CN107416903A - A kind of method for handling spent vanadium catalyst - Google Patents

A kind of method for handling spent vanadium catalyst Download PDF

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Publication number
CN107416903A
CN107416903A CN201710264944.3A CN201710264944A CN107416903A CN 107416903 A CN107416903 A CN 107416903A CN 201710264944 A CN201710264944 A CN 201710264944A CN 107416903 A CN107416903 A CN 107416903A
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parts
vanadium catalyst
vanadium
water
solution
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陈允至
尹振兴
陈国栋
刘富德
谢天锋
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Guangdong University of Technology
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Guangdong University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B18/04—Waste materials; Refuse
    • C04B18/0427—Dry materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04—Portland cements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
  • Civil Engineering (AREA)
  • Processing Of Solid Wastes (AREA)
  • Catalysts (AREA)

Abstract

The invention belongs to dead catalyst process field, discloses a kind of method for handling spent vanadium catalyst, and the process of this method includes grinding, water logging, reducing leaching, the separation of vanadium potassium, alkali soluble removal of impurities, adjustment pH, precipitation and roasting, obtains leached mud, V2O5Solid and potassium sulfate, described leached mud can be made into concrete.Sour usage amount during leaching vanadium is greatly lowered using the method for acidleach after first water logging in the present invention, nor needs to use the extractant of costliness, reduces production cost；Using sulfur dioxide as reducing agent, the form waste gas of sulfur dioxide of factory's discharge is efficiently utilized, reduces the pollution of environment；Realize and the synchronous of vanadium and potassium is reclaimed, also solve the process problem to the silica in spent vanadium catalyst, iron compound and aluminium compound, be one kind preferably without waste gas and waste sludge discharge processing method.

Description

A kind of method for handling spent vanadium catalyst
Technical field
The invention belongs to the field that waste catalyst recovery recycles, more particularly, to a kind of processing spent vanadium catalyst Method.
Background technology
Caused solid dead catalyst has 50~700,000 t every year in the whole world.If, not only can contaminated soil without processing (vanadic anhydride is noxious material, and the solubility in water is 8g/L), taking a large amount of soils, (10000 tons of waste residues of stockpiling will account for Soil with 1 mu), also result in the waste of rare precious metal resource.
Vanadium containing catalystses catalysis is used during gas washing in SA production.The active component of this catalyst is five oxidations two Vanadium, co-catalyst are potassium sulfates, and catalyst carrier is diatomite.In addition, this catalyst also containing a small amount of iron compound and Aluminium compound.Vanadium catalyst in use for some time, active component V2O5Can be because the fluorine, acid mist, the micronic dust pair that contain in gas Its caused toxic action, it is changed into the tetravalence vanadium of catalytically inactive.When the ratio of tetravalence vanadium is too high, vanadium catalyst will lose It is living, become spent vanadium catalyst.Therefore, the life-span of vanadium catalyst is generally 2~10 years.By current domestic sulfuric acid plant's Production rate, It will produce every year more than 10000t spent vanadium catalysts.Analysis result is shown, in spent vanadium catalyst, SiO2Content for 50~ 70%, K2SO4Content be 5~8%, V2O5Content be 5~8%, Al2O3Content be 2~4%, Fe2O3Content be 1.5 ~3%.Therefore, spent vanadium catalyst contains is worth with very high recycling.Importantly, waste catalyst recovery is brought Social benefit and environmental benefit it is very huge.
Have more research in terms of reclaiming vanadium in spent vanadium catalyst both at home and abroad, also achieve certain achievement, but still deposit In cost recovery height, it is difficult to the problems such as industrializing.Vanadium potassium silicon returns in the invention spent vanadium catalyst of patent 201410037134.0 Receiving method, a kind of recovery method of vanadium potassium silicon in spent vanadium catalyst is disclosed, water logging, reductic acid are carried out to spent vanadium catalyst first Leaching, total leaching rate >=95.0% of vanadium, silicon are separated in the form of phase analysis with the vanadium and potassium being transferred in leachate, and phase analysis is through alkali soluble Prepare liquid sodium silicate recovery silicon；Vanadium in leachate is separated with potassium by extracting realization:Raffinate phase produces sulphur through evaporative crystallization Sour potassium reclaims potassium；Extraction phase prepares vanadic anhydride recovery vanadium through processes such as back extraction, precipitation and roastings.The advantages of this application case It is to realize the recovery to the vanadium silicon potassium in spent vanadium catalyst.The invention is disadvantageous in that：1. extractant uses certain It can be failed after number, cause production cost to remain high；2. prepare liquid sodium silicate using the silica in spent vanadium catalyst With reclaim silicon in theory, it is technically feasible but economically impractical；3. the invention is not referred to the iron in spent vanadium catalyst The processing method of compound and aluminium compound.
