CN100510127C - Method for extracting iron titanium vanadium from high-titanium iron concentrate - Google Patents
Method for extracting iron titanium vanadium from high-titanium iron concentrate Download PDFInfo
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- CN100510127C CN100510127C CNB2006100214684A CN200610021468A CN100510127C CN 100510127 C CN100510127 C CN 100510127C CN B2006100214684 A CNB2006100214684 A CN B2006100214684A CN 200610021468 A CN200610021468 A CN 200610021468A CN 100510127 C CN100510127 C CN 100510127C
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Abstract
The invention discloses an iron-titanium-vanadium extracting method from high-titanium ferrovanadium concentrate ore. By adopting the method to make steel, fine TiCI4 and V2O5 have the advantages that: technological processes are simple and reasonable; energy consumption is low; yield rate of iron-titanium-vanadium is high and three wastes (waste gas, waste water and waste slag) are fewer. The method comprises the steps: iron smelting: a high furnace or an electric furnace is adopted to smelt iron to make melten iron containing vanadium and chromium and make titanium-enriched slag as byproduct and the rate of vanadium reduced and added into iron is 60-78 percent; single-slag steel-making: melten iron containing vanadium and chromium is put into a converter furnace directly to make steel by the function of oxygen blowing, and steel slag containing vanadium and chromium is obtained as byproduct; carbonized titanium-vanadium-chromium slag with 80-95 percent of carbonization rate is made by smelting reduction carbonization by the electric furnace smelting selection; TiCl4 containing vanadium is made by selective chlorination of carbonized titanium-vanadium-chromium slag in a fluidized bed at low temperature, and residual slag of chlorination containing CrCl3 is byproduct; vanadium titanium separation: VOCI3 is directly reduced by cycloolefine or naphthenic acid to make VOCl2 which can not dissolve in TiCI4, while the VOCI3 can be dissolved in TiCI4. Then the fine TiCI4 is made and the slurry TiCI4 containing rich vanadium is also made as byproduct; V2O5 is extracted from the rich vanadium containing slurry TiCI4.
Description
Technical field
The present invention relates to a kind of treatment process of multi-metallic minerals, be particularly suitable for the method for from high-titanium type vanadium iron ore concentrate and class gel mineral, separating the ferrotitanium vanadium.
Background technology
The high-titanium type vanadium iron ore concentrate is a kind of polymetallic ore product that contains iron, titanium, vanadium and chromium.To the development and use of these mineral products, the technology of domestic industry scale production is: ordinary blast is smelted to produce and is contained the attached product of vanadium chromium hot melt TiO
222-24% contains the rich titanium slag of vanadium.Containing the vanadium chromium hot melt and adopt converter oxygen blowing vanadium chromium slag---half steel converter steelmaking, is 70% from containing the vanadium chromium hot melt to the yield of commodity vanadium chromium slag vanadium, and the vanadium chromium slag ingredient is: V
2O
518.7%, TFe 35.0%, Cr
2O
31.0%, CaO 0.7%, and standard vanadium chromium slag (contains V
2O
510%) productive expense is 1.5 tons of pig iron value/t standard vanadium chromium slags.The vanadium extraction of this vanadium chromium slag oxidation sodium roasting water law, the expense of vanadium chromium slag accounts for V
2O
575% of production cost, from the vanadium iron concentrate to product V
2O
5, the casting yield of vanadium only is 50%, the slag and effluent quantity that vanadium extraction produces is big, is difficult to handle.The rich titanium slag of vanadium that contains of attached product only substitutes the use of sandstone material, and titanium in the slag and vanadium do not obtain recycling.
South Africa Hai Weierde steel vanadium company and New Zealand Steel Ltd. then adopt rotary kiln prereduction----metallization to expect that electric furnace restores production and contains the attached product of vanadium chromium hot melt TiO
232% contain the rich titanium slag of vanadium.Contain vanadium chromium hot melt South Africa and adopt shaking ladle process blowing vanadium chromium slag, New Zealand adopts hot metal ladle to add a cover blowing vanadium chromium slag, and half steel all adopts converter steelmaking.From the vanadium iron concentrate to V
2O
5Product, the casting yield of vanadium breaks through 50%.Contain the vanadium chromium hot melt and no matter adopt what method blowing vanadium chromium slag----semi-steel making all to exist to make the molten iron-steelmaking process complicated, the facility investment amount increases, steel-making comprehensive energy consumption height, and the iron steel is than problems such as the casting yield of increase, vanadium chromium slag productive expense height, vanadium are low.From the vanadium extraction tail washings, extract the chromium long flow path, the chemical reagent consumption is big.
A kind of method of preparing titanic chloride using carbon-containing slag in being the application for a patent for invention prospectus of CN87107488.5, the patent No. is disclosed, though the expanding test of this method is successful, also there is the control of industrial fluidized bed startup of slag low temperature chlorination of titanium carbide vanadium chromium and chlorination operation bed temperature, contains vanadium TiCl
4Refining and vanadium reclaims problems such as difficulty.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method of extracting the ferrotitanium vanadium from the high-titanium type vanadium iron ore concentrate, produces steel, smart TiCl by this method
4And V
2O
5, have that technical process is simple and direct rationally, energy consumption is low, ferrotitanium vanadium yield height and a few advantage of the three wastes.
The technical solution adopted for the present invention to solve the technical problems is: the method for extracting the ferrotitanium vanadium from the high-titanium type vanadium iron ore concentrate of the present invention comprises the steps:
1. blast furnace or electric furnace ironmaking are adopted in ironmaking, and production contains the vanadium chromium hot melt and attached product contains the rich titanium slag of vanadium, adds CaO desulfurization residue adjustment in the smelting process, makes the reduction of vanadium appropriateness, and it is 60～78% that vanadium reduces into the iron rate;
2. single slag steel-making contains the single slag direct steelmaking of vanadium chromium hot melt oxygen blast in converter, and attached product contains vanadium chromium steel slag, control the hot metal ratio slag to equal 1000: 70～90;
3. electric furnace fusion selective reduction carbonization will add containing vanadium chromium steel slag and containing the fusion selective reduction carbonization in electric furnace of the rich titanium slag of vanadium of carbon dust, and the production carbonation rate is 80～95% titanium carbide vanadium chromium slag, and control reduction and carbonization temperature is 1450～1750 ℃;
4. titanium carbide vanadium chromium slag fluidized-bed low temperature selective chlorination is produced and is contained vanadium TiCl
4Contain CrCl with attached product
3Chloride residue;
5. the vanadium titanium separates, and directly reduces with cycloolefin or naphthenic acid to be dissolved in TiCl
4In VOCl
3, generate and be insoluble to TiCl
4VOCl
2, realize that the vanadium titanium separates, thus refining TiCl
4And the rich vanadium TiCl of attached product
4Mud;
6. from rich vanadium TiCl
4Extract V in the mud
2O
5
The invention has the beneficial effects as follows that the depleted titanium was with the most important intermediates TiCl of titanium industry in the past
4Reclaimed, its casting yield reaches about 80%, the TiCl that the rich titanium material of production cost and higher-grade is produced
4Quite; V
2O
5Production cost be about and contain 50% of vanadium chromium hot melt blowing vanadium slag water law vanadium extraction, and the casting yield of vanadium improves about 30%; Contain the single slag steel-making of vanadium chromium hot melt Converter Oxigen Blowing and contain the vanadium chromium hot melt and bessemerize vanadium slag---semi-steel making is compared, and production efficiency improves nearly one times, the iron steel than and all decline to some extent of comprehensive energy consumption, iron loss drops to 4% by original 7%; Separation and Extraction ferrovanadium titanium production process produces the kind and the quantity of the three wastes all to be lacked, and is easy to handle, and social benefit is good.
