CN107586947A - The selecting smelting combination technique of vanadium, aluminium, potassium, silicon in a kind of synthetical recovery siliceous shale containing vanadium - Google Patents

The selecting smelting combination technique of vanadium, aluminium, potassium, silicon in a kind of synthetical recovery siliceous shale containing vanadium Download PDF

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CN107586947A
CN107586947A CN201710868885.0A CN201710868885A CN107586947A CN 107586947 A CN107586947 A CN 107586947A CN 201710868885 A CN201710868885 A CN 201710868885A CN 107586947 A CN107586947 A CN 107586947A
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vanadium
potassium
aluminium
silicon
recovery
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CN107586947B (en
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王丽
孙伟
胡岳华
张庆鹏
刘润清
高建德
张烨
纪斌
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Central South University
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Abstract

The present invention is a kind of using low-grade siliceous shale containing vanadium as raw material, the ore dressing field of metallurgy of synthetical recovery wherein vanadium, aluminium, potassium, silicon valuable component.Its step is using low-grade siliceous shale containing vanadium as raw material, vanadium siliceous shale method for floating desiliconization will first be contained, vanadium concentrate is calcined after uniformly being mixed with lime stone, the sodium carbonate of excess in rotary kiln high temperature, obtain the products such as potassium aluminate, potassium ferrite, metavanadic acid calcium, calcium orthosilicate, carbon dioxide, sintered product is subjected to dissolution in dilute alkaline soln, dissolution fluid is passed through carbon dioxide caused by rotary kiln in closed container and carries out carburizing reagent, separate out Al (OH) after desiliconization purifies3Precipitation, hydrolytic precipitation obtains thick vanadium to dealuminzation solution in acid condition, by thick vanadium alkali soluble solution, adds ammonium chloride and obtains ammonium metavanadate, last solution is rich potassium, rich sodium solution, and potash, soda are obtained through substep evaporation.It is of the invention thoroughly to solve problem of environmental pollution caused by the stockpiling of bone coal leached mud.

Description

The selecting smelting combination technique of vanadium, aluminium, potassium, silicon in a kind of synthetical recovery siliceous shale containing vanadium
Technical field
The present invention is a kind of using low-grade siliceous shale containing vanadium as raw material, synthetical recovery wherein valuable group of vanadium, aluminium, potassium, silicon The ore dressing field of metallurgy divided.
Technical background
Siliceous shale containing vanadium, abbreviation bone coal, it is that the exclusive characteristic in China contains vanadium resource.Mainly contain vanadium in siliceous shale containing vanadium Mineral are muscovite containing vanadium, roscoelite, and gangue mineral mainly has quartz, feldspar, calcite etc..The type navajoite is in China's reserves Extremely abundant, valuable component is more in ore, such as vanadium, aluminium, potassium etc., has higher comprehensive utilization value and fabulous exploitation Prospect.The characteristics of ore is that grade containing vanadium is low, and quartz, calcite equal size are higher, high with traditional smelting process vanadium extraction cost, Economic benefit is low.
Research of the China to the resource of siliceous shale containing vanadium starts from phase early 1960s, starts widely used chlorine the seventies Change roasting-water logging technique and calcification baking-water logging technique vanadium extraction.Wherein chloridising roasting-water logging technological process is simple, production cost Low, suitable for low calcium bone coal, but roasting process can produce the pernicious gases such as chlorine, hydrogen chloride, serious to ecological environmental pollution. Compare, calcification baking is applied to high calcium stone coal mine, and process environments pollution is small, and leached mud is free of sodium salt, rich in calcium, is advantageous to The synthetical recovery of slag.During calcification baking, vanadium and calcium agent generation calcium vanadate in bone coal, calcium vanadate can be with acid and alkali reaction Vanadium is leached afterwards.But calcification baking technique normally only considers the recovery of vanadium, time of other metals in bone coal is not accounted for Receive and utilize, such as the element such as silicon, potassium, aluminium, cause the waste of resource.Simultaneously as it does not account for returning for other elements Receive, when causing its calcification baking, its CaO used quality is generally the 6-8% of only ore quality.
Up to the present, it yet there are no the selecting smelting combination technique on vanadium, aluminium, potassium, silicon in synthetical recovery siliceous shale containing vanadium Relevant report.
The content of the invention
It is an object of the invention to provide a kind of siliceous vanadium-containing shale selecting smelting combination technique, synthetical recovery vanadium therein, potassium, The resources such as aluminium, silicon.