And for example patent publication No.：201110397978.2 publication date：On 06 13rd, 2012, invention and created name was：One The method of kind spent vanadium catalyst comprehensive reutilization, this application case disclose a kind of side of spent vanadium catalyst comprehensive reutilization Method, using spent vanadium catalyst as raw material, first by reducing acidleach, vanadium, potassium are transferred to realization and SiO in liquid phase2Point of precipitation From SiO2Liquid sodium silicate is prepared by alkali soluble to reclaim SiO2；Vanadium, potassium in liquid phase add the separation that alkali lye realizes vanadium and potassium, Then V is prepared respectively2O5And K2SO4.This method prepares V by spent vanadium catalyst2O5、K2SO4And liquid sodium silicate, realize vanadium, potassium Synchronization with silicon is reclaimed, V2O5Purity >=98.3%, yield >=92.0%, K2SO4Purity is with K2O meters >=51.2%, yield >= 95%, Na in liquid sodium silicate2O >=7.7%, SiO2>=24.6%, yield >=93.2%.The advantages of this application case is successfully to return Receive the vanadium silicon potassium in spent vanadium catalyst and extractant need not be used.This application case is disadvantageous in that：1. directly use Acidleach is reduced, causes the consumption of acid excessive；2. liquid sodium silicate is prepared using the silica in spent vanadium catalyst to reclaim Silicon is technically feasible, but economically impractical；3. this application case is not referred to the iron compound and aluminium in spent vanadium catalyst The processing method of compound.
In summary, how to design that a kind of cost recovery is low, being easy to the method for industrialized processing spent vanadium catalyst is A problem of the prior art.
The content of the invention
A kind of the defects of the invention aims to overcome prior art, there is provided method for handling spent vanadium catalyst.Should Method provides that cost recovery is low, is easy to the method for industrialized processing spent vanadium catalyst.Using the method for acidleach after first water logging, And by the use of sulfur dioxide as reducing agent, reduce the usage amount of acid, it is not required that use the extractant of costliness, realize to vanadium and The synchronous recovery of potassium, also solves the process problem to the silica in spent vanadium catalyst, iron compound and aluminium compound, is One kind is preferably without waste gas and waste sludge discharge processing method.
Above-mentioned purpose of the present invention is achieved by the following technical programs：
A kind of method for handling spent vanadium catalyst, is comprised the following specific steps that：
S1. spent vanadium catalyst is worn into particle, adds water and be well mixed, 0.5~4h of water logging at a temperature of 30~100 DEG C, Water logging product is separated, obtains infusion and water logging slag；
S2. acid solution and water logging slag are mixed, under the atmosphere of sulfur dioxide, react 0.5~4h, product is separated, Obtain pickle liquor and leached mud I；
S3. the pickle liquor in the infusion in step S1 and step S2 is mixed, KOH solution is added dropwise, adjust pH to 6~8, 30~120min is reacted at 40~80 DEG C, product is separated, obtains potassium sulfate solution and filter cake I；
S4. filter cake I is dissolved in aqueous slkali, adjusts pH to 13~14, add oxidant, boil, make solution by blue It is changed into yellow, product is separated, obtains leached mud II and filtrate I；
S5. acid solution is added drop-wise in filtrate I, regulation pH is 4.7~10, obtains leached mud III and filtrate II；
S6. ammonium salt solution or ammoniacal liquor are added drop-wise in filtrate II, adjust pH to 8, reacted 30~90min at room temperature, will produce Thing separates, and obtains ammonium metavanadate precipitate；
S7., ammonium metavanadate precipitate is heated to 300~500 DEG C in air or oxygen, is incubated 1~2h, then furnace cooling To room temperature, the V that purity is more than 97.5% is obtained2O5Solid；
S8. mixed after grinding leached mud I, leached mud II, leached mud III, be added to cement, middle sand, aggregate and strengthen fine Mixed in the mixture of dimension, add additive and water mixing, stir 2~4 minutes, concrete is made；
S9. potassium sulfate solution step S3 obtained concentrate and decrease temperature crystalline, obtains potassium sulfate.