Description of drawings
Fig. 1 is the present invention extracts the method for ferrotitanium vanadium from the high-titanium type vanadium iron ore concentrate a process flow sheet.
Embodiment
The present invention is further described below in conjunction with drawings and Examples.
With reference to Fig. 1, the present invention extracts the method for ferrotitanium vanadium from the high-titanium type vanadium iron ore concentrate, comprise the steps:
1. blast furnace or electric furnace ironmaking are adopted in ironmaking, and production contains the vanadium chromium hot melt and attached product contains the rich titanium slag of vanadium, adds CaO desulfurization residue adjustment in the smelting process, makes the reduction of vanadium appropriateness, and it is 60～78% that vanadium reduces into the iron rate.
When the attached product of blast furnace or electric furnace ironmaking contains vanadium richness titanium slag, adding CaO removes the sulphur in the molten iron and adjusts the slag composition, separate with slag iron in order to improving molten steel quality, the control vanadium reduces into the iron rate 60～78% (should be preferably 65～75%), so both can guarantee that ferric oxide was fully reduced, improve the carbon content of metal recovery rate and molten iron, not because of the vanadium over reduction increases the ironmaking energy consumption, the throughput of equipment is also fully played again.In the iron manufacturing process, basicity of slag is controlled at 0.6＜((CaO+MgO)/(SiO
2+ Al
2O
3))≤1.
Contain in the rich titanium slag of vanadium and contain TiO
218～45%.
2. single slag steel-making contains the single slag direct steelmaking of vanadium chromium hot melt oxygen blast in converter, and attached product contains vanadium chromium steel slag, and control hot metal ratio slag equals 1000: 70～90 (suitable preferred 1000: 75～85).Oxidized being enriched among the slag of vanadium chromium element in the molten iron is for containing vanadium chromium steel slag.Compare with currently used " contain the vanadium chromium hot melt and bessemerize vanadium slag---semi-steel making " method, production efficiency improves nearly one times, the iron steel than and all decline to some extent of comprehensive energy consumption, iron loss drops to 4% by original 7%.
3. electric furnace fusion selective reduction carbonization, containing vanadium chromium steel slag and containing the fusion selective reduction carbonization in electric furnace of the rich titanium slag of vanadium of carbon dust will be added, the production carbonation rate is 80～95% titanium carbide vanadium chromium slag, and control reduction and carbonization temperature is 1450～1750 ℃ (being preferably 1500～1650 ℃).
Determine earlier to contain the rich titanium slag quality of vanadium: contain vanadium chromium steel slag amount: carbon dust quality=800: (0～170): reduction contains the rich titanium slag of vanadium and contains the ratio of the required carbon dust quality of ferrotitanium vanadium chromated oxide in the vanadium chromium steel slag, containing vanadium chromium steel slag and pressing the mixed that mentioned above principle is determined some amount with carbon dust (100 orders account for 80% pulverized anthracite or coke powder), be pressed into the slag carbon dust ball oven dry of 20～30mm, contain the ratio that rich titanium slag of vanadium and slag carbon dust ball are also determined in mentioned above principle, fusion selective reduction carbonization production carbonization titanium carbide vanadium chromium slag in electric furnace.
4. titanium carbide vanadium chromium slag fluidized-bed low temperature selective chlorination is produced and is contained vanadium TiCl
4Contain CrCl with attached product
3Chloride residue.
TiC, V in the titanium carbide vanadium chromium slag
2C, Cr
4The reaction of C (Cr) and Fe and chlorine is strong thermopositive reaction, and chlorination reaction is just fierce quite rapidly once beginning.(TiC+V as calculated
2C+Cr
4C (Cr)+1/2Fe) mass percent is that titanium carbide vanadium chromium slag chlorination institute liberated heat under adiabatic condition of 14% is enough to reaction mass and product are heated to more than 1650 ℃.This temperature is far above containing the CaCl that calcium oxide and a large amount of chlorinations of magnesium oxide mineral and chlorination generate in the titanium carbide vanadium chromium slag
2, MgCl
2The temperature of fusing, the CaCl that generates in a large number and melt
2, MgCl
2An interior material particles adhesion or bonding are lost to flow and dead bed.
For realizing titanium carbide vanadium chromium slag fluidized-bed selective chlorination TiC, V
2C, Cr
4C (Cr) production contains vanadium TiCl
4Contain Cr Cl with attached product
3The chlorination operation technique direct motion of chloride residue, take continuous charging continuous discharging slag (can be interrupted in short-term) between the fluidized bed chlorination operational period, thick TiCl is handled in volatilization
4The TiCl that production process produces
4Mud is provided with nickelic stainless steel water (vapour) water cooler at the bed concentrated phase area and shifts out unnecessary reaction heat, bed concentrated phase area temperature is controlled to be lower than contain the CaCl that calcium oxide and a large amount of chlorinations of magnesium oxide mineral and chlorination generate in the titanium carbide vanadium chromium slag
2, MgCl
2The temperature of fusing, and be higher than TiC, V
2In the initial chlorating temperature range of C, Cr4C (Cr), in the scope of promptly 400～600 ℃ (can be preferably 450～550 ℃), guarantee that the interior material of bed has good fluidizing performance between the chlorination operational period, make the technology direct motion, TiC, V
2C, Cr
4C (Cr) is chlorinated fully, and contains calcium oxide and magnesian mineral seldom are chlorinated.
The heat interchanging area of nickelic stainless steel water (vapour) water cooler that is provided with at the bed concentrated phase area calculates with following formula:
F
Change=α q1F
Bed/ 86.4K
WaterΔ t
On average
In the formula:
F
ChangeThe heat interchanging area of----nickelic stainless steel water (vapour) water cooler, m
2
The unit surface production capacity of α----fluidized-bed, tTiCl
4/ (m
2D);
q
1Produce one ton under----concentrated phase area specified temperature and other conditions and contain vanadium TiCl
4, need high nickel and stainless steel water cooler to shift out the outer heat of bed, Kj/tTiCl
4
F
Bed----fluidized bed gas grid distributor place sectional area, m
2
Δ t
On average--the medial temperature of fluidized-bed concentrated phase area and water cooling medium, ℃;
K
Water----fluidized-bed concentrated phase area is to the heat transfer coefficient of water cooling medium, Kj/ (m
2℃).
