CN101381818A - Method for preparing intermediate salt during acid leaching and extraction of vanadium pentoxide from vanadium-containing stone coal ash - Google Patents

Method for preparing intermediate salt during acid leaching and extraction of vanadium pentoxide from vanadium-containing stone coal ash Download PDF

Info

Publication number
CN101381818A
CN101381818A CNA2008101211610A CN200810121161A CN101381818A CN 101381818 A CN101381818 A CN 101381818A CN A2008101211610 A CNA2008101211610 A CN A2008101211610A CN 200810121161 A CN200810121161 A CN 200810121161A CN 101381818 A CN101381818 A CN 101381818A
Authority
CN
China
Prior art keywords
vanadium
intermediate salt
add
filter residue
filtrate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA2008101211610A
Other languages
Chinese (zh)
Other versions
CN101381818B (en
Inventor
骆仲泱
施正伦
岑可法
方梦祥
高翔
王勤辉
程乐鸣
周劲松
余春江
王树荣
倪明江
陈盾
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Cneec-Zhejiang University Science & Technology Co Ltd
Zhejiang University ZJU
Original Assignee
Shanghai Cneec-Zhejiang University Science & Technology Co Ltd
Zhejiang University ZJU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Cneec-Zhejiang University Science & Technology Co Ltd, Zhejiang University ZJU filed Critical Shanghai Cneec-Zhejiang University Science & Technology Co Ltd
Priority to CN2008101211610A priority Critical patent/CN101381818B/en
Publication of CN101381818A publication Critical patent/CN101381818A/en
Application granted granted Critical
Publication of CN101381818B publication Critical patent/CN101381818B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention provides a preparation dissolution method for intermediate salt during the process of acid leaching extraction of vanadium pentoxide from vanadium-containing stone coal clinker. The method comprises the following steps: the vanadium-containing stone coal clinker undergoes acid leaching, so as to obtain an acid leaching solution; ammonium sulfate is added into the acid leaching solution to separate out tschermigite, so as to obtain a vanadium-bearing mother liquor as a raw material; the vanadium-containing mother liquor and iron elementary substance are added into a reaction vessel, wherein the mass of the iron elementary substance is 1 to 60 percent of that of the vanadium pentoxide in the vanadium-containing mother liquor; the mixture is stirred for full reaction, and is heated, evaporated and concentrated until the concentration of H<+> in the solution is between 18 and 22 mol per liter; after complete crystallization, the solution is cooled to the room temperature, and filtrate and filter residue are obtained through filtration; and the filter residue is taken, and intermediate salt solid is obtained. The method has the advantages that the method is simple; the operating environment is good; the whole process undergoes full-liquid phase operation; no pollution of toxic waste gas exists; more than 98 percent of vanadium in the mother liquor is enriched into the intermediate salt, thereby greatly simplifying the subsequent extraction operation; and a residual acid after preparation of the intermediate salt can be recovered, thereby greatly reducing the cost.

