CN107226484B - A kind of method that compound extracting prepares vanadic anhydride - Google Patents
A kind of method that compound extracting prepares vanadic anhydride Download PDFInfo
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Abstract
The present invention relates to the preparation methods of vanadic anhydride, provide a kind of method that compound extracting prepares vanadic anhydride, include the following steps: that (1) is leached；(2) it restores；(3) it extracts: extracting feed liquid containing vanadium with the composite extractant that phosphoric acid ester organic matter and modification agent are formulated, the load organic phases containing vanadium are made；(4) be stripped: with sulfuric acid or rich alum liquid is made in the back extraction load organic phases of the sulfuric acid solution containing vanadium；(5) it deacidifies: extracting excessive acid in rich vanadium liquid；(6) precipitation；(7) it calcines.The present invention can not only improve the recovery rate and purity of vanadium, to improve the yield and purity of vanadic anhydride product, moreover it is possible to reduce the consumption of alkali, reduce production cost using a kind of composite extractant extracting vanadium with stronger extracting power and back extraction ability.
Description
Technical field
The present invention relates to field of metallurgy, and in particular to one kind is by composite extractant extraction vanadium extraction to five oxidation two of preparation
The method of vanadium.
Background technique
Vanadium (symbol of element V) is a kind of argenteous high-melting-point refractory metal, and main oxide form includes five
V 2 O (V205), and vanadic anhydride is widely used in the industries such as metallurgy, chemical industry, as the high speed of China's modernization construction is sent out
Exhibition, the demand of vanadic anhydride are also increasing.In nature, navajoite resource is primarily present in the vanadium titanium magnetic with iron ore symbiosis
Iron ore and the substantially former of vanadic anhydride is then prepared with vanadium in the bone coal navajoite raw material of carbon symbiosis, is extracted from containing vanadium raw materials
Reason are as follows: enter vanadium in liquid phase by solid phase (such as: bone coal or bone coal calcine slag) by extract technology, obtain leachate, then adopt
Make vanadium enrichment with means such as extraction or ion exchanges, recycles the technologies such as precipitating, make vanadium by liquid-phase conversion solid phase, finally forge again
Burning solid phase precipitation can be obtained vanadic anhydride.It can be seen that the overall recovery rate of vanadium becomes the key of vanadic anhydride yield
Determinant.
The process route for extracting vanadium from containing vanadium raw materials in industry at present mainly has following manner: using after sodium calcination method
Go out to obtain leachate with water logging, obtains leachate with Ore Leaching using after blank calcination method, obtained using after calcification calcination method with Ore Leaching
Leachate and the direct Ore Leaching of raw ore obtain leachate.It is subsequent for grade containing vanadium (the useful object content of ore) higher raw material
The technique more mature to leachate be: after removal of impurities, it is rich that the higher vanadium of purity is directly obtained by way of oxidation-ammonium salt precipitation
Collect object；However raw material lower for grade containing vanadium contains more impurity since vanadium concentration is relatively low in gained leachate simultaneously
Element, if continuing using processing method above-mentioned, not only treating capacity is larger, but also the rate of recovery of vanadium is low, obtained rich containing vanadium
It is relatively low to collect object purity.Leachate lower for concentration containing vanadium applies more extraction process at present are as follows: leaching-solvent extraction
Take-be stripped rich vanadium-precipitating vanadium.
Leachate extraction process lower for concentration containing vanadium, studying more is constituted using dioctylphosphoric acid ester and TBP
Organic phase extract vanadium from the feed liquid of vanadium containing tetravalence, Chinese patent literature CN101418385A, CN101381818A,
CN101450814A, CN104017999A, CN101289705A, five oxygen of wet underwater welding in the slave vanadium concentrate that Yang Shaowen et al. is delivered
Change the research of two vanadium new processes, the dioctylphosphoric acid ester-TBP that Rites of the Zhou Dynasty chastity et al. is delivered extracts from Panzhihua vanadium titanium slag vanadium, titanium is ground
Study carefully and all uses this method in document；The concentration of vanadium in the pH value and feed liquid that this method passes through control feed liquid, using non-saponifiable extraction
Agent can be realized higher separating effect by multi-stage counter current extraction, be able to achieve 90% or more extraction yield, and back extraction gained contains vanadium
Impurity content is few in feed liquid, and the purity of vanadium is greater than 98%.But there are larger problems for the technique: anti-due to dioctylphosphoric acid ester
Extract indifferent, so needing stronger acid condition in stripping process, Acid concentration of stripping solution used is higher, about 1.5-
The sulfuric acid solution of 2.5mol/L, and need to control small compare (volume ratio of organic phase and water phase) and can be only achieved higher back extraction
Rate, sulfuric acid concentration is higher in the rich vanadium liquid of gained after back extraction, needs to consume a large amount of alkali in precipitation process and carrys out neutralisation of sulphuric acid, wastes
A large amount of acid and a large amount of alkali, making the technique, increased production cost, while salt content is higher in deposition vanadium mother liquid, both influences product
Purity, and many costs are increased to sewage treatment.