Δ t
On average=(t
Go out-t
Advance)/2.3lg ((t
Layer-t
Advance)/(t
Layer-t
Go out))
In the formula: t
Go outThe temperature of----nickelic stainless steel water (vapour) cooler outlet place water, ℃;
t
AdvanceThe temperature of----nickelic stainless steel water (vapour) cooler inlet place water, ℃;
t
Layer----fluidized-bed concentrated phase area bed temperature, ℃.
Titanium carbide vanadium chromium slag fluidized-bed selective chlorination TiC, V
2C, Cr
4When C (Cr) fluidized-bed starts, operating gas velocity when starting gas speed and must be equal to, or greater than normal chlorination operation, and bed concentrated phase area height 1/5～1/3 when having only normal chlorination operation, when water (vapour) water cooler that is arranged at the bed concentrated phase area shifts out the outer heat of bed and also only reaches normal chlorination operation 1/5～1/3.If do not reduce the thermal value when starting the quality chlorination of material list position and increase its thermal capacity, perhaps reduce the percentage volumetric molar concentration that starts chlorine in the gas and reduce the total calorific value that chlorination reaction produces when starting, bed temperature can raise rapidly when fluidized-bed started, and reached and surpassed the CaCl that contains calcium oxide and a large amount of chlorinations of magnesium oxide mineral and generation
2, MgCl
2The temperature of fusing, the CaCl of fusing
2And MgCl
2Can make an interior material adhesion or bonding and dead bed.
For realizing titanium carbide vanadium chromium slag fluidized-bed selective chlorination TiC, V
2C, Cr
4C (Cr) fluidized-bed is dead bed between the starting period, adopts in the titanium carbide vanadium chromium slag that uses when normal chlorination operation and adds the soft heat point〉700 ℃ difficult muriate (for example quartz sand, Al
2O
3Particle etc.), with (TiC+V in the titanium carbide vanadium chromium slag
2C+Cr
4C (Cr)+1/2Fe) the quality sum is diluted to 1～7% (preferably being diluted to 3～5%) startup material when starting as fluidized-bed, and the chlorine that uses during with normal chlorination operation makes to start the gas starting fluidized-bed.Perhaps add dry air, nitrogen and other inert gas, the chlorine that uses during with normal chlorination operation is diluted to the low concentration chlorine that the percentage volumetric molar concentration is 20～50% (can be preferably 30～40%), startup gas when starting as fluidized-bed, the titanium carbide vanadium chromium slag that normal chlorination operation is used are made to start material and are started fluidized-bed.Starting the preheating temperature of material in fluidized-bed is 180～450 ℃ (can be preferably 250～300 ℃), and bed concentrated phase area height was normal chlorination 1/5～1/3 when doing when fluidized-bed started.The CaCl that contains calcium oxide and a large amount of chlorinations of magnesium oxide mineral and generation is kept off or be no more than to bed concentrated phase area temperature when guaranteeing that fluidized-bed starts
2MgCl
2Infusible temperature, and more TiC, the V of being higher than
2C, Cr
4The initial chlorating temperature of C (Cr) makes fluidized-bed startup success and then changes normal chlorination operation over to.
5. the vanadium titanium separates, and directly reduces with cycloolefin or naphthenic acid to be dissolved in TiCl
4In VOCl
3, generate and be insoluble to TiCl
4VOCl
2, realize that the vanadium titanium separates, thus refining TiCl
4And the rich vanadium TiCl of attached product
4Mud.
To be contained vanadium TiCl by purified
4Put into reactor, under normal temperature and pressure and agitation condition, the cycloolefin or the naphthenic acid that add calculated amount lentamente, mixture heating up to 70-137 ℃ different temperature and time level carried out vanadium titanium separating reaction 1.5～2.5 hour thereafter, the mixture of termination reaction is through sedimentation, supernatant liquor is produced through simple distillation and is contained V＜0.0007%, meets the smart TiCl that chloride process titanium dioxide is produced required quality
4, kettle base solution and subsider underflow are to be rich vanadium TiCl
4Mud, the add-on of cycloolefin or naphthenic acid is for containing vanadium TiCl
4Middle VOCl
30.15～0.30 times of mass percent.Suitable preferred high-quality turps and the fraction products thereof of adopting of described cycloolefin, described naphthenic acid should preferably adopt and contain 2～3 five isocyclic naphthenic acid.
6. from rich vanadium TiCl
4Extract V in the mud
2O
5
With normal temperature or be heated to rich vanadium TiCl less than 150 ℃ (136 ℃ of preferred values)
4Mud sprays equably in the bed type is the external-heat inert particle fluidized bed of garden, awl complex body, is initial fluidizing medium with nitrogen, and bed temperature drying under the condition of 170-290 ℃ (can be preferably 200-250 ℃) is removed TiCl
4Described bed type is that garden, awl complex body are meant: 1/2 〉=(R
Little/ R
Greatly) 〉=1/4, R
LittleBe minimum place, fluidized-bed cross section radius, R
GreatlyBe fluidized-bed cross section maximum radius.
Press TiO in the dissolution fluid
2Mass concentration be that 150～200 grams per liters calculate, with the VOCl in the dried slag of diluted hydrochloric acid dissolution richness vanadium of 0.5～1M
2And TiCl
3, cleaner liquid with sodium chlorate with Ti
3+Be oxidized to Ti more than 97%
+ 4, with adding the crystal seed hydrolysis method metatitanic acid that settles out.The liquid of filtering metatitanic acid with sodium chlorate with Ti
3+All be oxidized to Ti
4+, transfer pH near zero with NaOH solution, titanium is all separated out with metatitanic acid form precipitation; Perhaps cleaner liquid directly transfers pH to zero neighbouring with Ti with NaOH solution
3+With Ti (OH)
3All precipitation filterings, the vanadium solution through purifying prepares ammonium hexavanadate and then produces V with known water law extraction vanadium method
2O
5
Described step 4. attached product contain CrCl
3Chloride residue can be used for extracting Cr
2O
3, whether extract and look CrCl in the chloride residue
3Content decision.CrCl in chloride residue
3Content greater than 0.5% o'clock, the acceptable salts acid concentration is 0～0.5M, contain trace Cr Cl
2, quality is the solution of chloride residue 25-45%, secondary leaches the CrCl in the stripping chloride residue
3, leach filtrate for the first time and use milk of lime adjust pH to 8.5～9.5, settling out contains Mg (OH)
2Cr (OH)
3Precipitation, the precipitation that leaches is dissolved Cr (OH) with NaOH solution
3Make it with CrO
2 -Change solution over to, contain CrO
2 -1Alkaline cleaner liquid be used for producing Cr
2O
3, lixivium leaches CrCl first as the next batch chloride residue for the second time
3Usefulness.This method is extracted Cr from chloride residue
2O
3Flow process is short, the main agents milk of lime low price of use, and the consumption of NaOH is few, Cr
2O
3Yield height, production cost low.