Description

Contain intermediate salt preparation method in the scherbinaite coal ash slag acid leaching extraction Vanadium Pentoxide in FLAKES process
(1) technical field
The present invention relates to a kind of preparation and dissolving method that contains intermediate salt in the scherbinaite coal ash slag acid leaching extraction Vanadium Pentoxide in FLAKES process.
(2) background technology
Vanadium is a kind of important strategic goods and materials.The mankind just had been found that v element before 160 years, but just began to be applied on the industrial production up to 20 beginnings of the century.The pure metal vanadium is silver gray, has good ductility and erosion resistance.The product category of vanadium is various, and metallurgic products such as existing high purity vanadium metal, vanadium iron, vananum, vanadium carbide and vanadium carbonitride also have Vanadium Pentoxide in FLAKES, ammonium meta-vanadate, Chemicals such as potassium vanadate, vanadic acid sodium, vanadium hydroxide and vanadium chloride.Because vanadium has high-melting-point and easy deformation machining characteristics, is widely used in fields such as Iron And Steel Industry, national defence sophisticated technology, chemical industry and light and textile industries.Wherein the most important thing is to do the interpolation element in the steel and alloy, make chemical industry effective catalyst, activator.The vanadium steel that contains vanadium additive has very high hardness, wear resistance and bears the loading of large impact power, and has higher yield-point and plasticity-, is the main raw material(s) of automobile, aviation, machine manufacturing and transportation by railroad.
According to reports, the consumption iron and steel of vanadium accounts for 85% in the world, and non-ferrous metal accounts for 4%, and chemical industry and pottery account for 3%, and cast iron accounts for 1%, and other accounts for 2%.Therefore, influencing the supply and demand of vanadium and the factor of market value mainly is the production of iron and steel and vanadium alloy.When the production of Iron and Steel Production boom, particularly steel alloy increases substantially.The consumption of vanadium and international market price also increase gradually.At present, the China of potential consumption big country, the application of vanadium in steel is far below developed country, and this and China are that the status of production and consumption big country is unbecoming.Recent years, this gap is dwindled, and we can say that the application market of Chinese vanadium and DEVELOPMENT PROSPECT will be good.
Vanadium is aboundresources, widely distributed metallic element in the world, and content is 0.015% in the earth's crust, can be but do not have separately for the rich ore of exploitation, and always with low-grade and other mineral paragenesis.Vanadium titano-magnetite and bone coal are the main raw materials of vanadium extraction, and the main raw material(s) of the vanadium of countries in the world production at present is the vanadium slag and the bone coal of vanadium titano-magnetite by-product in smelting process, and China is as the same.
In the v-ti magnetite ore resources of China, V 2O 5Total reserves be 1741.28 ten thousand tons, wherein Panzhihua Region has 1,600 ten thousand tons, accounts for V in the national vanadium titano-magnetite 2O 5More than 90% of total reserves.
Bone coal is a kind of carbonaceous shale that contains, and is the black caustobiolith that forms under reducing environment, belongs to the high sapanthracite of metamorphic grade more, is the shallow-sea facies settling.Its main characteristic is the ash height, and density is big, and thermal value is low, compact structure, and the point of ignition height, nonflammable and be difficult to perfect combustion.In China, bone coal is mainly composed and is stored in down in the Cambrian stratum, forms outside the material desilt, silicon of bone coal, the inorganic salt composition such as calcareous, and organic part mainly is the low forms of life, sponge and the still indefinite original animals and plants of some classification such as algae.Because the source difference of yeath land leftover in deposition process, complexing, the adsorption of matter planted in the corruption that formation condition of the low forms of life such as phycomycetes or putrescible phycomycetes produce, and the influences such as hydrothermal solution dip-dye of diagenesis, contain in the bone coal or compose the associated element that has collected more, as kind surplus vanadium, aluminium, iron, magnesium, calcium, nickel, molybdenum, uranium, copper, selenium, gallium, trowel and the precious metal etc. 60.In some layer position, one or more associated elements reach industry mining grade or cut-off grade separately, can be used as certain mineral wealth and exploit separately, and reclaim valuable component by smelting.
China is that unexpected the discovery has vanadium in the bone coal when generally investigating phosphorus ore the end of the fifties, and reserves are very abundant.Claim according to " southern bone coal resource comprehensive investigation report ": the total reserves of 10 provinces such as Hunan, Hubei, Zhejiang, Guangdong, Guangxi, Guizhou, Anhui, Henan, Shaanxi, autonomous region's bone coal resource is 618.8 hundred million tons, wherein proven reserve are 39.0 hundred million tons, and combining and examining reserves is 579.8 hundred million tons.Only in the bone coal ore deposit of 7 provinces such as Hunan, Hubei, Jiangxi, Zhejiang, Anhui, Guizhou, Shaanxi, V 2O 5Reserves just reach 11,797 ten thousand tons.W (V wherein 2O 5) 0.50% reserves are 7705.5 ten thousand tons, are V in China's vanadium titano-magnetite 2O 56.7 times of total reserves surpass the total reserves of other various countries' vanadium of the world.Found in provinces and regions such as Xinjiang, Gansu also in recent years that reserves contained the scherbinaite coal than horn of plenty.
In the bone coal differ greatly in the grade various places of vanadium, is generally 0.13～1.00%, with regard to nationwide, in the bone coal grade of vanadium on average be lower than 0.5% account for 60%.V in the bone coal 2O 5Average grade and occupation rate see Table 1.
Table 1: the average grade of vanadium and occupation rate in the bone coal
W(V 2O 5)％ <0.1 0.1～0.3 0.3～0.5 0.5～1 >1
Occupation rate % 3.1 23.7 33.6 33.8 2.8
