, speed of cooling is 2.0 ℃/min.Cooled oxidation crust block is through broken, levigate, granularity+100 orders～-200 orders, and through gravity treatment, flotation dumps mine tailing, obtains containing 41.8%TiO
2Rich ilmenite concentrate.In addition, also have 8.5g metallic iron microballon to be deposited on the slag ladle bottom, separate obtaining pig iron containing vanadium by magnetic separation.
Embodiment 4
Take by weighing the 200g titanium-containing blast furnace slag, its composition is 24.79%TiO
2, 20.14%CaO, 8.89%MgO, 13.86%Al
2O
3, 3.10%FeO, 5.89%MFe and 18.60%SiO
2The titanium slag that takes by weighing is contained in the slag ladle, and resistive heating makes the slag fusing, sprays into incendivity gas in slag, when regulating the slag temperature to 1400C, and steady temperature, aerating oxygen under molten state, oxidization time 5min, the branch of oxygen is pressed in 1-10
2In the kPa scope, the slag temperature is elevated to 1470 ℃ after the oxidation, lowers the temperature 2 ℃/min of speed of cooling in 1470～1100 ℃ of temperature ranges.Cooled oxidation crust block is through broken, levigate, granularity+100 orders～-200 orders, and through gravity treatment, flotation dumps mine tailing, obtains containing 38.9%TiO
2Rich ilmenite concentrate.In addition, also have 9g metallic iron microballon to be deposited on the slag ladle bottom, separate obtaining pig iron containing vanadium by magnetic separation.
Take by weighing the 200g titanium-containing blast furnace slag, its composition is 24.79%TiO
2, 20.14%CaO, 8.89%MgO, 13.86%Al
2O
3, 3.10%FeO, MFe5.89%MFe and 18.60%SiO
2The titanium slag that takes by weighing is contained in the slag ladle, and resistive heating makes the slag fusing, sprays into incendivity gas in slag, when regulating the slag temperature to 1400C, and steady temperature, aerating oxygen under molten state, oxidization time 2min, the branch of oxygen is pressed in 1-10
2In the kPa scope, the slag temperature is elevated to 1440 ℃ after the oxidation, lowers the temperature 2 ℃/min of speed of cooling in 1440～1100 ℃ of temperature ranges.Cooled oxidation crust block is through broken, levigate, granularity+100 orders～-200 orders, and through gravity treatment, flotation dumps mine tailing, obtains containing 36.3%TiO
2Rich ilmenite concentrate.In addition, also have 7g metallic iron microballon to be deposited on the slag ladle bottom, separate obtaining pig iron containing vanadium by magnetic separation.
Take by weighing the 200g titanium-containing blast furnace slag, its composition is 24.79%TiO
2, 20.14%CaO, 8.89%MgO, 13.86%Al
2O
3, 3.10%FeO, 5.89%MFe and 18.60%SiO
2The titanium slag that takes by weighing is contained in the slag ladle, and resistive heating makes the slag fusing, sprays into incendivity gas in slag, and when regulating the slag temperature to 1400C, steady temperature feeds oxygen-rich air under molten state, oxidization time 2min, and the branch of oxygen is pressed in 1-10
2In the kPa scope, the slag temperature is elevated to 1425 ℃ after the oxidation, lowers the temperature 2 ℃/min of speed of cooling in 1425～1100 ℃ of temperature ranges.Cooled oxidation crust block is through broken, levigate, granularity+100 orders～-200 orders, and through gravity treatment, flotation dumps mine tailing, obtains containing 36.7%TiO
2Rich ilmenite concentrate.In addition, also have 5g metallic iron microballon to be deposited on the slag ladle bottom, separate obtaining pig iron containing vanadium by magnetic separation.