Embodiment 1:
(composition is the high-titanium type vanadium iron ore concentrate: TFe 51.74%, FeO 29.65%, Fe
2O
350.65%, V
2O
50.56%, TiO
214.02%, Cr
2O
30.45%, SiO
24.77%, Al
2O
333.5%, CaO 1.79%, MgO 4.23%) add the melting of CaO benefit carbon through prereduction hot charging electric furnace, the control vanadium reduces and is the melting terminal point into iron rate 68%.The hot metal composition of output is: C 2.51%, V 0.49%, Cr 0.50%, Ti 0.15%, Si 0.16%, S 0.06%.The composition that contains the rich titanium slag of vanadium is TiO
240%, V
2O
50.35%, Cr
2O
30.25%, CaO 13.60%, MgO 12.01%, SiO
217.06%, Al
2O
313.43%, FeO 1.23%.The rate of tapping a blast furnace and slag rate are respectively: 500kg Fe/t concentrate, 350kg contain the rich titanium slag of vanadium/t concentrate.Contain the vanadium chromium hot melt and contain the raw material of vanadium chromium steel slag, contain the rich titanium slag of vanadium as the raw material of producing titanium carbide vanadium chromium slag as the attached product of steel-making.
Contain the single slag direct steelmaking of vanadium chromium hot melt Converter Oxigen Blowing:
Contain the single slag steel-making of vanadium chromium hot melt Converter Oxigen Blowing, control hot metal ratio slag=1000: 80 is produced qualified trade mark molten steel, contains vanadium chromium steel slag ingredient and is: MFe 2.00%, FeO 10.50%, V
2O
510.57%, Cr
2O
39.43%, SiO
25.70%, CaO 46.80%, MgO 2.55%, TiO
23.05%.Contain the raw material of vanadium chromium steel slag as subsequent production titanium carbide vanadium chromium slag.
Contain vanadium chromium steel slag and produce titanium carbide vanadium chromium slag with containing the carbonization of the rich titanium slag electric furnace melting and reducing of vanadium:
The reduction and carbonization agent of using is pulverized anthracite (100 orders account for 80%), and its composition is: fixed carbon 78%, ash content 11.0%, volatile matter 11.0%.In containing the ratio that the rich titanium slag ratio of vanadium contains vanadium chromium steel slag ratio pulverized anthracite=800: 90: 200, contain vanadium chromium steel slag and the pulverized anthracite mixing of some amount are pressed into the oven dry of slag carbon dust ball, the liquid state of some amount is contained the rich titanium slag of the vanadium carbonization electric furnace of packing into, add slag carbon dust ball in containing the ratio of the rich titanium slag of vanadium than slag carbon dust ball=800: 290, reduction and carbonization is produced titanium carbide vanadium chromium slag under 1500～1650 ℃ temperature.TiO
2, V
2O
5, Cr
2O
3The reduction and carbonization rate be 90% o'clock, the composition of titanium carbide vanadium chromium slag is: TiC 24.96%, TiO
23.98%, V
2C 0.88%, V
2O
50.15%, Cr
4C 0.80%, Cr
2O
30.12%, MFe 3.27%, CaO 17.80%, MgO 12.01%, SiO
218.07%, Al
2O
316.07%, C 3.05%.Titanium carbide vanadium chromium slag is produced as low temperature chlorination and is contained vanadium TiCl
4Attached product contains CrCl
3The raw material of chloride residue.
The control of titanium carbide vanadium chromium slag fluidized-bed low temperature selective chlorination bed temperature:
Contain vanadium TiCl with titanium carbide vanadium chromium slag for producing
4Raw material exists in continuous charging continuous discharging slag mode
Chlorination in the fluidized-bed of 2000mm, using the percentage volumetric molar concentration of chlorine is 80%, the unit surface production capacity of fluidized-bed is the thick TiCl of 25t
4/ m
2.d, the volatilize TiCl of treatment fluidized bed production capacity 10%
4Mud, the heat lost by radiation of fluidized-bed outer wall is emitted 3.5% of total heat for chlorination reaction in the bed, the concentrated phase area bed temperature is controlled at 500 ± 50 ℃, nickelic stainless steel water (vapour) the cooler inlet water temperature that is installed on the bed concentrated phase area is 20 ℃, outlet water temperature when being 60 ℃, and the total heat conduction area of water (vapour) water cooler is about 37m
2Being converted into external diameter is that 0.06m, length are the nickelic stainless steel sleeve tubular type watercooler of 2m, then needs at the bed concentrated phase area 98 above-mentioned telescoping watercoolers to be set.
The thick TiCl that the low temperature selective chlorination is worked continuously and produced
4Contain VOCl
33.03%, Cl
20.21%, FeCl
30.02%, chloride residue contains CrCl
33.02%.Respectively as refining TiCl
4With extraction V
2O
5, Cr
2O
3Raw material.
The startup of titanium carbide vanadium chromium slag low temperature selective chlorination fluidized-bed:
With quartz sand with (TiC+V in the above-mentioned titanium carbide vanadium chromium slag
2C+Cr
4C (Cr)+1/2Fe) mass concentration is diluted to 3.5%, startup material when starting as fluidized-bed, starting bed depth is 1/4 of normal chlorination operation, after the startup material is preheating to 250 ℃, feed the chlorine startup fluidized-bed that normal chlorination operation is used, enable the watercooler in bed simultaneously.When waiting the concentrated phase area bed temperature to reduce to 450 ℃ after logical chlorine starts, start charging machine and add the carbonization vanadium-titanium-chromium slag that normal chlorination operation is used, feed in raw material and stop to feed in raw material when making the concentrated phase area bed temperature be promoted to 550 ℃, so repetitive operation makes bed height reach design level, can change normal chlorination operation over to.
Contain vanadium TiCl
4Titanium vanadium separation and purification TiCl
4:
Implement the above-mentioned vanadium TiCl that contains with high-quality turps
4Titanium vanadium separation and purification TiCl
4The terebinthine add-on of high-quality is for containing vanadium TiCl
40.60% of quality is perhaps for containing vanadium TiCl
4Middle VOCl
30.20 times of mass percent.To be contained vanadium TiCl by purified
4Put into reactor, under normal temperature and pressure and agitation condition, the high-quality turps of calculated amount added lentamente contain vanadium TiCl
4In, thereafter mixture heating up was carried out to 70-137 ℃ of different temperature levels and time that the vanadium titanium separates and refining reaction 1.8 hours.The mixture of termination reaction is through sedimentation, and supernatant liquor must contain the smart TiCl of V＜0.0007% through simple distillation
4Product, from concentrate to smart TiCl
4The rate of recovery of titanium reaches 80%.Kettle base solution and subsider underflow are to be rich vanadium TiCl
4Mud is as extracting V
2O
5Raw material.
Rich vanadium TiCl
4Mud extracts V
2O
5:
With rich vanadium TiCl
4Be sprayed on to the mud quantitative and even bed temperature and be in 250 ℃ the external-heat inert particle fluidized bed concentrated phase layer and carry out drying, the dry mixed gas that produces discharges fluidized-bed after TiCl is reclaimed in dedusting, condensation
4, the TiCl of recovery
4Smart TiCl is produced in the supernatant liquor distillation of incorporating into behind the vanadium titanium separating reaction
4, dedusting is incorporated the dried slag work of rich vanadium of discharging from the fluidized-bed upflow tube into and is extracted V
2O
5Raw material.The dried slag ingredient of rich vanadium is V 16.10%, Ti 15.32%, C 8.01%.
