CN105671306A - Method for separating iron, vanadium and titanium in vanadic titanomagnetite - Google Patents
Method for separating iron, vanadium and titanium in vanadic titanomagnetite Download PDFInfo
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- CN105671306A CN105671306A CN201610162239.8A CN201610162239A CN105671306A CN 105671306 A CN105671306 A CN 105671306A CN 201610162239 A CN201610162239 A CN 201610162239A CN 105671306 A CN105671306 A CN 105671306A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1204—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent
- C22B34/1209—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 preliminary treatment of ores or scrap to eliminate non- titanium constituents, e.g. iron, without attacking the titanium constituent by dry processes, e.g. with selective chlorination of iron or with formation of a titanium bearing slag
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1218—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
Abstract
The invention provides a method for separating iron, vanadium and titanium in vanadic titanomagnetite. According to the method, most of vanadium is left in slag by controlling a direct reduction temperature, iron enters a magnetically-separated substance, a by-product sodium sulphate obtained through fractional crystallization carried out through sodium-modification vanadium extraction wastewater, is added in vanadium-titanium slag after magnetic separation, and vanadium is extracted in a water-leaching manner after oxidation roasting, so as to obtain vanadium-containing solution and titanium-rich slag. According to the method, on one hand, the recovery rate of vanadium is increased, on the other hand, due to a small amount of the vanadium-titanium slag, lots of sodium salt has no need to be added, and moreover, the small amount of the added sodium salt is treated by virtue of the sodium-modification vanadium extraction wastewater to obtain the by-product, thus cost is saved, secondary resource recycling is realized, and economic benefits are improved; and in addition, the magnetically-separated substance obtained in a manner of carrying out magnetic separation at first, and then adding sodium salt in vanadium-titanium slag and carrying out oxidation roasting, is relative pure compared with the magnetically-separated substance obtained in a manner of adding sodium salt and carrying out oxidation roasting at first, and then carrying out magnetic separation, a sulphur content of the magnetically-separated substance is low, and the quality is guaranteed.
Description
Technical field
The present invention relates to metallurgical technology field, be specifically related to a kind of method separating ferrum in vanadium titano-magnetite, vanadium, titanium.
Background technology
China's Panxi Diqu is richly stored with v-ti magnetite ore resources, at present, blast furnace bof process is still the main stream approach processing vanadium titano-magnetite, but the progress along with society, traditional process is also faced with the energy and environmental protection pressure that grow with each passing day, and the dependence of coking coal particularly becomes the bottleneck problem restricting its development. What is more important, blast furnace bof process processes vanadium titano-magnetite can only reclaim ferrum therein and vanadium, and titanium elements enters in blast furnace slag, due to the relatively low (TiO in blast furnace slag of grade2Content is 22%～25%), still it is used without effective ways at present, causes the waste of valuable titanium resource.
For improving the level of comprehensive utilization of ferrum, vanadium, titanium in schreyerite, insider is exploring new schreyerite always and is smelting approach. In recent years, the molten division technique of direct-reduction receives much concern, the ferrum in schreyerite, vanadium and titanium can be reclaimed because of it simultaneously, but this technique efficiency of energy utilization is not high, particularly in molten point process, in order to make more vanadium entrance molten iron make, electric furnace power consumption is high, refractory corrosion is serious, ultimately result in product cost height, lack the market competitiveness. In order to avoid the molten point of a large amount of power consumption of process, the relatively low direct-reduction magnetic separation process of normal-temperature operation, energy consumption is taken seriously gradually, mentions that more method includes following 3 kinds at present:
(1) high-temperature direct reduction produces the ferromagnetic choosing of pearl and separates ferrum and vanadium titanium, the method general control reduction temperature is more than 1300 DEG C, iron oxides is reduced, metallic iron is reunited and grows up, easily realize slag sluicing system, but this method Direct Reduction requires that temperature is high, the resistance to elevated temperatures of equipment is required significantly high, Maintenance and Repair are complicated, the more important thing is that the response rate of vanadium is not high, there are about the vanadium of about 50% and enter magnetic separation thing, and the vanadium of 50% enters slag phase, vanadium does not have Relatively centralized, and recovery difficult increases.