The mineral composition of research bone coal shows: quartz is the essential mineral that constitutes bone coal, secondly is carbonaceous and clay mineral (kaolinite, mica mineral etc.), also has pyrite, garnet mineral and rhombspar etc.Other are a small amount of or trace quantity mineral is of a great variety, and various places are different.Vanadium in the bone coal is mainly composed in the mica minerals such as being stored in roscoelite, hydromica, biotite, white mica and illite, secondly is to compose to be stored in the mineral of other types such as some organic carbonaceous and ettringite garnet.
At present, China's process for extracting vanadium from stone coal mainly contains: sodium-salt calcination vanadium extraction, lime mud roasting vanadium extraction, calcium salt roasting vanadium extraction, wet method vanadium extraction, bone coal are directly acid-leaching vanadium-extracted etc.
Contain scherbinaite coal ash slag acid leaching extraction Vanadium Pentoxide in FLAKES at present and get pickling liquor to contain scherbinaite coal ash slag through acidleach usually, adding ammonium sulfate again, to separate out the vanadium mother liquid that contains that obtains behind the tschermigite be the feedstock production intermediate salt, in preparation method's technology of existing intermediate salt, mostly be to contain the vitriol that the vanadium mother liquid evaporation concentration obtains vanadium, vitriol is put in the calcining furnace and is calcined, and vanadium, low price iron are oxidized to V at a low price 2O 5And Fe 2O 3, the product after the calcining through leaching, obtains containing vanadium solution and Fe again 2O 3Throw out contains vanadium solution again through purification steps such as extraction, reextraction, obtains described V 2O 5This method for preparing intermediate salt needs high-temperature calcination, and energy consumption is big.
(3) summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of preparation and dissolving method that contains intermediate salt in the scherbinaite coal ash slag acid leaching extraction Vanadium Pentoxide in FLAKES process is provided.
The technical solution used in the present invention is:
A kind of preparation and dissolving method that contains intermediate salt in the scherbinaite coal ash slag acid leaching extraction Vanadium Pentoxide in FLAKES process, described method comprises: get pickling liquor to contain scherbinaite coal ash slag through acidleach, adding ammonium sulfate again, to separate out the vanadium mother liquid that contains that obtains behind the tschermigite be raw material, in reaction vessel, add and contain vanadium mother liquid and iron simple substance, iron simple substance quality is to contain 1～60% of Vanadium Pentoxide in FLAKES quality in the vanadium mother liquid, stirring makes abundant reaction, and heating evaporation is concentrated into H in the solution +Concentration is 18～22mol/L, and the complete postcooling of crystallization filters to get filtrate and filter residue to room temperature, gets filter residue, obtains the intermediate salt solid.
Intermediate salt preparation of the present invention is to add iron simple substance, to contain vanadium enrichment in the vanadium mother liquid in the intermediate salt crystal, reduce follow-up operation element amount and the consumption that extracts workshop section significantly, make a large amount of spent acid in the solution turn back to step (1) reuse simultaneously, to reduce the acid consumption significantly, and, saved the energy owing to saved the high-temperature calcination process.Intermediate salt is carried out X-ray diffraction analysis show, wherein contain ferric ammonium sulfate NH 4Fe (SO4) 2, Vanadosulfuric acid ammonium NH 4V (SO 4) 2, potassium aluminium sulfate KAl (SO 4) 2, exsiccated ammonium alum NH 4Al (SO 4) 2, Vanadosulfuric acid potassium KV (SO 4) 2, ammonium poly-vanadate (NH 4) 2V 6O 161.5H 2O, vanadic acid calcium CaV 2O 6Or the like, it is a kind of mixing salt of complexity, content of vanadium is with V in the intermediate salt 2O 5Meter can reach 4～8%, promptly from lime-ash V 2O 5Content 1～1.5% enrichment several times, the collection stoste V that intermediate salt dissolving is made 2O 5Concentration can reach more than the 10g/L, and this has just simplified subsequent operations process and raw material consumption greatly.
Described intermediate salt solid is further made intermediate salt dissolving clear liquid; Described intermediate salt dissolving clear liquid preparation method is as follows: add intermediate salt solid and water in reaction vessel, the add-on of water is 1.5～4L/kg intermediate salt solid, is warming up to 80～100 ℃ of stirring and dissolving 1.5～4 hours, filters to get filtrate and filter residue, get filtrate, obtain intermediate salt dissolving clear liquid.Described intermediate salt dissolving clear liquid further can prepare collection stoste, and collection stoste finally can obtain the Vanadium Pentoxide in FLAKES product again through extraction, reextraction, oxidation precipitation, ammonium poly-vanadate pyrolysis.
Common, process with described intermediate salt dissolving clear liquid preparation collection stoste is as follows: the adding intermediate salt is dissolved clear liquid in reaction vessel, stirs to add reductive agent down, extremely uses the potassium thiocyanate indicator to measure till the solution nondiscoloration, being neutralized to the pH value with alkaline solution is 1.8～3.0, obtains the stoste of coming together; Described reductive agent is the common reductive agent that is used for the Vanadium Pentoxide in FLAKES preparation in this area, is preferably Sulfothiorine or iron.
Concrete, described method can be as follows:
(1) acidleach: add strong acid solution and contain scherbinaite coal ash slag in reaction vessel, the concentration of H+ is 8～12mol/L in the described strong acid solution, and the quality of described strong acid solution is that 2～3L/kg contains scherbinaite coal ash slag, be heated to 80～120 ℃ of dippings 3～9 hours, filter, get filtrate A, obtain pickling liquor; Concrete, the described scherbinaite coal ash slag that contains is to contain the lime-ash that the scherbinaite coal is discharged behind circulating fluidized bed combustion decarburization power generation and heat supply; Described strong acid is the common strong acid that is used for the Vanadium Pentoxide in FLAKES preparation in this area, as sulfuric acid, hydrochloric acid etc., is preferably sulfuric acid.
