CN106381401B - A kind of reduction enrichment method of vanadium in vanadium containing steel slag - Google Patents
A kind of reduction enrichment method of vanadium in vanadium containing steel slag Download PDFInfo
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- CN106381401B CN106381401B CN201611150353.5A CN201611150353A CN106381401B CN 106381401 B CN106381401 B CN 106381401B CN 201611150353 A CN201611150353 A CN 201611150353A CN 106381401 B CN106381401 B CN 106381401B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- 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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- C—CHEMISTRY; METALLURGY
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- C22B34/22—Obtaining vanadium
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Abstract
The invention discloses a kind of reduction enrichment methods of vanadium in vanadium containing steel slag, belong to v-bearing steel slag vanadium extraction technical field.The present invention is process object with vanadium in vanadium containing steel slag, makees modification agent with siliceous materials, v-bearing steel slag basicity is adjusted to CaO/SiO under Fe equilibrium conditions2=1~1.5, then be cooled to after 1250~1300 DEG C with 1~5 DEG C/min cooling rates and room temperature is cooled to arbitrary cooling rate, thus by vanadium enrichment in slag in vanadium iron Spinel.The richness vanadium mutually has the following properties that：Content of vanadium is high, with V2O5It calculates, content is higher than 20%；Degree of enrichment of the vanadium in enrichment phase is high, is more than 90%；Enrichment phase and other mineral facies density contrasts in slag are big, and relative density difference is more than 50%.Enrichment phase vanadium grade obtained by method using the present invention is high, and degree of enrichment is high, big with other mine phase densities difference, is conducive to subsequent separation.
Description
Technical field
The invention belongs to valuable element recovery technology fields in slag, more specifically to time of vanadium in solid waste containing vanadium
It receives and utilizes technical field.
Background technology
Currently, some iron and steel enterprises produce vanadium-bearing hot metal, these molten iron vanadium by blast furnace raw material of vanadium titano-magnetite both at home and abroad
Content height differs, and high vanadium ferroalloy water is used further to make steel after making vanadium slag process, and low vanadium-containing molten iron is then directly used in steel-making, no matter passes through
Which kind of process is gone through, a part of vanadium in molten iron eventually enters slag phase in converter steelmaking process, forms v-bearing steel slag.China is every
Year, the v-bearing steel slag of discharge was up to more than 100 ten thousand tons, and with natural containing vanadium mineral, such as bone coal (contains 0.3%-1.5%V2O5) compare, this
Kind of slag content of vanadium higher is a kind of important to contain vanadium resource.In addition, v-bearing steel slag is if dealt carefully with, high-valence state in slag
The vanadium of (+4 and+5 valences) is easy dissolution, to cause heavy metal pollution.Pollution of vanadium is very big to biohazard, such as inhibits plant growth
And development, it is serious to damage animal physiological system, reduce antitoxin, anti-cancer ability etc..Early in twentieth century eighties, united nations environment
Vanadium it has been suggested that is included in the preferential position of environmental hazard element inventory by Planning Department.Therefore, the vanadium recycled in v-bearing steel slag not only has
There is higher economic value, also there is important environment protection significance.
In this regard, metallargist has carried out a large amount of v-bearing steel slag vanadium extraction researchs, method, roasting-leaching method are such as directly leached.So
And these methods contain vanadium resource (with V both for high-grade2O5The recycling for counting vanadium 12%) content is not less than in, to vanadium grade phase
It is but less ideal that effect is applicable in relatively low v-bearing steel slag.In addition, being carried out to low-grade v-bearing steel slag using above-mentioned existing method
When processing, since vanadium grade is relatively low, will produce that mineral treating capacity is big, reagent consumption is big, pollution is big, tailings is difficult etc. asks
Topic.For that purpose it is necessary to improve the grade of vanadium, currently used method master of the raising containing vanadium grade in vanadium resource before wet method soaks vanadium
If Mineral separation method.Mineral separation method requires vanadium integrated distribution vanadium grade in one or two of mineral facies and in the phase in raw material
It is higher, however, vanadium in vanadium containing steel slag be distributed in different mine phases in multivalent state (+trivalent preservation in ferrous acid calcium phase ,+4 and+5 valence vanadium
It is solid-solution in dicalcium silicate phase), therefore directly effect is not obvious when being handled v-bearing steel slag using Mineral separation method, is also needed
Vanadium enrichment processing is carried out before Mineral separation.
