CN108754185A - A method of purification is containing silicon, phosphorus, arsenic in vanadium solution - Google Patents
A method of purification is containing silicon, phosphorus, arsenic in vanadium solution Download PDFInfo
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- CN108754185A CN108754185A CN201810514586.1A CN201810514586A CN108754185A CN 108754185 A CN108754185 A CN 108754185A CN 201810514586 A CN201810514586 A CN 201810514586A CN 108754185 A CN108754185 A CN 108754185A
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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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
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Abstract
The present invention relates to a kind of method of the purification containing silicon, phosphorus, arsenic in vanadium solution, using insoluble active aluminate as adsorbent, aluminate adsorption column is obtained by processes such as synthesis, granulation, drying, calcining, dress columns, vanadium solution will be contained to handle by aluminate adsorption column, silicon, phosphorus, the arsenic in solution are removed, scavenging solution containing vanadium is obtained.The present invention has purification process simple, adsorbent is cheap, be easy preparations, aperture structure complexity, large specific surface area, the porosity greatly, high mechanical strength, can multipath utilization, new impurity is not introduced, the features such as adsorption cleaning speed is fast, and production efficiency is high, and vanadium loss is few, it can realize that the vanadium solution that contains for being 1~14 to pH carries out deep purifying, the concentration for controlling impurity is less than 10ppm, and vanadium solution can prepare ultrapure vanadium product, with good economic efficiency and application prospect after purification.
Description
Technical field
The present invention relates to vanadium field of chemical metallurgical technology, and in particular to a kind of side of the purification containing silicon, phosphorus, arsenic in vanadium solution
Method.
Background technology
Vanadium is universally acknowledged narrow resources and grand strategy substance, vanadium with its excellent alloy property and catalytic performance,
The fields such as metallurgy, chemical industry, machinery, electronics, automobile, railway and light industry are widely used in, 85% vanadium is disappeared by steel industry
Consumption, wherein high-purity vanadium oxide is applied to the high-precision pointed collar domains such as all-vanadium flow battery, vananum, electrode material, catalyst.
China's vanadium production of articles raw material includes mainly vanadium slag, bone coal, vanadium-containing wasting catalyst, and no matter which kind of raw material contains
Silicon, some raw materials also contain phosphorus, and a small amount of raw material also contains arsenic.In current various raw material process for extracting vanadium, silicon, phosphorus, arsenic are difficult one
It is removed during step deep processing, silicon, phosphorus, arsenic seriously affect follow-up precipitation yield and vanadium product quality.In order to meet current height
Smart pointed collar domain obtains the high added value vanadium product of low silicon, low-phosphorous, low arsenic to the needs of high purity vanadium, needs to carry out to containing vanadium solution
Deep desilication, phosphorus, arsenic.
Vanadium slag accounts for the 60% of total raw materials for production, and vanadium product primary raw material is produced for China, though traditional sodium roasting technique
So have that technology maturation, stability is good, the advantages such as easy to operate, but contains the impurity such as a large amount of silicon, phosphorus in alkaline vanadium immersion liquid.For
Solve the problems, such as that silicon, phosphorus impurities, scientific worker carry out reducing impurity silicon, phosphorus from process for extracting vanadium and solution purification both direction
Determination study.One, sodium roasting is replaced using blank roasting or calcification baking.As CN101412539A,
The patents such as CN104894374A use calcification baking~process for extracting vanadium by acid leaching, although acidleach can utmostly reduce the leaching of silicon
Go out, but still has the leaching of a large amount of phosphorus in the process, and pickle liquor dephosphorization is difficult point, the also sad filter of the impurity colloid such as silicon, phosphorus
The problem of；Such as CN102560086A, CN103952565A, CN103937978A, CN104003442A, CN104831090A etc. are special
Profit is leached condition weakly acidic pH, it is sad to be solved impurity colloid substantially using the process for extracting vanadium of calcification or blank roasting ammonium salt leaching
The problem of filter, but still there is a small amount of silicon and phosphorus to be difficult to remove, and these techniques be not directly available the low silicon of high added value,
Low-phosphorous vanadium product.Two, in weak acid or weakly alkaline containing chemical precipitation method desiliconization, phosphorus in vanadium solution, as CN103966437A,
CN104480308A、CN101724756A、CN102251113A、CN101724757A、CN101182036A、
Calcium is added in the patents such as CN101709377A, CN102477493A, magnesium, aluminium, iron, strontium, the soluble salts such as zirconium and silicon, phosphorus act on to be formed it is heavy
It forms sediment, to play the role of purifying vanadium solution, but conventional chemical precipitation purification process inevitably introduces new foreign ion, and
And impurities removing efficiency is low, the impurity colloid such as silicon, phosphorus needs to stand for a long time, and filtration difficulty leads to low production efficiency, and has vanadic acid
The precipitations such as iron, calcium vanadate generate, and influence the rate of recovery of vanadium.
Bone coal accounts for the 30% of total raw materials for production, since main component is silica, the roasting of traditional sodium in bone coal
Firing technique can leach a large amount of silicon, such as CN101215636A, CN101451199A, CN103498047A, CN102583402A
Patent discloses the acid technological processes such as oxidizing roasting-acidleach, sulfuric acid curing-water logging, direct acidleach, although avoiding the leaching of a large amount of silicon
Go out, but since stone coal vanadium-containing amount is low, it is necessary to enriched vanadium process, therefore silicon, phosphorus, arsenic are also enriched with.CN103014377A,
CN101182596A、CN104232939A、CN104841682A、CN102828025A、CN101798113A、CN102936660A
Etc. patents handled using chemical precipitation method, but will produce and introduce new impurity, while bringing that the rate of recovery of vanadium is low, production effect
The problems such as rate is low.
Common spent vanadium catalyst has：Petroleum industry, sulfuric acid industry, SCR denitration spent vanadium catalyst, some catalyst be with
SiO2As carrier, the binder and dispersant that are used in some catalyst preparation process are silicate and phosphate, some are urged
Agent is easy to combine phosphorus, arsenic etc. that intoxicating phenomenon occurs in catalysis is reacted to become dead catalyst, therefore with spent vanadium catalyst vanadium extraction
Obtained vanadium immersion liquid still will appear the impurity such as silicon, phosphorus, arsenic.Clean chemical method often use or traditional, such as
CN106435197A、CN1940096A、CN104628032A、CN1631797A、CN106011503A、CN105648241A、
CN105565376A, CN102050492A etc., but the above problem is equally existed in processing procedure.
