CN106756117B - A kind of method of Rock coal containing alum and v-bearing steel slag joint vanadium enrichment - Google Patents
A kind of method of Rock coal containing alum and v-bearing steel slag joint vanadium enrichment Download PDFInfo
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- CN106756117B CN106756117B CN201611150370.9A CN201611150370A CN106756117B CN 106756117 B CN106756117 B CN 106756117B CN 201611150370 A CN201611150370 A CN 201611150370A CN 106756117 B CN106756117 B CN 106756117B
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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
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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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a kind of methods that Rock coal containing alum and v-bearing steel slag combine vanadium enrichment, belong to vanadium recovery technology field.The present invention mixes Rock coal containing alum with v-bearing steel slag, makes CaO% in mixture/(SiO2%+Al2O3%) between 0.8~1.4,15~25 minutes are kept the temperature after heating the mixture to 1450~1500 DEG C, then room temperature is cooled to after being cooled to 1200~1250 DEG C with 5~10 DEG C/min, rich vanadium mutually generates in temperature-fall period, predominantly high vanadium solid solution phase-(Fe, Mg) O (V, Al, Fe)2O3, content of vanadium is with V in the mine phase2O5Meter is not less than 20%, and bone coal is more than 80% with degree of enrichment of the vanadium in slag in the phase, and does not contain p and s in rich vanadium phase.The present invention contains vanadium mineral and the Combined Treatment of solid waste containing vanadium using low-grade, using the characteristic of two kinds of low-grade complementations of chemical composition containing vanadium resource, while the vanadium in two spike-type cultivars is extracted, and gained richness vanadium phase vanadium grade is high, it is easily isolated, is suitble to the recycling of vanadium in low grade vanadium resource.
Description
Technical field
The invention belongs to vanadium recovery technology fields, combine vanadium more specifically to a kind of Rock coal containing alum and v-bearing steel slag
The method of enrichment.
Background technology
Rock coal containing alum be it is a kind of it is important contain vanadium mineral, china natural resources reserves are very abundant, in Sichuan, Shaanxi, Hunan, peace
The ground such as emblem, Hubei have widely distributed, and total vanadium amount in Rock coal containing alum is up to 1.18 × 108T accounts for China V2O5The 87% of gross reserves.Together
When, some domestic and international iron and steel enterprises, such as hold steel, climb steel, using low vanadium-containing molten iron direct steelmaking, vanadium enters slag in converting process
Phase forms v-bearing steel slag.China has added up this slag of up to ten million tons, and is also increased with annual millions of tons of speed.
Vanadium is a kind of important raw material of industry, is widely used in chemical industry, metallurgy, material and automobile and other industries, therefore recycling contains
Vanadium steel slag and Rock coal containing alum etc. just have preferable economic benefit containing the vanadium in vanadium resource.In addition, the low vanadium resource of above two is all
Contain high-valence state vanadium：V4+And V5+, if do not dealt carefully with, can be leached by rainwater, heavy metal pollution be formed, to influence ecological ring
Border and human health.Therefore, the vanadium recycled in slag and bone coal also has important environment protection significance simultaneously.
Currently, the recycling containing vanadium in vanadium resource generally need to first produce vanadic anhydride, vanadic anhydride system is then recycled
Take other products.For industrial point of view, producing for vanadic anhydride there are certain requirements raw material vanadium grade, with V2O5Count content
12% should be not less than.And far below the numerical value, (v-bearing steel slag contains 1~5% to the grade of vanadium in v-bearing steel slag and Rock coal containing alum
V2O5, Rock coal containing alum is containing 0.3~1.5%V2O5).Therefore, the grade of vanadium in the low vanadium resource of above two need to be just improved, product are improved
Position customary way is Mineral separation.Mineral separation require raw material in vanadium concentrate in one or two of mineral (namely contain navajoite
Phase), and the vanadium grade of phase containing vanadium is sufficiently high.However, the vanadium in above two resource is in Dispersed precipitate, the experimental results table
It is bright：The equal unobvious of the aeneficiation effect of Rock coal containing alum and vanadium in vanadium containing steel slag, to need that above two is contained vanadium before ore dressing
The vanadium disperseed in resource focuses in one or two of mineral.