Leachate extraction process lower for concentration containing vanadium, there are also use 2- ethylhexyl phosphonic acids single 2-ethyl base
The method of ester and TBP hybrid extraction vanadium, Chinese patent literature CN104064799A, CN104064799A, Liu Zhuolin et al. are delivered
2- ethylhexyl phosphonic acids single 2-ethyl base ester from vanadium slag leachate in extracting vanadium Research Literature all use this method；It should
Extractant used in method is that base ester (20%-30%) and TBP are prepared the higher 2- ethylhexyl phosphonic acids single 2-ethyl of concentration
It forms, the pH for extracting feed liquid is 3~4, and extraction is comparably 5-1:1, and the extraction of 3-6 stage countercurrent is extracted with above-mentioned with dioctylphosphoric acid ester
The method taken is compared, and the load organic oppositing back-extraction of 2- ethylhexyl phosphonic acids single 2-ethyl base ester extracting vanadium can be selected lower
The sulfuric acid solution of concentration is stripped, and has excellent back extraction ability.But there is also larger problems for the technique, 2- ethyl is
The ability of base phosphonic acids single 2-ethyl base ester extracting vanadium is weaker than dioctylphosphoric acid ester extracting power very much, so in extracting vanadium
Needing higher concentration 2- ethylhexyl phosphonic acids single 2-ethyl, base ester and higher pH of leaching solution are just able to achieve higher extraction
Take rate, and this to will result directly in extraction process consumption alkali number more, generate more high-salt wastewater, increase cost of sewage disposal.
It can be seen that in order to improve the recovery rate of vanadium and purity, so that the yield and purity of vanadic anhydride product are improved,
The consumption of alkali is reduced, production cost is reduced, urgent need researches and develops a kind of existing stronger extracting power, and can be in lower acid item
The extractant of vanadium is stripped under part.
Summary of the invention
The purpose of the present invention is to provide a kind of methods that compound extracting prepares vanadic anhydride, are had using one kind relatively strong
Extracting power and back extraction ability composite extractant extracting vanadium, the recovery rate and purity of vanadium can not only be improved, thus improve five
The yield and purity of V 2 O product, moreover it is possible to reduce the consumption of alkali, reduce production cost.
In order to achieve the above objectives, base case of the invention is: providing the side that a kind of compound extracting prepares vanadic anhydride
Method includes the following steps:
(1) it leaches: containing vanadium raw materials with Ore Leaching, the leachate that vanadium content is 0.1g/L-10.0g/L is made；
(2) it restores: using reducing agent reducing leaching liquid, the feed liquid containing vanadium of pH=1.5-2.5 is made；
(3) it extracts: extracting feed liquid containing vanadium with the composite extractant that phosphoric acid ester organic matter and modification agent are formulated, be made
Load organic phases containing vanadium；
(4) be stripped: with sulfuric acid or rich vanadium liquid is made in the back extraction load organic phases of the sulfuric acid solution containing vanadium；
(5) it deacidifies: extracting excessive acid in rich vanadium liquid；
(6) precipitation: add rich vanadium liquid of the alkali to after deacidifying, adjust pH=6-7, stir 0.5h-1.2h, be aged 0.5h-1.2h；
(7) calcine: vanadic anhydride is made in oxygen-enriched calcining precipitation at 500 DEG C -600 DEG C.
When by adopting the above technical scheme, working principle is as follows:
(1) it leaches: referring to the reaction for releasing vanadium from ore raw materials by hydrogen ion, different types of ore leaches
Technique difference, only illustrates by taking the ore after sulfuric acid leaching oxidizing roasting as an example, specific Leach reaction formula is as follows herein:
2Fe(VO3)3+6H2SO4→3(VO2)2SO4+6H2O+Fe2(SO4)3
(2) it restores: i.e. by V5+It is reduced into the V being easily extracted4+Process, by taking Fe powder as an example, reaction equation is as follows:
Fe+2VO2 ++4H+→Fe2++2VO2++2H2O
Fe+2Fe3+→3Fe2+
(3) it extracts: different component in feed liquid containing vanadium being utilized to have different solubility in composite extractant, make vanadium from containing
It is separated in vanadium feed liquid into the operation in composite extractant (load organic phases).Use (HR) herein2Composite extractant is represented,
The reaction equation of extraction is as follows:
mVO2++n(HR)2→(VO)m(R)2m(HR)2(n-m)+2mH+
(4) be stripped: the inverse process extracted, vanadium return to the process of water phase from load organic phases.By taking sulfuric acid as an example, instead
The reaction equation of extraction is as follows:
mH2SO4+(VO)mR2m(HR)2(n-m)→mVOSO4+H2mR2m(HR)2(n-m)
(5) deacidify: the acid containing higher concentration in resulting richness vanadium liquid after back extraction extracts most in rich vanadium liquid
Acid can effectively reduce the consumption of alkali in subsequent precipitation step.
(6) precipitation: tetravalent vanadium ion becomes the vanadium precipitating of solid phase in the presence of alkali, and by taking ammonium hydroxide as an example, reaction equation is as follows:
2VOSO4+6NH4OH→(NH4)2V2O5↓+2(NH4)2SO4+3H2O
(7) it calcines: precipitation drying being placed in oxygen-enriched heat resolve at 500 DEG C -600 DEG C, vanadic anhydride, reaction is made
Formula is as follows:
2(NH4)2V2O5+O2→2V2O5+4NH3↑+2H20↑
The beneficial effect of above-mentioned technical proposal is:
It solves during dioctylphosphoric acid ester in the prior art extracts tetravalence vanadium and is stripped and 2- ethyl in the presence of easily extraction hardly possible
There is difficult extraction easily back extraction in base ester to base phosphonic acids single 2-ethyl, and phosphoric acid ester organic matter and modification agent are answered
With obtained composite extractant, not only there is stronger extracting power, also there is stronger back extraction ability, it can be in lower acid
Property under the conditions of be stripped vanadium, and when extraction or back extraction can be effectively prevented in modification agent, occurs emulsification or generates third phase；This
Composite extractant energy enriched concentration is lower to contain vanadium solution, by promoting extraction and the back extraction ratio of vanadium, to effectively improve total
The yield of the recovery rate of vanadium, final vanadic anhydride is also improved.