For current chemical precipitation method there are the problem of, vanadium industry also has flocculant method except the impurity such as silicon, phosphorus, arsenic, flocculates
The advantages of agent method, which is flocculant, makes silica gel particle become larger, and solves the problems, such as silica gel filtration difficulty, as CN103643039A,
CN101585553A, CN104831069A etc., but organic flocculant has the problems such as complicated component, of high cost, needs stringent
Control parameter, addition can excessively cause vanadium largely to lose, and the very few removal of impurities of addition is not thorough.It is removed to solve organic flocculant
Miscellaneous problem, CN103787414A disclose a kind of side of the impurity such as silicon, phosphorus in inorganic polymeric aluminium, magnesium, calcium salt purification vanadium solution
Method, but the inorganic flocculating agent still can introduce new impurity and enter system, and still have standing flocculation time too long, production
Efficiency is low, the problems such as needing strictly to control removal of impurities parameter.CN105087932A discloses impurity silicon in a kind of rich acidic vanadium liquid
Minimizing technology mixes soluble aluminum series flocculants with bentonite, soluble sodium salt sylvite additive, is granulated, and washing is removed
Soluble-salt obtains porous flocculation adsorption agent, and vanadium solution to be clean is added in gained flocculant, stirs, and stands, and takes out flocculant,
Complete purification process.Flocculant is fixed on bentonite by this method, the impurity not being introduced into flocculant, environmental-friendly, can be had
Colloidal silica in effect removal acid solution containing vanadium.Flocculant preparation method does not have calcination process and purification process to need stirring at low speed
It is found that the flocculant is more broken, mechanical strength is not high, is easy to bring the soluble salt that inside does not elute into vanadium solution after broken
In.And purification process needs standing 5~10 hours, and production efficiency is not also high.The flocculant is can be seen that from the effect except silicon
Silicon can be removed to 0.03g/L, desiliconization effect is general.It is also a ask that whether the flocculant, which can be stabilized, under alkaline condition
Topic.
From the foregoing, it will be observed that deposition condition is harsh when traditional precipitation method purification is containing impurity such as silicon, phosphorus, arsenic in vanadium solution, often need
PH and control addition are accurately adjusted, inappropriate pH and very few addition can cause impurity removal to be not thorough, excessively
The addition of chemical agent introduce the loss of a large amount of foreign ion and vanadium again, and the impurity colloid such as silicon, phosphorus needs to grow
Time stands, and filtration difficulty leads to low production efficiency, it is therefore desirable to study new purification containing impurity such as silicon, phosphorus, arsenic in vanadium solution
Method.
Invention content
In order to solve the above technical problems, the present invention provides a kind of method of the purification containing silicon, phosphorus, arsenic in vanadium solution, use
Insoluble activity aluminate obtains aluminate absorption as adsorbent, by processes such as synthesis, granulation, drying, calcining, dress columns
Column will contain vanadium solution and be handled by aluminate adsorption column, remove silicon, phosphorus, arsenic in solution, obtain scavenging solution containing vanadium.This
Invention has many advantages, such as that impurity deep purifying, applied widely, purification efficiency is high, vanadium loses less, adsorbent is simple and cleaned
New impurity is not introduced in journey, overcomes various disadvantages in the prior art, with good economic efficiency and application prospect.
In order to achieve the above objectives, the present invention uses following technical scheme：
The present invention provides a kind of method of the purification containing silicon, phosphorus, arsenic in vanadium solution, the method is：Vanadium solution will be contained to lead to
It crosses aluminate adsorption column to be handled, removes silicon, phosphorus, the arsenic in solution, obtain scavenging solution containing vanadium.
According to the present invention, the vanadium solution that contains is solution or vanadium product after vanadium industry vanadium extraction leaching liquid, vanadium leaching liquid enrichment
In weight solution any one or at least two combination；Such as can be vanadium industry vanadium extraction leaching liquid, vanadium leaching liquid enrichment after
Solution or vanadium product weigh any one in solution, and typical but non-limiting is combined as：Vanadium industry vanadium extraction leaching liquid and vanadium leaching
Solution after liquid enrichment, vanadium is taken to leach solution and vanadium product weight solution vanadium product weight solution after liquid enrichment, vanadium industry vanadium extraction leaching liquid
With vanadium product weight solution, vanadium industry vanadium extraction leaching liquid, vanadium leach solution and vanadium product weight solution after liquid enrichment.
According to the present invention, the vanadium extraction raw material of the vanadium industry vanadium extraction leaching liquid is in vanadium slag, bone coal or vanadium-containing wasting catalyst
Any one or at least two combination；Such as can be any one in vanadium slag, bone coal or vanadium-containing wasting catalyst, it is typical
But non-limiting is combined as：Vanadium slag and bone coal, vanadium slag and vanadium-containing wasting catalyst, bone coal and vanadium-containing wasting catalyst, vanadium slag, bone coal
And vanadium-containing wasting catalyst.
The applicable vanadium solution type of the present invention is more, is related to the various vanadium raw materials leaching liquids of vanadium industry, vanadium enrichment liquid and object containing vanadium
Material weight solution.Such as can be used for the removal of impurities to vanadium slag sodium roasting traditional handicraft vanadium immersion liquid, solution silicon, the phosphorus concentration are relatively
Height can be also used for the removal of impurities to vanadium slag blank/calcification baking-sulfuric acid/ammonium leaching and vanadium extraction technique vanadium immersion liquid, and the solution silicon, phosphorus are dense
It spends relatively low, can achieve the purpose that deep purifying.The present invention can be also used in the vanadium-containing materials vanadium immersion liquid such as bone coal, dead catalyst
The high concentration of impurity silicon, phosphorus, the purification of arsenic and low-concentration vanadium-containing solution after Adsorption/Extraction is enriched with is containing the net of vanadium solution
Change, and the purification etc. to the vanadium product such as ammonium metavanadate, vanadic anhydride, sodium vanadate, potassium vanadate weight solution.
According to the present invention, the pH containing vanadium solution is 1~14, for example, can be 1,2,3,4,5,6,7,8,9,10,11,
12, the specific point value between 13 or 14 and above-mentioned numerical value, as space is limited and for concise consideration, the present invention no longer limit
It enumerates.
According to the present invention, the pH containing vanadium solution is preferably 2~12, and further preferably 5~10.
Present invention may apply to the direct purifications of a variety of process for extracting vanadium difference pH stostes, and it is molten to be also applied for pregnant solution/weight
The purification of vanadium solution after the stoste and adjustment pH of liquid, applicable pH containing vanadium solution is 1~14.Such as traditional vanadium slag sodium roasting
The pH of technique is 8~12 infusions, and the alkalescent that the pH of vanadium slag oxidizing roasting-ammonium leaching and vanadium extraction is 7~9 contains vanadium solution, calcification roasting
The pickle liquor that the pH of burning-process for extracting vanadium by acid leaching is 2~5, the stripping liquid of pH=7~13 after bone coal vanadium immersion liquid Pro-concentration with ion exchange process,
The vanadium solution that the strip liquor adjustment pH of bone coal vanadium immersion liquid extracting and enriching is 2~8, and the molten rear pH of such as metavanadic acid weight are 5~8 weight
Solution etc., but it is non-be only limitted to this, other pH are 1~14 containing vanadium solution to be equally applicable to the present invention.
According to the present invention, a concentration of 0.005~50g/L containing silicon in vanadium solution, such as can be 0.005g/L,
0.01g/L, 0.05g/L, 0.1g/L, 1g/L, 5g/L, 10g/L, 20g/L, 30g/L, 40g/L or 50g/L and above-mentioned numerical value
Between specific point value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the concentration containing silicon in vanadium solution is preferably 0.020~5g/L, and further preferably 0.050
~0.5g/L.