Vanadium, aluminium, potassium, the selecting smelting combination technique of silicon in a kind of synthetical recovery siliceous shale containing vanadium of the present invention；Including following steps Suddenly：
The preliminary desiliconization of step 1
Siliceous vanadium-containing shale is crushed into ore grinding to -200 mesh and accounts for 45%-55% fineness, obtains ore pulp to be selected, treats ore dressing slurry Flotation is carried out, obtains vanadium concentrate and gangue；The pH of the ore pulp to be selected is 2-5, and solid-liquid mass ratio is 1 in the ore pulp to be selected： 2.5-1:3.5, collecting agent used is cation-collecting agent during flotation, and dispersant used is selected from calgon, prodan, water At least one of glass；
Step 2 high calcium basic roasting
Aluminum oxide, the amount of silica in the gained vanadium concentrate of measuring process one, according to mol ratio, sodium carbonate：In vanadium concentrate Aluminum oxide=0.7-1.3:1 with taking sodium carbonate；According to according to mol ratio, Ca：Silica=1.8-2.1 in ore, with taking stone Ash and/or lime stone；After with vanadium concentrate is well mixed obtained by the sodium carbonate, lime and/or the lime stone that take and step 1, 850-950 DEG C of progress high-temperature roasting at least 2h, obtains product to be leached；
Step 3 desiliconization again
Product to be leached obtained by step 2 is placed in aqueous slkali and leached；Obtain leachate and leach residue；Leach When, it is 80-85 DEG C to control extraction temperature, mass ratio is 1 to liquid admittedly:1-3:1st, extraction time is more than or equal to 0.5h,
Step 4 carbonization treatment
Leachate obtained by step 3 is placed in container, in confined conditions, carbon dioxide is blasted, is 1- in air pressure Stirring reaction at least 2 hours, stands under conditions of 1.2MPa, temperature are 60-80 DEG C, filtering, obtains be carbonized extraction raffinate and hydroxide Aluminum precipitation；
Step 5 analyses vanadium
The pH value of adjustment carbonization extraction raffinate separates out thick vanadium, filters, obtain thick vanadium and except vanadium extraction raffinate to 2-3；Thick vanadium is through alkali soluble Afterwards, ammonia radical ion is added, obtains ammonium metavanadate precipitate；It is filtrated to get ammonium metavanadate and filtrate；
Step 6 separation sodium, potassium
Substep evaporation is carried out after being well mixed by filtrate obtained by step 5 and except vanadium extraction raffinate and obtains potash and soda.
Vanadium, aluminium, potassium, the selecting smelting combination technique of silicon in a kind of synthetical recovery siliceous shale containing vanadium of the present invention；Institute in step 1 State cation-collecting agent and be selected from least one of lauryl amine, DTAC, ether amines.Preferably, the sun Ion collecting agent, the ratio that 50-80g is added in ore per ton add.
Vanadium, aluminium, potassium, the selecting smelting combination technique of silicon in a kind of synthetical recovery siliceous shale containing vanadium of the present invention；Dispersant is by every The ratio that ton ore adds 200-400g adds.
Vanadium, aluminium, potassium, the selecting smelting combination technique of silicon in a kind of synthetical recovery siliceous shale containing vanadium of the present invention；In step 1, warp Roughing three times, desiliconization is scanned twice, obtain vanadium concentrate and gangue.
Vanadium, aluminium, potassium, the selecting smelting combination technique of silicon in a kind of synthetical recovery siliceous shale containing vanadium of the present invention；In step 2, survey Aluminum oxide, the amount of silica in vanadium concentrate obtained by step 1 are measured, according to mol ratio, sodium carbonate：Aluminum oxide in vanadium concentrate= 0.7-1.3:1 with taking sodium carbonate；According to mol ratio, Ca：Silica=1.8-2.1 in ore, with taking lime stone；By with taking After sodium carbonate, lime stone and step 1 gained vanadium concentrate are well mixed, high-temperature roasting 2-3h is carried out at 850-950 DEG C, is obtained Product and carbon dioxide to be leached；Carbon dioxide is used for step 4.The product to be leached includes potassium aluminate (K2O.Al2O3), the product such as potassium ferrite (K2O.Fe2O3), metavanadic acid calcium (CaO.V2O5), calcium orthosilicate (2CaO.SiO2).