(2) low temperature direct-reduction magnetic separation separation ferrum and vanadium titanium, general control reduction temperature is below 1100 DEG C, although can retain in the vanadium titanium slag after most vanadium stays magnetic separation, but owing to reaction temperature is low, the reunion of metallic iron is insufficient, and magnetic separation process ferrum is not thorough with separating of titanium elements so that in magnetic separation thing, Iron grade is not high, in vanadium titanium slag, titanium grade is not high, and value of the product reduces.
(3) additive reduction roasting water logging vanadium extraction magnetic separation separation ferrum and titanium are added, this technique is capable of the separation of ferrum, vanadium, titanium, however it is necessary that the substantial amounts of sodium salt additive of addition, generally needed to be added about the 20% of concentrate quality even more, so many sodium salt be follow-up solution containing vanadium, tailings harmless treatment bring a lot of problem, part element sulphur enters in magnetic separation thing simultaneously, pollutes magnetic separation thing, limits product and uses scope.
Publication number is the patent of invention of CN104263871A, disclose the smelting process of a kind of vanadium titano-magnetite, coal-based direct reduction-magnetic separation process is adopted to process vanadium titano-magnetite, this invention it is important that magnetic separator and relevant auxiliary equipment, description for technique is very simple, present invention focuses on the improvement to technique.
Publication number is the patent of invention of CN104212927A, disclosing a kind of vanadium titano-magnetite is the production technology that raw material carrys out Magnetite (processed), the method adopting tunnel kiln direct reduced-magnetic separation-magnetic separation thing secondary direct-reduction carrys out producing iron powder, with the present invention's, this invention differs primarily in that the restriction scope to reducing condition is dramatically different, simultaneously, the present invention proposes the separation-extraction technology after direct reduction of V-Ti magnetite and magnetic separation to the middle vanadium of vanadium titanium slag and titanium, and in the patent of invention that publication number is CN104212927A and the separation and Extraction of not mentioned vanadium, titanium.
Publication number is the patent of invention of CN103757199A, propose a kind of method utilizing high-chromic vanadium titanium magnet ore concentrate to prepare vanadium chromium titanium slag, ferrum is separated by the method adopting direct-reduction-magnetic separation, obtain vanadium chromium titanium slag, the present invention differring primarily in that except separating except ferrum element with it, is also easily separated vanadium and titanium.
Publication number is the patent of invention of CN103526051A, propose the processing method of ferrum, vanadium and titanium in a kind of schreyerite, by pressure ball after schreyerite, sodium sulfate, reducing agent and binding agent dispensing by a certain percentage, in rotary hearth furnace, under 1000～1300 DEG C of conditions, roasting 20～60min obtains metallized pellet, leach after the metallization group of going is broken, obtain solution containing vanadium; Obtain rich iron charge and rich-titanium material through two-stage magnetic separation after extractum is broken. Patent of the present invention be different in that from schreyerite to extract from this patent ferrum, vanadium, titanium method different, the present invention adopts reduction roasting-magnetic separation process to obtain rich iron charge and vanadium titanium slag, and then vanadium titanium slag carries out subsequent treatment separation v element and titanium elements. Publication number is the method for the patent of invention employing reduction roasting of CN103526051A, and then water logging vanadium extraction, after vanadium extraction, residue adopts magnetic separation process separation ferrum and titanium. Although two patents have certain overlap in process choice, but the substantially separation sequence difference of ferrum, vanadium, titanium, and the present invention is not related to add substantial amounts of sodium salt additive, the later stage processes simple, and the amount opposing metallic pellet amount of vanadium titanium slag to reduce about 2/3, processing cost reduces.
Publication number is that the patent of invention of CN103468849A proposes a kind of external heated shaft furnace reduction grinding sefstromite concentrate and prepares the technique of micro alloy iron powder, and its inventive point is external heated shaft furnace technology transplant to be come, and substitutes tunnel cave. By comparison, the present invention is more focused on the development innovation of Technology.
Publication number is that the patent of invention of CN105018721A proposes and a kind of separates the method for ferrovanadium titanium in vanadium titano-magnetite, the separation of ferrum in schreyerite, vanadium and titanium is realized by adding sodium salt-reduction roasting-leaching vanadium extraction-series of steps such as filtering residue magnetic separation separation ferrum and vanadium in concentrate, but, this technique needs add substantial amounts of sodium salt additive, tailings, filtrate intractability are big, and environmental issue is difficult to solve. By comparison, present invention process is added without additive during reduction roasting-magnetic separation, only adds a small amount of additive in vanadium titanium slag separation process, and additive capacity is about in this patent of invention the 1/10 of additive amount, considers of great advantage from economic and environment-friendly angle.