For v-bearing steel slag, there is a kind of selective enrichment method at present, i.e., under oxidative conditions, by most of vanadium in slag
+ 5 valences are oxidized to, and create suitable physical and chemical condition, form it into the precipitation of vanadium calcium phosphate solid solution phase.Vanadium oxidation at present is rich
Collection research has obtained initial success, as Chinese Patent Application No. 200510094963 discloses a kind of enrichment of vanadium in vanadium containing steel slag
Method, the following additives of one or more that this application passes through the addition quantity of slag 5-16% in v-bearing steel slag：SiO2、Al2O3、
Mullite (3SiO2·2Al2O3), and in aerial oxygen position or melt processed under the conditions of higher than aerial oxygen position, it is then cooling, keep the temperature after
V-bearing steel slag is taken out and quenching in air, to make 80% or more the vanadium of Dispersed precipitate in v-bearing steel slag be transferred to a richness
It is enriched in cenotype containing vanadium and crystallizes precipitation and obtain high-grade rich vanadium phase.This application is under oxidative conditions by vanadium in slag
Major part is oxidized to pentavalent and forms rich vanadium phase-vanadium calcium phosphate solid solution phase with phosphorus pentoxide, calcium oxide.But due to using upper
Rich vanadium phase physical property and the other mineral in slag for stating the acquisition of selective enrichment method are more close, so as to cause rich vanadium phase and its
Its mine is mutually difficult to detach, this bottleneck problem being also recycled to the vanadium in low-grade v-bearing steel slag at obstruction.
For Rock coal containing alum, generally use wet underwater welding recycles the vanadium in Rock coal containing alum in the prior art, specifically
Ground V is extracted by sodium roasting → leaching → precipitation → calcination process2O5, but due to will produce during sodium roasting
A large amount of HCl, Cl2、SO2Equal gases, to which serious pollution can be caused to environment, and using existing method in Rock coal containing alum
Vanadium vanadium when being recycled recovery rate it is relatively low.As the application case of Patent No. 961184507 discloses one kind from bone coal
The method that vanadium pentoxide is extracted in navajoite, concrete technology operating procedure are：Broken ore is after the decarburization of part, ratio
It is the NaCl and CaCO within ore weight 8%3It is added simultaneously in ore and enters ball milling, balling-up process, balling-up exists later
It is roasted at a temperature of 750-850 DEG C, the pellet after roasting, which is directly placed into the acid solution that PH is 1-3, to be leached, what quiet leaching came
Solution is added flocculant and is purified, and is then extracted and is stripped, and is stripped the vanadium taken out and heats 40-100 DEG C in weak base
Property under purified, then carry out heavy ammonium metavanadate, filtration washing drying and dry thermal cracking again.This application is using sodium
Low Valent Vanadium is converted into what high price vanadium extracted by the mode of roasting, serious so as to cause environmental pollution, and to the recovery rate of vanadium
It is relatively low.
In conclusion for the low-grade enriching and recovering containing vanadium in vanadium resource such as v-bearing steel slag and Rock coal containing alum, at present also
There is no practicable method, needs to continue to explore new direction.
Invention content
1. technical problems to be solved by the inivention
It is an object of the invention to overcome to use the prior art to the vanadium progress in low-grade Rock coal containing alum and v-bearing steel slag
Above shortcomings when recycling, and a kind of method of Rock coal containing alum and v-bearing steel slag joint vanadium enrichment is provided.The present invention
By the combination of Rock coal containing alum and v-bearing steel slag, richness can be carried out at the same time to the vanadium in low-grade Rock coal containing alum and v-bearing steel slag
Collection, the grade of vanadium is higher in gained richness vanadium phase, and vanadium enrichment degree is high, the physical property difference of rich vanadium phase and other mine phases in material compared with
Greatly, to be conducive to subsequent rich vanadium phase separation, and environmental pollution is small.