Embodiment 7
Take by weighing the 200g titanium-containing blast furnace slag, its composition is 24.79%TiO
2, 20.14%CaO, 8.89%MgO, 13.86%Al
2O
3, 3.10%FeO, 5.89%MFe and 18.60%SiO
2The titanium slag that takes by weighing is contained in the slag ladle, and resistive heating makes the slag fusing, sprays into incendivity gas in slag, when regulating the slag temperature to 1400C, and steady temperature, bubbling air under molten state, oxidization time 12min, the branch of oxygen is pressed in 1-10
2In the kPa scope, the slag temperature is elevated to 1439 ℃ after the oxidation, lowers the temperature 2 ℃/min of speed of cooling in 1430～1100 ℃ of temperature ranges.Cooled oxidation crust block fragmentation, levigate, granularity+200 orders～-300 orders.Cooled oxidation crust block is through broken, levigate, granularity+100 orders～-200 orders, and through gravity treatment, flotation dumps mine tailing, obtains containing 38.7%TiO
2Rich ilmenite concentrate.In addition, also have 8.6g metallic iron microballon to be deposited on the slag ladle bottom, separate obtaining pig iron containing vanadium by magnetic separation
Embodiment 8
Take by weighing the 200g titanium-containing blast furnace slag, its composition is 24.79%TiO
2, 20.14%CaO, 8.89%MgO, 13.86%Al
2O
3, 3.10%FeO, 5.89%MFe and 18.60%SiO
2The titanium slag that takes by weighing is contained in the slag ladle, and resistive heating makes slag fusing, sprays into incendivity gas in slag, and when regulating slag temperature to 1400 ℃, steady temperature feeds oxygen-rich air under molten state, oxidization time 2min, and the branch of oxygen is pressed in 1-10
2In the kPa scope, the slag temperature is elevated to 1438 ℃ after the oxidation, lowers the temperature 2 ℃/min of speed of cooling in 1430～1100 ℃ of temperature ranges.Cooled oxidation crust block is through broken, levigate, granularity+100 orders～-200 orders, and through gravity treatment, flotation dumps mine tailing, obtains containing 37.2%TiO
2Rich ilmenite concentrate.In addition, also have 6.9g metallic iron microballon to be deposited on the slag ladle bottom, separate obtaining pig iron containing vanadium by magnetic separation.
Embodiment 9
Take by weighing the 200g titanium-containing blast furnace slag, its composition is 24.79%TiO
2, 20.14%CaO, 8.89%MgO, 13.86%Al
2O
3, 3.10%FeO, 5.89%MFe and 18.60%SiO
2The titanium slag that takes by weighing is contained in the slag ladle, and resistive heating makes slag fusing, sprays into incendivity gas in slag, when regulating slag temperature to 1420 ℃, and steady temperature, aerating oxygen under molten state adds addition of C aF simultaneously
210g, oxidization time 3min, the branch of oxygen is pressed in 1-10
2In the kPa scope, the slag temperature is elevated to 1470 ℃ after the oxidation, lowers the temperature 2 ℃/min of speed of cooling in 1470～1100 ℃ of temperature ranges.Cooled oxidation crust block is through broken, levigate, granularity+100 orders～-200 orders, and through gravity treatment, flotation dumps mine tailing, obtains containing 41.8%TiO
2Rich ilmenite concentrate.In addition, also have 8.8g metallic iron microballon to be deposited on the slag ladle bottom, separate obtaining pig iron containing vanadium by bifurcation.
Take by weighing the 200g titanium-containing blast furnace slag, its composition is 24.79%TiO
2, 20.14%CaO, 8.89%MgO, 13.86%Al
2O
3, 3.10%FeO, 5.89%MFe and 18.60%SiO
2The titanium slag that takes by weighing is contained in the slag ladle, and resistive heating makes the slag fusing, sprays into incendivity gas in slag, when regulating the slag temperature to 1420C, and steady temperature, aerating oxygen under molten state adds addition of C aO 4g and CaF simultaneously
28g, oxidization time 3min, the branch of oxygen is pressed in 1-10
2In the kPa scope, the slag temperature is elevated to 1460 ℃ after the oxidation, lowers the temperature 2 ℃/min of speed of cooling in 1460～1100 ℃ of temperature ranges.Cooled oxidation crust block is through broken, levigate, granularity+100 orders～-200 orders, and through gravity treatment, flotation dumps mine tailing, obtains containing 41.3%TiO
2Rich ilmenite concentrate.In addition, also have 8.9g metallic iron microballon to be deposited on the slag ladle bottom, separate obtaining pig iron containing vanadium by magnetic separation.