The patent of invention that publication number is CN104789726A proposes a kind of method separating ferrum in vanadium titano-magnetite, vanadium, titanium, it is characterized in that adopting the method production pearl ferrum passing into high-temperature flue gas externally to rotary hearth furnace, then adopt the method for magnetic separation to realizing the separation of ferrum element and other two kinds of elements, then realized the separation of vanadium and titanium by the method for oxidizing roasting, water logging vanadium extraction. The present invention and this patent are distinctive in that the reduction temperature scope of the present invention is relatively low, do not produce iron shot, because experiment proves, in time producing pearl ferrum, the vanadium of nearly 50% can enter in magnetic separation thing, and the vanadium of 50% is stayed in vanadium titanium slag, thus causing that v element yield is low. The present invention controls reduction temperature so that ferrum can reduce, and has the vanadium of about 80% to stay in vanadium titanium slag during magnetic separation, improves the yield of vanadium.
Summary of the invention
Instant invention overcomes the deficiencies in the prior art, it is provided that solve.
For achieving the above object, the present invention is by the following technical solutions:
A kind of method separating ferrum in vanadium titano-magnetite, vanadium, titanium, it is characterised in that it comprises the following steps:
Step a, after sefstromite concentrate, reducing agent and bonding agent being mixed by a certain percentage, makes pelletizing or briquetting;
Step b, carries out reduction roasting 3-5h by the pelletizing made in step a or briquetting when temperature is 1100-1200 DEG C;
Step c, cools down the pelletizing of reduction treatment in step b or briquetting or adopts quenching cooling of fetching water, the metallized pellet after cooling or briquetting are carried out magnetic separation, obtains magnetic separation thing and vanadium titanium slag when protective atmosphere;
Step d, adds the sodium salt of 5-10% in the step c vanadium titanium slag obtained; Sodium salt is sodium sulfate or sodium carbonate;
Step e, step d will add vanadium titanium slag oxidizing roasting 1-2h under 1000-1200 DEG C of condition of sodium salt, the calcining that oxidizing roasting is obtained crushes, and then carries out water logging vanadium extraction 90-100 DEG C of water bath with thermostatic control and when being stirred, is filtrated to get solution containing vanadium and Ti-enriched slag.
Further technical scheme is, controlling the mol ratio of carbon and oxygen in the compound of sefstromite concentrate, reducing agent and bonding agent composition in described step a is 1.0-1.2.
Further technical scheme is, described reducing agent is anthracite or coke powder, and described bonding agent is bentonite.
Further technical scheme is, in described step b, the reaction atmosphere of reduction roasting is reducing atmosphere, and concentration≤2.0% of oxygen in this reducing atmosphere.
Further technical scheme is, the consersion unit used in described step b is rotary kiln, rotary hearth furnace or shaft (tower) furnace.
Further technical scheme is, carries out magnetic separation after the metallized pellet after cooling or briquetting being crushed to its particle diameter < 0.074mm in described step c, and the magnetic field intensity of magnetic separation is 100-200mT.
Further technical scheme is, the sodium salt in described step d can adopt the side-product that vanadium extracting waste water crystallization obtains, this side-product sulfur acid sodium 98%, liquid containing ammonium sulfate 1%.
Further technical scheme is, the calcining in described step e, oxidizing roasting obtained is crushed to its particle diameter < 0.074mm, then carrying out water logging vanadium extraction 90-100 DEG C of water bath with thermostatic control and when being stirred, the mass ratio of described calcining and water is 1:4～6.
Further technical scheme is, the method also includes, as the raw material of sulfate process titanium dioxide after the Ti-enriched slag drying later using removing v element.
In the technical program, processed by agglomeration after sefstromite concentrate, reducing agent and bonding agent are mixed by a certain percentage, adopt carbonaceous reducing agent (such as, anthracite or coke powder), controlling the mol ratio of carbon and oxygen in compound is 1.0～1.2, being expressed as C/O=1.0～1.2, wherein carbon is from the fixed carbon content in carbonaceous reducing agent, and oxygen is from the Fe in sefstromite concentrate2O3And FeO.