Since this composite extractant has stronger back extraction ability, so only needing in stripping process using low concentration
Sulfuric acid well vanadium can be stripped out, and most of acid all extraction and separation in rich vanadium liquid are come out after being stripped, institute
With acid remaining during subsequent precipitation with regard to seldom, the corresponding consumption that will significantly reduce alkali, so that in precipitation step
The salt that acid-base neutralization generates is also few, effectively increases the purity of product, reduces cost of sewage disposal, reduces and be produced into
This.
Further, reducing agent is one or more of iron powder, sodium sulfite, sulfur dioxide, ascorbic acid.Use reducing agent
Reduction, can not only be by V5+It is reduced into the V being easily extracted4+, moreover it is possible to make Fe3+It is reduced to be not easy to be extracted by this composite extractant
Fe2+, the influence of impurity can be reduced, product purity is effectively improved.
Further, composite extractant is mixed by di-phosphate ester extractant, phosphate monoester extractant and modification agent, and is heated to
65 DEG C of -90 DEG C of stirring 0.8h-1.2h are made, by volume fraction, wherein di-phosphate ester extractant 50%-80%, and phosphate monoester
Extractant 10%-40%, remaining is modification agent.Di-phosphate ester extractant extracting power in the technical program is stronger, mono phosphoric acid ester
The extracting power of ester extractant is relatively weak, but under the premise of controlling liquid ratio, the extracting power of this composite extractant
Still very strong, can easily extraction and separation go out vanadium from sulfuric acid solution, effectively improve the recovery rate of vanadium；Di-phosphate ester extraction
The back extraction ability of agent is relatively weak, but phosphate monoester extractant has very strong back extraction ability；This composite extractant pass through by
The two mixing is complementary, can effectively improve the recovery rate of vanadium；And this composite extractant can be stripped vanadium under lower acid condition,
Energy enriched concentration is lower to contain vanadium solution, and extraction and the stripping efficiency of vanadium is substantially improved, effectively improves the recovery rate of vanadium, to mention
The yield of high final products vanadic anhydride.
Further, modification agent is containing carbon number between one or more of the alkylol of 8-13.Modification agent can effectively be prevented
Emulsification occurs when only extracting or be stripped or generates third phase, water phase and organic phase are efficiently separated, kept away
Exempting from water phase entrainment organic phase causes organic phase to lose, and causes damages so that vanadium be avoided to enter water phase, effectively increases the extraction of vanadium
Rate.
Further, composite extractant is diluted to the organic phase of volumetric concentration 5%-55% with diluent, organic phase when extraction
Volume ratio with water phase is 1-1.5:1, is extracted using 2-6 stage countercurrent.Extraction uses multi-stage counter current extraction, and multi-stage counter current extraction is
Feed liquid (water phase) and extractant (organic phase) are successively by opposite direction by different levels, and final extraction phase is discharged from feed end, organic phase
From adding one end of extractant to be discharged, the MULTI CONTACT process that this water phase and organic phase flow in the opposite direction can be with less
Extractant obtain relatively high extraction yield.Not only increase the recovery rate of vanadium, moreover it is possible to it is miscellaneous to efficiently separate out vanadium and iron ion etc.
Matter improves product purity, while being also greatly reduced the dosage of extractant, reduces production cost.
Further, sulfuric acid back extraction concentration is 0.3mol/L-1mol/L, and the volume ratio of organic phase and water phase is 5-8 when back extraction:
1, it is stripped using 3-8 stage countercurrent.Stripping process also uses the mode of multi-stage countercurrent, and principle is similar with multi-stage counter current extraction, i.e.,
It allows water phase and organic phase to flow in the opposite direction, carries out MULTI CONTACT, relatively high back extraction ratio can be obtained with less sulfuric acid.
The recovery rate of vanadium is not only further improved, while being also greatly reduced the dosage of sulfuric acid, reduces production cost.
Further, the organic phase after back extraction is using one of the hydrochloric acid of 0.3mol/L-0.6mol/L or oxalic acid or two
Kind removes iron, washing, and is recycled as composite extractant in step (3).In organic phase (i.e. composite extractant) after back extraction
Containing a certain amount of iron ion, back extraction is carried out with one of hydrochloric acid or oxalic acid or two kinds and removes iron, is then suitably washed
It washs, the composite extractant after washed removal of impurities can also be recycled in extraction step, and it is this organic that composite extractant is effectively reduced
The consumption of solvent, further decreases production cost.
Further, the extractant that step (5) uses is the amine extractant of volumetric concentration 10%-30%, and when extraction is organic
It is mutually 1-5:1 with the volume ratio of water phase, extraction series is 1-3 grades.There is the nitrogen-atoms of lone pair electrons in amine extracted agent molecule,
It can be with the H in inorganic acid+Stable coordinate bond is formed, so that most acid in rich vanadium liquid is extracted, so that subsequent precipitation
Remaining sour less, the corresponding consumption that will significantly reduce alkali in journey, so that the salt generated in precipitation step acid-base neutralization
Also few, the purity of product is effectively increased, cost of sewage disposal is reduced, to reduce the production cost of vanadic anhydride.