Preferably, the particle diameter of particle described in step S1 is 1~125 micron.
Preferably, the mass ratio of spent vanadium catalyst and water described in step S1 is 1：(1.5~5).
Preferably, the mass ratio of acid solution and water logging slag described in step S2 is (1.5~5)：1, the sulfur dioxide Concentration be 5~99%.
Preferably, acid solution described in step S2 and S5 is one or more of sulfuric acid, nitric acid, citric acid or hydrochloric acid.
Preferably, aqueous slkali described in step S4 is in sodium hydroxide solution, potassium hydroxide solution or aqua calcis More than one.
Preferably, oxidant described in step S4 is one or more of permanganate, sodium chlorate or hydrogen peroxide.
Preferably, ammonium salt solution described in step S6 is ammonium chloride, ammonium sulfate, ammonium hydrogen sulfate, ammonium nitrate, ammonium carbonate or carbon One or more of sour hydrogen ammonium.
Preferably, the component of concrete is as follows described in step S8：100~300 parts of leached mud, 200~300 parts of cement； Middle 300~600 parts of sand, 600~1000 parts of aggregate, 10~20 parts of reinforcing fibre, 5~10 parts of additive, 170~210 parts of water；
Preferably, the additive includes 35 parts of poly carboxylic acid series water reducer, 6 parts of silane coupler, polyvinylpyrrolidone 3 Part, 2 parts of carborundum, 8 parts of coated with silica titanium dioxide, 5 parts of jelly powder, 12 parts of bentonite, 10 parts of nano-carbon powder, glucose 4 parts of 4 parts of sour sodium and acetate phenol.
Preferably, the modulus of fineness of the middle sand is 2.3~3, and the aggregate is cinder, slag, blast furnace slag or stone, institute The particle diameter for stating aggregate is 10~20mm；The modulus of fineness of the aggregate is 1.6~1.8；The cement is portland cement, described The intensity index of portland cement is 32.5 or 42.5；The reinforcing fibre is one in steel fibre, glass fibre or carbon fiber More than kind, the length of the reinforcing fibre is 9~30mm
Compared with prior art, the invention has the advantages that：
1. the present invention using the method for acidleach after first water logging, drastically reduce the area sour usage amount during leaching vanadium, Also without the extractant for using costliness, production cost is reduced.
2. the present invention, as reducing agent, is not only reduced production cost, is also effectively utilized factory row using sulfur dioxide The form waste gas of sulfur dioxide gone out, reduce the pollution to environment.
Vanadium and the synchronous of potassium are reclaimed 3. the present invention realizes, also solved to the silica in spent vanadium catalyst, iron The process problem of compound and aluminium compound, it is a kind of preferably discharge method without waste gas and waste residue.
Brief description of the drawings
Fig. 1 is the process chart of present invention processing spent vanadium catalyst.
Embodiment
Present disclosure is further illustrated with reference to specific embodiment, but should not be construed as limiting the invention. Unless otherwise specified, the conventional meanses that technological means used in embodiment is well known to those skilled in the art.Except non-specifically Illustrate, reagent that the present invention uses, method and apparatus is the art conventional reagent, method and apparatus.
The grinding device described in embodiment 1-3 is ball mill, and the equipment for separating liquid from solid is filter press；The reaction is held Device is autoclave, enamel reaction still, stainless steel cauldron or fiberglass reactor；PH value is respectively arranged with the reaction vessel Sensor, temperature sensor and pressure sensor, the heater are heating furnace.
Fig. 1 is the process chart of present invention processing spent vanadium catalyst.It is useless that processing is illustrated with reference to embodiment 1-3 The method of vanadium catalyst.
Embodiment 1
A kind of method for handling spent vanadium catalyst, comprises the following steps：
1. grinding：Spent vanadium catalyst is delivered into ball mill grinding to particle diameter and is less than 125 microns；125 microns of particle diameter i.e. 120 Mesh；
2. water logging：It is well mixed by the spent vanadium catalyst after grinding with water, solid-liquid weight ratio is 1：4；At a temperature of 30 DEG C Leaching 2 hours；30% vanadic anhydride and the mixture of vanadium tetraoxide, 50% potassium sulfate can be leached by water logging. As 6≤pH≤8, pentavalent vanadium ion is in water with VO3(OH)2-、V3O9 3-、V4O12 4-Form exist, be insoluble in water.Four oxidations Two vanadium are soluble in water.Water logging product is separated with filter press, obtains infusion and water logging slag；Infusion is directly entered vanadium and potassium point From process；Water logging slag enters reducing leaching process.