Currently, only having Selective separation-out method with the relevant research of vanadium enrichment processing, Selective separation-out method includes two steps：
Selective enrichment and Selective Separation.It is typically in oxic gas to carry out selective enrichment to the vanadium in v-bearing steel slag in existing research
It under atmosphere, is modified, promote the formation of rich vanadium phase-vanadium calcium phosphate solid solution phase and grown up by slag.Above-mentioned vanadium selectivity is rich at present
Collection research has obtained initial success, but the rich vanadium phase due to being obtained using existing selective enrichment method and main body mine phase-silicic acid
The physical property (density and magnetism) of salt phase is more close, to cause larger difficulty to subsequent Selective Separation, this
It is the main bugbear for hindering to be recycled the vanadium in low-grade v-bearing steel slag at present.
Through retrieval, have about the patent report for carrying out concentration and separation to the vanadium in v-bearing steel slag related open.
Such as, Chinese Patent Application No. 200510094963 discloses a kind of enrichment method of vanadium in vanadium containing steel slag, this application
The following additives of one or more that case 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 will contain vanadium
Slag taking-up and in air quenching are rich in vanadium to make 80% or more the vanadium of Dispersed precipitate in v-bearing steel slag be transferred to one
It is enriched in cenotype and crystallizes precipitation and obtain high-grade rich vanadium phase.This application is under oxidative conditions that vanadium in slag is most of
It is oxidized to pentavalent and forms rich vanadium phase-vanadium calcium phosphate solid solution phase, the enrichment phase and main body in slag with phosphorus pentoxide, calcium oxide
The physical property (density and magnetism) of mine phase-silicate phase is more close, so as to cause rich vanadium phase-vanadium calcium phosphate solid solution phase
Separation is difficult.
For another example, the patent that Chinese Patent Application No. is 201310395406.X discloses a kind of rich vanadium life of v-bearing steel slag smelting
The method of iron, this application are by 63~67 parts of v-bearing steel slags, 14~18 parts of iron powders, 8~12 parts of silicas, 4~6 parts of carbon dusts and 3
~4 parts of aluminum shots are added in smelting furnace, and the mixed material heating of gained is melted and waits for detaching clinker and molten iron after reaction.The Shen
Please case in v-bearing steel slag 85% vanadium enrichment can be obtained to the rich vanadium pig iron in the pig iron, but P content is higher in the gained richness vanadium pig iron,
It is difficult to detach P with V in subsequent technique, is difficult to be used effectively so as to cause the rich vanadium pig iron.
Therefore, the vanadium in v-bearing steel slag how to be made to carry out the vanadium enrichment phase obtained after selective enrichment processing and main body in slag
Mine phase-silicate phase is easily isolated, and prevents P elements to recycling the influence of vanadium resource later use for low-grade high alkalinity
The recycling of vanadium in vanadium containing steel slag is most important.
Invention content
1. technical problems to be solved by the inivention
It is an object of the invention to overcome to carry out at enrichment the vanadium in v-bearing steel slag using existing selective enrichment method
When reason, gained richness vanadium phase and other mineral facies physical properties are more close, so as to cause the deficiency detached is difficult to, provide one kind
The reduction enrichment method of vanadium in vanadium containing steel slag.When method using the present invention carries out enrichment processing to the vanadium in v-bearing steel slag, shape
At vanadium enrichment phase and other mineral facies physical properties differ greatly and not phosphorus element-containing, to be easy to the separation of follow-up rich vanadium phase
Operation, can effectively ensure that the recycling of vanadium in vanadium containing steel slag.
2. technical solution
To achieve the above object, technical solution provided by the invention is：
A kind of reduction enrichment method of vanadium in vanadium containing steel slag of the present invention, this method is by adding silicon into v-bearing steel slag
Matter material carries out modifying process to v-bearing steel slag, and controls rational temperature schedule, to make the vanadium enrichment in slag in vanadium iron point
Spar phase.