Further, the organic phase after step (5) deacidification washs depickling using deposition vanadium mother liquid and/or neutral water, when washing
The volume ratio of organic phase and water phase is 1:1-5, and washing series is 3-5 grades；Organic phase after washing is recycled；Water after washing
Sulfuric acid is added in phase, is recycled in step (1) and (4).It is female with neutral water or precipitation after amine extractant comes out acid extraction
The mixture of liquid or water and deposition vanadium mother liquid carries out multistage washing；Organic phase (i.e. amine extractant) after multistage washing can be with
It is recycled, the consumption of this organic solvent of amine extractant is effectively reduced, and then remained in the water phase after multistage washing
The acid that is added when part is stripped, at this time only need to add a certain amount of acid just and can be recycled again in leaching step or
Stripping steps reduce consumption sour in entire technique, reduce production cost.
Further, the alkali that precipitation step uses is one or more of ammonium hydrogen carbonate, sodium hydroxide, ammonium hydroxide, ammonium carbonate.
Tetravalent vanadium ion becomes the vanadium precipitating of solid phase in the presence of alkali, and vanadium precipitating can not only be effectively made in the alkali in the technical program,
And cost is relatively low, can further decrease the production cost of vanadic anhydride.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Embodiment 1
The method that a kind of compound extracting provided in this embodiment prepares vanadic anhydride, includes the following steps:
(1) it leaches: leaching feed liquid containing vanadium with dilute sulfuric acid, liquid-solid ratio is leached by control, it is 0.1g/L's that vanadium content, which is made,
Leachate.
(2) it restores: being restored with the iron powder of 1.2 times of theoretical additive amounts, obtain the feed liquid containing vanadium that pH is 1.5, reducing agent
Additive amount be greater than theoretical value, reducing agent and pentavalent vanadium, impurity F e can be increased3+Contact area, improve technological reaction efficiency.
(3) extract: mixed volume score is 80% di-phosphate ester extractant, 10% phosphate monoester extractant and 10%
Isooctanol, wherein di-phosphate ester extractant can be dioctylphosphoric acid ester or two (1- methylhexyl) phosphoric acid, the present embodiment are excellent
Dioctylphosphoric acid ester is selected, phosphate monoester extractant can be 2- ethylhexyl phosphonic acids single 2-ethyl base ester or styryl phosphonic acid
Single (2- ethylhexyl) ester, base ester, heating water bath stir the preferred 2- ethylhexyl phosphonic acids single 2-ethyl of the present embodiment to 65 DEG C
Mix 0.8h be made composite extractant, and with diluent MextralDT100 be diluted to volumetric concentration be 5% organic phase, by its with
With concentration 5% dioctylphosphoric acid ester+3%TBP, 5%2- ethylhexyl phosphonic acids single 2-ethyl base ester+3%TBP organic phase into
The extraction situation of three kinds of organic phases vanadium after extraction back extraction is compared in row comparison, and the results are shown in Table 1.Extracted with aforementioned organic phase
Take feed liquid containing vanadium, the volume ratio of organic phase and water phase is 1:1, extraction time 6min when extraction, is extracted using 2 stage countercurrents, system
The load organic phases of vanadium must be contained.
(4) it is stripped: being stripped the load organic phases containing vanadium with the sulfuric acid of 1mol/L, the body of organic phase and water phase when back extraction
Product is stripped, single-stage Stripping times 8min using 3 stage countercurrents than being 8:1, richness vanadium liquid is made.Organic phase after back extraction uses
The hydrochloric acid of 0.3mol/L removes iron, except the organic phase after iron continues to make by can be used as the organic phase of extraction step after washing appropriate
With, it can the vanadium in cycling extraction feed liquid containing vanadium.
(5) it deacidifies: excessive acid in the rich vanadium liquid is extracted using 30% lauryl amine, organic phase and water phase when extraction
Volume ratio be 5:1, extraction series be 1 grade.Organic phase (i.e. lauryl amine phase) after extraction acid is using neutral water washing depickling, washing
When organic phase and water phase volume ratio be 1:5, washing series be 3 grades, the organic phase after washing can be recycled, it can use
Acid in cycling extraction richness vanadium liquid；In wash water (i.e. water phase contains a certain amount of acid) after washing, a certain amount of sulphur is added
Acid just can be used as the sulfuric acid solution circulation containing vanadium for leaching step or stripping steps again.
(6) precipitation: the inorganic phase (i.e. rich vanadium liquid) after extraction acid, acid content is lower, and ammonium carbonate is added, adjusts the pH=of solution
6, mixing time 30min, digestion time is 30min, it can be achieved that the rate of deposition of vanadium is greater than 99%.
(7) calcine: gained precipitating drying oxygen-enriched calcining under the conditions of 500~600 DEG C can be obtained grade is greater than 99% five
V 2 O.
Table 1
It can be seen that although composite extractant extracting power is declined slightly compared to dioctylphosphoric acid ester from experiment acquired results,
But back extraction performance is higher than dioctylphosphoric acid ester；Although composite extractant is stripped ability and compares 2- ethylhexyl phosphonic acids single 2-ethyl
Base ester is declined slightly, but extraction ability is higher than 2- ethylhexyl phosphonic acids single 2-ethyl base ester.NEW TYPE OF COMPOSITE extractant
The recovery rate highest of vanadium.