2. technical solution
In order to achieve the above objectives, technical solution provided by the invention is：
The method of a kind of Rock coal containing alum and v-bearing steel slag joint vanadium enrichment of the present invention, its step are as follows：
(1) material mixes：Rock coal containing alum and v-bearing steel slag are mixed to get mixture in proportion；
(2) heating and cooling treatment：After obtained mixed material heating is kept the temperature 15-25 minutes to 1450~1500 DEG C, with 5
The cooling rate of~10 DEG C/min is cooled to 1200~1250 DEG C, then cooled to room temperature, to make Rock coal containing alum and contain
Vanadium in vanadium steel slag enters same vanadium enrichment phase.
Further, CaO%/(SiO in the middle gained mixture of the step (1)2%+Al2O3%)=0.8~1.4,
The sum of mass percent of FeO and MgO is not less than 10%.
Further, the Rock coal containing alum includes the component of following mass percent：50~70%SiO2, 5~
20%Al2O3, 2~6%FeOt, 0.3~1.3%V2O5, 1~4%P2O5, 1~4%S and 10~20%C.
Further, the v-bearing steel slag includes the component of following mass percent：40~55%CaO, 10~
20%SiO2, 20-30%FeO, 1~5%V2O5, 1~4%P2O5With 3~12%MgO.
Further, the mixed material heating is stirred to being blown into nitrogen after 1450~1500 DEG C, to make bone coal
It is fully dissolved in slag.
Further, by mixed material heating in the step (2) and after being cooled to room temperature, gained vanadium enrichment is mutually rich vanadium
Solid solution phase-(Fe, Mg) O (V, Al, Fe)2O3。
Further, the content of vanadium in gained vanadium enrichment phase is with V2O5Meter is not less than 20%, and Rock coal containing alum and V-alloyed steel
Degree of enrichment of the vanadium in the phase in slag is more than 80%.
Further, gained vanadium enrichment further includes mutually MgO and Al2O3, and MgO and Al2O3The sum of mass percent no
Higher than 35%.
Further, S and P is not contained in gained vanadium enrichment phase.
3. advantageous effect
Using technical solution provided by the invention, compared with existing known technology, there is following remarkable result：
(1) method of of the invention a kind of Rock coal containing alum and v-bearing steel slag joint vanadium enrichment, by by v-bearing steel slag with contain
Scherbinaite coal joint carries out vanadium enrichment, and control effectively to the basicity and cooling system of mixture, so as to V-alloyed steel
Slag is carried out at the same time enrichment with the vanadium in Rock coal containing alum, and the degree of enrichment of vanadium is higher, and environmental pollution is small in enrichment processing procedure, and institute
It obtains vanadium enrichment phase and differs larger with the physical property of other mine phases, consequently facilitating the separation of follow-up vanadium enrichment phase.
(2) method of a kind of Rock coal containing alum and v-bearing steel slag joint vanadium enrichment of the invention, gained vanadium enrichment phase (Fe, Mg)
O·(V,Al,Fe)2O3Middle vanadium exists with trivalent form, it is not easy to solid solution is formed with the phosphorus pentoxide in slag, so as to
Effectively phosphorus is avoided to dissolve in vanadium enrichment phase, have very important effect to subsequent solution vanadium-rich mineral vanadium extraction, ensures recycling vanadium resource
Performance.
(3) method of a kind of Rock coal containing alum and v-bearing steel slag joint vanadium enrichment of the invention, under the reducing conditions by vanadium richness
Collect rich vanadium solid solution phase-(Fe, Mg) O (V, Al, Fe)2O3In, this is mutually highly stable, is not easy to leach in natural water,
So as to avoid pollution of the residual vanadium to environment in tailings.In addition, the tailings after its rich vanadium phase separation can be used as the buildings such as cement
Material, to reduce the secondary pollution of waste residue.
Description of the drawings
Fig. 1 is the mark scan Electronic Speculum photograph that Rock coal containing alum of the present invention and v-bearing steel slag combine square iron stone phase in vanadium enrichment sample
Piece；
Fig. 2 is the constituent analysis collection of illustrative plates of the square iron stone phase of Fig. 1 labels；
Fig. 3 is the stereoscan photograph that Rock coal containing alum of the present invention and v-bearing steel slag combine silicate phase in vanadium enrichment sample；
Fig. 4 is the constituent analysis collection of illustrative plates of the silicate phase marked in Fig. 3；
Fig. 5 is the mark scan Electronic Speculum photograph that Rock coal containing alum of the present invention and v-bearing steel slag combine rich vanadium phase in vanadium enrichment sample
Piece；
Fig. 6 is the constituent analysis collection of illustrative plates of the rich vanadium phase marked in Fig. 5.