(2) tschermigite is produced: add pickling liquor and ammonium sulfate in reaction vessel, ammonium sulfate quality addition be in the pickling liquor 1.3～2 times of the aluminium sesquioxide quality (in the pickling liquor aluminium sesquioxide content after measured after, accurate calculation ammonium sulfate addition), stir, be cooled to 5～40 ℃, crystallization and separate out the tschermigite crystal, filter, filter residue B is thick tschermigite, and liquor B is for containing vanadium mother liquid; Thick tschermigite can obtain the smart tschermigite byproduct of high purity through adding the water heating for dissolving, filtering and remove impurity, recrystallization; Contain compound impurity such as the aluminium that leached simultaneously, iron in the pickling liquor that acidleach workshop section obtains, particularly a large amount of aluminium sesquioxides generates Tai-Ace S 150 with sulfuric acid reaction, and it will and extract workshop section to the subsequent preparation intermediate salt and have a negative impact.This step purpose is the Tai-Ace S 150 of removing substantially in the pickling liquor, produces the byproduct tschermigite, reclaims the bauxite resource in the lime-ash;
(3) intermediate salt preparation: add in reaction vessel and contain vanadium mother liquid and iron simple substance, iron simple substance quality is to contain 1～60% of Vanadium Pentoxide in FLAKES quality in the vanadium mother liquid, stirs and makes abundant reaction, and heating evaporation is concentrated into H in the solution +Concentration is 18～221mol/L, and the complete postcooling of crystallization is to room temperature, and filter to get filtrate C and filter residue C get filter residue C, obtain the intermediate salt solid; Liquor C can be back to step (1);
(4) intermediate salt dissolving: in reaction vessel, add intermediate salt solid and water, the add-on of water is 1.5～4L/kg intermediate salt solid, is warming up to 80～100 ℃ of stirring and dissolving 1.5～4 hours, and D and filter residue D filter to get filtrate, get filtrate D, obtain intermediate salt dissolving clear liquid.Filter residue D can be back to step (1);
More specifically, described method is as follows:
(1) acidleach: add 4～6mol/L sulphuric acid soln and contain scherbinaite coal ash slag in reaction vessel, the sulphuric acid soln consumption is that 2～3L/kg contains scherbinaite coal ash slag, is heated to 80～120 ℃ of dippings 3～9 hours, filters and washing, gets filtrate A, is pickling liquor;
(2) tschermigite is produced: add pickling liquor and ammonium sulfate in reaction vessel, ammonium sulfate quality addition is 1.3～2 times of aluminium sesquioxide quality in the pickling liquor, stirs, crystallization separates out the tschermigite crystal, filter, get liquor B and filter residue B, filter residue B is thick tschermigite, and liquor B is for containing vanadium mother liquid;
(3) intermediate salt preparation: add in reaction vessel and contain vanadium mother liquid and iron powder, the iron powder quality is to contain 1～60% of Vanadium Pentoxide in FLAKES quality in the vanadium mother liquid, stirs and makes abundant reaction, and heating evaporation is concentrated into H in the solution +Concentration is 18～22mol/L, and the complete postcooling of crystallization is to room temperature, and filter to get filtrate C and filter residue C get filter residue C and be the intermediate salt solid, and liquor C reclaims the sulphuric acid soln preparation that is applied to step (1);
(4) intermediate salt dissolving: in reaction vessel, add intermediate salt solid and water, the add-on of water is 1.5～4L/kg intermediate salt solid, be warming up to 80～100 ℃ of stirring and dissolving 2～4 hours, D and filter residue D filter to get filtrate, get filtrate D and be intermediate salt dissolving clear liquid, filter residue D reclaims and contains the vanadium ash components as step (1).
Utilizing the inventive method to make intermediate salt dissolving clear liquid, to prepare the step of Vanadium Pentoxide in FLAKES as follows:
1) collection stoste preparation: adding intermediate salt dissolving clear liquid in reaction vessel, stirring adds Sulfothiorine or iron powder reducing agent down, and extremely with till the nondiscoloration of potassium thiocyanate indicator mensuration solution, being neutralized to the pH value with ammoniacal liquor is 1.8～3.0, and stoste obtains coming together;
2) extraction: the collection stoste and the organic extractant that add volume ratio and be 1:1 in reaction vessel carry out extracting operation, separate organic phase and water, obtain containing vanadium organic phase and raffinate, described organic extractant is the mixture of 2-ethylhexyl phosphoric acid, tributyl phosphate and sulfonated kerosene volume ratio 10:5:85, and described extraction progression is 3～5 grades;
3) strip: adding volume ratio in reaction vessel is the sulphuric acid soln that contains vanadium organic phase and concentration 1.25～1.75mol/L of 5～10:1, strips, and water phase separated and organic phase obtain containing the vanadium water, and described extraction progression is 3～5 grades;
4) oxidation precipitation: in reaction vessel, add and contain the vanadium water, 50～60 ℃ of stirrings add sodium chlorate to solution down and are become by blueness till the yellow, and the ammoniacal liquor adjust pH was 1.9～2.5, in 90～100 ℃ of following precipitations 2～4 hours, cooling, crystallization, filtration, dehydration obtain the ammonium poly-vanadate crystal;
5) ammonium poly-vanadate pyrolysis: ammonium poly-vanadate crystal pyrolysis deamination obtains Vanadium Pentoxide in FLAKES.
The beneficial effect of the inventive method is mainly reflected in:
1, method is simple, and all processing units can all use homemade; Good operational environment, labour intensity is low, mechanization degree height, advanced technology, labour productivity height.
2, the full liquid-phase operation of whole process, no poisonous fume pollutes; Processing wastewater, waste liquid fully recovering, environmental friendliness.
3, technico-economical comparison advanced person, the resource recovery height.Vanadium in the mother liquor is enriched to more than 98% in the intermediate salt, and follow-up extracting operation is simplified greatly.
But 4, the spent acid reuse after the system intermediate salt, contain that vanadium mother liquid is not made intermediate salt and direct extraction phase ratio with system behind the tschermigite, sour consumption can reduce more than 50%, the alkali lye consumption when having reduced simultaneously preparation collection stoste significantly, thereby simplify the operation greatly, reduce cost significantly.
(4) description of drawings
Fig. 1 is for containing scherbinaite coal ash slag acid leaching extraction Vanadium Pentoxide in FLAKES process flow sheet, and wherein frame of broken lines inside is divided into intermediate salt and comes together former liquid and preparation method thereof.