Press TiO in the dissolution fluid
2Mass concentration be that 160 grams per liters calculate, with 0.5M dilute hydrochloric acid consumption, dissolve the VOCl in the rich vanadium slag
2And TiCl
3, the clear liquid of filtering carbon dust and other foreign material adds the sodium chlorate solution with Ti
3+Be oxidizing to 3 grams per liters, add the crystal seed hydrolysis metatitanic acid that settles out then, the liquid of filtering metatitanic acid adds the sodium chlorate solution once more with Ti
3+All be oxidized to Ti
4+, when transferring pH extremely zero, titanium all is precipitated out with NaOH solution; Perhaps the clear liquid of filtering carbon dust and other foreign material directly transfers PH to zero neighbouring with Ti as NaOH solution
3+With Ti (OH)
3All settle out, the sedimentary rich vanadium scavenging solution of filtering is by prior art for preparing ammonium hexavanadate and then production V
2O
5The vanadium extraction tail washings adds milk of lime and reclaims the heavy calcium of ammonia still process behind the residual vanadium, and the heavy surplus liquid of calcium send chlor-alkali workshop preparation electrolytic solution.From the concentrate to V
2O
5The rate of recovery of product vanadium is 80%.
From chloride residue, extract Cr
2O
3:
Contain trace Cr Cl with chloride residue quality 35%
2, concentration is that the dilute hydrochloric acid of 0.5M leaches chloride residue stripping CrCl for twice
3Leach for the first time clear liquid and transfer pH to 9 with milk of lime, settling out contains Mg (OH)
2Cr (OH) Deng impurity
3Precipitation, the precipitation that leaches is dissolved Cr (OH) with NaOH solution
3Make it with CrO
2 -Change solution over to, contain CrO
2 -Cleaner liquid produce Cr with known method
2O
3Product leaches as the next batch chloride residue and leach Cr first for the second time
2Cl
3Usefulness, Cr
2O
3Yield be 60%.
Embodiment 2:
(composition is the high-titanium type vanadium iron ore concentrate: TFe 62.0%, FeO 30.6%, Fe
2O
355.0%, V
2O
50.57%, TiO
26.1%, Cr
2O
30.75%, SiO
21.6%, Ae
2O
32.5%, CaO 1.79%, MgO 2.6%) add the melting of CaO benefit carbon through prereduction hot charging electric furnace, the control vanadium reduces and is the melting terminal point into iron rate 71%.The hot metal composition of output is: C 2.72%, V 0.38%, Cr 0.55%, Ti 0.18%, Si 0.16%, Si 0.20%.The composition that contains the rich titanium slag of vanadium is TiO
226.50%, V
2O
50.62%, Cr
2O
30.75%, CaO 17.50%, MgO 10.20%, SiO
220.6%, Al
2O
319.31%, FeO 1.05%.The rate of tapping a blast furnace and slag rate are respectively: 610kg Fe/t concentrate, 230kg contain the rich titanium slag of vanadium/t concentrate.Contain the vanadium chromium hot melt and contain the raw material of vanadium chromium steel slag, contain the rich titanium slag of vanadium as the raw material of producing titanium carbide vanadium chromium slag as the attached product of steel-making.
Contain the single slag direct steelmaking of vanadium chromium hot melt Converter Oxigen Blowing:
Contain the single slag steel-making of vanadium chromium hot melt Converter Oxigen Blowing, control hot metal ratio slag=1000: 80 is produced qualified trade mark molten steel, contains vanadium chromium steel slag ingredient and is: MFe 2.10%, FeO 11.0%, V
2O
58.93%, Cr
2O
310.80%, SiO
25.31%, CaO 45.52%, MgO 7.10%, TiO
23.75%.Contain the raw material of vanadium chromium steel slag as subsequent production titanium carbide vanadium chromium slag.
Contain vanadium chromium steel slag and produce titanium carbide vanadium chromium slag with containing the carbonization of the rich titanium slag electric furnace melting and reducing of vanadium:
The reduction and carbonization agent of using is coke powder (100 orders account for 80%), and its composition is: fixed carbon 84%, ash content 14%, volatile matter 1.50%.In containing the ratio that the rich titanium slag ratio of vanadium contains vanadium chromium steel slag ratio coke powder=800: 170: 167, with some amount contain vanadium chromium steel slag and the coke powder mixing is pressed into the oven dry of slag carbon dust ball.The liquid state of some amount is contained the rich titanium slag of the vanadium carbonization electric furnace of packing into, add slag carbon dust ball, under 1500～1650 ℃ temperature, carry out reduction and carbonization and produce titanium carbide vanadium chromium slag in containing the ratio of the rich titanium slag of vanadium than slag carbon dust ball=800: 337.TiO
2, V
2O
5, Cr
2O
3The reduction and carbonization rate be 90% o'clock, the composition of titanium carbide vanadium chromium slag is: TiC 14.78%, TiO
22.19%, V
2C 1.18%, V
2O
50.26%, Cr
4C 1.57%, Cr
2O
30.24%, MFe 2.14%, CaO 23.86%, MgO 9.41%, SiO
218.65%, Al
2O
317.71%, C 2.10%.Titanium carbide vanadium chromium slag is produced as low temperature chlorination and is contained vanadium TiCl
4Attached product contains Cr Cl
3The raw material of chloride residue.
The control of titanium carbide vanadium chromium slag fluidized-bed low temperature selective chlorination bed temperature:
Contain vanadium TiCl with titanium carbide vanadium chromium slag for producing
4Raw material exists in continuous charging continuous discharging slag mode
Chlorination in the fluidized-bed of 2000mm, using the percentage volumetric molar concentration of chlorine is 80%, the unit surface production capacity of fluidized-bed is the thick TiCl of 25t
4/ m
2.d, the volatilize TiCl of treatment fluidized bed production capacity 10%
4Mud, the heat lost by radiation of fluidized-bed outer wall is emitted 3.5% of total heat for chlorination reaction in the bed, the concentrated phase area bed temperature is controlled at 500 ± 50 ℃, nickelic stainless steel water (vapour) the cooler inlet water temperature that is installed on the bed concentrated phase area is 20 ℃, outlet water temperature when being 60 ℃, and the total heat conduction area of water (vapour) water cooler is about 35m
2Being converted into external diameter is that 0.06m, length are the nickelic stainless steel sleeve tubular type watercooler of 2m, then needs at the bed concentrated phase area 93 above-mentioned telescoping watercoolers to be set.
The thick TiCl that the low temperature selective chlorination is worked continuously and produced
4Contain VOCl
36.99%, Cl
20.25%, FeCl
30.03%, chloride residue CrCl
35.64%.Respectively as refining TiCl
4With extraction V
2O
5, Cr
2O
3Raw material.