Specific implementation mode
The method of Rock coal containing alum and v-bearing steel slag the joint vanadium enrichment of the present invention, is by a certain percentage and to contain Rock coal containing alum
Vanadium steel slag mixes, and makes CaO% in mixture/(SiO2%+Al2O3%) mass ratio is between 0.8~1.4, FeO+MgO mass hundred
Point than content not less than 10% (rich vanadium solid solution, which needs at least one of both oxides, in the present invention to form,
Content is too low to be unfavorable for rich vanadium and is mutually formed), other constituent contents are unlimited.By above-mentioned mixed material heating to 1450 DEG C~1500 DEG C,
Under the conditions of molten iron balances, 1200~1250 DEG C are cooled to 5~10 DEG C/min, rear cooled to room temperature.Rich vanadium is mutually dropping
It is generated during temperature, gained vanadium enrichment is mutually rich vanadium solid solution phase-(Fe, Mg) O (V, Al, Fe)2O3, have the following properties that：
(1) content of vanadium is with V2O5Meter is not less than 20%；(2) bone coal is more than 80% with degree of enrichment of the vanadium in slag in the phase；(3) rich
Vanadium phase MgO%+Al2O3The content of % is not higher than 35%, and does not contain p and s, to reduce the processing after rich vanadium phase separation
Difficulty.
The present invention is existing insufficient for existing Rock coal containing alum and vanadium in vanadium containing steel slag enrichment extraction, such as rich using selectivity
When set method extracts the vanadium in v-bearing steel slag, the physical property of gained richness vanadium phase and main body mine phase silicate phase in slag compared with
It is close, so as to cause being difficult to that rich vanadium is separated out.And the vanadium in Rock coal containing alum is returned using existing wet underwater welding
Time receiving can cause environment serious pollution, and the recovery rate of vanadium is relatively low.Simultaneously because vanadium belongs to non-ferrous metal, extracting vanadium from stone coal
It is all gone in for the study all the time by the scholar of nonferrous metallurgy industry, and nonferrous metallurgy usage of trade wet underwater welding；V-bearing steel slag
It is the waste of iron and steel metallurgical industry, relevant research work is undertaken by the scholar of the industry, and iron and steel metallurgical industry tends to fire
Method is extracted, and is not intersected substantially between each other.Therefore, all it is usually in the prior art that v-bearing steel slag and Rock coal containing alum is independent
It is handled, the present invention innovatively proposes to carry out enrichment processing to vanadium therein by the combination of Rock coal containing alum and v-bearing steel slag
Method, and the mixed proportion of Rock coal containing alum and v-bearing steel slag is controlled, ensure the basicity of mixture be 0.8~1.4 it
Between, FeO+MgO contents are not less than 10%, while being optimized to the heating and cooling system of mixture, so as to promote
Make vanadium enrichment phase (Fe, Mg) OV, Al, Fe in cooling procedure)2O3Formation, make the equal energy of vanadium in Rock coal containing alum and v-bearing steel slag
It is effectively enriched in the phase.Gained vanadium enrichment phase (Fe, Mg) O (V, Al, Fe)2O3Physical property and other mine phases in slag
Physical property difference is larger, so as to ensure efficiently separating for follow-up vanadium enrichment phase, and in the phase vanadium degree of enrichment it is higher, it is rich
It is small to collect environmental pollution in processing procedure.Since vanadium exists in the form of vanadium trioxide in the phase, be trivalent, it is not easy to in slag
Phosphorus pentoxide formed solid solution have to subsequent solution vanadium-rich mineral vanadium extraction so as to effectively avoid phosphorus from dissolving in vanadium enrichment phase
Very important effect ensures the performance of recycling vanadium resource.