(5) embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1:
Thermal Power Engineering institute of Zhejiang University, the direct acid leaching extraction V of intermediate salt method stone coal ash 2O 5Pilot plant (comprises the acidleach glassed steel reaction vessels, tschermigite is produced glassed steel reaction vessels, intermediate salt evaporation glassed steel reaction vessels, intermediate salt dissolving glassed steel reaction vessels, collection stoste prepares glassed steel reaction vessels, the tower extractor of synthetic glass, the tower stripper of synthetic glass, oxidation precipitation glassed steel reaction vessels and ammonium poly-vanadate electricity pyrolysis oven), contain vanadium lime-ash processing power 800kg/d, end slag and the dedusting ash of used lime-ash for after circulating fluidized bed combustion, discharging, press slag 25% at the bottom of the mass ratio, dedusting ash 75%, mix the back as the lime-ash raw material, its chemical ingredients is: V 2O 51.26%, SiO 261.83%, Fe 2O 36.90%, Al 2O 316.58%, CaO 0.30%, and MgO 1.31%.The occurrence status analysis revealed of vanadium in the lime-ash, most of vanadium is composed and is stored in the MICA, belongs to the difficult ore deposit of leaching.
The processing condition and the parameter thereof of pilot plant operation:
Acidleach: 100～110 ℃ of temperature, sulfuric acid concentration 4～5mol/L, leaching time 4～6h, liquid-solid ratio 3 (being that the sulphuric acid soln consumption is that 3L/kg contains scherbinaite coal ash slag);
Tschermigite is produced: it is 1.8 times of aluminium sesquioxide quality in the pickling liquor that ammonium sulfate adds quality, stirs and is cooled to room temperature;
Intermediate salt preparation: the vanadium mother liquid of producing behind the tschermigite that contains adds the iron powder quality for containing V in the vanadium mother liquid in the intermediate salt evaporating kettle 2O 530% of quality, the stirring heating evaporation concentration is to H +Concentration 19～21mol/L, the complete postcooling of crystallization obtain intermediate salt solid V to room temperature after the vacuum filtration 2O 5Mass content is 4.8～8%, V in the filtrate 2O 5Only be 0.05g/l, the intermediate salt percent crystallization in massecuite reaches 98.8%;
The intermediate salt dissolving: in the intermediate salt dissolution kettle, add the intermediate salt solid, the stirring at normal temperature water dissolution, liquid-solid ratio 4,90～100 ℃ of solvent temperatures, dissolution time 4h, the intermediate salt dissolution rate reaches 99%;
Collection stoste preparation: in collection stoste preparation still, make reductive agent with iron powder, add-on till the solution nondiscoloration, is neutralized to pH2.5～3.0 with ammoniacal liquor, V in the collection stoste that makes with the potassium thiocyanate indicator 2O 5Concentration is 11g/L.
Extraction is stripped: the organic phase proportioning is P 204, TPB and sulfonated kerosene volume ratio be 10:5:85, organic phase: the water volume ratio is 1:1, the extraction of adverse current level Four, normal temperature; Reverse-extraction agent is a sulphuric acid soln, concentration 1.5mol/L, load organic phases: reverse-extraction agent volume ratio=10:1, four-stage counter-current back extraction, normal temperature;
The oxidation precipitation: add under 50～60 ℃ of heated and stirred of temperature till the sodium chlorate oxygenant makes solution become yellow by blueness, regulating pH with ammoniacal liquor is 2～2.3,95～100 ℃ of precipitation temperature, 3 hours precipitation time;
The pyrolysis deamination: 500～550 ℃ of pyrolysis temperatures obtain powdery V 2O 5
The key technical indexes that the pilot plant operation reaches:
The acid leaching efficiency of vanadium: 〉=85%;
The detersive efficiency of vanadium: 〉=95%;
Level Four extraction efficiency: 〉=99%;
Level Four reextraction efficient: 〉=99%;
Precipitation yield: 〉=98%;
Pyrolysis yield: 〉=98%;
The total recovery of vanadium: 〉=75%;
The by-product tschermigite:〉80kg/kg V 2O 5
V 2O 5Purity: 98.2%.
Embodiment 2:
The used scherbinaite coal ash slag that contains is the end slag and the dedusting ash of discharging after circulating fluidized bed combustion, press slag 25% at the bottom of the mass ratio, and dedusting ash 75% is mixed afterwards as the lime-ash raw material, and its chemical ingredients is: V 2O 51.26%, SiO 261.83%, Fe 2O 36.90%, Al 2O 316.58%, CaO 0.30%, MgO1.31%.The occurrence status analysis revealed of vanadium in the lime-ash, most of vanadium is composed and is stored in the MICA, belongs to the difficult ore deposit of leaching.
The Vanadium Pentoxide in FLAKES extraction step is as follows:
(1) acidleach: add 5mol/L sulphuric acid soln 1590L and contain scherbinaite coal ash slag 533kg in the acidleach glassed steel reaction vessels, be heated to 110～115 ℃ of dippings 4 hours, filter and washing, get filtrate, obtain pickling liquor, the residue butt contains V 2O 50.26% (w/w); Residue can be delivered to the slag field and be used for the material of construction comprehensive utilization;
(2) tschermigite is produced: produce adding pickling liquor 2057L (recording wherein, aluminium sesquioxide content is 63kg) and ammonium sulfate 113kg in the glassed steel reaction vessels at tschermigite, stir, be cooled to room temperature, the tschermigite crystal is separated out in crystallization, vacuum filtration, getting filter residue is thick tschermigite 458kg, gets filtrate for containing vanadium mother liquid 1937L; Thick tschermigite is removed impurity, recrystallization through heat of solution, filtration, can obtain the smart tschermigite byproduct of high purity;
(3) intermediate salt preparation: add in intermediate salt evaporation glassed steel reaction vessels and contain vanadium mother liquid 1715L (recording wherein, pentoxide content is 4.785kg) and waste iron filing 1.44kg, the stirring heating evaporation concentration is to H +Concentration 19～21mol/L, the complete postcooling of crystallization cross the leaching filter residue to room temperature, obtain intermediate salt solid 115kg, and the intermediate salt butt contains Vanadium Pentoxide in FLAKES 4.55%;
(4) intermediate salt dissolving: in intermediate salt dissolving glassed steel reaction vessels, add intermediate salt solid 115kg and water 460L, be warming up to 90～95 ℃, stirring and dissolving 4 hours is crossed leaching filtrate, obtain intermediate salt dissolving clear liquid 300L, clear liquid pentoxide content 13.52g/L;