Further, reduction enrichment method of the invention the specific steps are：
(1) slag modifies：Siliceous materials are added into molten state v-bearing steel slag as modification agent, by slag basicity CaO/
SiO2It adjusts to 1~1.5；
(2) temperature schedule：By the molten steel slag modified in step (1) with the cooling rate of 1~5 DEG C/min under Fe balances
1250~1300 DEG C are cooled to, is then cooled to room temperature, i.e., by the vanadium enrichment in v-bearing steel slag in vanadium iron Spinel.
Further, siliceous materials are added to after v-bearing steel slag in the step (1) make molten steel slag not less than
8-15 minutes are kept the temperature at 1500 DEG C.
Further, it is molten steel slag quality that the siliceous materials, which select quartz sand or flyash, additive amount,
15-25%.
Further, the v-bearing steel slag makes steel the clinker generated for vanadium-bearing hot metal comprising following quality hundred
Divide the chemical constituent of ratio：1~5%V2O5, 40~55%CaO, 10~20%SiO2, 3~12%MgO, 20~30%FeO, 0~
4%P2O5, 0~5%Al2O3, 5~10%Fe.
Further, the major components of gained vanadium enrichment phase vanadium iron Spinel are V2O3And FeO, the wherein content of vanadium
With V2O5It calculates and is higher than 20%, and degree of enrichment of the vanadium in the enrichment phase is more than 90%.
Further, it is 0~3%MgO and 0~3%Al that gained vanadium iron Spinel, which further includes mass percentage,2O3。
Further, gained vanadium iron Spinel and the relative density difference of other mineral facies in slag are more than 50%, and vanadium
P element is free of in hercynite phase.
3. advantageous effect
Using technical solution provided by the invention, compared with existing known technology, there is following remarkable result：
(1) the reduction enrichment method of a kind of vanadium in vanadium containing steel slag of the invention, by adding siliceous object into v-bearing steel slag
Material carries out modifying process to v-bearing steel slag, and controls rational temperature schedule, so as to keep the vanadium in v-bearing steel slag mainly rich
Combine in vanadium iron Spinel, the physical property of gained vanadium iron Spinel differed with the physical property of other mineral facies in slag compared with
Greatly.
(2) the reduction enrichment method of a kind of vanadium in vanadium containing steel slag of the invention, the embedding cloth of gained vanadium iron Spinel is in FeO phases
In, ferrous oxide has certain magnetism, therefore can be used the mode of magnetic separation separation to vanadium iron Spinel/FeO and other mineral into
Row separation, further ensures the effective recycling of vanadium, while also achieving making full use of for ferriferous oxide in slag.In addition,
Method using the present invention can make vanadium in slag and phosphorus enter different mineral facies, realize vanadium, phosphorus efficiently separates, Fu Fan
Phosphorus is not contained in phase, to be conducive to the utilization after vanadium enrichment phase separation, is solved in the prior art since phosphorus, vanadium are difficult to detach
To influence the problem that rich vanadium mutually uses.
(3) the reduction enrichment method of a kind of vanadium in vanadium containing steel slag of the invention, since vanadium exists with vanadium iron spinel form,
The mineral are highly stable, are not easily accessible in water phase, even if having small part to remain in tailings after the phase separation of rich vanadium, will not cause
Heavy metal pollution.
Description of the drawings
Fig. 1 is the distribution stereoscan photograph of vanadium iron Spinel in slag specimen of the present invention；
The chemical composition of EDS analyses of the Fig. 2 by marking vanadium iron Spinel in Fig. 1；
Fig. 3 is the distribution stereoscan photograph of square iron stone phase in slag specimen of the present invention；
The chemical composition of EDS analyses of the Fig. 4 by marking square iron stone phase in Fig. 3；
Fig. 5 is the distribution stereoscan photograph of silicate phase in slag specimen of the present invention；
The chemical composition of EDS analyses of the Fig. 6 by marking silicate phase in Fig. 5.
Specific implementation mode
To further appreciate that present disclosure, with reference to specific embodiment, the invention will be further described.