Inventor has found during the experiment, since the vanadium in v-bearing steel slag exists with a variety of valence states of+3 ,+4 and+5 valences, because
This is unfavorable for the enrichment processing of vanadium, and the phosphorus in slag inevitably enters rich vanadium phase, V together with vanadium2O5With P2O5It is difficult to
Separation, to influence the normal use of subsequent recovery vanadium resource.Therefore, a difficult point of the invention is that how to avoid in slag
The influence of phosphorus.On the one hand the present invention can neutralize respective soda acid by the way that Rock coal containing alum and v-bearing steel slag are carried out Combined Treatment
It spends (v-bearing steel slag is high alkalinity slag, and Rock coal containing alum is acid mineral), and to basicity CaO%/(SiO of mixture2%+
Al2O3%) and the sum of the content of FeO+MgO optimizes control, so as to be rich vanadium phase (Fe, Mg) O (V, Al, Fe)2O3
Formation suitable condition is provided.Vanadium in another aspect Rock coal containing alum is present in+trivalent in alumino-silicate substantially, by containing
CaO in vanadium steel slag and silicate reaction destroy its crystal structure, are released so as to general+trivalent vanadium；In v-bearing steel slag
Vanadium exist with multivalent state, since the presence of carbon in Rock coal containing alum can restore part iron oxide in slag to form metallic state
Iron, while certain reducing atmosphere is created, to uniformly provide condition for the price of vanadium in slag, make two kinds to contain vanadium resource
In vanadium exist with trivalent form, and then phosphorus in slag can effectively be avoided to enter rich vanadium phase together.In addition, in Rock coal containing alum
The presence of carbon can also provide heat for mixture high-temperature process, reduce energy consumption, be convenient for industrial operation, promote rich vanadium solid solution
The formation of body phase.V-bearing steel slag and Rock coal containing alum are carried out Combined Treatment by the present invention, contain vanadium resource since both are low-grade
Studying point has complementarity, and the tailings after rich vanadium phase separation can be used as construction material, to reduce environmental pollution.
To further appreciate that present disclosure, with reference to specific embodiment, the invention will be further described.
Embodiment 1
The method of a kind of Rock coal containing alum and v-bearing steel slag joint vanadium enrichment of the present embodiment, its step are as follows：
(1) material mixes：Rock coal containing alum and v-bearing steel slag are mixed to get mixture in proportion, make CaO% in mixture/
(SiO2%+Al2O3The sum of mass percent of %)=0.8, FeO and MgO is not less than 10%.Above-mentioned Rock coal containing alum includes as follows
The component of mass percent：63.4%SiO2, 7.4%Al2O3, 6.6%CaO, 2.8%Fe2O3, 2.2%K2O, 0.9%V2O5(contain
Vanadium in scherbinaite coal exists with trivalent form, and this field is usually to be converted into V2O5Content afterwards is measured), 1.0%P2O5、
1.3%S, 10.7%C and a small amount of other ingredients 1.3%.V-bearing steel slag includes the component of following mass percent：40.5%
CaO, 10.5%SiO2, 25.3%Fe2O3, 2.6%V2O5, 3.2%P2O5, 10.5%MgO and on a small quantity other ingredients 2.9%.
(2) heating and cooling treatment：By obtained mixed material heating to 1450 DEG C keep the temperature 25 minutes, while be blown into nitrogen into
Row stirring, to make bone coal be fully dissolved in slag.Then mixture is made to be cooled to 1250 DEG C with the cooling rate of 5 DEG C/min, so
Cooled to room temperature afterwards, to make Rock coal containing alum enter same vanadium enrichment phase with the vanadium in v-bearing steel slag.Institute in the present embodiment
It is rich vanadium solid solution phase-(Fe, Mg) O (V, Al, Fe) to obtain vanadium enrichment mutually2O3, the content of vanadium in gained vanadium enrichment phase is with V2O5Meter
Not less than 20%, Rock coal containing alum is more than 80% with degree of enrichment of the vanadium in v-bearing steel slag in the phase.The vanadium enrichment mutually also wraps
Include MgO and Al2O3, and MgO and Al2O3The sum of mass percent be not higher than 35%, gained vanadium enrichment does not contain p and s mutually.