(5) collection stoste prepares: prepare in collection stoste and add step (4) intermediate salt dissolving clear liquid in the glassed steel reaction vessels, stir adding reductive agent iron powder down, extremely use the potassium thiocyanate indicator to measure till the solution nondiscoloration, being neutralized to the pH value with ammoniacal liquor is 2.6, obtain the stoste of coming together, collection stoste V 2O 5Concentration is 13.12g/L;
(6) extraction: the collection stoste and the organic phase that add volume ratio and be 1:1 in the tower extractor of synthetic glass are carried out extracting operation, and extraction progression is 4 grades, separates organic phase and water, obtains containing vanadium organic phase and raffinate, and described organic phase is P 204, TBP and sulfonated kerosene volume ratio 10:5:85 mixture;
(7) strip: add in the tower stripper of synthetic glass and contain vanadium organic phase 200L and 1.5mol/L sulphuric acid soln 40L, strip, reextraction progression is 3 grades, and water phase separated and organic phase obtain containing the vanadium water;
(8) oxidation precipitation: in oxidation precipitation glassed steel reaction vessels, add and contain the vanadium water, 50～60 ℃ of stirrings add sodium chlorate to solution down and are become by blueness till the yellow, and the ammoniacal liquor adjust pH was 2.2, in 95～100 ℃ of following precipitations 4 hours, cooling, crystallization, filtration, dehydration obtain the ammonium poly-vanadate crystal;
(9) ammonium poly-vanadate pyrolysis: add the ammonium poly-vanadate crystal in ammonium poly-vanadate electricity pyrolysis oven, 500～550 ℃ of pyrolysis deaminations promptly get powdery V after the cooling 2O 5Product.
In this technological process: the acid leaching efficiency of vanadium is 85.20%; The detersive efficiency of vanadium is 96.21%; The level Four extraction efficiency is 99.35%; Three grades of reextraction efficient are 99.98%; The precipitation yield is 99.29%; The pyrolysis yield is 99.12%; The total recovery of vanadium is 80.11%; The by-product tschermigite is 81kg/kg V 2O 5V 2O 5Purity is 98.22%.
Embodiment 3:
The used scherbinaite coal ash slag that contains is the end slag and the dedusting ash of discharging after circulating fluidized bed combustion, press slag 25% at the bottom of the mass ratio, and dedusting ash 75% is mixed afterwards as the lime-ash raw material, and its chemical ingredients is: V 2O 51.26%, SiO 261.83%, Fe 2O 36.90%, Al 2O 316.58%, CaO0.30%, MgO1.31%.The occurrence status analysis revealed of vanadium in the lime-ash, most of vanadium is composed and is stored in the MICA, belongs to the difficult ore deposit of leaching.
The Vanadium Pentoxide in FLAKES extraction step is as follows:
(1) acidleach: in the acidleach glassed steel reaction vessels, add 5mol/L sulphuric acid soln 2364L (this sulphuric acid soln forms for high acidity filtrate and the initiate sulfuric acid mixed preparing that step 3 among the embodiment 2 obtains) and contain scherbinaite coal ash slag 788kg, be heated to 110～115 ℃ of dippings 4 hours, filter and washing, get filtrate, obtain pickling liquor, the residue butt contains V 2O 50.21%; Residue can be delivered to the slag field and be used for the material of construction comprehensive utilization;
(2) tschermigite is produced: produce adding pickling liquor 2458L (recording wherein, aluminium sesquioxide content is 82kg) and ammonium sulfate 124kg in the glassed steel reaction vessels at tschermigite, stir, be cooled to room temperature, the tschermigite crystal is separated out in crystallization, vacuum filtration, getting filter residue is thick tschermigite 752kg, gets filtrate for containing vanadium mother liquid 2330L; Thick tschermigite is removed impurity, recrystallization through heat of solution, filtration, can obtain the smart tschermigite byproduct of high purity;
(3) intermediate salt preparation: add in intermediate salt evaporation glassed steel reaction vessels and contain vanadium mother liquid 2330L (recording wherein, pentoxide content is 7.444kg) and waste iron filing 2.233kg, the stirring heating evaporation concentration is to H +Concentration 19～21mol/L, the complete postcooling of crystallization cross the leaching filter residue to room temperature, obtain intermediate salt solid 137kg, and the intermediate salt butt contains Vanadium Pentoxide in FLAKES 6.23%;
(4) intermediate salt dissolving: in intermediate salt dissolving glassed steel reaction vessels, add intermediate salt solid 137kg and water 530L, be warming up to 90～95 ℃, stirring and dissolving 4 hours is crossed leaching filtrate, obtain intermediate salt dissolving clear liquid 353L, clear liquid pentoxide content 19.22g/L;
(5) collection stoste prepares: prepare in collection stoste and add step (4) intermediate salt dissolving clear liquid in the glassed steel reaction vessels, stir adding reductive agent iron powder down, extremely use the potassium thiocyanate indicator to measure till the solution nondiscoloration, being neutralized to the pH value with ammoniacal liquor is 2.6, obtain the stoste of coming together, collection stoste V 2O 5Concentration is 18.88g/L;
(6) extraction: the collection stoste and the organic phase that add volume ratio and be 1:1 in the tower extractor of synthetic glass are carried out extracting operation, and extraction progression is 4 grades, separates organic phase and water, obtains containing vanadium organic phase and raffinate, and described organic phase is P 204, TBP and sulfonated kerosene volume ratio 10:5:85 mixture;
(7) strip: add in the tower stripper of synthetic glass and contain vanadium organic phase 250L and 1.5mol/L sulphuric acid soln 60L, strip, reextraction progression is 3 grades, and water phase separated and organic phase obtain containing the vanadium water;
(8) oxidation precipitation: in oxidation precipitation glassed steel reaction vessels, add and contain the vanadium water, 50～60 ℃ of stirrings add sodium chlorate to solution down and are become by blueness till the yellow, and the ammoniacal liquor adjust pH was 2.2, in 95～100 ℃ of following precipitations 4 hours, cooling, crystallization, filtration, dehydration obtain the ammonium poly-vanadate crystal;
(9) ammonium poly-vanadate pyrolysis: add the ammonium poly-vanadate crystal at ammonium poly-vanadate electricity pyrolysis oven, 500～550 ℃ of pyrolysis deaminations promptly get powdery V after the cooling 2O 5Product.
In this technological process: the acid leaching efficiency of vanadium is 85.35%; The detersive efficiency of vanadium is 95.61%; The level Four extraction efficiency is 99.55%; Three grades of reextraction efficient are 99.95%; The precipitation yield is 99.16%; The pyrolysis yield is 98.92%; The total recovery of vanadium is 79.64%; The by-product tschermigite is 95kg/kg V 2O 5V 2O 5Purity is 98.42%.