Embodiment 1
A kind of reduction enrichment method of vanadium in vanadium containing steel slag of the present embodiment, this method are by being added into v-bearing steel slag
Siliceous materials carry out modifying process to v-bearing steel slag, and control rational temperature schedule, to make the vanadium enrichment in slag in vanadium iron
Spinel, the specific steps are：
(1) slag modifies：The quartz sand of molten steel slag quality 15% is added into molten state v-bearing steel slag as modification agent,
Thus by slag basicity CaO/SiO2It adjusts to 1.5, so that slag is kept the temperature 10 minutes at not less than 1500 DEG C, make modification agent
Fully dissolving.
Above-mentioned v-bearing steel slag makes steel the clinker generated for vanadium-bearing hot metal, and chemical composition is：2.8%V2O5, 45.0%
CaO, 14.7%SiO2, 3.8%MgO, 22.7%FeO, 1.3%P2O5, 1.1%Al2O3, 6.5%Fe, TiO2, other oxygen such as MnO
Compound content summation is 1.8%, remaining is inevitable impurity.
(2) temperature schedule：The molten steel slag modified in step (1) is cold with the cooling rate of 5 DEG C/min under Fe balances
But to 1250 DEG C, room temperature is then cooled to arbitrary rate of temperature fall, i.e., by the vanadium enrichment in v-bearing steel slag in vanadium iron Spinel.
The major components of gained vanadium enrichment phase vanadium iron Spinel are V2O3And FeO, further include that mass percentage is
3.2%MgO and 1.1%Al2O3.Wherein the content of vanadium is with V2O5It calculates and is higher than 20%, and degree of enrichment of the vanadium in the enrichment phase is big
In 90%, degree of enrichment is higher.Vanadium iron Spinel and the relative density difference of other mineral facies in slag obtained by the present embodiment are more than
50%, consequently facilitating the separation of vanadium iron Spinel and other mineral facies, can carry out the vanadium in v-bearing steel slag effectively also
Original enrichment.For the embedding cloth of vanadium iron Spinel in FeO phases, ferrous oxide has certain magnetism, therefore the mode of magnetic separation separation can be used
Vanadium iron Spinel/FeO is detached with other mineral, further ensures the effective recycling of vanadium, while also being realized
Ferriferous oxide makes full use of in slag.In addition, it is different vanadium in slag and phosphorus can be made to enter using the method for the present embodiment
Mineral facies, realize vanadium, phosphorus efficiently separates, and phosphorus is not contained in rich vanadium phase, to be conducive to the utilization after vanadium enrichment phase separation,
It solves the problems, such as in the prior art since phosphorus, vanadium are difficult to detach to influence rich vanadium mutually to use.
Currently, when carrying out enrichment processing to the vanadium in low vanadium steel slag in the prior art, typically under oxidizing atmosphere, pass through
Slag modification promotes the formation of rich vanadium phase-vanadium calcium phosphate solid solution phase and grows up, but due to gained richness vanadium phase and main body mine phase-silicon
The physical property (density and magnetism) of hydrochlorate phase is more close, and difficult so as to cause the separation of rich vanadium phase, this is also to hinder at present
The main bugbear that vanadium in low-grade v-bearing steel slag is recycled.