Mine phase composition in cold conditions slag is detected, specific method is：It is sampled at different locations, in scanning electricity
(as shown in Fig. 1, Fig. 3, Fig. 5) is detected under mirror, using the mineral facies in scanning electron microscope analysis slag specimen, and passes through sweep attachment power spectrum
Analyze the chemical composition of each phase (analysis result is respectively as shown in Fig. 2, Fig. 4 and Fig. 6).Wherein table 1 show each mine in cold conditions slag
The specific chemical composition of object phase can be seen that in conjunction with attached drawing and table 1：Square iron stone is mutually free of vanadium in the present embodiment, and vanadium is mainly enriched with
In high vanadium solid solution phase-(Fe, Mg) O (V, Al, Fe)2O3, this mutually contains part magnesium and aluminium, and content of vanadium reaches 18% or more, and
(Fe,Mg)O·(V,Al,Fe)2O3In it is not phosphorous, phosphorus is enriched in silicic acid calcium phase.
1 the present embodiment Rock coal containing alum of table combines the chemical composition of each mineral facies in vanadium enrichment cold conditions sample with v-bearing steel slag
Embodiment 2
The method of a kind of Rock coal containing alum and v-bearing steel slag joint vanadium enrichment of the present embodiment, its step are as follows：
(1) material mixes：Rock coal containing alum and v-bearing steel slag are mixed to get mixture in proportion, make CaO% in mixture/
(SiO2%+Al2O3The sum of mass percent of %)=1.4, FeO and MgO is not less than 10%.Above-mentioned Rock coal containing alum includes as follows
The component of mass percent：51.8%SiO2, 13.6%Al2O3, 5.8%FeOt, 1.1%V2O5, 1.3%P2O5, 4.3%S,
1.2%MgO, 3.4%K2O, 17.5%C and a small amount of other ingredients.V-bearing steel slag includes the component of following mass percent：
45.0%CaO, 14.7%SiO2, 26.6%FeO, 3.3%V2O5, 2.0%P2O5, 3.7%MgO, 1.7%Al2O3And it is a small amount of
Other ingredients 3.2%.
(2) heating and cooling treatment：By obtained mixed material heating to 1500 DEG C keep the temperature 15 minutes, while be blown into nitrogen into
Row stirring, to make bone coal be fully dissolved in slag.Then mixture is made to be cooled to 1200 DEG C with the cooling rate of 10 DEG C/min, so
Cooled to room temperature afterwards, to make Rock coal containing alum enter same vanadium enrichment phase with the vanadium in v-bearing steel slag.Institute in the present embodiment
It is rich vanadium solid solution phase-(Fe, Mg) O (V, Al, Fe) to obtain vanadium enrichment mutually2O3, the content of vanadium in gained vanadium enrichment phase is with V2O5Meter
Not less than 20%, Rock coal containing alum is more than 80% with degree of enrichment of the vanadium in v-bearing steel slag in the phase.The vanadium enrichment mutually also wraps
Include MgO and Al2O3, and MgO and Al2O3The sum of mass percent be not higher than 35%, gained vanadium enrichment does not contain p and s mutually.
Mine phase composition in cold conditions slag obtained by the present embodiment is detected, testing result is closer to embodiment 1.
Embodiment 3
The method of a kind of Rock coal containing alum and v-bearing steel slag joint vanadium enrichment of the present embodiment, its step are as follows：
(1) material mixes：Rock coal containing alum and v-bearing steel slag are mixed to get mixture in proportion, make CaO% in mixture/
(SiO2%+Al2O3The sum of mass percent of %)=1.0, FeO and MgO is not less than 10%.Above-mentioned Rock coal containing alum includes as follows
The component of mass percent：63.2%SiO2, 10.1%Al2O3, 3.9%Fe2O3, 3.0%K2O, 1.6%MgO, 1.3%V2O5、
1.9%P2O5, 2.2%S, 12.2%C and a small amount of other ingredients 0.7%.V-bearing steel slag includes the group of following mass percent
Point：46.1%CaO, 12.6%SiO2, 24.4%Fe2O3, 1.6%V2O5, 2.4%P2O5, 7.5%MgO and it is a small amount of it is other at
Divide 3.9%.