Vanadium, aluminium, potassium, the selecting smelting combination technique of silicon in a kind of synthetical recovery siliceous shale containing vanadium of the present invention；, will in step 3 Product to be leached, which is placed in aqueous slkali, obtained by step 2 is leached；Obtain leachate and leach residue；During leaching, control is leached Temperature is 80-85 DEG C, the solid mass ratio of liquid is 1:1-3:1st, extraction time 0.5-1h, the concentration of alkali is 50- in the aqueous slkali 100g/L.It is low sodium calcium silicates and/or low sodium orthosilicic acid calcium salt to leach residue, and it can be directly used as the raw material for producing cement.
Vanadium, aluminium, potassium, the selecting smelting combination technique of silicon in a kind of synthetical recovery siliceous shale containing vanadium of the present invention；, will in step 4 Leachate obtained by step 3 is placed in container, in confined conditions, blasts carbon dioxide, is 1-1.2MPa, temperature in air pressure Spend for stirring reaction 2-3 hours under conditions of 60-80 DEG C, stand, filtering, obtain be carbonized extraction raffinate and aluminum hydroxide precipitation, stirring When, it is 200-300r/min to control mixing speed.Precipitation of alumina can sell after drying process or for produce aluminium or It is directly used as catalyst use.
Vanadium, aluminium, potassium, the selecting smelting combination technique of silicon in a kind of synthetical recovery siliceous shale containing vanadium of the present invention；In step 5, use The pH value of acid solution adjustment carbonization extraction raffinate separates out thick vanadium, filters, obtain thick vanadium and except vanadium extraction raffinate to 2-3；The acid solution is selected from salt At least one of acid, sulfuric acid, phosphoric acid.
Vanadium, aluminium, potassium, the selecting smelting combination technique of silicon in a kind of synthetical recovery siliceous shale containing vanadium of the present invention；In step 5, slightly Vanadium adds ammonium chloride after soda ash solution dissolves, sedimentation time 12-15h after being 5wt%-10wt% to ammonium chloride concentration.
Vanadium, aluminium, potassium, the selecting smelting combination technique of silicon in a kind of synthetical recovery siliceous shale containing vanadium of the present invention；The V rate of recovery is big The rate of recovery for being more than 90%, aluminium element in the rate of recovery equal to 97%, element silicon is more than more than or equal to the rate of recovery point of 94%, potassium The rate of recovery equal to 92%, sodium is more than or equal to 93%.
Compared with prior art, the features of the present invention and beneficial effect are：
(1) heretofore described ore dressing pretreatment process, 50%-70% mine tailing, makes in the siliceous shale that can dish out V2O5 grade brings up to 1.5%-3% in roasting raw material, greatly reduces calcination process amount, has saved the production of whole technique Cost.
(2) heretofore described calcification baking process, by adding proper amount of sodium carbonate and excessive lime stone, can incite somebody to action Potassium, sodium, aluminium, v element are completely converted into the aluminate of solubility in siliceous shale concentrate, and unnecessary Ca can be complete with element silicon Portion is converted into calcium silicates, so as to comprehensively utilize each element in follow-up processing so that siliceous vanadium-containing shale concentrate resource obtains To all of without leached mud exclusion；
(3) heretofore described alkali soaking technology, the main mine of leached mud is mutually calcium orthosilicate, realize silico-calcium and sodium, Potassium, vanadium efficiently separate, so as to as cement raw material, solve the problem of tailings discharge；
(4) carbon dioxide used in heretofore described carbonisation is caused by during calcification baking produces, not only sharp With heat energy therein, production cost is reduced, and considerably reduces the discharge capacity of roasting process carbon dioxide, is realized It is discarded to utilize, protect ecological environment；
(5) heretofore described carbonisation, the aluminium element in leachate can be precipitated out first, realizes aluminium Recycling；
(6) heretofore described carbonisation, the leaching except realizing vanadium, synthetical recovery potassium therein, sodium are gone back Resource, so as to realize the zero-emission of bone coal resource substantially.
(7) illustrate
Fig. 1 is the process chart of the present invention.
In conjunction with embodiment, the invention will be further described.
Embodiment 1
The raw material siliceous rock containing vanadium in Shaanxi somewhere, color is khaki, and each composition predominant amount is V2O5：0.65%, SiO2：68.28%, CaO：1.02%, Al2O3：18.76%, K2O：1.58%, Na2O：0.08%, MgO：0.65%, TFe： 3.00%.