Embodiment 11
Take by weighing the 200g titanium-containing blast furnace slag, its composition is 24.79%TiO
2, 20.14%CaO, 8.89%MgO, 13.86%Al
2O
3, 3.10%FeO, 5.89%MFe and 18.60%SiO
2The titanium slag that takes by weighing is contained in the slag ladle, and resistive heating makes the slag fusing, sprays into incendivity gas in slag, when regulating the slag temperature to 1420C, and steady temperature, aerating oxygen under molten state adds addition of C aO 4g and CaF simultaneously
28g, oxidization time 3min, the branch of oxygen is pressed in 1-10
2In the kPa scope, the slag temperature is elevated to 1460 ℃ after the oxidation, lowers the temperature 0.5 ℃/min of speed of cooling in 1460～1100 ℃ of temperature ranges.Cooled oxidation crust block is through broken, levigate, granularity+100 orders～-200 orders, and through gravity treatment, flotation dumps mine tailing, obtains containing 42.5%TiO
2Rich ilmenite concentrate.In addition, also have 7.9g metallic iron microballon to be deposited on the slag ladle bottom, separate obtaining pig iron containing vanadium by magnetic separation.
Utilize the titaniferous blast furnace slag of insulation slag ladle splendid attire 1300kg from blast furnace, its composition is 21.32%TiO
2, 23.35%CaO, 7.76%MgO, 14.74%Al
2O
3, 2.20%FeO, 6.74%MFe and 20.50%SiO
2, the slag temperature is 1370 ℃, sprays into incendivity gas in slag, when regulating the slag temperature to 1400C, steady temperature feeds oxygen-rich air under molten state, and oxidization time 30min, the branch of oxygen is pressed in 1-10
2In the kPa scope, the slag temperature is elevated to 1480 ℃ after the oxidation, lowers the temperature furnace cooling in 1480～1100 ℃ of temperature ranges.Cooled oxidation crust block is through broken, levigate, granularity+100 orders～-200 orders, and through gravity treatment, flotation dumps mine tailing, obtains containing 42.9%TiO
2Rich ilmenite concentrate.In addition, also have 80kg metallic iron microballon to be deposited on the slag ladle bottom, separate obtaining pig iron containing vanadium by magnetic separation.
Embodiment 13
Utilize the titaniferous blast furnace slag of insulation slag ladle splendid attire 1300kg from blast furnace, its composition is 21.48%TiO
2, 22.41%CaO, 7.87%MgO, 14.69%Al
2O
3, 2.10%FeO, 8.08%MFe and 19.69%SiO
2The slag temperature is 1350 ℃.In slag, spray into incendivity gas, when regulating the slag temperature to 1400C, steady temperature, bubbling air under molten state,, oxidization time 30min, the branch of oxygen is pressed in 1-10
2In the kPa scope, the slag temperature is elevated to 1460 ℃ after the oxidation, lowers the temperature furnace cooling in 1400～1200 ℃ of temperature ranges.Cooled oxidation crust block is through broken, levigate, granularity+100 orders～-200 orders, and through gravity treatment, flotation dumps mine tailing, obtains containing 40.12%TiO
2Rich ilmenite concentrate.In addition, also have 95kg metallic iron microballon to be deposited on the slag ladle bottom, separate obtaining pig iron containing vanadium by magnetic separation.