According to the present invention, a concentration of 0.005~10g/L containing phosphorus in vanadium solution, such as can be 0.005g/L,
Tool between 0.01g/L, 0.05g/L, 0.1g/L, 0.5g/L, 1g/L, 3g/L, 5g/L, 8g/L or 10g/L and above-mentioned numerical value
Body point value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the concentration containing phosphorus in vanadium solution is preferably 0.008~1g/L, further preferably 0.01~
0.25g/L。
According to the present invention, a concentration of 0.005~5g/L containing arsenic in vanadium solution, such as can be 0.005g/L,
Tool between 0.01g/L, 0.05g/L, 0.1g/L, 0.5g/L, 1g/L, 2g/L, 3g/L, 4g/L or 5g/L and above-mentioned numerical value
Body point value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, the concentration containing arsenic in vanadium solution is preferably 0.008~0.5g/L, and further preferably 0.01
~0.25g/L.
The present invention can purify the silicon, phosphorus, arsenic impurities of various concentration, adaptable, be better than the traditional chemical precipitation method and wadding
Solidifying agent method, and can achieve the purpose that deep purifying.
According to the present invention, the aluminate is calcium aluminate, magnesium aluminate, calcium aluminoferrite, iron magnesium aluminate, carbon calcium aluminate, carbon aluminium
In sour magnesium, calcium sulphoaluminate or sulphur magnesium aluminate any one or at least two combination, preferably calcium aluminate, magnesium aluminate, iron aluminium
In sour calcium or iron magnesium aluminate any one or at least two combination, further preferably calcium aluminate and/or calcium aluminoferrite.
The aluminate that the present invention uses is insoluble aluminate, will not be dissociated under condition of different pH, will not
New impurity is introduced in vanadium solution.
Aluminate of the present invention can come from commercially available and/or self-control.
The aluminate that of the present invention commercially available or pyrogenic process is made by oneself uses after pretreatment, the preprocess method
For：Block is broken, ball milling, and powder is soaked, is filtered, washed.
According to the present invention, aluminate is prepared using improved wet synthetic technology, the method is：To sodium aluminate solution
Middle addition surfactant is stirred, and is slowly added to reagent needed for common process synthesizing aluminate, is filtered, washed.
Reagent needed for the common process synthesizing aluminate is that salt, the present invention such as calcium commonly used in the art, magnesium do not do this
Particular determination.
According to the present invention, the surfactant be ethanol amine, polyacrylamide, in polyethylene glycol any one or extremely
Few two kinds of combination.
According to the present invention, the surfactant addition is sodium aluminate solution quality 0.001~0.1%, such as can be with
It is specific between 0.001%, 0.005%, 0.01%, 0.03%, 0.05%, 0.08% or 0.1% and above-mentioned numerical value
Value, as space is limited and for concise consideration, the present invention no longer exclusive list.
Sodium aluminate solution of the present invention adds water to be formulated from commercially available sodium aluminate, preferably by bone coal industry byproduct
Alum is prepared.Preferably, the method that the alum prepares sodium aluminate solution is to be dissolved in water alum to obtain aluminium hydroxide
And gained aluminium hydroxide routinely wet processing alkali soluble is obtained sodium aluminate solution by filtrate.
The aluminate that the present invention selects equally can also use conventional wet method or thermal process system by being commercially available
It is standby to obtain, but in contrast, the aluminate prepared using improved wet synthetic technology provided by the invention can be put down
Equal aperture is mesoporous, even size distribution aluminate wet-milling, has the active site in conjunction with impurity, clean-up effect is more preferably.
Surfactant plays the role of dispersion in the present invention, can prevent particle aggregation from settling, gained sorbent product
Structure is uniform, large specific surface area, and primary aperture is mesoporous, and building-up process is simple, and remaining organic surface active agent can be follow-up
It is removed completely in drying, calcination process, and pore creating material can be played the role of.
Present invention is particularly suitable for extracting vanadium from stone coal industry, and byproduct alum obtained by extracting vanadium from stone coal is decomposed, crude product hydrogen is obtained
Then aluminium oxide synthesizes required adsorbent using crude product aluminium hydroxide as silicon source.This method takes full advantage of the money of the aluminium in bone coal
Source, clean environment firendly realize the effect of mineral comprehensive utilization.
According to the present invention, the vanadium solution that will contain is treated by aluminate adsorption column in journey, and vanadium is contained in adsorption column
Solution flow rate be 0.5~30BV/h, such as can be 0.5BV/h, 1BV/h, 5BV/h, 10BV/h, 15BV/h, 20BV/h,
Specific point value between 25BV/h or 30BV/h and above-mentioned numerical value, as space is limited and for simple consideration, the present invention is no longer
Exclusive list.
According to the present invention, flow velocity containing vanadium solution is preferably 1~15BV/h in the adsorption column, further preferably 2~
10BV/h。
Impurity breakthrough point in adsorption column efflux is controlled according to the present invention, in the processing procedure is：Silicon vanadium concentration ratio Si/
V≤0.00030, phosphorus vanadium concentration ratio P/V≤0.00025, arsenic vanadium concentration ratio P/V≤0.00010.
Above-mentioned breakthrough point refers to the concentration ratio of impurity element and v element in efflux.
The present invention controls the different breakthrough points of silicon, phosphorus, arsenic in efflux to meet different quality vanadium product requirement.Example
Such as need to produce ultrapure (purity >=99.9%) vanadium product, need to control lower efflux impurity silicon (Si/V≤0.00030),
Phosphorus (P/V≤0.00025), arsenic (P/V≤0.00010) concentration.And production metallurgy vanadium product, then impurity concentration can in efflux
It is some higher to control.After impurity concentration is more than breakthrough point in adsorption column efflux of the present invention, which is stopped, washing
The adsorbent more renewed afterwards is devoted oneself to work again.Most of vanadium can be eluted and be recycled by water-washing process, and water-washing process
Only a small amount of impurity is eluted, and most of impurity also remains in the aperture structure of adsorbent complexity.Used adsorbent is still
So there are complicated aperture structure and stronger mechanical strength, and the material of the larger porosity is be especially suitable for fire proofed wood
Material, thermal insulation material, to realize the purpose of homogenous material multiple use.
Method of the purification containing silicon in vanadium solution, phosphorus, arsenic of the present invention is as a preferred technical solution,：It is molten vanadium will to be contained
Liquid is handled by aluminate adsorption column, and it is 0.5~30BV/h, stream that flow velocity containing vanadium solution in adsorption column is controlled in processing procedure
Going out impurity breakthrough point in liquid is：Silicon vanadium concentration ratio Si/V≤0.00030, phosphorus vanadium concentration ratio P/V≤0.00025, arsenic vanadium concentration ratio
P/V≤0.00010 obtains scavenging solution containing vanadium.
The present invention prepares the aluminate adsorption column according to the following steps：
(1) aluminate, binder and pore creating material are mixed, is granulated；
(2) finished product adsorbent is obtained after the particle that step (1) obtains being dried, calcined, by adsorbent mounted in absorption
After column, aluminate adsorption column is obtained.
Aluminate used in step (1) of the present invention before mixing all by impregnating, washing, main purpose is in order to will be solvable
Property substance dissolution, prevent in adsorption process pollution to contain vanadium solution.
According to the present invention, step (1) described binder is methylcellulose and/or polyvinyl alcohol.