In view of problem above, seminar where inventor has been devoted to carry out enrichment processing to the vanadium in low vanadium steel slag
Research, it is intended to overcome the shortcomings of that rich vanadium phase separation is difficult by the optimization design of rich vanadium phase.Since the design of rich vanadium phase is necessary
In view of subsequent rich vanadium is separated, the main body in slag is mutually silicate phase, and the property and its difference of rich vanadium phase are bigger, more have
Conducive to separation.Inventor combines lot of experiments to find by analyzing the mine phase composition of v-bearing steel slag and property,
(V,Al)2O3Solid solution, vanadium magnesia spinel-MgV2O4And vanadium iron spinelle-FeV2O4The main body mine phase silicon of mine phase and v-bearing steel slag
The density difference of sour calcium mineral is larger, is suitable as vanadium enrichment phase.But due to (V, Al)2O3Solid solution can only in acid slag shape
At, it cannot achieve in alkaline slag, while considering that FeO contents (20-30%) are more much higher than MgO (3-12%) in slag,
Therefore inventor's final choice vanadium iron spinelle is as vanadium enrichment phase.But inventor has found during the experiment, due to V-alloyed steel
Vanadium in slag exists with a variety of valence states of+3 ,+4 and+5 valences, therefore is unfavorable for the enrichment processing of vanadium, it is therefore desirable to first to different valence state
Vanadium carry out valence state be uniformly processed.Tradition enrichment theory thinks：Element is unified relatively easy to highest price or lowest price, it is unified
Degree is also relatively high, so generally by the element of extraction with the highest price (side that Chinese Patent Application No. 200510094963 uses
Method) or lowest price (method that Chinese Patent Application No. 101824503B is used) enrichment.Wherein to make vanadium with pentavalent by oxidation
The mode that mode carries out enrichment processing is the most commonly used, but this kind of mode of use to vanadium be enriched with when handling, and the phosphorus in slag is not
Avoidable ground can enter rich vanadium phase, and V together with vanadium2O5With P2O5It is difficult to detach, to influence the normal of subsequent recovery vanadium resource
It uses.Therefore how to ensure V2O5With P2O5Efficiently separate, prevent P2O5The influence of performance to recycling vanadium resource is tired
Disturb the problem of inventor's maximum.
Inventor passes through many experiments, finally found that the method using the present embodiment, that is, utilizes v-bearing steel slag itself contained
The presence of metallic iron under the conditions of iron balance, and carries out slag modification by siliceous materials and adjusts basicity to 1~1.5, thus
Vanadium can be made to be enriched to vanadium iron Spinel in the form of trivalent, gained vanadium iron spinelle is enriched with phase density and main body phase density in slag
Difference is larger, to be conducive to the Selective Separation of follow-up vanadium enrichment phase.Simultaneously because vanadium is deposited in the form of vanadium trioxide in the phase
It is being trivalent, it is not easy to solid solution is formed with the phosphorus pentoxide in slag, so as to effectively avoid phosphorus from dissolving in vanadium enrichment phase,
There is very important effect to subsequent solution vanadium-rich mineral vanadium extraction, ensures the performance of recycling vanadium resource.
According to above-mentioned analysis it is found that the key being enriched with to vanadium in the present embodiment is different price in v-bearing steel slag
The vanadium of state is unified to+trivalent.Inventor has found that the valence state of vanadium is mainly determined by two factors in slag under study for action：First, basicity
(CaO%/SiO2%), second is that reducing atmosphere, only controls the two just to can guarantee vanadium iron spinelle when suitable range
The formation of phase.Studies have shown that when basicity is more than 1.5, a big chunk vanadium then forms calcium vanadate (vanadium is in the compound in slag
+ 5 valences) it is solid-solution in dicalcium silicate phase, but when basicity is too low, vanadium is then dissolved in tetravalence in silica, above-mentioned two situations
All it is unfavorable for the formation of vanadium iron Spinel.
The present embodiment it is bright by be added into v-bearing steel slag siliceous materials carry out modification to the basicity of v-bearing steel slag into
Row adjustment.In addition, strongly reducing atmosphere can be by VO in slagx、FeOt、P2O5Equal oxides restore to form high phosphorus vanadium-bearing hot metal, it is seen that
Vanadium iron spinelle can not also be formed under strong reducing condition, therefore just need that weak reducing condition, weakly reducing atmosphere is used generally to use
CO/CO2Or H2/H2O mixed gas is realized, but since converter tapping slag is carried out in open space, above-mentioned two groups easy
Combustion, explosive/toxic gas can not be applied.Inventor has found in the course of the research：Carry 5-10% when slagging tap due to converter in slag secretly
Metallic iron, can also be unified to+trivalent by vanadium under the conditions of iron balance, the present invention be not only utilized using the method for iron balance
The characteristic of slag itself, and it is also beneficial to field conduct.