The startup of titanium carbide vanadium chromium slag low temperature selective chlorination fluidized-bed:
Startup material when the titanium carbide vanadium chromium slag that uses with normal chlorination operation starts as fluidized-bed, starting bed depth is 1/4 of normal chlorination operation, to start the material be preheating to 270 ℃ after, feeding starts fluidized-bed with dry air or nitrogen dilution to the low dense chlorine of percentage volumetric molar concentration 32%, enable water (vapour) water cooler of being located in the bed simultaneously, when reducing to 450 ℃ Deng bed concentrated phase area layer temperature, starting charging machine feeds intake in fluidized-bed, and increase the chlorine gas concentration that feeds in the fluidized-bed simultaneously when bed concentrated phase area temperature is raised to 550 ℃, stop to increase chlorine gas concentration.So repetitive operation makes bed height reach design level, can change normal gasification operation over to.
Contain vanadium TiCl
4Titanium vanadium separation and purification TiCl
4:
Implement the above-mentioned vanadium TiCl that contains with high-quality turps
4Titanium vanadium separation and purification TiCl
4The terebinthine add-on of high-quality is for containing vanadium TiCl
41.13% of quality is perhaps for containing vanadium TiCl
4Middle VOCl
30.162 times of mass percent.To be contained vanadium TiCl by purified
4Put into reactor, under normal temperature and pressure and agitation condition, the high-quality turps of calculated amount added lentamente contain vanadium TiCl
4In, thereafter mixture heating up was carried out to 70-137 ℃ of different temperature levels and time that the vanadium titanium separates and refining reaction 2.5 hours.The mixture of termination reaction is through sedimentation, and supernatant liquor must contain the smart TiCl of V＜0.0007% through simple distillation
4Product, from concentrate to smart TiCl
4The rate of recovery of titanium reaches 80%.Kettle base solution and subsider underflow are to be rich vanadium TiCl
4Mud is as extracting V
2O
5Raw material.
Rich vanadium TiCl
4Mud extracts V
2O
5:
With rich vanadium TiCl
4Be sprayed on to the mud quantitative and even bed temperature and be in 230 ℃ the external-heat inert particle fluidized bed concentrated phase layer and carry out drying, the dry mixed gas that produces discharges fluidized-bed after TiCl is reclaimed in dedusting, condensation
4, the TiCl of recovery
4Smart TiCl is produced in the supernatant liquor distillation of incorporating into behind the vanadium titanium separating reaction
4, dedusting is incorporated the dried slag work of rich vanadium of discharging from the fluidized-bed upflow tube into and is extracted V
2O
5Raw material.The dried slag ingredient of rich vanadium is V 20.12%, Ti 14.232%, C 7.50%, Cl
-156.2%.
Press TiO in the dissolution fluid
2Mass concentration be that 175 grams per liters calculate 0.7M dilute hydrochloric acid consumption, dissolve the VOCl in the rich vanadium slag
2And TiCl
3, the clear liquid of filtering carbon dust and other foreign material adds the sodium chlorate solution with Ti
3+Be oxidizing to 3.5 grams per liters, add the crystal seed hydrolysis metatitanic acid that settles out then, the liquid of filtering metatitanic acid adds the sodium chlorate solution once more with Ti
3+All be oxidized to Ti
4+, when transferring pH extremely zero, titanium all is precipitated out with NaOH solution; Perhaps the clear liquid of filtering carbon dust and other foreign material directly transfers PH to zero neighbouring with Ti as NaOH solution
3+With Ti (OH)
3All settle out, the sedimentary rich vanadium scavenging solution of filtering filtering is by prior art for preparing ammonium hexavanadate and then production V
2O
5The vanadium extraction tail washings adds milk of lime and reclaims the heavy calcium of ammonia still process behind the residual vanadium, and the heavy surplus liquid of calcium send chlor-alkali workshop preparation electrolytic solution.From the concentrate to V
2O
5The rate of recovery of product vanadium is 80%.
From chloride residue, extract Cr
2O
3:
Contain trace Cr Cl with chloride residue quality 40%
2, concentration is that the dilute hydrochloric acid of 0.4M leaches chloride residue stripping CrCl for twice
3Leach for the first time clear liquid and transfer pH to 9.2 with milk of lime, settling out contains Mg (OH)
2Cr (OH) Deng impurity
3Precipitation, the precipitation that leaches is dissolved Cr (OH) with NaOH solution
3Make it with CrO
2 -Change solution over to, contain CrO
2 -Cleaner liquid produce Cr with known method
2O
3Product leaches as the next batch chloride residue and leach Cr first for the second time
2Cl
3Usefulness, Cr
2O
3Yield be 70%.
Embodiment 3:
The blast-furnace smelting composition is: TFe 51.52%, FeO 32.26%, V
2O
50.49%, Cr
2O
30.03%, TiO
212.73%, SiO
23.37%, MgO 4.66%, Al
2O
34.59%, S 0.24%) the high-titanium type vanadium iron ore concentrate, produce and to contain the attached product of vanadium chromium hot melt and contain the rich titanium slag of vanadium, vanadium reduces into iron rate 75%.Containing vanadium chromium hot melt composition is: C 4.3%, SiO 20.2%, Ti 0.2%, V 0.34%, Cr 0.06%.The composition that contains the rich titanium slag of vanadium is TiO
223.10%, V
2O
50.27%, Cr
2O
30.014%, CaO 26.80%, FeO 0.5%, MgO 8.08%, SiO
223.336%, Al
2O
313.80%, TFe 2.1%, slag ratio iron=0.8.Contain the raw material of vanadium chromium hot melt, contain the rich titanium slag of vanadium as the raw material of producing titanium carbide vanadium chromium slag as the attached product chrome-bearing steel slag of steel-making.
Contain the single slag direct steelmaking of vanadium chromium hot melt Converter Oxigen Blowing:
Contain the single slag steel-making of vanadium chromium hot melt Converter Oxigen Blowing, control hot metal ratio slag is=1000: 80, produces qualified trade mark molten steel, contains vanadium chromium steel slag ingredient and is: MFe 2.05%, FeO 12.50%, SiO
29.16%, CaO 47.56%, Al
2O
37.75%, TiO
23.80%, V
2O
57.25%, Cr
2O
30.06%.Contain the raw material of vanadium chromium steel slag as subsequent production titanium carbide vanadium chromium slag.
Contain vanadium chromium steel slag and produce titanium carbide vanadium chromium slag with containing the carbonization of the rich titanium slag electric furnace melting and reducing of vanadium:
The reduction and carbonization agent of using is pulverized anthracite (100 orders account for 80%), and its composition is: fixed carbon 78%, ash content 11.0%, volatile matter 11.0%.In containing the ratio that the rich titanium slag ratio of vanadium contains vanadium chromium steel slag ratio pulverized anthracite=800: 120: 131, contain vanadium chromium steel slag and the pulverized anthracite mixing of some amount are pressed into the oven dry of slag carbon dust ball, the liquid state of some amount is contained the rich titanium slag of the vanadium carbonization electric furnace of packing into, add slag carbon dust ball in containing the ratio of the rich titanium slag of vanadium than slag carbon dust ball=800: 251, reduction and carbonization is produced titanium carbide vanadium chromium slag under 1500～1650 ℃ temperature.TiO
2, V
2O
5, Cr
2O
3The reduction and carbonization rate be 90% o'clock, the composition of titanium carbide vanadium chromium slag is: TiC 14.21%, TiO
22.10%, V
2C 0.70%, V
2O
50.12%, Cr
4C 0.05%, CaO 30.16%, MgO 8.28%, SiO
223.01%, Al
2O
314.36%, TiFe 3.38%, C 3.0%.Gained titanium carbide vanadium chromium slag is produced as low temperature chlorination and is contained vanadium TiCl
4Attached product contains Cr Cl
3The raw material of chloride residue.