Carbon in strict control compound, oxygen mol ratio are obtained in that the stable metallization material at certain level of reduction degree, general degree of metalization (MFe/TFe) represents the reducing degree of the metallization material after reduction roasting, degree of metalization is high, such as MFe/TFe >=95%, showing that reduction is comparatively thorough, the iron oxides of the overwhelming majority has been reduced to metallic iron. Degree of metalization is low, such as MFe/TFe≤50%, then it represents that reducing degree is not high, and only the ferrum of less than half is reduced and exists with the form of metallic iron.
Reduction process is mainly the oxygen that carbon element is captured in iron oxides, and generates the process of CO, it is possible to represent with following two equation:
Fe2O3+ 3C=2Fe+3CO;
FeO+C=Fe+CO
Owing to reaction temperature is higher than 1000 DEG C, thus CO can stable existence, theoretically, as C/O=1.0, iron oxides can react completely generation metallic iron. Certainly part CO is had to may proceed to participate in reduction reaction and generate CO2, but under the high temperature conditions, part carbon element certainly will with the O in surrounding atmosphere2Occur chemical reaction thus consuming partial reduction agent. Suitable C/O is explored by carrying out substantial amounts of experiment, it is shown that when C/O=1.0～1.2, under the reaction temperature of 1100 DEG C～1200 DEG C, the degree of metalization of metallized pellet can stably more than 92%, simultaneously possibly together with the residual carbon content of 0～3% in pelletizing.
If C/O < 1.0 in compound, then reduction dosage is on the low side, under the reaction temperature of 1100 DEG C～1200 DEG C, it is difficult to obtain the metallized pellet of degree of metalization >=92% continually and steadily, degree of metalization is on the low side, causes follow-up magnetic separation weak effect, and slag sluicing system is not thorough; As C/O > 1.2, reducing agent is excessive more, under the reaction temperature of 1100 DEG C～1200 DEG C, although the metallized pellet of degree of metalization >=92% can be obtained, but carbon element surplus one is to cause the waste of resource, improve production cost, two is cause that the residual carbon content in metallized pellet raises, and in the vanadium titanium slag after magnetic separation, carbon content can substantially rise, and reduces the grade of vanadium and titanium, meanwhile, inhibition is played in the oxidizing roasting after adding sodium salt. In a word, it is necessary to control the C/O in mixed material at optimum range, to ensure good ferrum, vanadium, titanium separating effect.
Owing to controlling reduction temperature below 1100 DEG C, although can retain in the vanadium titanium slag after most vanadium stays magnetic separation, but owing to reaction temperature is low, the reunion of metallic iron is insufficient, magnetic separation process ferrum is not thorough with separating of titanium elements, make Iron grade in magnetic separation thing not high, in vanadium titanium slag, titanium grade is not high, value of the product reduces, control reduction temperature more than 1300 DEG C simultaneously, iron oxides is reduced, metallic iron is reunited and grows up, easily realize slag sluicing system, but this method Direct Reduction requires that temperature is high, the resistance to elevated temperatures of equipment is required significantly high, Maintenance and Repair are complicated, so the pelletizing made in step a or briquetting are carried out reduction roasting 3-5h by the technical program when temperature is 1100-1200 DEG C, by carrying out reduction roasting under these conditions, first overcome temperature lower than 1100 DEG C or temperature higher than 1300 DEG C exist defects, simultaneously can abundant reduced iron.
The pelletizing of reduction treatment in step b or briquetting are cooled down when protective atmosphere or adopt quenching cooling of fetching water by the technical program; metallized pellet after cooling or briquetting are carried out brokenly mill process so that metallized pellet powder particle size < 0.074mm. Metallized pellet is carried out wet magnetic separation, and magnetic field intensity is 100-200mT, can obtain the magnetic separation thing of TFe >=80%, and remainder is vanadium titanium slag, thus realizing ferrum and the separation of vanadium titanium.
In magnetic separation process, raw meal particle size and magnetic field intensity are the principal elements affecting magnetic separation effect. By direct-reduction roasting, degree of metalization >=92% in metallized pellet, namely having the ferrum element of more than 92% to exist with the form of metallic iron, residue ferrum element is many to be existed with FeO form. Metallic iron is magnetic, and FeO does not have magnetic. During magnetic separation, metallic iron microgranule enters in magnetic separation thing, FeO, SiO2、CaO、MgO、Al2O3、TiO2、V2O5Enter in vanadium titanium slag Deng namagnetic substance. If the particle diameter that metallized pellet breaks mill is excessive, then iron granule and other nonmagnetics still can be combined closely, and necessarily selected together with close nonmagnetics impurity in combination by iron granule during magnetic separation, and in magnetic separation thing, Iron grade declines accordingly; If the broken abrasive particle footpath of metallized pellet is too small, although favourable for selecting of ferrum, but have to considering that granularity diminishes the high request to equipment, ore grinding cost improves accordingly simultaneously. Accordingly, it would be desirable to take into account magnetic separation effect and economy.