According to the present invention, the addition of step (1) described binder be aluminic acid salt quality 0.1~30%, preferably 1~
15%, such as can be specific between 0.1%, 1%, 5%, 10%, 15%, 20%, 25% or 30% and above-mentioned numerical value
Point value, as space is limited and for simple consideration, the present invention no longer exclusive list.
Binder, which is added, in the present invention can make materials from bonding be convenient for molding together, can also improve semi-finished product adsorbent
Intensity, organic binder can remove completely in subsequent drying, calcination process.Its addition can be according to prilling not
It is same to be specifically chosen.
According to organic and/or inorganic pore creating material commonly used in the art, preferably carbon may be selected in step (1) described pore creating material
In powder, urea, starch, polyacrylamide or polyethylene glycol any one or at least two combination；Such as can be carbon dust,
Any one in urea, starch, polyacrylamide or polyethylene glycol, typical but non-limiting is combined as：Carbon dust and urea,
Starch and polyacrylamide, carbon dust and starch, polyacrylamide and polyethylene glycol etc., as space is limited and for concise consideration,
The present invention no longer exclusive list.
According to the present invention, the addition of step (1) described pore creating material is aluminic acid salt quality 0.1~10%, preferably 0.1~
5%；Such as can be 0.1%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10% and above-mentioned numerical value it
Between specific point value, as space is limited and for concise consideration, the present invention no longer exclusive list.
The purpose that pore creating material is added in the present invention is to improve the porosity in follow-up drying, calcination process, and common forges
Temperature is too high during burning can make part holes close or disappear, and the too low then adsorbent intensity of temperature is low, is added of the present invention
Pore creating material can improve adsorbent intensity and the high porosity to avoid these problems.
Pore creating material of the present invention can be inorganic and/or organic pore-forming agents, and organic pore-forming agents are by subsequently drying, forging
Burning can remove completely.Inorganic pore creating material does not introduce new impurity, by subsequent drying, calcining, or after dress column by acid,
The washing of alkali, water can also remove completely.
According to the present invention, step (1) described prilling be compression granulations, extruder grain, slurry-spraying pelletizing, roll granulation or
Any one in fluidization granulation.
The present invention is in order to adapt to demand of the different process to the purification and impurity removal containing vanadium solution, by powdery aluminate by being granulated work
Skill obtains the granulated sorbent of different sizes and shape, is relatively beneficial to dress column and keeps mechanical strength, while being granulated
The addition of binder and pore creating material can make adsorbent have preferably dispersibility and keep more preferable pore-size distribution and hole in journey
Structure.
According to the present invention, step (2) described drying is constant pressure and dry or vacuum drying, is preferably dried in vacuo, and vacuum is dry
It is dry that the substance sublimates such as water can volatilize away under cryogenic, using calcining, sorbent shapes and inside can be kept
Structure is constant, remains the hole that sublimate leaves.
According to the present invention, the temperature of the constant pressure and dry is 50~200 DEG C, preferably 70~150 DEG C；Such as can be 50
DEG C, 80 DEG C, 100 DEG C, 120 DEG C, 150 DEG C, 180 DEG C or the specific point value between 200 DEG C and above-mentioned numerical value, as space is limited and
For concise consideration, the present invention no longer exclusive list.
Calcination temperature of the present invention should change according to the addition of binder and pore creating material, control highest calcination temperature
And soaking time, it can ensure that pore structure is not damaged.
According to the present invention, the vacuum drying temperature is -60~-10 DEG C；Such as can be -60 DEG C, -50 DEG C, -40
DEG C, -30 DEG C, -20 DEG C or the specific point value between -10 DEG C and above-mentioned numerical value, as space is limited and for concise consideration, this
Invention no longer exclusive list.
According to the present invention, the water content < 5% of the adsorbent after step (2) described drying.
According to the present invention, the temperature of step (2) described calcining is 100~1000 DEG C, preferably 400~700 DEG C；Such as it can
To be 100 DEG C, 200 DEG C, 300 DEG C, 400 DEG C, 500 DEG C, 600 DEG C, 700 DEG C, 800 DEG C, 900 DEG C or 1000 DEG C and above-mentioned number
Specific point value between value, as space is limited and for concise consideration, the present invention no longer exclusive list.
According to the present invention, step (2) the calcination process heating rate is 100~300 DEG C/h, such as can be 100 DEG C/
H, 130 DEG C/h, 150 DEG C/h, 180 DEG C/h, 200 DEG C/h, 230 DEG C/h, 250 DEG C/h, 280 DEG C/h or 300 DEG C/h and above-mentioned number
Specific point value between value, as space is limited and for concise consideration, the present invention no longer exclusive list.
The present invention will calcine heating rate control within the above range, be in order to not influence being molded and shape in drying process
At pore structure, and pore creating material is decomposed to form gas, forms new pore structure, and retain these pore structures.
The finished product adsorbent of the present invention dried, obtained after calcining has abundant pore structure, specific surface area >=50m2/
g.Whole preparation process makes adsorbent generate the stomata of opening, obtains a large amount of macropore open pore, obtained adsorbent aperture
Complex distribution, specific surface area and pore-size distribution are controllable.Big stomata allows solution quickly to flow and reaches adsorption site, is being situated between
Absorption is completed in hole, and then is realized and efficiently purified to containing vanadium solution.
According to the present invention, step (2) described adsorption column is fixed bed or moving bed adsorption column.
It is of the present invention by synthesis, be granulated, drying, calcine technology, obtain that aperture is abundant, face shaping is controllable, machinery
The high granulated sorbent of intensity, after adsorbent is filled column, by adjusting the rate of outflow, when control is contacted containing vanadium solution with adsorbent
Between, qualified efflux is finally obtained, traditional agitation and filtration purification pattern is avoided, it can be big by adsorption column direct purification
It is big to improve production efficiency.
Carrying out weak acid, weak base and water according to the present invention, after step (2) the adsorbent dress column, alternately dynamic is washed, can
To wash off adsorbent synthesis, be granulated, remaining soluble matter after dry, calcine technology, can not only draw to avoid in containing vanadium solution
Enter impurity, but also activates adsorbent.
The aluminate finished product adsorbent that the present invention is prepared has the function of deep impurity-removing, is primarily due to adsorbent energy
Complicated physics, chemical action occur for enough and impurity.It is easy to generate insoluble matter aluminosilicate with aluminate containing silicon in vanadium solution, it is multiple
Miscellaneous aperture structure can adsorb again, flocculated impurities, and newly-generated aluminosilicate carries phosphorus secretly, arsenic is co-precipitated.By adsorbing, wadding a quilt with cotton
The a series of physical chemical processes such as solidifying, precipitation, co-precipitation obtain deep purifying containing vanadium solution, so as to produce ultrapure vanadium
Product.
Compared with prior art, the present invention at least has the advantages that：
(1) impurity deep purifying：The present invention may be implemented to the deep purifying containing the impurity such as silicon, phosphorus, arsenic in vanadium solution, control
The concentration of impurity processed is less than 10ppm, realizes the preparation of ultrapure vanadium product.
(2) applied widely：The present invention can carry out removal of impurities processing for 1~14 to pH containing vanadium solution, save de-regulation pH's
Process.
(3) new impurity is not introduced：The adsorbent that the present invention obtains will not dissociate under condition of different pH, will not
New impurity is introduced in vanadium solution.