3. reducing leaching：It is 5 in mass ratio by 3mol/L sulfuric acid solution and spent vanadium catalyst:1 ratio is mixed to form Mixed liquor, it is added in fiberglass reactor；Mixed liquor into fiberglass reactor is at the uniform velocity passed through the dioxy that concentration is 99% Change sulphur, react 2 hours；SO 2 tail gas is absorbed with sodium hydroxide solution；Remaining vanadium oxygen can be leached by reducing leaching Compound and potassium sulfate；Under normal temperature and pressure, 9.4 grams of sulfur dioxide can be dissolved per 100ml water；2/3rds sulfur dioxide is dissolved in Generation sulfurous acid is reacted after water with water；Sulfurous acid can make pentavalent vanadium be converted into tetravalence vanadium soluble in water as reducing agent；With Filter press separates reducing leaching product, obtains pickle liquor and leached mud I.
4. the separation of vanadium and potassium：Pickle liquor in the infusion and step 4 of step 2 is added in fiberglass reactor, 1mol/L KOH solution is slow added into, pH to 7 is adjusted, is reacted 90 minutes at 60 DEG C；Using KOH solution obtain purpose be Foreign ion is not introduced before isolating potassium sulfate solution；With filter press by vanadium, potassium separation product separate, obtain potassium sulfate solution and Filter cake I.
5. alkali soluble cleans：Step 4 gained filter cake I is dissolved in potassium hydroxide solution, regulation pH is less than 14 to being more than 13.When During 13≤pH≤14, pentavalent vanadium ion is in water with VO4 3-Form exist, it is soluble in water.Oxidant sodium chlorate is added, is boiled Boiling, makes solution be changed into yellow by blue；Now, tetravalence vanadium has been converted into pentavalent vanadium；Alkali soluble is cleaned product with filter press Separation, obtains leached mud II and filtrate I；
6. adjust pH：Step 5 gained filtrate I is added in fiberglass reactor, then hydrochloric acid solution is added dropwise, regulation pH is 8；Obtain leached mud III and filtrate II；PH value is adjusted to 8 generations for being advantageous to ammonium metavanadate precipitate.
7. precipitation：Filtrate II obtained by adjustment pH is added in reaction vessel, then ammonium sulfate is added dropwise；React at room temperature 90 minutes；Precipitation product is separated with filter press, obtains ammonium metavanadate precipitate.
8. roasting：Step 7 gained ammonium metavanadate precipitate is put into and is heated to 420 DEG C in heating furnace in air atmosphere, is protected Temperature 2 hours, then cool to room temperature with the furnace, obtain the V that purity is more than 97%2O5Solid；The NH of discharge3Waste gas is inhaled with hydrochloric acid solution Receive, generate ammonium chloride solution, return to precipitation process.
9. concrete production：Mixed after leached mud I, leached mud II, leached mud III are ground, then with cement, middle sand, bone Material, reinforcing fibre mix, and add additive and water, stir 4 minutes, obtain concrete.
The quality of each component of above-mentioned concrete is as follows：100 parts of leached mud, 200 parts of portland cement, portland cement Intensity index is 32.5；Modulus of fineness is 2.7 300 parts of middle sand, 600 parts of stone, the particle diameter of the stone is 10mm~20mm, The powder containing quantity of stone is 5.4%, modulus of fineness 1.8,20 parts of steel fibre, and the length of the steel fibre is 9mm, 5 parts of additive, 170 parts of water.
Additive be 35 parts of poly carboxylic acid series water reducer, 6 parts of silane coupler, 3 parts of polyvinylpyrrolidone, 2 parts of carborundum, 8 parts of coated with silica titanium dioxide, 5 parts of jelly powder, 12 parts of bentonite, 10 parts of nano-carbon powder, 4 parts of sodium gluconate and acetic acid The mixture that 4 parts of ester phenol.
10. potassium sulfate production：Concentrated, concentrated out in the inspissator that the potassium sulfate solution that step 4 is obtained is delivered to Distilled water, obtain concentrate；Concentrate is delivered into decrease temperature crystalline in crystallization kettle, obtains the potassium sulfate solid that purity is more than 98%.