The present invention determines the technological parameter comparatively optimized on the basis of great many of experiments, metallized pellet particle diameter < 0.074mm is industrially easily achieved, when this particle diameter, determine the scope of magnetic field intensity, i.e. 100～200mT, magnetic field intensity is too low, and magnetic separation thing amount is few, and the yield of ferrum is low; Magnetic field intensity is too high, and magnetic separation thing amount is many, but Iron grade declines, therefore, it is necessary to determine suitable magnetic field intensity scope, the quality to guarantee magnetic separation thing is relatively stable.
The vanadium titanium slag obtained in step c in the technical program adds the sodium salt of 5-10%, so being added without additive during reduction roasting-magnetic separation, only thus overcome in prior art at the vanadium titanium slag separation phase a small amount of sodium salt of addition and need to add substantial amounts of sodium salt additive, generally needed to be added about the 20% of concentrate quality even more, so many sodium salt be follow-up solution containing vanadium, tailings harmless treatment bring a lot of problem, part element sulphur enters in magnetic separation thing simultaneously, pollute magnetic separation thing, limit product and use the deficiency of scope.
Adopt simultaneously and climb the side-product that steel vanadium products factory sodium vanadium extracting waste water fractional crystallization obtains, this product sulfur acid sodium 98%, liquid containing ammonium sulfate 1%, about 1% is amounted to containing materials such as vanadium, magnesium, calcium, aluminum, adopt the sodium sulfate of this products substitution market purchasing and sodium carbonate while reaching instructions for use, can reducing cost of material, secondary resource is used adequately reasonably, and can receive good economic and social benefit.
By the vanadium titanium slag oxidizing roasting 1～2h under 1000～1200 DEG C of conditions by adding sodium salt in the technical program, the calcining that oxidizing roasting is obtained crushes, particle diameter < 0.074mm, water logging vanadium extraction is carried out 90～100 DEG C of waters bath with thermostatic control and when being stirred, the mass ratio of calcining and water is 1:(4～6), filter, obtain V2O5Concentration is the solution containing vanadium of 3.5～5.5g/L, and TiO2The Ti-enriched slag of content >=40%.
After sodium salt and the mixing of vanadium titanium slag, oxidizing roasting under 1000～1200 DEG C of conditions, then the barium oxide in vanadium titanium slag can with the vanadic acid sodium (Na of sodium salt generation chemical reaction generation solubility3VO4), oxidation calcining after broken is in water bath with thermostatic control with when being stirred, the vanadic acid sodium of solubility can dissolve in entrance water bath shampoo, owing to the composition of metallized pellet is relatively stable, the then stable components of vanadium titanium slag, so when the ratio aoxidizing calcining and the water-bath water yield is different, result in the difference of vanadium concentration in water bath shampoo, generally using in the industry V2O5Characterize total content of vanadium, therefore be typically expressed as V2O5Content is that certain value obtains solution containing vanadium.Filter in the tailings removing solution containing vanadium because of rich in TiO2, therefore it is called Ti-enriched slag.
In the technical program, the method also includes, and as the raw material of sulfate process titanium dioxide after the Ti-enriched slag drying later using removing v element, can utilize the waste material after processing fully by above-mentioned steps, so can save the energy and cost.