(4) purification efficiency is high：The adsorbent that the present invention obtains have complicated aperture structure, larger specific surface area, compared with
Strong mechanical strength is suitble to purification of the various flow velocitys containing vanadium solution, solution to contact the short period with adsorbent, you can to reach depth
The purpose of purification solves traditional difficulty and cleaned by a variety of physical chemistry synergy such as absorption, flocculation, precipitation, co-precipitation
Difficult problem is filtered, purification speed is fast, improves production efficiency, it can be achieved that industrial applications.
(5) vanadium loss is few：The present invention only has a small amount of vanadium to be adsorbed on adsorbent in purification process, used adsorbent
Most of vanadium can be eluted by simply washing, eluent containing vanadium is recyclable, and vanadium loss is less.
(6) adsorbent is simple：Commercially available or homemade adsorbent may be used in the present invention, and adsorbent derives from a wealth of sources, price
It is cheap, and it is simple to make adsorbent preparation process by oneself.
(7) adsorbent realizes multiple use：The used adsorbent of the present invention still have complicated aperture structure and compared with
Strong mechanical strength, and the material of the larger porosity can be applied to make be especially suitable for refractory material, thermal insulation material
Standby byproduct, it is with good economic efficiency.
Specific implementation mode
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
(1) preparation of adsorbent：Commercially available calcium aluminate is soaked, is filtered, washed to obtain wet-milling, it is calcareous that aluminic acid is added
Amount 8.45% polyvinyl alcohol as binder, while be added the carbon dust of calcium aluminate quality 0.5%, 1% starch, 3% gather
Ethylene glycol pore creating material is uniformly mixed, the granular semi-finished product adsorbent of strip is obtained by extruder grain technique；It is dry to put it into vacuum
Dry equipment is dried at -30 DEG C to water content about 4%, and taking-up is placed in calciner, and control heating rate is 114.02 DEG C/
H is warming up to 640.3 DEG C and stops heating, after keeping the temperature 0.5h, obtain finished product adsorbent, obtained finished product adsorbent is packed into and is fixed
In bed adsorption column, aluminate adsorption column is obtained；
(2) vanadium solution is purified：It is adsorbed using the aluminate that weak acid, weak base and water alternating dynamic washing step (1) obtain
Column washes off adsorbent residual impurity and soluble matter；The PH bone coal ion exchange stripping liquids for being 12 are purified, are contained in solution
V 33.64g/L, Si 0.012g/L, P 0.0085g/L, As 0.0073g/L；It will be passed through with the flow velocity of 0.5BV/h containing vanadium solution
Aluminate adsorption column waits for containing V 32.81g/L, Si 0.0023g/L, P 0.00026g/L, As 0.00023g/L in efflux
When, out of service, the adsorbent that adsorption column more renews after washing can devote oneself to work again, and used adsorbent can be used as resistance to
Fiery material, thermal insulation material.
Embodiment 2
(1) preparation of adsorbent：The alum that bone coal pickle liquor crystallizes is added to the water stirring and dissolving filtering, obtains hydrogen
Aluminium oxide and filtrate, by gained aluminium hydroxide, routinely wet processing alkali soluble obtains sodium aluminate solution, and sodium aluminate solution matter is added
0.001% ethanol amine of amount and 0.008% polyacrylamide surfactant are stirred, and are slowly added to calcium salt and molysite,
It is filtered, washed to obtain calcium aluminate and calcium aluminoferrite mixing wet-milling；Then the methyl of calcium aluminate and calcium aluminoferrite quality 30% is added
Cellulose, as pore creating material, is uniformly mixed as binder, 2% urea and 5% polyacrylamide, and work is granulated by rolling
Skill obtains spherical semi-finished product adsorbent, it is dried at 50 DEG C to water content about 3%, taking-up is placed in calciner, is controlled
Heating rate is 100 DEG C/h, is warming up to 1000 DEG C and stops heating, keep the temperature 0.5h, obtain finished product adsorbent, obtained finished product is inhaled
Attached dose is fitted into ADSORPTION IN A FIXED BED column, obtains aluminate adsorption column；
(2) vanadium solution is purified：It is adsorbed using the aluminate that weak acid, weak base and water alternating dynamic washing step (1) obtain
Column washes off adsorbent residual impurity and soluble matter, is purified to pH its 1 bone coal extraction strip liquors, V is contained in solution
55.83g/L, Si 0.059g/L, P 0.013g/L, As 0.0087g/L；Absorption is passed through with the flow velocity of 30BV/h containing vanadium solution
Column stops fortune when waiting for containing V 54.94g/L, Si 0.0044g/L, P 0.00049g/L, As 0.00033g/L in efflux
Row, the adsorbent that adsorption column more renews after washing can devote oneself to work again, and used adsorbent can be used as refractory material, protect
Adiabator.
Embodiment 3
(1) preparation of adsorbent：By aluminium-containing substance and substance containing magnesium routinely thermal process pyroreaction, broken, ball milling,
It soaks, is filtered, washed to obtain magnesium aluminate wet-milling；1% methylcellulose of magnesium aluminate quality and 20% polyethylene is added
Alcohol is uniformly mixed as binder, 10% urea as pore creating material, and spherical semi-finished product absorption is obtained by compressing prilling
Agent；It puts it into vacuum dryer to be dried at -60 DEG C to water content about 2.5%, taking-up is placed in calciner, and control rises
Warm rate is 300 DEG C/h, is warming up to 700 DEG C and stops heating, keep the temperature 0.5h, obtain finished product adsorbent, obtained finished product is adsorbed
Agent is fitted into ADSORPTION IN A FIXED BED column, obtains aluminate adsorption column；
(2) vanadium solution is purified：It is adsorbed using the aluminate that weak acid, weak base and water alternating dynamic washing step (1) obtain
Column washes off adsorbent residual impurity and soluble matter, is purified to the pH vanadium-containing wasting catalyst sodium roasting leachates for being 14, molten
Contain V 12.56g/L, Si 1.24g/L, P 10.82g/L, As 5.47g/L in liquid；It is logical with the flow velocity of 15BV/h containing vanadium solution
Adsorption column is crossed, when waiting for containing V 12.44g/L, Si 0.0026g/L, P 0.0031g/L, As 0.0012g/L in efflux, is stopped
It only runs, the adsorbent that adsorption column more renews after washing can devote oneself to work again, and used adsorbent can be used as fire proofed wood
Material, thermal insulation material.
Embodiment 4
(1) preparation of adsorbent：Preparation sodium aluminate solution, the ethanol amine of addition sodium aluminate solution quality 0.002%,
0.05% polyacrylamide and 0.02% polyglycol surfactants, are stirred, are slowly added to calcium oxide and carbon
Sour sodium obtains carbon calcium aluminate wet-milling after being filtered, washed；The methylcellulose of calcium aluminate quality 0.1% is added as binder, carbon
The starch of calcium aluminate quality 0.5% and 5% urea are uniformly mixed, are obtained by fluidized gramulating process spherical as pore creating material
Semi-finished product adsorbent；Vacuum dryer is put it into, is dried at -40 DEG C to water content about 5%, taking-up is placed on calciner
In, control heating rate is 150 DEG C/h, is warming up to 400 DEG C and stops heating, keeps the temperature 0.5h, finished product adsorbent is obtained, by what is obtained
Finished product adsorbent is fitted into ADSORPTION IN A FIXED BED column, obtains aluminate adsorption column；
(2) vanadium solution is purified：It is adsorbed using the aluminate that weak acid, weak base and water alternating dynamic washing step (1) obtain
Column washes off adsorbent residual impurity and soluble matter；The pH vanadium-containing wasting catalyst sodium roasting leachates for being 10 are purified, it is molten
Contain V 5.71g/L, Si 1.72g/L, P 1.39g/L, As 0.58g/L in liquid, suction is passed through with 10BV/h flow velocitys containing vanadium solution
Attached column stops fortune when waiting for containing V 5.63g/L, Si 0.00073g/L, P 0.0010g/L, As 0.00051g/L in efflux
Row, the adsorbent that adsorption column more renews after washing can devote oneself to work again, and used adsorbent can be used as refractory material, protect
Adiabator.