Embodiment 2
The method that a kind of compound extracting provided in this embodiment prepares vanadic anhydride, includes the following steps:
(1) it leaches: leaching feed liquid containing vanadium with dilute sulfuric acid, liquid-solid ratio is leached by control, it is 0.5g/L's that vanadium content, which is made,
Leachate.
(2) it restores: being restored with the sulfur dioxide of 1.3 times of theoretical additive amounts, obtain the feed liquid containing vanadium that pH is 1.8, also
The additive amount of former agent is greater than theoretical value, can increase reducing agent and pentavalent vanadium, impurity F e3+Contact area, improve technological reaction
Efficiency.
(3) extract: mixed volume score is 70% di-phosphate ester extractant, 20% phosphate monoester extractant and 10%
Isononyl alcohol, wherein di-phosphate ester extractant can be dioctylphosphoric acid ester or two (1- methylhexyl) phosphoric acid, the present embodiment are excellent
Dioctylphosphoric acid ester is selected, phosphate monoester extractant can be 2- ethylhexyl phosphonic acids single 2-ethyl base ester or styryl phosphonic acid
Single (2- ethylhexyl) ester, base ester, heating water bath stir the preferred 2- ethylhexyl phosphonic acids single 2-ethyl of the present embodiment to 70 DEG C
Mix 1h be made composite extractant, and with diluent MextralDT100 be diluted to volumetric concentration be 8% organic phase, by its with it is same
Base ester+4%TBP organic phase carries out 8% dioctylphosphoric acid ester+4%TBP, 8%2- ethylhexyl phosphonic acids single 2-ethyl of concentration
The extraction situation of three kinds of organic phases vanadium after extraction back extraction is compared in comparison, and the results are shown in Table 2.With aforementioned organic extractant phase
Feed liquid containing vanadium, the volume ratio of organic phase and water phase is 1.2:1, extraction time 6min when extraction, is extracted using 2 stage countercurrents, system
The load organic phases of vanadium must be contained.
(4) it is stripped: being stripped the load organic phases containing vanadium with the sulfuric acid of 0.8mol/L, organic phase and water phase when back extraction
Volume ratio is 7:1, is stripped using 5 stage countercurrents, single-stage Stripping times 7min, and richness vanadium liquid is made.Organic phase after back extraction uses
The hydrochloric acid of 0.5mol/L removes iron, except the organic phase after iron continues to make by can be used as the organic phase of extraction step after washing appropriate
With, it can the vanadium in cycling extraction feed liquid containing vanadium.
(5) it deacidifies: excessive acid in the rich vanadium liquid is extracted using 30% undecylamine, organic phase and water phase when extraction
Volume ratio be 4:1, extraction series be 1 grade.Organic phase (i.e. undecylamine phase) after extraction acid washs depickling using deposition vanadium mother liquid, washes
The volume ratio of organic phase and water phase is 1:4 when washing, and washing series is 3 grades, and the organic phase after washing can be recycled, it can
For the acid in cycling extraction richness vanadium liquid；In wash water (i.e. water phase contains a certain amount of acid) after washing, add a certain amount of
Sulfuric acid just can be used as the sulfuric acid solution circulation containing vanadium for leaching step or stripping steps again.
(6) precipitation: the inorganic phase (i.e. rich vanadium liquid) after extraction acid, acid content is lower, and ammonium hydroxide is added, adjusts the pH=of solution
6.5, mixing time 30min, digestion time is 30min, it can be achieved that the rate of deposition of vanadium is greater than 99%.
(7) calcine: gained precipitating drying oxygen-enriched calcining under the conditions of 500~600 DEG C can be obtained grade is greater than 99% five
V 2 O.
Table 2
It can be seen that although composite extractant extracting power is declined slightly compared to dioctylphosphoric acid ester from experiment acquired results,
But back extraction performance is higher than dioctylphosphoric acid ester；Although composite extractant is stripped ability and compares 2- ethylhexyl phosphonic acids single 2-ethyl
Base ester is declined slightly, but extraction ability is higher than 2- ethylhexyl phosphonic acids single 2-ethyl base ester.NEW TYPE OF COMPOSITE extractant
The recovery rate highest of vanadium.
Embodiment 3
The method that a kind of compound extracting provided in this embodiment prepares vanadic anhydride, includes the following steps:
(1) it leaches: leaching feed liquid containing vanadium with dilute sulfuric acid, liquid-solid ratio is leached by control, it is 3.0g/L's that vanadium content, which is made,
Leachate.
(2) it restores: being restored with the ascorbic acid of 1.2 times of theoretical additive amounts, obtain the feed liquid containing vanadium that pH is 2, reduction
The additive amount of agent is greater than theoretical value, can increase reducing agent and pentavalent vanadium, impurity F e3+Contact area, improve technological reaction effect
Rate.