Claims (4)
1, a kind of from titanium-containing blast furnace slag the method for the rich titanium material of separation of produced, it is characterized in that: adopt following three steps:
1. titanium component selective enrichment:
Utilize insulation slag ladle splendid attire titanium-containing blast furnace slag, feed incendivity gas heating slag then in slag ladle, control slag temperature adds additive at 1400-1450 ℃ in slag ladle, and additive therefor is for containing CaO or CaF
2In a kind of or both mixture, the consumption of additive is 1%～5% of a slag gross weight, when adding additive or afterwards, the oxidizing gas of jetting in slag makes slag at a middle or low price titanylization the time, the slag oxidation discharges a large amount of heats, the slag temperature raises, and gas constantly stirs slag, the influence of the oxidated property of the ratio of oxidization time and titanium-containing blast furnace slag gas flow, to be controlled at minute: gram=1: 10～50 is advisable, and the dividing potential drop of oxygen is controlled at 1-10 in the oxidizing gas
2In the kPa scope, make be scattered in the slag titanium component of various titaniferous in mutually optionally be enriched in uhligite mutually in, the metallic iron microballon that is mingled with in the slag takes place to assemble and grow up;
2. the uhligite phase selectivity is grown up:
Through step 1 make titanium component in 1450-1400 ℃ of temperature range, optionally be enriched in uhligite mutually after, slag cooling is grown up the uhligite phase selectivity; Control slag speed of cooling is cooled to room temperature in 0.5-5 ℃/min scope; Meanwhile, the metallic iron microballon that is mingled with in the slag takes place to assemble and grow up, and the iron microballon finally is deposited on the slag ladle bottom;
3. the uhligite phase selectivity is separated:
Crust block after step 1 handled with 2, through broken, levigate, adopt beneficiation method with the uhligite phase selectivity in the crust block separate, obtain containing 40-45%TiO
2Rich titanium material, meanwhile, the metallic iron microballon that adopts magnetic selection method will be deposited in the crust block of slag ladle bottom is separated, and contains higher vanadium in the metallic iron, can be used as pig iron containing vanadium and uses.
2, according to claim 1 from titanium-containing blast furnace slag the method for the rich titanium material of separation of produced, it is characterized in that: in the chemical constitution of described blast furnace slag, titanium oxide content is 15-30%.
3, the method for utilizing titanium-containing blast furnace slag separating titanium component according to claim 1, it is characterized in that: the isolating method of described ore dressing is with the crust block after the titanium component selective enrichment and the processing of growing up, through broken, levigate be+150 orders～-300 orders to granularity after, with gravity treatment, flotation, or gravity treatment is separated out with the uhligite in the crust block in conjunction with the integrated processes of flotation, obtains rich titanium material.
4, the method for utilizing titanium-containing blast furnace slag separating titanium component according to claim 1 is characterized in that: described insulation slag ladle is inside and outside tank body bilayer structure, and the slag ladle top is provided with insulation cover, fills heat-insulating material between the inside and outside tank body perisporium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101342603A CN100402678C (en) | 2006-11-14 | 2006-11-14 | Process for separation and production of titanium-rich materials from titanium-containing blast furnace slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101342603A CN100402678C (en) | 2006-11-14 | 2006-11-14 | Process for separation and production of titanium-rich materials from titanium-containing blast furnace slag |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1952188A true CN1952188A (en) | 2007-04-25 |
| CN100402678C CN100402678C (en) | 2008-07-16 |
Family
ID=38058744
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101342603A Expired - Fee Related CN100402678C (en) | 2006-11-14 | 2006-11-14 | Process for separation and production of titanium-rich materials from titanium-containing blast furnace slag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100402678C (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768673A (en) * | 2010-03-08 | 2010-07-07 | 中南大学 | Method for preparing titanium-rich material from titanium-containing slag |