(2) heating and cooling treatment：By obtained mixed material heating to 1450~1500 DEG C keep the temperature 20 minutes, be blown into simultaneously
Nitrogen is stirred, to make bone coal be fully dissolved in slag.Then mixture is made to be cooled to 1230 with the cooling rate of 7 DEG C/min
DEG C, then cooled to room temperature, to make Rock coal containing alum enter same vanadium enrichment phase with the vanadium in v-bearing steel slag.The present embodiment
Middle gained vanadium enrichment is mutually rich vanadium solid solution phase-(Fe, Mg) O (V, Al, Fe)2O3, content of vanadium in gained vanadium enrichment phase with
V2O5Meter is not less than 20%, and Rock coal containing alum is more than 80% with degree of enrichment of the vanadium in v-bearing steel slag in the phase.The vanadium enrichment phase
Further include MgO and Al2O3, and MgO and Al2O3The sum of mass percent be not higher than 35%, gained vanadium enrichment do not contain mutually phosphorus and
Sulphur.Mine phase composition in cold conditions slag obtained by the present embodiment is detected, testing result is closer to embodiment 1.
According to embodiment 1-3, the method for Rock coal containing alum and v-bearing steel slag joint vanadium enrichment using the present invention, vanadium is nearly all
It is enriched in high vanadium solid solution phase-(Fe, Mg) O (V, Al, Fe)2O3, the phase vanadium grade is high and does not contain phosphorus, is a kind of good
Vanadium enrichment phase.
Claims (8)
1. a kind of method of Rock coal containing alum and v-bearing steel slag joint vanadium enrichment, which is characterized in that its step are as follows：
(1) material mixes：Rock coal containing alum and v-bearing steel slag are mixed to get mixture in proportion, CaO% in gained mixture/
(SiO2%+Al2O3The sum of mass percent of %)=0.8~1.4, FeO and MgO is not less than 10%；
(2) heating and cooling treatment：After obtained mixed material heating is kept the temperature 15-25 minutes to 1450~1500 DEG C, with 5~10
DEG C/cooling rate of min is cooled to 1200~1250 DEG C, then cooled to room temperature, to make Rock coal containing alum and V-alloyed steel
Vanadium in slag enters same vanadium enrichment phase.
2. the method for a kind of Rock coal containing alum according to claim 1 and v-bearing steel slag joint vanadium enrichment, it is characterised in that：Institute
The Rock coal containing alum stated includes the component of following mass percent：50~70%SiO2, 5~20%Al2O3, 2~6%FeOt、0.3
~1.3%V2O5, 1~4%P2O5, 1~4%S and 10~20%C.
3. the method for a kind of Rock coal containing alum according to claim 1 and v-bearing steel slag joint vanadium enrichment, it is characterised in that：Institute
The v-bearing steel slag stated includes the component of following mass percent：40-55%CaO, 10~20%SiO2, 20-30%FeO, 1~
5%V2O5, 1~4%P2O5With 3~12%MgO.
4. the method for a kind of Rock coal containing alum according to any one of claim 1-3 and v-bearing steel slag joint vanadium enrichment,
It is characterized in that：The mixed material heating is stirred to being blown into nitrogen after 1450~1500 DEG C, to make bone coal be fully dissolved in steel
Slag.
5. the method for a kind of Rock coal containing alum according to any one of claim 1-3 and v-bearing steel slag joint vanadium enrichment,
It is characterized in that：By mixed material heating in the step (2) and after being cooled to room temperature, gained vanadium enrichment is mutually rich vanadium solid solution phase-
(Fe,Mg)O·(V,Al,Fe)2O3。
6. the method for a kind of Rock coal containing alum according to claim 5 and v-bearing steel slag joint vanadium enrichment, it is characterised in that：Institute
The content of vanadium in vanadium enrichment phase is obtained with V2O5Meter is not less than 20%, and richness of the Rock coal containing alum with the vanadium in v-bearing steel slag in the phase
Intensity is more than 80%.
7. the method for a kind of Rock coal containing alum according to claim 6 and v-bearing steel slag joint vanadium enrichment, it is characterised in that：Institute
It further includes mutually MgO and Al to obtain vanadium enrichment2O3, and MgO and Al2O3The sum of mass percent be not higher than 35%.
8. the method for a kind of Rock coal containing alum according to claim 7 and v-bearing steel slag joint vanadium enrichment, it is characterised in that：Institute
It obtains and does not contain S and P in vanadium enrichment phase.
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