The control of titanium carbide vanadium chromium slag fluidized-bed low temperature selective chlorination bed temperature:
Contain vanadium TiCl with titanium carbide vanadium chromium slag for producing
4Raw material exists in continuous charging continuous discharging slag mode
Chlorination in the fluidized-bed of 2000mm, using the percentage volumetric molar concentration of chlorine is 80%, the unit surface production capacity of fluidized-bed is the thick TiCl of 25t
4/ m
2.d, the TiCl4 mud of the treatment fluidized bed production capacity 10% of volatilizing, the heat lost by radiation of fluidized-bed outer wall is for emitting 3.5% of total heat for chlorination reaction in the bed, the concentrated phase area bed temperature is controlled at 500 ± 50 ℃, nickelic stainless steel water (vapour) the cooler inlet water temperature that is installed on the bed concentrated phase area is 20 ℃, outlet water temperature when being 60 ℃, and the total heat conduction area of water (vapour) water cooler is about 33m
2Being converted into external diameter is that 0.06m, length are the nickelic stainless steel sleeve tubular type watercooler of 2m, then needs at the bed concentrated phase area 88 above-mentioned telescoping watercoolers to be set.
The thick TiCl that the low temperature selective chlorination is worked continuously and produced
4Contain VOCl
34.57%, Cl
20.22%, FeCl
30.02%, chloride residue contains CrCl
30.15%.Contain vanadium TiCl
4Smart TiCl is produced in separation as the vanadium titanium
4Raw material.
The startup of titanium carbide vanadium chromium slag low temperature selective chlorination fluidized-bed:
With quartz sand with (TiC+V in the above-mentioned titanium carbide vanadium chromium slag
2C+Cr
4C (Cr)+1/2Fe) mass concentration is diluted to 4.0%, startup material when starting as fluidized-bed, starting bed depth is 1/5 of normal chlorination operation, after the startup material is preheating to 230 ℃, feed the chlorine startup fluidized-bed that normal chlorination operation is used, enable the watercooler in bed simultaneously.When waiting the concentrated phase area bed temperature to reduce to 450 ℃ after logical chlorine starts, start charging machine and add the carbonization vanadium-titanium-chromium slag that normal chlorination operation is used, feed in raw material and stop to feed in raw material when making the concentrated phase area bed temperature be promoted to 550 ℃, so repetitive operation makes bed height reach design level, can change normal gasification operation over to.
Contain vanadium TiCl
4Titanium vanadium separation and purification TiCl
4:
Implement the above-mentioned vanadium TiCl that contains with containing 2～3 five isocyclic naphthenic acid
4Titanium vanadium separation and purification TiCl
4The add-on of naphthenic acid is for containing vanadium TiCl as calculated
40.97% of quality is perhaps for containing vanadium TiCl
4Middle VOCl
30.212 times of mass percent.To be contained vanadium TiCl by purified
4Put into reactor, under normal temperature and pressure and agitation condition, the naphthenic acid of calculated amount added lentamente contain vanadium TiCl
4In, thereafter mixture heating up was carried out to 70-137 ℃ of different temperature levels and time that the vanadium titanium separates and refining reaction 2.1 hours.The mixture of termination reaction is through sedimentation, and supernatant liquor must contain the smart TiCl of V＜0.0007% through simple distillation
4Product, from concentrate to smart TiCl
4The rate of recovery of titanium reaches 80%.Kettle base solution and subsider underflow are to be rich vanadium TiCl
4Mud is as extracting high-purity V
2O
5Raw material.
Rich vanadium TiCl
4Mud extracts V
2O
5:
With rich vanadium TiCl
4Be sprayed on to the mud quantitative and even bed temperature and be in 230 ℃ the external-heat inert particle fluidized bed concentrated phase layer and carry out drying, the dry mixed gas that produces discharges fluidized-bed after TiCl is reclaimed in dedusting, condensation
4, the TiCl of recovery
4Smart TiCl is produced in the supernatant liquor distillation of incorporating into behind the vanadium titanium separating reaction
4, dedusting is incorporated the dried slag work of rich vanadium of discharging from the fluidized-bed upflow tube into and is extracted V
2O
5Raw material.The dried slag ingredient of rich vanadium is V 18.20%, Ti 13.72%, C 7.80%, Cl
-157.02%.
Press TiO in the dissolution fluid
2Mass concentration be that 185 grams per liters calculate, with 0.4M dilute hydrochloric acid consumption, dissolve the VOCl in the rich vanadium slag
3And TiCl
3, the clear liquid of filtering carbon dust and other foreign material adds the sodium chlorate solution with Ti
3+Be oxidizing to 3.5 grams per liters, add the crystal seed hydrolysis metatitanic acid that settles out then, the liquid of filtering metatitanic acid adds the sodium chlorate solution once more with Ti
3+All be oxidized to Ti
4+, when transferring pH extremely zero, titanium all is precipitated out with NaOH solution; Perhaps the clear liquid of filtering carbon dust and other foreign material directly transfers PH to zero neighbouring with Ti as NaOH solution
3+With Ti (OH)
3All settle out, the sedimentary rich vanadium scavenging solution of filtering is by the prior art for preparing ammonium hexavanadate and then produce high-purity V
2O
5Product.The vanadium extraction tail washings adds milk of lime and reclaims the heavy calcium of ammonia still process behind the residual vanadium, and the heavy surplus liquid of calcium send chlor-alkali workshop preparation electrolytic solution.