Claims (9)

1. preparation method who contains intermediate salt in the scherbinaite coal ash slag acid leaching extraction Vanadium Pentoxide in FLAKES process, described method comprises: get pickling liquor to contain scherbinaite coal ash slag through acidleach, adding ammonium sulfate again, to separate out the vanadium mother liquid that contains that obtains behind the tschermigite be raw material, in reaction vessel, add and contain vanadium mother liquid and iron simple substance, iron simple substance quality is to contain 1～60% of Vanadium Pentoxide in FLAKES quality in the vanadium mother liquid, stirring makes abundant reaction, and heating evaporation is concentrated into H in the solution +Concentration is 18～22mol/L, and the complete postcooling of crystallization filters to get filtrate and filter residue to room temperature, gets filter residue, obtains the intermediate salt solid.
2. the method for claim 1 is characterized in that, described intermediate salt solid is further made intermediate salt dissolving clear liquid; Described intermediate salt dissolving clear liquid preparation method is as follows: add intermediate salt solid and water in reaction vessel, the add-on of water is 1.5～4L/kg intermediate salt solid, is warming up to 80～100 ℃ of stirring and dissolving 1.5～4 hours, filters to get filtrate and filter residue, get filtrate, obtain intermediate salt dissolving clear liquid.
3. method as claimed in claim 1 or 2 is characterized in that described iron simple substance derives from: iron powder or waste iron filing.
4. the method for claim 1 is characterized in that described method is as follows:
(1) acidleach: in reaction vessel, add strong acid solution and contain scherbinaite coal ash slag, H in the described strong acid solution +Concentration be 8～12mol/L, the quality of described strong acid solution is that 2～3L/kg contains scherbinaite coal ash slag, is heated to 80～120 ℃ of dippings 3～9 hours, filters, and gets filtrate A, obtains pickling liquor;
(2) tschermigite is produced: add pickling liquor and ammonium sulfate in reaction vessel, ammonium sulfate quality addition is 1.3～2 times of aluminium sesquioxide quality in the pickling liquor, stirs, is cooled to 5～40 ℃, crystallization and separate out the tschermigite crystal, filters, filter residue B is thick tschermigite, and liquor B is for containing vanadium mother liquid;
(3) intermediate salt preparation: add in reaction vessel and contain vanadium mother liquid and iron simple substance, iron simple substance quality is to contain 1～60% of Vanadium Pentoxide in FLAKES quality in the vanadium mother liquid, stirs and makes abundant reaction, and heating evaporation is concentrated into H in the solution +Concentration is 18～22mol/L, and the complete postcooling of crystallization is to room temperature, and filter to get filtrate C and filter residue C get filter residue C, obtain the intermediate salt solid;
(4) intermediate salt dissolving: add intermediate salt solid and water in reaction vessel, the add-on of water is 1.5～4L/kg intermediate salt solid, is warming up to 80～100 ℃ of stirring and dissolving 1.5～4 hours, and filter to get filtrate D and filter residue D get filtrate D, obtains intermediate salt dissolving clear liquid.
5. the method for claim 1 is characterized in that the described strong acid solution of described step (1) is a sulphuric acid soln.
6. the method for claim 1 is characterized in that in the described step (2), and the thick tschermigite of filter residue B obtains the by product tschermigite through adding the water heating for dissolving, filtering and remove impurity, recrystallization.
7. the method for claim 1 is characterized in that in the described step (3), described iron simple substance derives from: iron powder or waste iron filing.
8. the method for claim 1 is characterized in that: in the described step (3), described liquor C reclaims the strong acid solution preparation that is applied to step (1); In the described step (4), described filter residue D reclaims as containing scherbinaite coal ash slag component in the step (1).
9. the method for claim 1, described method comprises following sequential steps:
(1) acidleach: add 4～6mol/L sulphuric acid soln and contain scherbinaite coal ash slag in reaction vessel, the sulphuric acid soln consumption is that 2～3L/kg contains scherbinaite coal ash slag, is heated to 80～120 ℃ of dippings 3～9 hours, filters, and gets filtrate A, is pickling liquor;
(2) tschermigite is produced: add pickling liquor and ammonium sulfate in reaction vessel, ammonium sulfate quality addition is 1.3～2 times of aluminium sesquioxide quality in the pickling liquor, stir, be cooled to 5～40 ℃ of crystallizations and separate out the tschermigite crystal, filter, get liquor B and filter residue B, filter residue B is thick tschermigite, and liquor B is for containing vanadium mother liquid;
(3) intermediate salt preparation: add in reaction vessel and contain vanadium mother liquid and iron powder, the iron powder quality is to contain 1～60% of Vanadium Pentoxide in FLAKES quality in the vanadium mother liquid, stirs and makes abundant reaction, and heating evaporation is concentrated into H in the solution +Concentration is 18～22mol/L, and the complete postcooling of crystallization is to room temperature, and filter to get filtrate C and filter residue C get filter residue C and be the intermediate salt solid, and liquor C reclaims the sulphuric acid soln preparation that is applied to step (1);
(4) intermediate salt dissolving: in reaction vessel, add intermediate salt solid and water, the add-on of water is 1.5～4L/kg intermediate salt solid, be warming up to 80～100 ℃ of stirring and dissolving 1.5～4 hours, D and filter residue D filter to get filtrate, get filtrate D and be intermediate salt dissolving clear liquid, filter residue D reclaims and contains the vanadium ash components as step (1).
CN2008101211610A 2008-09-29 2008-09-29 Method for preparing intermediate salt during acid leaching and extraction of vanadium pentoxide from vanadium-containing stone coal ash Expired - Fee Related CN101381818B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2008101211610A CN101381818B (en) 2008-09-29 2008-09-29 Method for preparing intermediate salt during acid leaching and extraction of vanadium pentoxide from vanadium-containing stone coal ash