The present invention provides a kind of method separating ferrum in vanadium titano-magnetite, vanadium, titanium, adopts direct-reduction-magnetic separation-vanadium titanium slag sodium roasting-calcining water logging vanadium extraction PROCESS FOR TREATMENT sefstromite concentrate. making most vanadium stay in slag by controlling direct-reduction temperature, ferrum enters in magnetic separation thing, and the vanadium titanium slag after magnetic separation is separated adds the byproduct sulfite of sodium vanadium extracting waste water fractional crystallization, water logging vanadium extraction after oxidizing roasting, obtains solution containing vanadium and Ti-enriched slag. the method improves the response rate of vanadium on the one hand, on the other hand because the amount of vanadium titanium slag is less, therefore without adding substantial amounts of sodium salt, and, the a small amount of sodium salt added adopts the side-product that sodium vanadium extracting waste water obtains after processing, not only save cost, achieve secondary resource to recycle, and improve economic benefit, in addition, adopting first magnetic separation to add sodium salt again in vanadium titanium slag, to carry out the mode of oxidizing roasting more relatively pure than the magnetic separation thing that the mode being initially charged sodium salt reduction roasting and carrying out magnetic separation obtains, in order to save cost, usually, sodium salt all can select sodium sulfate, and containing element sulphur in sodium sulfate, according to the method restoring roasting after adding sodium salt, then in reducing roasting process, part element sulphur can be combined generation FeS with ferrum, and FeS also has magnetic, enter when metallized pellet being carried out magnetic separation in magnetic separation thing, thus the sulfur content improved in magnetic separation thing. if and the method that after selecting first reduction roasting, magnetic separation adds sodium salt oxidizing roasting, in magnetic separation step after the addition of sodium salt, in magnetic separation thing, sulfur content is low, and quality is protected.
Compared with prior art, the invention has the beneficial effects as follows:
What the present invention proposed separate ferrum in vanadium titano-magnetite, vanadium, titanium method can obtain the iron powder of TFe >=80%, V2O5Concentration is solution containing vanadium and the TiO of 3.5～5.5g/L2The Ti-enriched slag of content >=40%, it is achieved that recycling while three kinds of beneficial elements, economic and social benefit is obvious.
Detailed description of the invention
The present invention is further elaborated below.
A kind of method separating ferrum in vanadium titano-magnetite, vanadium, titanium, it comprises the following steps: step a, after sefstromite concentrate, reducing agent and bonding agent being mixed by a certain percentage, makes pelletizing or briquetting; Step b, carries out reduction roasting 3-5h by the pelletizing made in step a or briquetting when temperature is 1100-1200 DEG C; Step c, cools down the pelletizing of reduction treatment in step b or briquetting or adopts quenching cooling of fetching water, the metallized pellet after cooling or briquetting are carried out magnetic separation, obtains magnetic separation thing and vanadium titanium slag when protective atmosphere; Step d, the vanadium titanium slag obtained in step c adds the sodium salt of 5-10%; Step e, step d will add vanadium titanium slag oxidizing roasting 1-2h under 1000-1200 DEG C of condition of sodium salt, the calcining that oxidizing roasting is obtained crushes, and then carries out water logging vanadium extraction 90-100 DEG C of water bath with thermostatic control and when being stirred, is filtrated to get solution containing vanadium and Ti-enriched slag.
Embodiment 1,
It is raw material with Panzhihua Region sefstromite concentrate, for reducing agent, the process of the present invention is illustrated with anthracite coal dust.
The composition of sefstromite concentrate and anthracite coal dust is such as shown in table 1, table 2.
Concentrate composition climbed by table 1
Table 2 coal dust chemical composition
Agglomeration process needs to add binding agent to improve balling-up effect, and choosing bentonite is binding agent, and composition is as shown in table 3.
Table 3 bentonite composition
(1) sefstromite concentrate, anthracite coal dust, bentonite are carried out dispensing, pressure ball after mix homogeneously according to the ratio that mass ratio is 100:21.94:1, the pit coal mixing pelletizing that green-ball obtains carbon after drying, oxygen mol ratio is 1.2.
(2) utilizing rotary kiln that pit coal mixing pelletizing carries out direct-reduction, the temperature controlling rotary kiln high temperature reduction district is 1200 DEG C, and material is 3.0h in the time of staying of high-temperature region.
(3) to the metallized pellet water quenching cooling after reduction, to the metallized pellet pulverizing and jevigating cooled down to granularity < 200 order, magnetic separation, magnetic field intensity 150mT, obtain magnetic separation thing and vanadium titanium slag, this step achieves ferrum and the separation of vanadium titanium, obtains iron powder and TiO that TFe content is 83.96%2Content is 41.02%, V2O5Content is the vanadium titanium slag of 2.18%.
(4) sodium salt is added by the 8% of vanadium titanium slag quality, sodium salt can be sodium carbonate or sodium sulfate, preferably, adopt and climb the side-product that steel vanadium products factory sodium vanadium extracting waste water fractional crystallization obtains, this product sulfur acid sodium 98%, liquid containing ammonium sulfate 1%, containing materials about 1% such as vanadium, magnesium, calcium, aluminum, technological requirement is met it is demonstrated experimentally that be fully able to this product. Vanadium titanium slag mix homogeneously with sodium salt after pelletizing drying.