(3) extract: mixed volume score is 60% di-phosphate ester extractant, 30% phosphate monoester extractant and 10%
Decyl alcohol, wherein di-phosphate ester extractant can be dioctylphosphoric acid ester or two (1- methylhexyl) phosphoric acid, the present embodiment are preferred
Dioctylphosphoric acid ester, phosphate monoester extractant can be 2- ethylhexyl phosphonic acids single 2-ethyl base ester or styryl phosphonic acid list
(2- ethylhexyl) ester, base ester, heating water bath stir the preferred 2- ethylhexyl phosphonic acids single 2-ethyl of the present embodiment to 75 DEG C
1h is made composite extractant, and is diluted to the organic phase that volumetric concentration is 10% with diluent MextralDT100, by its with it is same
10% dioctylphosphoric acid ester+5%TBP, 10%2- ethylhexyl phosphonic acids single 2-ethyl of concentration base ester+5%TBP organic phase into
The extraction situation of three kinds of organic phases vanadium after extraction back extraction is compared in row comparison, and the results are shown in Table 3.Extracted with aforementioned organic phase
Taking feed liquid containing vanadium, the volume ratio of organic phase and water phase is 1.2:1, extraction time 5min when extraction, it is extracted using 2 stage countercurrents,
The load organic phases containing vanadium are made.
(4) it is stripped: being stripped the load organic phases containing vanadium with the sulfuric acid of 0.6mol/L, organic phase and water phase when back extraction
Volume ratio is 6:1, is stripped using 6 stage countercurrents, single-stage Stripping times 5min, and richness vanadium liquid is made.Organic phase after back extraction uses
The hydrochloric acid of 0.6mol/L removes iron, except the organic phase after iron continues to make by can be used as the organic phase of extraction step after washing appropriate
With, it can the vanadium in cycling extraction feed liquid containing vanadium.
(5) it deacidifies: excessive acid in the rich vanadium liquid is gone out using 30% Extraction of Acids with Trioctylamine, organic phase and water phase when extraction
Volume ratio be 3:1, extraction series be 2 grades.Organic phase (i.e. trioctylamine phase) after extraction acid is using neutral water washing depickling, washing
When organic phase and water phase volume ratio be 1:3, washing series be 3 grades, the organic phase after washing can be recycled, it can use
Acid in cycling extraction richness vanadium liquid；In wash water (i.e. water phase contains a certain amount of acid) after washing, a certain amount of sulphur is added
Acid just can be used as the sulfuric acid solution circulation containing vanadium for leaching step or stripping steps again.
(6) precipitation: the inorganic phase (i.e. rich vanadium liquid) after extraction acid, acid content is lower, and sodium hydroxide is added, adjusts the pH of solution
=6.5, mixing time 30min, digestion time is 30min, it can be achieved that the rate of deposition of vanadium is greater than 99%.
(7) calcine: gained precipitating drying oxygen-enriched calcining under the conditions of 500~600 DEG C can be obtained grade is greater than 99% five
V 2 O.
Table 3
It can be seen that although composite extractant extracting power is declined slightly compared to dioctylphosphoric acid ester from experiment acquired results,
But back extraction performance is higher than dioctylphosphoric acid ester；Although composite extractant is stripped ability and compares 2- ethylhexyl phosphonic acids single 2-ethyl
Base ester is declined slightly, but extraction ability is higher than 2- ethylhexyl phosphonic acids single 2-ethyl base ester.NEW TYPE OF COMPOSITE extractant
The recovery rate highest of vanadium.
Embodiment 4
The method that a kind of compound extracting provided in this embodiment prepares vanadic anhydride, includes the following steps:
(1) it leaches: leaching feed liquid containing vanadium with dilute sulfuric acid, liquid-solid ratio is leached by control, it is 4.0g/L's that vanadium content, which is made,
Leachate.
(2) it restores: being restored with the iron powder of 1.2 times of theoretical additive amounts and sodium sulfite mixture, obtaining pH is 2.5
The additive amount of feed liquid containing vanadium, reducing agent is greater than theoretical value, can increase reducing agent and pentavalent vanadium, impurity F e3+Contact area, mention
High technology reaction efficiency.
(3) extract: mixed volume score is 50% di-phosphate ester extractant, 40% phosphate monoester extractant and 10%
Tridecanol, wherein di-phosphate ester extractant can be dioctylphosphoric acid ester or two (1- methylhexyl) phosphoric acid, the present embodiment are excellent
Dioctylphosphoric acid ester is selected, phosphate monoester extractant can be 2- ethylhexyl phosphonic acids single 2-ethyl base ester or styryl phosphonic acid
Single (2- ethylhexyl) ester, base ester, heating water bath stir the preferred 2- ethylhexyl phosphonic acids single 2-ethyl of the present embodiment to 85 DEG C
It mixes 1h and composite extractant is made, and be diluted to the organic phase that volumetric concentration is 13.5% with diluent MextralDT100, by it
With 13.5% dioctylphosphoric acid ester+6%TBP, 13.5%2- ethylhexyl phosphonic acids single 2-ethyl of same concentration base ester+6%TBP
Organic phase compares, and compares the extraction situation of three kinds of organic phases vanadium after extraction back extraction, the results are shown in Table 4.With aforementioned
Organic extractant phase feed liquid containing vanadium, the volume ratio of organic phase and water phase is 1.5:1, extraction time 5min when extraction, inverse using 2 grades
Stream extraction, is made the load organic phases containing vanadium.
(4) it is stripped: being stripped the load organic phases containing vanadium with the sulfuric acid of 0.4mol/L, organic phase and water phase when back extraction
Volume ratio is 5:1, is stripped using 7 stage countercurrents, single-stage Stripping times 5min, and richness vanadium liquid is made.Organic phase after back extraction uses
The oxalic acid of 0.6mol/L removes iron, except the organic phase after iron continues to make by can be used as the organic phase of extraction step after washing appropriate
With, it can the vanadium in cycling extraction feed liquid containing vanadium.