CrCl in the chloride residue
2Content is 0.15% only, does not have much extractions to be worth.CrCl
3Be slightly soluble in water (the water leaching test shows dissolution rate＜0.03%), needn't special disposal CrCl during the comprehensive utilization chloride residue
3
Claims (9)
1, from the high-titanium type vanadium iron ore concentrate, extracts the method for ferrotitanium vanadium, comprise the steps:
1. blast furnace or electric furnace ironmaking are adopted in ironmaking, and production contains the vanadium chromium hot melt and attached product contains the rich titanium slag of vanadium, adds CaO desulfurization residue adjustment in the smelting process, makes the reduction of vanadium appropriateness, and it is 60～78% that vanadium reduces into the iron rate;
2. single slag steel-making contains the single slag direct steelmaking of vanadium chromium hot melt oxygen blast in converter, and attached product contains vanadium chromium steel slag, control the hot metal ratio slag to equal 1000: 70～90;
3. electric furnace fusion selective reduction carbonization will add containing vanadium chromium steel slag and containing the fusion selective reduction carbonization in electric furnace of the rich titanium slag of vanadium of carbon dust, and the production carbonation rate is 80～95% titanium carbide vanadium chromium slag, and control reduction and carbonization temperature is 1450～1750 ℃;
4. titanium carbide vanadium chromium slag fluidized-bed low temperature selective chlorination is produced and is contained vanadium TiCl
4Contain CrCl with attached product
3Chloride residue;
5. the vanadium titanium separates, and directly reduces with cycloolefin or naphthenic acid to be dissolved in TiCl
4Middle VOCl
3, generate and be insoluble to TiCl
4VOCl
2, realize that the vanadium titanium separates, thus refining TiCl
4And the rich vanadium TiCl of attached product
4Mud;
6. from rich vanadium TiCl
4Extract V in the mud
2O
5
2, the method for from the high-titanium type vanadium iron ore concentrate, extracting the ferrotitanium vanadium as claimed in claim 1, it is characterized in that: described step is 3. in the electric furnace fusion selective reduction carbonization, to contain vanadium chromium steel slag and carbon dust by the mixed of determining, be pressed into the slag carbon dust ball of 20～30mm, dry again, slag carbon dust ball with contain the rich titanium slag of vanadium in the ratio of determining, titanium carbide vanadium chromium slag is produced in fusion selective reduction carbonization in electric furnace.
3, the method for from the high-titanium type vanadium iron ore concentrate, extracting the ferrotitanium vanadium as claimed in claim 1, it is characterized in that: described step is 4. in the titanium carbide vanadium chromium slag fluidized-bed low temperature selective chlorination, take the continuous charging continuous discharging slag between the fluidized bed chlorination operational period, thick TiCl is handled in volatilization
4The TiCl that production process produces
4Mud is provided with nickelic stainless steel water water cooler at the bed concentrated phase area and shifts out unnecessary reaction heat, bed concentrated phase area temperature is controlled in 400～600 ℃ the scope, guarantees to realize selective chlorination TiC, V
2C, Cr
4C or Cr productions contain vanadium TiCl
4, attached product contains CrCl
3The chlorination operation of chloride residue normally carry out.
4, the method for from the high-titanium type vanadium iron ore concentrate, extracting the ferrotitanium vanadium as claimed in claim 3, it is characterized in that: described step is 4. in the titanium carbide vanadium chromium slag fluidized-bed low temperature selective chlorination, fluidized-bed adds the soft heat point when starting〉700 ℃ difficult muriate, TiC+V in the titanium carbide vanadium chromium slag that normal chlorination operation is used
2C+Cr
4C+1/2Fe quality sum or TiC+V
2C+Cr+1/2Fe quality sum is diluted to 1～7% startup material when starting as fluidized-bed, and the chlorine that uses during with normal chlorination operation makes to start the gas starting fluidized-bed.
5, the method for from the high-titanium type vanadium iron ore concentrate, extracting the ferrotitanium vanadium as claimed in claim 3, it is characterized in that: described step is 4. in the titanium carbide vanadium chromium slag fluidized-bed low temperature selective chlorination, add dry air, nitrogen and other rare gas elementes, it is 20～50% low concentration chlorine that the chlorine that uses during with normal chlorination operation is diluted to the percentage volumetric molar concentration, startup gas when starting as fluidized-bed, the titanium carbide vanadium chromium slag that normal chlorination operation is used are made to start material and are started fluidized-bed.
6, as claim 4 or the 5 described methods of from the high-titanium type vanadium iron ore concentrate, extracting the ferrotitanium vanadium, it is characterized in that: described step is 4. in the titanium carbide vanadium chromium slag low temperature fluidized-bed selective chlorination, starting the preheating temperature of material in fluidized-bed is 180～450 ℃, 1/5～1/3 when bed concentrated phase area height was normal chlorination operation when fluidized-bed started.
7, the method for extracting the ferrotitanium vanadium from the high-titanium type vanadium iron ore concentrate as claimed in claim 1 is characterized in that: described step will be contained vanadium TiCl by purified during 5. the vanadium titanium separates
4Put into reactor, under normal temperature and pressure and agitation condition, the cycloolefin or the naphthenic acid that add calculated amount lentamente, mixture heating up to 70-137 ℃ different temperature and time level carried out vanadium titanium separating reaction 1.5～2.5 hour thereafter, the mixture of termination reaction is through sedimentation, and supernatant liquor is produced through simple distillation and contained V＜0.0007%, meets the smart TiCl that chloride process titanium dioxide is produced required quality
4, kettle base solution and subsider underflow are to be rich vanadium TiCl
4Mud, the add-on of cycloolefin or naphthenic acid is for containing vanadium TiCl
4Middle VOCl
30.15～0.30 times of mass percent.
8, the method for from the high-titanium type vanadium iron ore concentrate, extracting the ferrotitanium vanadium as claimed in claim 6, it is characterized in that: described cycloolefin is turps and fraction products thereof, described naphthenic acid is for containing 2～3 five isocyclic naphthenic acid.
9, the method for extracting the ferrotitanium vanadium from the high-titanium type vanadium iron ore concentrate as claimed in claim 1 is characterized in that: described step 4. attached product contain CrCl
3Chloride residue be used to extract Cr
2O
3In, be 0～0.5M, contain trace Cr Cl with concentration of hydrochloric acid
2, quality is the solution of chloride residue 25～45%, secondary leaches the CrCl in the stripping chloride residue
3, leach filtrate for the first time and use milk of lime adjust pH to 8.5～9.5, settling out contains Mg (OH)
2Cr (OH)
3Precipitation, the precipitation that leaches is dissolved Cr (OH) with NaOH solution
3Make it with CrO
2 -Change solution over to, contain CrO
2 -Alkaline cleaner liquid be used for producing Cr
2O
3Lixivium leaches CrCl first as the next batch chloride residue for the second time
2Usefulness.
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| CN113072150B (en) * | 2021-04-22 | 2022-06-17 | 重庆理工大学 | Method for preparing iron-titanium-vanadium ternary inorganic polymeric flocculant based on sulfuric acid acidolysis vanadium-titanium magnetite two-step method |
| CN113846236B (en) * | 2021-09-18 | 2022-11-25 | 中南大学 | Method for removing vanadium, manganese and chromium impurities in acid-soluble titanium slag |
| CN117488104A (en) * | 2023-11-02 | 2024-02-02 | 聚挪机械科技(上海)有限公司 | Method for preparing high-vanadium slag by treating vanadium-containing slurry by fluidized bed |
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| CN1033264A (en) * | 1987-10-27 | 1989-06-07 | 冶金工业部攀枝花钢铁公司钢铁研究院 | The method of preparing titanic chloride using carbon-containing slag |
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|---|---|---|---|---|
| US4117076A (en) * | 1976-04-12 | 1978-09-26 | Quebec Iron And Titanium Corporation | Titanium slag-coke granules suitable for fluid bed chlorination |
| CN1033264A (en) * | 1987-10-27 | 1989-06-07 | 冶金工业部攀枝花钢铁公司钢铁研究院 | The method of preparing titanic chloride using carbon-containing slag |
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