Embodiment 5
(1) preparation of adsorbent：Prepare sodium aluminate solution, be added sodium aluminate solution quality 0.005% ethanol amine and
0.005% polyglycol surfactants, are stirred, and are slowly added to magnesium hydroxide and sodium carbonate liquor, are filtered, washed
To carbon magnesium aluminate wet-milling；The polyvinyl alcohol of magnesium aluminate quality 15% is added as binder, 0.25% polyethylene glycol and 7.5%
Polyacrylamide as pore creating material, be uniformly mixed, spherical semi-finished product adsorbent obtained by slurry-spraying pelletizing technique；By it 70
DEG C dry to water content about 3.5%, taking-up is placed in calciner, and control heating rate is 200 DEG C/h, is warming up to 500 DEG C
Stop heating, keeps the temperature 0.5h, obtain finished product adsorbent, obtained finished product adsorbent is fitted into ADSORPTION IN A FIXED BED column, aluminium is obtained
Hydrochlorate adsorption column；
(2) vanadium solution is purified：It is adsorbed using the aluminate that weak acid, weak base and water alternating dynamic washing step (1) obtain
Column washes off adsorbent residual impurity and soluble matter；The vanadium slag sodium roasting leachate of pH=11 is purified, is contained in solution
V 17.38g/L, Si 3.69g/L, P 0.25g/L, As 0.0051g/L are waited for 2BV/h flow velocitys by adsorption column containing vanadium solution
It is out of service when containing V 17.19g/L, Si 0.0015g/L, P 0.00021g/L, As 0.0013g/L in efflux, absorption
The adsorbent that column more renews after washing can devote oneself to work again, and used adsorbent can be used as refractory material, thermal insulation material.
Embodiment 6
(1) preparation of adsorbent：By aluminium hydroxide and calcium carbonate, iron oxide routinely thermal process pyroreaction, be crushed,
Ball milling is soaked, and is filtered, washed to obtain calcium aluminoferrite wet-milling；Be added calcium aluminoferrite quality 10% methylcellulose and
10% polyvinyl alcohol is uniformly mixed as pore creating material, is obtained by compressing prilling as binder, 0.1% starch
Spherical semi-finished product adsorbent；It is dried at 200 DEG C to water content about 5%, taking-up is placed in calciner, control heating
Rate is 250 DEG C/h, is warming up to 800 DEG C and stops heating, keeps the temperature 0.5h, obtain finished product adsorbent, the finished product adsorbent that will be obtained
It is fitted into ADSORPTION IN A FIXED BED column, obtains aluminate adsorption column；
(2) vanadium solution is purified：It is adsorbed using the aluminate that weak acid, weak base and water alternating dynamic washing step (1) obtain
Column washes off adsorbent residual impurity and soluble matter；The pH vanadium slag calcification baking pickle liquors for being 3 are purified, V is contained in solution
16.82g/L, Si 1.27g/L, P 0.17g/L, As 0.0022g/L pass through adsorption column, outflow containing vanadium solution with 1BV/h flow velocitys
It is out of service when containing V 16.39g/L, Si 0.0018g/L, P 0.0011g/L, As 0.00082g/L in liquid, adsorption column warp
The adsorbent more renewed after washing can devote oneself to work again, and used adsorbent can be used as refractory material, thermal insulation material.
Embodiment 7
(1) preparation of adsorbent：By aluminium oxide and calcium hydroxide, routinely thermal process pyroreaction, broken, ball milling add
Water impregnates, and is filtered, washed to obtain calcium aluminate wet-milling；The methylcellulose of calcium aluminate quality 1% is added as binder, 5%
Polyacrylamide is uniformly mixed as pore creating material, spherical semi-finished product adsorbent is obtained by extruder grain technique；It puts it into true
Empty drying equipment is dried at -20 DEG C to water content about 2.5%, and taking-up is placed in calciner, and control heating rate is 110
DEG C/h, it is warming up to 900 DEG C and stops heating, after keeping the temperature 0.5h, obtain finished product adsorbent, obtained finished product adsorbent is packed into and is fixed
In bed adsorption column, aluminate adsorption column is obtained；
(2) vanadium solution is purified：It is adsorbed using the aluminate that weak acid, weak base and water alternating dynamic washing step (1) obtain
Column washes off adsorbent residual impurity and soluble matter；Vanadium liquid is extracted to the pH vanadium slag ammoniums for being 8 to purify, and V is contained in solution
15.64g/L, Si 0.058g/L, P 0.015g/L, As 0.0014g/L are waited for 5BV/h flow velocitys by adsorption column containing vanadium solution
It is out of service when containing V 15.27g/L, Si 0.00091g/L, P 0.00011g/L, As 0.00006g/L in efflux, it inhales
The adsorbent that attached column more renews after washing can devote oneself to work again, and used adsorbent can be used as refractory material, thermal insulating material
Material.,
Embodiment 8
(1) preparation of adsorbent：The alum that bone coal pickle liquor crystallizes is added to the water stirring and dissolving filtering, obtains hydrogen
Aluminium oxide and filtrate, by gained aluminium hydroxide, routinely wet processing alkali soluble obtains sodium aluminate solution, and sodium aluminate solution matter is added
The polyacrylamide surfactant of amount 0.05%, is stirred, is slowly added to calcium salt and magnesium salt solution, be filtered, washed to obtain
Calcium aluminate and magnesium aluminate mixing mixing wet-milling；8% methylcellulose of calcium aluminate and magnesium aluminate quality is added as binder,
2.5% polyethylene glycol is uniformly mixed as pore creating material, and spherical semi-finished product adsorbent is obtained by rolling prilling；By its
It is dried at 150 DEG C to water content about 1.5%, taking-up is placed in calciner, and control heating rate is 220 DEG C/h, heating
Stop heating to 600 DEG C, after keeping the temperature 0.5h, obtain finished product adsorbent, obtained finished product adsorbent is packed into ADSORPTION IN A FIXED BED column
In, obtain aluminate adsorption column；
(2) vanadium solution is purified：It is adsorbed using the aluminate that weak acid, weak base and water alternating dynamic washing step (1) obtain
Column washes off adsorbent residual impurity and soluble matter；The pH stone coal sodium roasting leachates for being 13 are purified, are contained in solution
V 4.84g/L, Si 50.93g/L, P 0.20g/L, As 0.0083g/L, pass through absorption containing vanadium solution with the flow velocity of 20BV/h
Column, waits for V 4.76g/L in efflux, out of service when Si 0.0014g/L, P 0.00081g/L, As 0.00076g/L, inhales
The adsorbent that attached column more renews after washing can devote oneself to work again, and used adsorbent can be used as refractory material, thermal insulating material
Material.