The composition that different mine phases in v-bearing steel slag are modified to solid-state is detected, and specific method is：At different locations into
Row sampling, (as shown in Fig. 1, Fig. 3, Fig. 5) is detected under scanning electron microscope, and chemical composition (the analysis knot of each phase is analyzed by EDS
Fruit is respectively as shown in Fig. 2, Fig. 4 and Fig. 6).Wherein table 1 show the chemical composition of each mineral facies in reduction enrichment slag, can by table 1
To find out：Vanadium in vanadium containing steel slag is distributed in square iron stone phase and vanadium iron Spinel in the present embodiment, content of vanadium in square iron stone phase
Relatively low, vanadium iron Spinel content of vanadium is very high, 18% or more has been reached in terms of V, silicate phase is free of vanadium, successfully realizes vanadium
Reduction enrichment.
The chemical composition of vanadium enrichment phase and other mine phases in 1 slag of table
Embodiment 2
A kind of reduction enrichment method of vanadium in vanadium containing steel slag of the present embodiment, this method are by being added into v-bearing steel slag
Siliceous materials carry out modifying process to v-bearing steel slag, and control rational temperature schedule, to make the vanadium enrichment in slag in vanadium iron
Spinel, the specific steps are：
(1) slag modifies：The quartz sand of molten steel slag quality 25% is added into molten state v-bearing steel slag as modification agent,
Thus by slag basicity CaO/SiO2It adjusts to 1, so that slag is kept the temperature 8 minutes at not less than 1500 DEG C, modification agent is made to fill
Divide dissolving.Above-mentioned v-bearing steel slag makes steel the clinker generated for vanadium-bearing hot metal, and chemical composition is：2.2%V2O5, 43.6%
CaO, 18.2%SiO2, 5.0%MgO, 20.4%FeO, 1.3%P2O5, 0.8%Al2O3, 6.9%Fe, TiO2, other oxygen such as MnO
Compound content summation is 1.6%.
(2) temperature schedule：The molten steel slag modified in step (1) is cold with the cooling rate of 3 DEG C/min under Fe balances
But to 1300 DEG C, room temperature is then cooled to arbitrary rate of temperature fall, i.e., by the vanadium enrichment in v-bearing steel slag in vanadium iron Spinel.
The major components of gained vanadium enrichment phase vanadium iron Spinel are V2O3And FeO, wherein the content of vanadium is with V2O5It calculates high
In 20%, and degree of enrichment of the vanadium in the enrichment phase is more than 90%, and gained vanadium iron Spinel further includes that mass percentage is
2%MgO.Vanadium iron Spinel obtained by the present embodiment and the relative density difference of other mineral facies in slag are more than 50%, and vanadium iron point
P element is free of in spar phase, to be easy to the separation of follow-up rich vanadium phase and other mineral facies, and prevents phosphorus to recycling vanadium usability
The influence of energy, ensures that it is subsequently efficiently used.
Embodiment 3
A kind of reduction enrichment method of vanadium in vanadium containing steel slag of the present embodiment, this method are by being added into v-bearing steel slag
Siliceous materials carry out modifying process to v-bearing steel slag, and control rational temperature schedule, to make the vanadium enrichment in slag in vanadium iron
Spinel, the specific steps are：
(1) slag modifies：The flyash of molten steel slag quality 20% is added into molten state v-bearing steel slag as modification agent,
Thus by slag basicity CaO/SiO2It adjusts to 1.3, so that slag is kept the temperature 15 minutes at not less than 1500 DEG C, make modification agent
Fully dissolving.
Above-mentioned v-bearing steel slag makes steel the clinker generated for vanadium-bearing hot metal, and chemical composition is：2.5%V2O5, 47.4%
CaO, 16.1%SiO2, 3.7%MgO, 21.8%FeO, 1.1%P2O5, 0.9%Al2O3, 5.3%Fe, TiO2, other oxygen such as MnO
Compound content summation is 1.2%.
(2) temperature schedule：The molten steel slag modified in step (1) is cold with the cooling rate of 1 DEG C/min under Fe balances
But to 1280 DEG C, room temperature is then cooled to arbitrary rate of temperature fall, i.e., by the vanadium enrichment in v-bearing steel slag in vanadium iron Spinel.