Embodiment 2
A kind of method for handling spent vanadium catalyst, comprises the following steps：
1. grinding：Spent vanadium catalyst is delivered into ball mill grinding to particle diameter and is less than 125 microns, 125 microns of particle diameter i.e. 120 Mesh.
2. water logging：It is well mixed by the spent vanadium catalyst after grinding with water, solid-liquid weight ratio is 1：3；At a temperature of 100 DEG C Leaching 3 hours；50% vanadic anhydride and the mixture of vanadium tetraoxide, 70% potassium sulfate can be leached by water logging. As 6≤pH≤8, pentavalent vanadium ion is in water with VO3(OH)2-、V3O9 3-、V4O12 4-Form exist, be insoluble in water.Four oxidations Two vanadium are soluble in water.Water logging product is separated with filter press, obtains infusion and water logging slag；Infusion is directly entered vanadium, potassium point From process；Water logging slag enters reducing leaching process.
3. reducing leaching：It is 4 in mass ratio by 2mol/L sulfuric acid solution and spent vanadium catalyst:1 ratio is mixed to form Mixed liquor, it is added in enamel reaction still；Mixed liquor into enamel reaction still is at the uniform velocity passed through the sulfur dioxide that concentration is 99%, Reaction 2 hours；SO 2 tail gas is absorbed with sodium hydroxide solution；By reducing leaching can leach remaining barium oxide and Potassium sulfate；Under normal temperature and pressure, 9.4 grams of sulfur dioxide can be dissolved per 100ml water；2/3rds sulfur dioxide be dissolved in after water with Water reaction generation sulfurous acid；Sulfurous acid can make pentavalent vanadium be converted into tetravalence vanadium soluble in water as reducing agent；Use filter press Reducing leaching product is separated, obtains pickle liquor and leached mud I.
4. the separation of vanadium and potassium：Pickle liquor in the infusion and step 4 of step 2 is added in fiberglass reactor, 1mol/L KOH solution is slow added into, pH to 7 is adjusted, is reacted 90 minutes at 60 DEG C；Using KOH solution obtain purpose be Foreign ion is not introduced before isolating potassium sulfate solution；With filter press by vanadium, potassium separation product separate, obtain potassium sulfate solution and Filter cake I.
5. alkali soluble cleans：Step 4 gained filter cake I is dissolved in potassium hydroxide solution, regulation pH is less than 14 to being more than 13.When During 13≤pH≤14, pentavalent vanadium ion is in water with VO4 3-Form exist, it is soluble in water.Oxidant sodium chlorate is added, is boiled Boiling, makes solution be changed into yellow by blue；Now, tetravalence vanadium has been converted into pentavalent vanadium；Alkali soluble is cleaned product with filter press Separation, obtains leached mud II and filtrate I.
6. adjust pH：Step 5 gained filtrate I is added in fiberglass reactor, then hydrochloric acid solution is added dropwise, regulation pH is arrived 8；Obtain leached mud III and filtrate II；PH value is adjusted to 8 generations for being advantageous to ammonium metavanadate precipitate.
7. precipitation：Filtrate II obtained by adjustment pH is added in reaction vessel, then ammonium chloride solution is added dropwise；React at room temperature 90 minutes；Precipitation product is separated with filter press, obtains ammonium metavanadate precipitate.
8. roasting：Put step 7 gained ammonium metavanadate precipitate into heating furnace heat resolve, be heated to 320 DEG C, insulation 2 Hour, then cool to room temperature with the furnace, obtain the V that purity is more than 97%2O5Solid；The NH of discharge3Waste gas is absorbed with sulfuric acid solution, Ammonium sulfate is generated, returns to precipitation process.
9. concrete production：Mixed after leached mud I, leached mud II, leached mud III are ground, then with cement, middle sand, bone Material, reinforcing fibre mix, and add additive, water, stir 4 minutes, obtain concrete.
The mass parts of each component of the concrete are as follows：300 parts of leached mud, intensity index are 32.5 portland cements 300 parts；Modulus of fineness be 2.7 600 parts of middle sand, 600 parts of cinder, 20 parts of 20mm glass fibres, 10 parts of additive, 210 parts of water.