(5) it deacidifies: excessive acid in the rich vanadium liquid is extracted using 20% tridecylamine, organic phase and water phase when extraction
Volume ratio be 2:1, extraction series be 3 grades.Organic phase (i.e. tridecylamine phase) after extraction acid washs depickling using deposition vanadium mother liquid, washes
The volume ratio of organic phase and water phase is 1:2 when washing, and washing series is 4 grades, and the organic phase after washing can be recycled, it can
For the acid in cycling extraction richness vanadium liquid；In wash water (i.e. water phase contains a certain amount of acid) after washing, add a certain amount of
Sulfuric acid just can be used as the sulfuric acid solution circulation containing vanadium for leaching step or stripping steps again.
(6) precipitation: the inorganic phase (i.e. rich vanadium liquid) after extraction acid, acid content is lower, and ammonium hydrogen carbonate is added, adjusts the pH of solution
=7, mixing time 60min, digestion time is 60min, it can be achieved that the rate of deposition of vanadium is greater than 99%.
(7) calcine: gained precipitating drying oxygen-enriched calcining under the conditions of 500~600 DEG C can be obtained grade is greater than 99% five
V 2 O.
Table 4
It can be seen that although composite extractant extracting power is declined slightly compared to dioctylphosphoric acid ester from experiment acquired results,
But back extraction performance is higher than dioctylphosphoric acid ester；Although composite extractant is stripped ability and compares 2- ethylhexyl phosphonic acids single 2-ethyl
Base ester is declined slightly, but extraction ability is higher than 2- ethylhexyl phosphonic acids single 2-ethyl base ester.NEW TYPE OF COMPOSITE extractant
The recovery rate highest of vanadium.
Embodiment 5
The method that a kind of compound extracting provided in this embodiment prepares vanadic anhydride, includes the following steps:
(1) it leaches: leaching feed liquid containing vanadium with dilute sulfuric acid, liquid-solid ratio is leached by control, it is 10.0g/L's that vanadium content, which is made,
Leachate.
(2) it restores: being restored, obtained with iron powder, sodium sulfite and the ascorbic acid mixture of 1.2 times of theoretical additive amounts
The additive amount of the feed liquid containing vanadium that pH is 2.5, reducing agent is greater than theoretical value, can increase reducing agent and pentavalent vanadium, impurity F e3+Connect
Contacting surface product, improves technological reaction efficiency.
(3) extract: mixed volume score is 50% di-phosphate ester extractant, 40% phosphate monoester extractant and 10%
Lauryl alcohol, wherein di-phosphate ester extractant can be dioctylphosphoric acid ester or two (1- methylhexyl) phosphoric acid, the present embodiment are excellent
Dioctylphosphoric acid ester is selected, phosphate monoester extractant can be 2- ethylhexyl phosphonic acids single 2-ethyl base ester or styryl phosphonic acid
Single (2- ethylhexyl) ester, base ester, heating water bath stir the preferred 2- ethylhexyl phosphonic acids single 2-ethyl of the present embodiment to 90 DEG C
It mixes 1.2h and composite extractant is made, and be diluted to the organic phase that volumetric concentration is 55% with diluent MextralDT100, by it
Base ester+10%TBP has with 55% dioctylphosphoric acid ester+10%TBP, 55%2- ethylhexyl phosphonic acids single 2-ethyl of same concentration
Machine mutually compares, and compares the extraction situation of three kinds of organic phases vanadium after extraction back extraction, the results are shown in Table 5.Have with aforementioned
Machine mutually extracts feed liquid containing vanadium, and the volume ratio of organic phase and water phase is 1.5:1, extraction time 5min when extraction, using 6 stage countercurrents
The load organic phases containing vanadium are made in extraction.
(4) it is stripped: being stripped the load organic phases containing vanadium with the sulfuric acid of 0.3mol/L, organic phase and water phase when back extraction
Volume ratio is 5:1, is stripped using 8 stage countercurrents, single-stage Stripping times 5min, and richness vanadium liquid is made.Organic phase after back extraction uses
The hydrochloric acid and oxalic acid mixture of 0.6mol/L removes iron, except the organic phase after iron is by can be used as extraction step after washing appropriate
Organic phase continues to use, it can the vanadium in cycling extraction feed liquid containing vanadium.
(5) it deacidifies: excessive acid in the rich vanadium liquid is extracted using 10% TNA trinonylamine, organic phase and water phase when extraction
Volume ratio be 1:1, extraction series be 3 grades.Organic phase (i.e. TNA trinonylamine phase) after extraction acid is using neutral water washing depickling, washing
When organic phase and water phase volume ratio be 1:1, washing series be 5 grades, the organic phase after washing can be recycled, it can use
Acid in cycling extraction richness vanadium liquid；In wash water (i.e. water phase contains a certain amount of acid) after washing, a certain amount of sulphur is added
Acid just can be used as the sulfuric acid solution circulation containing vanadium for leaching step or stripping steps again.
(6) precipitation: the inorganic phase (i.e. rich vanadium liquid) after extraction acid, acid content is lower, and the mixed of ammonium hydrogen carbonate and ammonium carbonate is added
Object is closed, the pH=7 of solution, mixing time 1.2h are adjusted, digestion time is 1.2h, it can be achieved that the rate of deposition of vanadium is greater than 99%.