(5) adopt rotary kiln to add sodium salt vanadium titanium slag at 1200 DEG C of condition oxidizing roasting 1h, the calcining that oxidizing roasting is obtained crushes, granularity < 200 order, the mass ratio carrying out water logging vanadium extraction, calcining and water 95 DEG C of waters bath with thermostatic control and when being stirred is 1:5. Obtaining the solution containing vanadium that vanadium concentration is 4.15g/L after water logging vanadium extraction, secondary solution containing vanadium can as preparation V by evaporation and concentration and remove impurity2O5The material of product.
(6) raw material that can be used as sulfate process titanium dioxide after the later Ti-enriched slag of v element is dried, its TiO are removed2Content is 41.89%.
The essence of the present invention is described in detail by above detailed description of the invention; but protection scope of the present invention can not be limited; apparently; under the enlightenment of the present invention; the art those of ordinary skill can also carry out many improvement and modification; it should be noted that these improve and modify within the claims all dropping on the present invention.
Claims (9)
1. the method separating ferrum in vanadium titano-magnetite, vanadium, titanium, it is characterised in that it comprises the following steps:
Step a, after sefstromite concentrate, reducing agent and bonding agent being mixed by a certain percentage, makes pelletizing or briquetting;
Step b, carries out reduction roasting 3-5h by the pelletizing made in step a or briquetting when temperature is 1100-1200 DEG C;
Step c, cools down the pelletizing of reduction treatment in step b or briquetting or adopts quenching cooling of fetching water, the metallized pellet after cooling or briquetting are carried out magnetic separation, obtains magnetic separation thing and vanadium titanium slag when protective atmosphere;
Step d, adds the sodium salt of 5-10% in the step c vanadium titanium slag obtained; Sodium salt is sodium sulfate or sodium carbonate;
Step e, step d will add vanadium titanium slag oxidizing roasting 1-2h under 1000-1200 DEG C of condition of sodium salt, the calcining that oxidizing roasting is obtained crushes, and then carries out water logging vanadium extraction 90-100 DEG C of water bath with thermostatic control and when being stirred, is filtrated to get solution containing vanadium and Ti-enriched slag.
2. the method for ferrum, vanadium, titanium in separation vanadium titano-magnetite according to claim 1, it is characterised in that controlling the mol ratio of carbon and oxygen in the compound of sefstromite concentrate, reducing agent and bonding agent composition in described step a is 1.0-1.2.
3. the method for ferrum, vanadium, titanium in separation vanadium titano-magnetite according to claim 1 and 2, it is characterised in that described reducing agent is anthracite or coke powder, and described bonding agent is bentonite.
4. the method for ferrum, vanadium, titanium in separation vanadium titano-magnetite according to claim 1, it is characterised in that in described step b, the reaction atmosphere of reduction roasting is reducing atmosphere, and concentration≤2.0% of oxygen in this reducing atmosphere.
5. the method for ferrum, vanadium, titanium in the separation vanadium titano-magnetite according to claim 1 or 4, it is characterised in that the consersion unit used in described step b is rotary kiln, rotary hearth furnace or shaft (tower) furnace.
6. the method for ferrum, vanadium, titanium in separation vanadium titano-magnetite according to claim 1, it is characterized in that in described step c to cooling after metallized pellet or briquetting be crushed to its particle diameter < 0.074mm after carry out magnetic separation, the magnetic field intensity of magnetic separation is 100-200mT.
7. the method for ferrum, vanadium, titanium in separation vanadium titano-magnetite according to claim 1, it is characterised in that the sodium salt in described step d can adopt the side-product that vanadium extracting waste water crystallization obtains, this side-product sulfur acid sodium 98%, liquid containing ammonium sulfate 1%.
8. the method for ferrum, vanadium, titanium in separation vanadium titano-magnetite according to claim 1, it is characterized in that the calcining in described step e, oxidizing roasting obtained is crushed to its particle diameter < 0.074mm, then carrying out water logging vanadium extraction 90-100 DEG C of water bath with thermostatic control and when being stirred, the mass ratio of described calcining and water is 1:4～6.
9. the method for ferrum, vanadium, titanium in separation vanadium titano-magnetite according to claim 1, it is characterised in that the method also includes, as the raw material of sulfate process titanium dioxide after the Ti-enriched slag drying later using removing v element.
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