Additive by 35 parts of poly carboxylic acid series water reducer, 6 parts of silane coupler, 3 parts of polyvinylpyrrolidone, 2 parts of carborundum, 8 parts of coated with silica titanium dioxide, 5 parts of jelly powder, 12 parts of bentonite, 10 parts of nano-carbon powder, 4 parts of sodium gluconate, acetic acid 4 parts of ester phenol mixes.
10. potassium sulfate production：Concentrated, concentrated out in the inspissator that the potassium sulfate solution that step 4 is obtained is delivered to Distilled water, obtain concentrate；Concentrate is delivered into decrease temperature crystalline in crystallization kettle, obtains the potassium sulfate solid that purity is more than 98%.
Embodiment 3
A kind of method for handling spent vanadium catalyst, comprises the following steps：
1. grinding：Spent vanadium catalyst is delivered into ball mill grinding to particle diameter and is less than 125 microns；125 microns of particle diameter i.e. 120 Mesh.
2. water logging：It is well mixed by the spent vanadium catalyst after grinding with water, solid-liquid weight ratio is 1：3；At a temperature of 80 DEG C Leaching 2 hours；30% vanadic anhydride and the mixture of vanadium tetraoxide, 50% potassium sulfate can be leached by water logging. As 6≤pH≤8, pentavalent vanadium ion is in water with VO3(OH)2-、V3O9 3-、V4O12 4-Form exist, be insoluble in water.Four oxidations Two vanadium are soluble in water.Water logging product is separated with filter press, obtains infusion and water logging slag；Infusion is directly entered vanadium, potassium point From process；Water logging slag enters reducing leaching process.
3. reducing leaching：It is 5 in mass ratio by 1mol/L sulfuric acid solution and spent vanadium catalyst:1 ratio is mixed to form Mixed liquor, it is added in enamel reaction still；Mixed liquor into enamel reaction still is at the uniform velocity passed through the sulfur dioxide that concentration is 50%, Reaction 2 hours；SO 2 tail gas is absorbed with sodium hydroxide solution；The enamel reaction still is built with pH sensor, temperature Sensor and pressure sensor；Remaining barium oxide and potassium sulfate can be leached by reducing leaching；Under normal temperature and pressure, often 100ml water can dissolve 9.4 grams of sulfur dioxide；2/3rds sulfur dioxide is dissolved in after water and reacts generation sulfurous acid with water；It is sub- Sulfuric acid can make pentavalent vanadium be converted into tetravalence vanadium soluble in water as reducing agent；Reducing leaching product is separated with filter press, Obtain pickle liquor and leached mud I；
4. the separation of vanadium and potassium：Pickle liquor in the infusion and step 4 of step 2 is added in fiberglass reactor, 1mol/L KOH solution is slow added into, pH to 7 is adjusted, is reacted 90 minutes at 60 DEG C；Using KOH solution obtain purpose be Foreign ion is not introduced before isolating potassium sulfate solution；With filter press by vanadium, potassium separation product separate, obtain potassium sulfate solution and Filter cake I；
5. alkali soluble cleans：Step 4 gained filter cake I is dissolved in alkaline solution, regulation pH is less than 14 to being more than 13.When 13≤ During pH≤14, pentavalent vanadium ion is in water with VO4 3-Form exist, it is soluble in water.Oxidant potassium chlorate is added, is boiled, is made Solution is changed into yellow by blue；Now, tetravalence vanadium has been converted into pentavalent vanadium；Alkali soluble removal of impurities product is separated with filter press, Obtain leached mud II and filtrate I；
6. adjust pH：Step 5 gained filtrate I is added in fiberglass reactor, is slow added into sulfuric acid solution, is adjusted PH to 8；Obtain leached mud III and filtrate II；PH value is adjusted to 8 generations for being advantageous to ammonium metavanadate precipitate；
7. precipitation：Filtrate II obtained by adjustment pH is added in reaction vessel, then ammonium chloride solution is added dropwise；React at room temperature 90 minutes；Precipitation product is separated with filter press, obtains ammonium metavanadate precipitate；
8. roasting：Put step 7 gained ammonium metavanadate precipitate into heating furnace heat resolve, be heated to 320 DEG C, insulation 2 Hour, then cool to room temperature with the furnace, obtain the V that purity is more than 97%2O5Solid；The NH of discharge3Waste gas is absorbed with sulfuric acid solution, Ammonium sulfate is generated, returns to precipitation process；
9. concrete production：Mixed after leached mud I, leached mud II, leached mud III are ground, then with cement, middle sand, bone Material, reinforcing fibre mix, and add additive, water, stir 4 minutes, obtain concrete；