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2008101211610A CN101381818B (en) 2008-09-29 2008-09-29 Method for preparing intermediate salt during acid leaching and extraction of vanadium pentoxide from vanadium-containing stone coal ash

Publications (2)

Publication Number Publication Date
CN101381818A true CN101381818A (en) 2009-03-11
CN101381818B CN101381818B (en) 2010-08-25

Family

ID=40461870

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2008101211610A Expired - Fee Related CN101381818B (en) 2008-09-29 2008-09-29 Method for preparing intermediate salt during acid leaching and extraction of vanadium pentoxide from vanadium-containing stone coal ash

Country Status (1)

Country Link
CN (1) CN101381818B (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102000585A (en) * 2010-08-16 2011-04-06 华电电力科学研究院 Denitration catalyst and preparation method thereof
CN102134649A (en) * 2011-03-03 2011-07-27 东北大学 Comprehensive utilization method for vanadium slag
CN102732736A (en) * 2012-07-23 2012-10-17 中南大学 Method for extracting vanadium from burning slag of stone coal vanadium mine fluidized bed
CN102747225A (en) * 2012-07-10 2012-10-24 中南大学 Method for comprehensively recycling copper, selenium and uranium from stone coal extraction vanadic acid immersion liquid
CN102912130A (en) * 2012-11-13 2013-02-06 吉首大学 Method for separating vanadium enriched in stone coal leaching solution
CN104046786A (en) * 2013-10-15 2014-09-17 攀钢集团攀枝花钢铁研究院有限公司 Method for recovering metals from vanadium slag
CN104195330A (en) * 2014-08-07 2014-12-10 西北有色地质研究院 Technique for recovering crystals of aluminum potassium sulfate dodecahydrate in process of vanadium extraction via fly ash acid leaching
CN106399694A (en) * 2016-10-08 2017-02-15 河钢股份有限公司承德分公司 Method for synchronously extracting vanadium and aluminum from waste vanadium oxide smelter refractory brick
CN114350964A (en) * 2021-11-30 2022-04-15 攀钢集团研究院有限公司 Method for preparing vanadium pentoxide by using high-phosphorus high-calcium vanadium slag and recycling leachate

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102000585B (en) * 2010-08-16 2015-09-23 华电电力科学研究院 A kind of denitrating catalyst and preparation method thereof
CN102000585A (en) * 2010-08-16 2011-04-06 华电电力科学研究院 Denitration catalyst and preparation method thereof
CN102134649B (en) * 2011-03-03 2013-01-23 东北大学 Comprehensive utilization method for vanadium slag
CN102134649A (en) * 2011-03-03 2011-07-27 东北大学 Comprehensive utilization method for vanadium slag
CN102747225A (en) * 2012-07-10 2012-10-24 中南大学 Method for comprehensively recycling copper, selenium and uranium from stone coal extraction vanadic acid immersion liquid
CN102732736B (en) * 2012-07-23 2015-01-14 中南大学 Method for extracting vanadium from burning slag of stone coal vanadium mine fluidized bed
CN102732736A (en) * 2012-07-23 2012-10-17 中南大学 Method for extracting vanadium from burning slag of stone coal vanadium mine fluidized bed
CN102912130A (en) * 2012-11-13 2013-02-06 吉首大学 Method for separating vanadium enriched in stone coal leaching solution
CN104046786A (en) * 2013-10-15 2014-09-17 攀钢集团攀枝花钢铁研究院有限公司 Method for recovering metals from vanadium slag
CN104046786B (en) * 2013-10-15 2016-08-31 攀钢集团攀枝花钢铁研究院有限公司 A kind of method reclaiming metal from vanadium slag
CN104195330A (en) * 2014-08-07 2014-12-10 西北有色地质研究院 Technique for recovering crystals of aluminum potassium sulfate dodecahydrate in process of vanadium extraction via fly ash acid leaching
CN106399694A (en) * 2016-10-08 2017-02-15 河钢股份有限公司承德分公司 Method for synchronously extracting vanadium and aluminum from waste vanadium oxide smelter refractory brick
CN114350964A (en) * 2021-11-30 2022-04-15 攀钢集团研究院有限公司 Method for preparing vanadium pentoxide by using high-phosphorus high-calcium vanadium slag and recycling leachate
CN114350964B (en) * 2021-11-30 2024-01-26 攀钢集团研究院有限公司 Method for preparing vanadium pentoxide by utilizing high-phosphorus high-calcium vanadium slag and recycling leaching liquid

Also Published As

Publication number Publication date
CN101381818B (en) 2010-08-25

Similar Documents

Publication Publication Date Title
CN101381103B (en) Vanadium pentoxide extraction method by direct acid dipping of stone coal ash containing vanadium
CN101381818B (en) Method for preparing intermediate salt during acid leaching and extraction of vanadium pentoxide from vanadium-containing stone coal ash
CN102051483B (en) Method for reclaiming metals from molybdenum-containing waste catalyst
CN102212694B (en) Method for extracting valuable metal from waste hydrogenation catalyst
CN101457296B (en) Method for recovering metallic oxide from waste aluminum base V-Mo-Ni catalyst
CN102041388B (en) Method for recycling metal from waste catalyst containing molybdenum and nickel
CN100482814C (en) Extraction of vanadium and molybdenum compound from refused materials containing vanadium and molybdenum etc. multiple elements
CN102050492B (en) Method for recovering metal from molybdenum-containing spent catalyst
CN108751259B (en) Method and device for producing ammonium metatungstate by tungsten-containing waste
CN101914695B (en) Method for recycling vanadium from vanadium ore containing high silicon and high carbon via wet process
CN101230419A (en) Method for extracting vanadium pentoxide and comprehensively extracting ammonium alum and iron-oxide red from vanadium-containing stone coal or vanadium-containing ash slag
CN103290223B (en) Comprehensive recovery method for multiple metals of waste catalyst
CN101914678B (en) Method for producing industry molybdenum oxide from molybdenum concentrate
CN103193213B (en) Method for comprehensively utilizing low-grade phosphate ores
CN101717858B (en) Method for extracting molybdenum, nickel, vanadium and ferrum from polymetallic black-shale paragentic minerals
CN103911514B (en) The recovery and treatment method of scrap hard alloy grinding material
CN104178632A (en) Method for comprehensively utilizing titanium white waste acid
CN100519783C (en) Technique for comprehensive utilization clean production of phosphorus block ore and extracting rare earth form the phosphorus block ore
CN106337135A (en) Novel method for producing vanadium pentoxide through ammonium-free vanadium precipitation
CN109706312A (en) A method of vanadic anhydride and chemical electrode manganese dioxide are prepared simultaneously using vanadium chromium slag and low-grade pyrolusite
CN101481754A (en) Method for separating molybdenum and nickel in molybdenum- and nickel-containing black shale
CN112725629A (en) Preparation method for extracting nonferrous metal and reduced iron from steel slag
CN101712491A (en) Process method for producing vanadic oxide from vanadium-contained wastewater slag
CN102220499A (en) Roasting-leaching method of fine vanadium slags
CN106282571A (en) A kind of comprehensive recycling process of stannum copper gold silver waste material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20100825

Termination date: 20170929