Embodiment 9
(1) preparation of adsorbent：The alum that bone coal pickle liquor crystallizes is added to the water stirring and dissolving filtering, obtains hydrogen
Aluminium oxide and filtrate, by gained aluminium hydroxide, routinely wet processing alkali soluble obtains sodium aluminate solution, and sodium aluminate solution matter is added
The ethanol amine surfactant of amount 0.1% is stirred, and is slowly added to calcium chloride and metabisulfite solution, is filtered, washed to obtain sulphur
Calcium aluminate wet-milling；5% polyvinyl alcohol of calcium sulphoaluminate quality is added as binder, 1% starch is as pore creating material, mixing
Uniformly, spherical semi-finished product adsorbent is obtained by slurry-spraying pelletizing technique；Vacuum dryer is put it into, is dried extremely at -50 DEG C
Water content about 5%, taking-up are placed in calciner, and control heating rate is 180 DEG C/h, are warming up to 650 DEG C and are stopped heating, protect
After warm 0.5h, finished product adsorbent is obtained, obtained finished product adsorbent is fitted into ADSORPTION IN A FIXED BED column, obtains aluminate absorption
Column；
(2) vanadium solution is purified：It is adsorbed using the aluminate that weak acid, weak base and water alternating dynamic washing step (1) obtain
Column washes off adsorbent residual impurity and soluble matter；The pH thick ammonium metavanadate product weight solution for being 6 is purified, is contained in solution
There are V 22.53g/L, Si 0.0092g/L, P 0.0053g/L, As 0.0058g/L to pass through suction containing vanadium solution with 25BV/h flow velocitys
Attached column stops when waiting for containing V 21.91g/L, Si 0.0013g/L, P 0.00011g/L, As 0.00007g/L in efflux
Operation, the adsorbent that adsorption column more renews after washing can devote oneself to work again, used adsorbent can be used as refractory material,
Thermal insulation material.
Embodiment 10
(1) preparation of adsorbent：Sodium aluminate solution is prepared, the polyethylene glycol surface of sodium aluminate solution quality 0.05% is added
Activating agent is stirred, and is slowly added to magnesium salts and molysite, is filtered, washed to obtain iron magnesium aluminate wet-milling；Iron magnesium aluminate quality is added
10% polyvinyl alcohol as binder, 0.5% urea is uniformly mixed, is obtained by extruder grain technique as pore creating material
To spherical semi-finished product adsorbent；It is dried at 180 DEG C to water content about 4%, taking-up is placed in calciner, control heating
Rate is 295 DEG C/h, is warming up to 550 DEG C and stops heating, after keeping the temperature 0.5h, obtain finished product adsorbent, obtained finished product is adsorbed
Agent is fitted into ADSORPTION IN A FIXED BED column, obtains aluminate adsorption column；
(2) vanadium solution is purified：It is adsorbed using the aluminate that weak acid, weak base and water alternating dynamic washing step (1) obtain
Column washes off adsorbent residual impurity and soluble matter；The pH vanadium-containing wasting catalyst vanadium enrichment liquid for being 4 is purified, is contained in solution
There are V 43.91g/L, Si 0.45g/L, P 0.036g/L, As 0.006g/L, containing vanadium solution with 8BV/h flow velocitys by adsorption column,
Wait for V 43.28g/L in efflux, when Si 0.0043g/L, P 0.0035g/L, As 0.0017g/L, out of service, adsorption column
The adsorbent more renewed after washing can devote oneself to work again, and used adsorbent can be used as refractory material, thermal insulation material.
Embodiment 11
(1) preparation of adsorbent：By aluminium oxide, calcium carbonate and magnesium sulfate routinely thermal process pyroreaction, it is crushed, ball
Mill, soaks, is filtered, washed to obtain sulphur magnesium aluminate wet-milling；The methylcellulose and 15% of sulphur magnesium aluminate quality 1% is added
Polyvinyl alcohol is uniformly mixed as binder, 0.1% carbon dust as pore creating material, and spherical half is obtained by fluidized gramulating process
Finished product adsorbent；It is dried at 75 DEG C to water content about 3%, taking-up is placed in calciner, and control heating rate is
It 174.09 DEG C/h, is warming up to 450 DEG C and stops heating, after keeping the temperature 0.5h, obtain finished product adsorbent, obtained finished product adsorbent is filled
Enter in ADSORPTION IN A FIXED BED column, obtains aluminate adsorption column；
(2) vanadium solution is purified：It is adsorbed using the aluminate that weak acid, weak base and water alternating dynamic washing step (1) obtain
Column washes off adsorbent residual impurity and soluble matter；The pH of extracting vanadium by acid leaching of stone coal liquid is adjusted to 2, it is purified, in solution
Absorption is passed through with 10BV/h flow velocitys containing vanadium solution containing V 2.96g/L, Si 0.02g/L, P 0.01g/L, As 0.005g/L
Column, it is out of service when containing V 2.86g/L, Si 0.00029g/L, P 0.00026g/L, As 0.00019g/L in efflux,
The adsorbent that adsorption column more renews after washing can devote oneself to work again, and used adsorbent can be used as refractory material, heat preservation
Material.
Embodiment 12
In addition to by other than the rich vanadium solution to be clean replaced with containing vanadium solution in CN105087932A embodiments 1, other steps
Rapid and condition is identical with the embodiment of the present invention 1, and after purification, V 15.79g/L, Si 0.0014g/ are contained in efflux
L。
Embodiment 13
In addition to by other than the rich vanadium solution to be clean replaced with containing vanadium solution in CN105087932A embodiments 2, other steps
Rapid and condition is identical with the embodiment of the present invention 5, and after purification, V 15.87g/L, Si 0.0009g/ are contained in efflux
L。
Embodiment 14
In addition to by other than the rich vanadium solution to be clean replaced with containing vanadium solution in CN105087932A embodiments 3, other steps
Rapid and condition is identical with the embodiment of the present invention 8, and after purification, V 15.82g/L, Si 0.0012g/ are contained in efflux
L。
Applicant states that the present invention illustrates detailed process equipment and the technological process of the present invention by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological processes, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, the selection etc. of concrete mode all fall within the present invention's
Within protection domain and the open scope.
Claims (10)
1. a kind of method of the purification containing silicon, phosphorus, arsenic in vanadium solution, which is characterized in that the method is：Vanadium solution will be contained and pass through aluminium
Hydrochlorate adsorption column is handled, and is removed silicon, phosphorus, arsenic in solution, is obtained scavenging solution containing vanadium.
2. the method as described in claim 1, which is characterized in that the vanadium solution that contains is vanadium industry vanadium extraction leaching liquid, vanadium leaching
After liquid enrichment in solution or vanadium product weight solution any one or at least two combination；
Preferably, the vanadium extraction raw material of the vanadium industry vanadium extraction leaching liquid is any one in vanadium slag, bone coal or vanadium-containing wasting catalyst
Kind or at least two combination.