The mass parts of each component are as follows：100 parts of leached mud, intensity index are 42.5 200 parts of portland cement；Carefully Spend 300 parts of the middle sand that modulus is 2.7,600 parts of the stone that particle diameter 20mm, powder containing quantity 5.4%, modulus of fineness are 1.8,10mm 20 parts of carbon fiber, 5 parts of additive, 190 parts of water；
Additive by 35 parts of poly carboxylic acid series water reducer, 6 parts of silane coupler, 3 parts of polyvinylpyrrolidone, 2 parts of carborundum, 8 parts of coated with silica titanium dioxide, 5 parts of jelly powder, 12 parts of bentonite, 10 parts of nano-carbon powder, 4 parts of sodium gluconate, acetic acid 4 parts of ester phenol mixes；
10. potassium sulfate production：Concentrated, concentrated out in the inspissator that the potassium sulfate solution that step 4 is obtained is delivered to Distilled water, obtain concentrate；Concentrate is delivered into decrease temperature crystalline in crystallization kettle, obtains the potassium sulfate solid that purity is more than 98%.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine and simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (10)

  1. A kind of 1. method for handling spent vanadium catalyst, it is characterised in that comprise the following specific steps that：
    S1. spent vanadium catalyst is worn into particle, adds water and be well mixed, 0.5~4h of water logging at a temperature of 30~100 DEG C, by water Product separation is soaked, obtains infusion and water logging slag；
    S2. acid solution and water logging slag are mixed, under the atmosphere of sulfur dioxide, reacts 0.5~4h, product is separated, obtained Pickle liquor and leached mud I；
    S3. the pickle liquor in the infusion in step S1 and step S2 is mixed, KOH solution is added dropwise, pH to 6~8 is adjusted, 40 30~120min is reacted at~80 DEG C, product is separated, obtains potassium sulfate solution and filter cake I；
    S4. filter cake I is dissolved in aqueous slkali, adjusts pH to 13~14, add oxidant, boil, solution is changed by blue For yellow, product is separated, obtains leached mud II and filtrate I；
    S5. acid solution is added drop-wise in filtrate I, regulation pH is 4.7~10, obtains leached mud III and filtrate II；
    S6. ammonium salt solution or ammoniacal liquor are added drop-wise in filtrate II, adjust pH to 8, react 30~90min at room temperature, by product point From obtaining ammonium metavanadate precipitate；
    S7., ammonium metavanadate precipitate is heated to 300~500 DEG C in air or oxygen, is incubated 1~2h, then cool to room with the furnace Temperature, obtain the V that purity is more than 97.5%2O5Solid；
    S8. mixed after grinding leached mud I, leached mud II, leached mud III, be added to cement, middle sand, aggregate and reinforcing fibre Mixed in mixture, add additive and water mixing, stir 2~4 minutes, concrete is made；
    S9. potassium sulfate solution step S3 obtained concentrate and decrease temperature crystalline, obtains potassium sulfate.
  2. 2. the method for processing spent vanadium catalyst according to claim 1, it is characterised in that the grain of particle described in step S1 Footpath is 1~125 micron.
  3. 3. the method for processing spent vanadium catalyst according to claim 1, it is characterised in that vanadium catalysis of being given up described in step S1 The mass ratio of agent and water is 1：(1.5~5).
  4. 4. the method for processing spent vanadium catalyst according to claim 1, it is characterised in that acid solution described in step S2 Mass ratio with water logging slag is (1.5~5)：1, the concentration of the sulfur dioxide is 5~99%.
  5. 5. the method for processing spent vanadium catalyst according to claim 1, it is characterised in that acid described in step S2 and S5 Solution is one or more of sulfuric acid, nitric acid, citric acid or hydrochloric acid.
  6. 6. the method for processing spent vanadium catalyst according to claim 1, it is characterised in that aqueous slkali is described in step S4 One or more of sodium hydroxide solution, potassium hydroxide solution or aqua calcis, the oxidant are permanganate, chloric acid One or more of sodium or hydrogen peroxide.
  7. 7. the method for processing spent vanadium catalyst according to claim 1, it is characterised in that ammonium salt solution described in step S6 For one or more of ammonium chloride, ammonium sulfate, ammonium hydrogen sulfate, ammonium nitrate, ammonium carbonate or ammonium hydrogen carbonate.