The major components of gained vanadium enrichment phase vanadium iron Spinel are V2O3And FeO, wherein the content of vanadium is with V2O5It calculates high
In 20%, and degree of enrichment of the vanadium in the enrichment phase is more than 90%, and gained vanadium iron Spinel further includes mass percentage 3%
Al2O3.Vanadium iron Spinel obtained by the present embodiment and the relative density difference of other mineral facies in slag are more than 50%, and vanadium iron point is brilliant
Shi Xiangzhong is free of P element, to be easy to the separation of follow-up rich vanadium phase and other mineral facies, and prevents phosphorus to recycling vanadium performance
Influence, ensure that it is subsequently efficiently used.
According to embodiment 1-3, the vanadium enrichment phase and the density contrast of other mine phases that method using the present invention obtains are big, are easy to
Separation；Without containing phosphorus, be conducive to the utilization after rich vanadium phase separation；Chemical property is stablized, and the remnants after separation are free from environmental pollution, are
A kind of environmentally protective vanadium enrichment method.
Claims (7)
1. a kind of reduction enrichment method of vanadium in vanadium containing steel slag, which is characterized in that this method is by being added into v-bearing steel slag
Siliceous materials carry out modifying process to v-bearing steel slag, and control rational temperature schedule, to make the vanadium enrichment in slag in vanadium iron
Spinel, the specific steps are：
(1) slag modifies：Siliceous materials are added into molten state v-bearing steel slag as modification agent, by slag basicity CaO/SiO2It adjusts
It is whole to 1~1.5；
(2) temperature schedule：The molten steel slag modified in step (1) is cooled down under Fe balances with the cooling rate of 1~5 DEG C/min
To 1250~1300 DEG C, it is then cooled to room temperature, i.e., by the vanadium enrichment in v-bearing steel slag in vanadium iron Spinel.
2. a kind of reduction enrichment method of vanadium in vanadium containing steel slag according to claim 1, it is characterised in that：The step
(1) siliceous materials, which are added to after v-bearing steel slag, in makes molten steel slag keep the temperature 8-15 minutes at not less than 1500 DEG C.
3. a kind of reduction enrichment method of vanadium in vanadium containing steel slag according to claim 1 or 2, it is characterised in that：Described
It is the 15-25% of molten steel slag quality that siliceous materials, which select quartz sand or flyash, additive amount,.
4. a kind of reduction enrichment method of vanadium in vanadium containing steel slag according to claim 3, it is characterised in that：Described contains vanadium
Slag makes steel the clinker generated for vanadium-bearing hot metal comprising the chemical constituent of following mass percent：1~5%V2O5, 40~
55%CaO, 10~20%SiO2, 3~12%MgO, 20~30%FeO, 0~4%P2O5, 0~5%Al2O3, 5~10%Fe.
5. a kind of reduction enrichment method of vanadium in vanadium containing steel slag according to claim 4, it is characterised in that：Gained vanadium enrichment
The major components of phase vanadium iron Spinel are V2O3And FeO, wherein the content of vanadium is with V2O5It calculates and is higher than 20%, and vanadium is in the richness
The degree of enrichment collected in phase is more than 90%.
6. a kind of reduction enrichment method of vanadium in vanadium containing steel slag according to claim 5, it is characterised in that：Gained vanadium iron point
Spar further includes mutually that mass percentage is 0~3%MgO and 0~3%Al2O3。
7. a kind of reduction enrichment method of vanadium in vanadium containing steel slag according to claim 5, it is characterised in that：Gained vanadium iron point
The relative density difference of spar phase and other mineral facies in slag is more than 50%, and P element is free of in vanadium iron Spinel.
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| CN108374082B (en) * | 2018-02-08 | 2019-06-07 | 北京科技大学 | A method of vanadium grade in vanadium concentrate is improved by oxidation processes-magnetic separation separation |
| CN110683580B (en) * | 2018-07-06 | 2020-11-06 | 中国科学院过程工程研究所 | Method for preparing high-purity vanadium pentoxide from high-calcium high-phosphorus vanadium slag through low-temperature chlorination |
| CN110592400A (en) * | 2019-08-15 | 2019-12-20 | 中南大学 | Novel vanadium extraction and dressing combined method for high-silicon low-calcium stone coal |
| CN110699554A (en) * | 2019-10-16 | 2020-01-17 | 中冶赛迪工程技术股份有限公司 | Method for producing vanadium-rich iron from vanadium-rich slag |
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