| CN101905327A (en) * | 2010-05-21 | 2010-12-08 | 隋智通 | Method and equipment for separating titanium-rich material and entrained iron from titanium-containing blast furnace slag |
| CN101988158A (en) * | 2010-12-07 | 2011-03-23 | 东北大学 | Comprehensive utilization method of titanium-containing waste residues |
| CN102758030A (en) * | 2012-08-03 | 2012-10-31 | 四川省川威集团有限公司 | Seed crystal and method for facilitating increase of perovskite phase in titanium-bearing blast furnace slag |
| CN103343174A (en) * | 2013-07-11 | 2013-10-09 | 东北大学 | Method for separating titanium, iron, vanadium and calcium from mixed titaniferous slag |
| CN103695631A (en) * | 2013-12-19 | 2014-04-02 | 北京科技大学 | Mineral separation and enrichment process for ferrotitanium oxide ore |
| CN106378252A (en) * | 2016-09-29 | 2017-02-08 | 中国地质科学院矿产综合利用研究所 | Beneficiation and enrichment method for primary scandium ore |
| WO2018014363A1 (en) * | 2016-07-18 | 2018-01-25 | 东北大学 | Method for smelting reduction, recycling and tempering of titaniferous mixed slag |
| CN108384963A (en) * | 2018-04-20 | 2018-08-10 | 四川星明能源环保科技有限公司 | A kind of ferrotianium synthetic method and the method using titanium-containing blast furnace slag |
| CN108384962A (en) * | 2018-04-20 | 2018-08-10 | 四川省川威集团有限公司 | A kind of ferrotianium synthetic method and the method using titanium-containing blast furnace slag |
| CN108441643A (en) * | 2018-04-20 | 2018-08-24 | 四川省川威集团有限公司 | Titanium is enriched in the additive and method of Perovskite Phase in promotion high-titanium blast furnace slag |
| CN108504873A (en) * | 2018-04-20 | 2018-09-07 | 四川省川威集团有限公司 | Promote the increased additive of Perovskite Phase and method in high-titanium blast furnace slag |
| CN108611498A (en) * | 2018-04-20 | 2018-10-02 | 四川省川威集团有限公司 | The additive and method being enriched with conducive to titanium in high-titanium blast furnace slag |
| CN108677026A (en) * | 2018-08-07 | 2018-10-19 | 重庆大学 | A kind of centrifugal granulation detaches the device and method of titanium resource in titanium-containing blast furnace slag |
| CN108950226A (en) * | 2018-08-07 | 2018-12-07 | 重庆大学 | The device and method of titanium resource in a kind of high temperature concentration and separation titanium-containing blast furnace slag |
| CN109499744A (en) * | 2018-11-23 | 2019-03-22 | 宜宾天原集团股份有限公司 | A method of chlorination rich-titanium material is prepared using high contents of calcium and magnesium silicon ilmenite concentrate |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ239070A (en) * | 1990-07-25 | 1992-11-25 | Anglo Amer Corp South Africa | Recovery of titanium values from a complex matrix by chlorinating titanium nitride in the matrix |
| AR007955A1 (en) * | 1996-07-24 | 1999-11-24 | Holderbank Financ Glarus | PROCEDURE FOR SEPARATING TITANIUM AND / OR VANADIUM FROM GROSS IRON |
| CN1089374C (en) * | 1998-11-10 | 2002-08-21 | 东北大学 | Process for separating titanium component from titanium-contained slags |
-
2006
- 2006-11-14 CN CNB2006101342603A patent/CN100402678C/en not_active Expired - Fee Related
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768673A (en) * | 2010-03-08 | 2010-07-07 | 中南大学 | Method for preparing titanium-rich material from titanium-containing slag |
| CN101905327A (en) * | 2010-05-21 | 2010-12-08 | 隋智通 | Method and equipment for separating titanium-rich material and entrained iron from titanium-containing blast furnace slag |
| CN101905327B (en) * | 2010-05-21 | 2012-07-04 | 隋智通 | Method and equipment for separating titanium-rich material and entrained iron from titanium-containing blast furnace slag |
| CN101988158A (en) * | 2010-12-07 | 2011-03-23 | 东北大学 | Comprehensive utilization method of titanium-containing waste residues |
| CN102758030A (en) * | 2012-08-03 | 2012-10-31 | 四川省川威集团有限公司 | Seed crystal and method for facilitating increase of perovskite phase in titanium-bearing blast furnace slag |
| CN103343174B (en) * | 2013-07-11 | 2014-12-10 | 东北大学 | Method for separating titanium, iron, vanadium and calcium from mixed titaniferous slag |
| CN103343174A (en) * | 2013-07-11 | 2013-10-09 | 东北大学 | Method for separating titanium, iron, vanadium and calcium from mixed titaniferous slag |
| CN103695631B (en) * | 2013-12-19 | 2016-03-02 | 北京科技大学 | A kind of beneficiation enrichment technique of ferrotianium oxidized ore |
| CN103695631A (en) * | 2013-12-19 | 2014-04-02 | 北京科技大学 | Mineral separation and enrichment process for ferrotitanium oxide ore |
| WO2018014363A1 (en) * | 2016-07-18 | 2018-01-25 | 东北大学 | Method for smelting reduction, recycling and tempering of titaniferous mixed slag |
| CN106378252A (en) * | 2016-09-29 | 2017-02-08 | 中国地质科学院矿产综合利用研究所 | Beneficiation and enrichment method for primary scandium ore |