  8. 8. the method for processing spent vanadium catalyst according to claim 1, it is characterised in that concrete described in step S8 Component is as follows：100~300 parts of leached mud, 200~300 parts of cement；Middle 300~600 parts of sand, 600~1000 parts of aggregate, strengthen 10~20 parts of fiber, 5~10 parts of additive, 170~210 parts of water.
  9. 9. the method for processing spent vanadium catalyst according to claim 8, it is characterised in that the additive includes polycarboxylic acids 35 parts of based water reducer, 6 parts of silane coupler, 3 parts of polyvinylpyrrolidone, 2 parts of carborundum, coated with silica titanium dioxide 8 Part, 5 parts of jelly powder, 12 parts of bentonite, 10 parts of nano-carbon powder, 4 parts of sodium gluconate and 4 parts of acetate phenol.
  10. 10. the method for processing spent vanadium catalyst according to claim 8, it is characterised in that the modulus of fineness of the middle sand For 2.3~3, the aggregate is cinder, slag, blast furnace slag or stone, and the particle diameter of the aggregate is 10~20mm；The aggregate Modulus of fineness is 1.6~1.8；The cement is portland cement, and the intensity index of the portland cement is 32.5 or 42.5； The reinforcing fibre is one or more of steel fibre, glass fibre or carbon fiber, the length of the reinforcing fibre for 9~ 30mm。
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CN108315572A (en) * 2018-02-05 2018-07-24 中南大学 A method of the Leaching Vanadium chromium from containing vanadium and chromium solid material
CN109913660A (en) * 2019-03-18 2019-06-21 东北大学 A method of rich vanadium richness iron charge is prepared using v-bearing steel slag
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CN112320846A (en) * 2020-10-16 2021-02-05 成都先进金属材料产业技术研究院有限公司 Preparation of high-purity V by high-efficiency synergistic impurity removal of alkaline vanadium-containing leaching solution2O5Method (2)
CN113337737A (en) * 2021-06-01 2021-09-03 贵州威顿催化技术有限公司 Method for recovering waste vanadium catalyst by using chromatographic technique
CN114107677A (en) * 2021-12-03 2022-03-01 贵州威顿催化技术有限公司 Method for recovering vanadium and potassium from acid-making waste vanadium catalyst under assistance of microwaves
CN114231760A (en) * 2021-12-20 2022-03-25 安徽工业大学 Method for recycling waste vanadium catalyst in sulfuric acid industry
CN114291879A (en) * 2021-11-23 2022-04-08 攀钢集团研究院有限公司 Preparation method of aluminum silicate

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Cited By (10)

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Publication number Priority date Publication date Assignee Title
CN108315572A (en) * 2018-02-05 2018-07-24 中南大学 A method of the Leaching Vanadium chromium from containing vanadium and chromium solid material
CN109913660A (en) * 2019-03-18 2019-06-21 东北大学 A method of rich vanadium richness iron charge is prepared using v-bearing steel slag
CN111304451A (en) * 2020-04-10 2020-06-19 贵州威顿催化技术有限公司 Method for recycling waste vanadium catalyst by using phosphoric acid solution
CN111304451B (en) * 2020-04-10 2022-01-14 贵州威顿催化技术有限公司 Method for recycling waste vanadium catalyst by using phosphoric acid solution
CN112320846A (en) * 2020-10-16 2021-02-05 成都先进金属材料产业技术研究院有限公司 Preparation of high-purity V by high-efficiency synergistic impurity removal of alkaline vanadium-containing leaching solution2O5Method (2)
CN113337737A (en) * 2021-06-01 2021-09-03 贵州威顿催化技术有限公司 Method for recovering waste vanadium catalyst by using chromatographic technique
CN114291879A (en) * 2021-11-23 2022-04-08 攀钢集团研究院有限公司 Preparation method of aluminum silicate
CN114291879B (en) * 2021-11-23 2023-09-05 攀钢集团研究院有限公司 Preparation method of aluminum silicate
CN114107677A (en) * 2021-12-03 2022-03-01 贵州威顿催化技术有限公司 Method for recovering vanadium and potassium from acid-making waste vanadium catalyst under assistance of microwaves
CN114231760A (en) * 2021-12-20 2022-03-25 安徽工业大学 Method for recycling waste vanadium catalyst in sulfuric acid industry

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Application publication date: 20171201