3. method as claimed in claim 1 or 2, which is characterized in that the pH containing vanadium solution be 1~14, preferably 2~
12, further preferably 5~10；
Preferably, a concentration of 0.005~50g/L containing silicon in vanadium solution, the preferably 0.020~5g/L, further preferably
For 0.050~0.5g/L；
Preferably, a concentration of 0.005~10g/L containing phosphorus in vanadium solution, the preferably 0.008~1g/L, further preferably
For 0.01~0.25g/L；
Preferably, a concentration of 0.005~5g/L containing arsenic in vanadium solution, the preferably 0.008~0.5g/L, further preferably
For 0.01~0.25g/L.
4. such as claims 1 to 3 any one of them method, which is characterized in that the aluminate is calcium aluminate, magnesium aluminate, iron
Any one in calcium aluminate, iron magnesium aluminate, carbon calcium aluminate, carbon magnesium aluminate, calcium sulphoaluminate or sulphur magnesium aluminate or at least two
Combination, preferably any one in calcium aluminate, magnesium aluminate, calcium aluminoferrite or iron magnesium aluminate or at least two combination, into one
Step is preferably calcium aluminate and/or calcium aluminoferrite；
Preferably, the aluminate is prepared using improved wet synthetic technology, the method is：Add into sodium aluminate solution
Enter surfactant to be stirred, is slowly added to reagent needed for common process synthesizing aluminate, is filtered, washed, obtain aluminate
Product；
Preferably, the surfactant is any one in ethanol amine, polyacrylamide, polyethylene glycol or at least two
Combination；
Preferably, the surfactant addition is sodium aluminate solution quality 0.001~0.1%.
5. such as Claims 1 to 4 any one of them method, which is characterized in that the vanadium solution that will contain is adsorbed by aluminate
Column is treated in journey, in adsorption column flow velocity containing vanadium solution be 0.5~30BV/h, preferably 1~15BV/h, further preferably
For 2~10BV/h；
Preferably, impurity breakthrough point in adsorption column efflux is controlled in the processing procedure is：Silicon vanadium concentration ratio Si/V≤
0.00030, phosphorus vanadium concentration ratio P/V≤0.00025, arsenic vanadium concentration ratio P/V≤0.00010.
6. such as Claims 1 to 5 any one of them method, which is characterized in that the method is：Vanadium solution will be contained and pass through aluminic acid
Salt adsorption column is handled, and it is 0.5~30BV/h that flow velocity containing vanadium solution in adsorption column is controlled in processing procedure, impurity in efflux
Breakthrough point is：Silicon vanadium concentration ratio Si/V≤0.00030, phosphorus vanadium concentration ratio P/V≤0.00025, arsenic vanadium concentration ratio P/V≤
0.00010, obtain scavenging solution containing vanadium.
7. such as claim 1~6 any one of them method, which is characterized in that prepare the aluminate according to the following steps and inhale
Attached column：
(1) aluminate, binder and pore creating material are mixed, is granulated；
(2) finished product adsorbent is obtained after the particle that step (1) obtains being dried, calcined, by adsorbent after adsorption column,
Obtain aluminate adsorption column.
8. the method for claim 7, which is characterized in that step (1) described binder is methylcellulose and/or poly- second
Enol；
Preferably, the addition of step (1) described binder is 0.1~30%, preferably the 1~15% of aluminic acid salt quality；
Preferably, step (1) described pore creating material is any one in carbon dust, urea, starch, polyacrylamide or polyethylene glycol
Or at least two combination；
Preferably, the addition of step (1) described pore creating material be aluminic acid salt quality 0.1~10%, preferably 0.1~5%；
Preferably, step (1) described prilling is compression granulation, extruder grain, slurry-spraying pelletizing, rolls granulation or fluidization granulation
In any one.
9. such as claim 7~8 any one of them method, which is characterized in that step (2) described drying is for constant pressure and dry or very
Sky is dry；
Preferably, the temperature of the constant pressure and dry is 50~200 DEG C, preferably 70~150 DEG C；
Preferably, the vacuum drying temperature is -60~-10 DEG C；
Preferably, the water content < 5% of the adsorbent after step (2) described drying；
Preferably, the temperature of step (2) described calcining is 100~1000 DEG C, preferably 400~700 DEG C；
Preferably, step (2) the calcination process heating rate is 100~300 DEG C/h.
10. such as claim 7~9 any one of them method, which is characterized in that step (2) described adsorption column be fixed bed or
Moving bed adsorption column；
Preferably, the alternately dynamic washing of weak acid, weak base and water is carried out after step (2) the adsorbent dress column, washes off adsorbent
Residual impurity and soluble matter.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109706330A (en) * | 2019-01-21 | 2019-05-03 | 成都虹波钼业有限责任公司 | A method of from removal vanadium in molybdate solution containing vanadium |
| CN112095025A (en) * | 2020-08-24 | 2020-12-18 | 河钢承德钒钛新材料有限公司 | Method for removing silicon and phosphorus from blank roasting-ammonia leaching vanadium liquid |
| CN115814565A (en) * | 2022-11-30 | 2023-03-21 | 攀钢集团攀枝花钢铁研究院有限公司 | Potassium-sodium absorption method and absorbent for preparing vanadium-nitrogen alloy by pushed slab kiln calcination |
| CN115872450A (en) * | 2022-12-30 | 2023-03-31 | 四川省银河化学股份有限公司 | Method and system for continuously and directionally removing silicon from sodium chromate alkali solution |
| CN115976341A (en) * | 2022-12-30 | 2023-04-18 | 四川省银河化学股份有限公司 | Method for removing silicon and phosphorus in vanadium slag sodium salt roasting production system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109706330A (en) * | 2019-01-21 | 2019-05-03 | 成都虹波钼业有限责任公司 | A method of from removal vanadium in molybdate solution containing vanadium |
| CN109706330B (en) * | 2019-01-21 | 2021-12-07 | 成都虹波钼业有限责任公司 | Method for removing vanadium from vanadium-containing molybdate solution |
| CN112095025A (en) * | 2020-08-24 | 2020-12-18 | 河钢承德钒钛新材料有限公司 | Method for removing silicon and phosphorus from blank roasting-ammonia leaching vanadium liquid |
| CN115814565A (en) * | 2022-11-30 | 2023-03-21 | 攀钢集团攀枝花钢铁研究院有限公司 | Potassium-sodium absorption method and absorbent for preparing vanadium-nitrogen alloy by pushed slab kiln calcination |
| CN115814565B (en) * | 2022-11-30 | 2024-05-31 | 攀钢集团攀枝花钢铁研究院有限公司 | Potassium-sodium absorption method and absorbent for preparing vanadium-nitrogen alloy by pushed slab kiln calcination |
| CN115872450A (en) * | 2022-12-30 | 2023-03-31 | 四川省银河化学股份有限公司 | Method and system for continuously and directionally removing silicon from sodium chromate alkali solution |
| CN115976341A (en) * | 2022-12-30 | 2023-04-18 | 四川省银河化学股份有限公司 | Method for removing silicon and phosphorus in vanadium slag sodium salt roasting production system |
| CN115976341B (en) * | 2022-12-30 | 2023-07-25 | 四川省银河化学股份有限公司 | Method for removing silicon and phosphorus in vanadium slag sodium roasting production system |
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