| CN108384963A (en) * | 2018-04-20 | 2018-08-10 | 四川星明能源环保科技有限公司 | A kind of ferrotianium synthetic method and the method using titanium-containing blast furnace slag |
| CN108384962A (en) * | 2018-04-20 | 2018-08-10 | 四川省川威集团有限公司 | A kind of ferrotianium synthetic method and the method using titanium-containing blast furnace slag |
| CN108441643A (en) * | 2018-04-20 | 2018-08-24 | 四川省川威集团有限公司 | Titanium is enriched in the additive and method of Perovskite Phase in promotion high-titanium blast furnace slag |
| CN108504873A (en) * | 2018-04-20 | 2018-09-07 | 四川省川威集团有限公司 | Promote the increased additive of Perovskite Phase and method in high-titanium blast furnace slag |
| CN108611498A (en) * | 2018-04-20 | 2018-10-02 | 四川省川威集团有限公司 | The additive and method being enriched with conducive to titanium in high-titanium blast furnace slag |
| CN108677026A (en) * | 2018-08-07 | 2018-10-19 | 重庆大学 | A kind of centrifugal granulation detaches the device and method of titanium resource in titanium-containing blast furnace slag |
| CN108950226A (en) * | 2018-08-07 | 2018-12-07 | 重庆大学 | The device and method of titanium resource in a kind of high temperature concentration and separation titanium-containing blast furnace slag |
| CN109499744A (en) * | 2018-11-23 | 2019-03-22 | 宜宾天原集团股份有限公司 | A method of chlorination rich-titanium material is prepared using high contents of calcium and magnesium silicon ilmenite concentrate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100402678C (en) | 2008-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100402678C (en) | Process for separation and production of titanium-rich materials from titanium-containing blast furnace slag | |
| Sahu et al. | An overview on the production of pigment grade titania from titania-rich slag | |
| CN103343174B (en) | Method for separating titanium, iron, vanadium and calcium from mixed titaniferous slag | |
| CN102154531B (en) | Method for producing artificial rutile from titanium-containing blast furnace slags | |
| CN109880955B (en) | Smelting method and smelting device for treating iron-based multi-metal ore material in short process | |
| CN104313361B (en) | A kind of Leaching of Vanadium from Vanadium slag containing chromium and the process of coproduction chromium-base alloy | |
| CN101905327B (en) | Method and equipment for separating titanium-rich material and entrained iron from titanium-containing blast furnace slag | |
| CN101827951B (en) | Recovery of residues containing copper and other valuable metals | |
| CN102168156B (en) | Iron and aluminum melting separation method for complicated and hard-dressing aluminum and iron intergrowth ore | |
| CN103695631B (en) | A kind of beneficiation enrichment technique of ferrotianium oxidized ore | |
| CN106065435A (en) | A kind of method and system processing vanadium slag | |
| CN106521139A (en) | Method for preparing high titanium slag through low temperature reduction and separation of titanium-containing iron ore | |
| CN106834716B (en) | A kind of method of arsenic-containing smoke dust dearsenification and valuable element comprehensive reutilization | |
| CN110055371A (en) | The method that molten iron production vanadium slag containing sodium directly leaches vanadium extraction | |
| CN108384950A (en) | The method of smelting titanium slag | |
| CN102812143A (en) | Method For Preparing Ferro Molybdenum From Molybdenite | |
| CN105969978B (en) | The system and method for preparing ferrochrome | |
| CN105907968A (en) | Method of extracting iron and titanium with ferrotitanium compound minerals as raw material and filtering equipment | |
| CN106315584A (en) | Method for preparing carbon-doped titanium oxide or/and titanium carbide from titanium-containing mineral or slag | |
| CN104561551B (en) | A kind of method of the valuable constituent element separation and Extraction of boron magnesium iron mineral intergrowth | |
| CN109477161A (en) | The method of the nickeliferous copper sulphide material of continuous converting | |
| CN107381654A (en) | A kind of method that liquid industrial frerrous chloride is converted into by hydrochloric acid pickling waste liquor | |
| WO2023193714A1 (en) | Method and system for coupling copper slag recycling with co2 mineralization based on industrial solid waste | |
| CN110042191A (en) | The method of converter producing vanadium slag containing sodium and its Oxidation Leaching | |
| CN108893572A (en) | A kind of method of valuable constituent element comprehensive reutilization in paigeite |
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 | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080716 Termination date: 20101114 |