(7) calcine: gained precipitating drying oxygen-enriched calcining under the conditions of 500~600 DEG C can be obtained grade is greater than 99% five
V 2 O.
Table 5
It can be seen that although composite extractant extracting power is declined slightly compared to dioctylphosphoric acid ester from experiment acquired results,
But back extraction performance is higher than dioctylphosphoric acid ester；Although composite extractant is stripped ability and compares 2- ethylhexyl phosphonic acids single 2-ethyl
Base ester is declined slightly, but extraction ability is higher than 2- ethylhexyl phosphonic acids single 2-ethyl base ester.NEW TYPE OF COMPOSITE extractant
The recovery rate highest of vanadium.
What has been described above is only a preferred embodiment of the present invention, it is noted that for those skilled in the art,
Without departing from the inventive concept of the premise, several modifications and improvements can also be made, these also should be considered as guarantor of the invention
Range is protected, these all will not influence the effect and patent practicability that the present invention is implemented.The present invention omits the technology of description, shape
Shape, construction portion are well-known technique.
Claims (9)
1. a kind of method that compound extracting prepares vanadic anhydride, which comprises the steps of:
(1) it leaches: containing vanadium raw materials with Ore Leaching, the leachate that vanadium content is 0.1g/L-10.0g/L is made；
(2) it restores: restoring the leachate with reducing agent, the feed liquid containing vanadium of pH=1.5-2.5 is made；
(3) it extracts: being mixed with di-phosphate ester extractant, phosphate monoester extractant and modification agent, and be heated to 65 DEG C of -90 DEG C of stirrings
Composite extractant is made in 0.8h-1.2h, and extracts the feed liquid containing vanadium using the composite extractant, and the load containing vanadium, which is made, to be had
Machine phase；By volume fraction, di-phosphate ester extractant 50%-80% in the composite extractant, phosphate monoester extractant 10%-
40%, remaining is modification agent；
(4) be stripped: with sulfuric acid or the sulfuric acid solution containing vanadium is stripped the load organic phases and rich vanadium liquid is made；
(5) it deacidifies: excessive acid in the extraction rich vanadium liquid；
(6) precipitation: add rich vanadium liquid of the alkali to after deacidifying, adjust pH=6-7, stir 0.5h-1.2h, be aged 0.5h-1.2h；
(7) calcine: vanadic anhydride is made in oxygen-enriched calcining precipitation at 500 DEG C -600 DEG C.
2. the method that a kind of compound extracting according to claim 1 prepares vanadic anhydride, which is characterized in that the reduction
Agent is one or more of iron powder, sodium sulfite, sulfur dioxide, ascorbic acid.
3. the method that a kind of compound extracting according to claim 2 prepares vanadic anhydride, which is characterized in that the modification
Agent is containing carbon number between one or more of the alkylol of 8-13.
4. the method that a kind of compound extracting according to claim 1 prepares vanadic anhydride, which is characterized in that described compound
Extractant is diluted to the organic phase of volumetric concentration 5%-55% with diluent, and the volume ratio of organic phase and water phase is 1- when extraction
1.5:1 is extracted using 2-6 stage countercurrent.
5. the method that a kind of compound extracting according to claim 1 prepares vanadic anhydride, which is characterized in that the sulfuric acid
Back extraction concentration is 0.3mol/L-1mol/L, and the volume ratio of organic phase and water phase is 5-8:1 when back extraction, anti-using 3-8 stage countercurrent
Extraction.
6. the method that a kind of compound extracting according to claim 5 prepares vanadic anhydride, which is characterized in that the back extraction
Organic phase afterwards removes iron using one or both of the hydrochloric acid of 0.3mol/L-0.6mol/L or oxalic acid, washs, and as multiple
Extractant is closed to be recycled in step (3).
7. the method that a kind of compound extracting according to claim 1 prepares vanadic anhydride, which is characterized in that step (5)
The extractant used is the amine extractant of volumetric concentration 10%-30%, and the volume ratio of organic phase and water phase is 1-5 when extraction:
1, extraction series is 1-3 grades.
8. the method that a kind of compound extracting according to claim 7 prepares vanadic anhydride, which is characterized in that the step
(5) organic phase after deacidifying washs depickling using deposition vanadium mother liquid and/or neutral water, the volume ratio of organic phase and water phase when washing
For 1:1-5, washing series is 3-5 grades；Organic phase after washing is recycled；Sulfuric acid is added in water phase after washing, circulation makes
For step (1) and (4).
9. the method that a kind of compound extracting according to claim 1 prepares vanadic anhydride, which is characterized in that the precipitation
The alkali that step uses is one or more of ammonium hydrogen carbonate, sodium hydroxide, ammonium hydroxide, ammonium carbonate.
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| CN109306404B (en) * | 2018-12-04 | 2020-03-17 | 攀钢集团攀枝花钢铁研究院有限公司 | Extraction method of vanadium-containing solution |
| CN112708758A (en) * | 2020-11-27 | 2021-04-27 | 核工业北京化工冶金研究院 | Method for extracting vanadium from iron-rich vanadium ore |
| CN114015882A (en) * | 2021-10-29 | 2022-02-08 | 苏州博萃循环科技有限公司 | Method for recovering vanadium and nickel from POX carbon black |
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