(1) siliceous vanadium-containing shale is crushed into ore grinding to -200 mesh first and accounts for 45% fineness, obtained ore pulp to be selected, treat ore dressing Starch into roughing three times of passing through, scan desiliconization twice, obtain vanadium concentrate and gangue；Collecting agent lauryl amine used in flotation and octadecylamine Hybrid collector, the collecting agent, the ratio that 55g is added in ore per ton add；It is calgon and fluorine silicon that flotation is used The mixture of sour sodium；The ratio that dispersant is added 250g in ore per ton adds.The pH of the ore pulp to be selected is 5.
(2) aluminum oxide, the amount of silica in the gained vanadium concentrate of measuring process one, according to mol ratio, sodium carbonate：Vanadium concentrate Middle aluminum oxide=0.9:1 with taking sodium carbonate；According to mol ratio, Ca：Silica=1.8 in ore, with taking lime stone；It will match somebody with somebody and take Sodium carbonate, lime stone and gained vanadium concentrate it is well mixed after, carry out high-temperature roasting 2.5h at 920 DEG C, obtain production to be leached Thing and carbon dioxide.
(3) product to be leached is subjected to dissolution in dilute alkaline soln, diluted alkaline concentration used is 50g/L during dissolution, dissolution temperature Spend for 82 DEG C, liquid-solid ratio 3:1, extraction time 0.5h, leached mud is filtrated to get calcium orthosilicate product, cement raw can be used as Material.
(4) dissolution fluid is passed through carbon dioxide (two caused by step (1) after desiliconization purifies in closed container Carbonoxide is all of coming in) carburizing reagent is carried out, carbon dioxide now is caused by calcification baking process, and carbonization was decomposed The carbon dioxide gas pressure that journey is passed through is 1MPa, reaction time 2h, mixing speed 200r/min, reaction temperature 75 ℃。
(5) it is aluminium hydroxide that obtained precipitation is decomposed in carbonization, and leachate adjusts pH to 2.5 with hydrochloric acid, hydrolyzes precipitation 1.5h, filtering, obtains thick vanadium and except vanadium extraction raffinate.Thick vanadium blasts ammonia, obtains ammonium metavanadate precipitate after alkali soluble；It is filtrated to get Ammonium metavanadate and filtrate；
(6) carry out substep evaporation after being well mixed obtained by (5) except vanadium extraction raffinate and filtrate and obtain potash and soda.
In the present embodiment, the V rate of recovery is 98.5%, the rate of recovery of element silicon is 92%, the rate of recovery of aluminium element is 95%th, potassium, the rate of recovery of sodium are respectively 93%, 97% (when calculating the rate of recovery of sodium, it is contemplated that the dosage of sodium carbonate used).
Embodiment 2
The siliceous rock containing vanadium of raw material Certain District, Hunan, color are grey, and each composition predominant amount is V2O5：0.87%, SiO2：67.55%, CaO：0.77%, Al2O3：15.64%, K2O：1.12%, Na2O：0.15%, MgO：0.54%, TFe： 2.11%.
(1) siliceous vanadium-containing shale is crushed into ore grinding to -200 mesh first and accounts for 49% fineness, obtained ore pulp to be selected, treat ore dressing Starch into secondary roughing of passing through, scan desiliconization three times, obtain vanadium concentrate and gangue；Collecting agent used in flotation is ether amines, the collecting Agent, the ratio that 70g is added in ore per ton add；Flotation is used for calgon and the mixture of prodan；Dispersant The ratio that 400g is added in ore per ton adds.The pH of the ore pulp to be selected is 5.
(2) aluminum oxide, the amount of silica in the gained vanadium concentrate of measuring process one, according to mol ratio, sodium carbonate：Vanadium concentrate Middle aluminum oxide=1:1 with taking sodium carbonate；According to mol ratio, Ca：Silica=2.1 in ore, with taking lime stone；By with taking After sodium carbonate, lime stone and gained vanadium concentrate are well mixed, high-temperature roasting 2h are carried out at 900 DEG C, obtain product to be leached and Carbon dioxide.
(3) product to be leached is subjected to dissolution in dilute alkaline soln, diluted alkaline concentration used is 50g/L during dissolution, dissolution temperature Spend for 80 DEG C, liquid-solid ratio 2:1, extraction time 1h, leached mud is as cement raw material.
(4) dissolution fluid is passed through carbon dioxide in closed container and carries out carburizing reagent, now after desiliconization purifies Carbon dioxide is caused by calcification baking process, and the carbon dioxide gas pressure that carbonization decomposable process is passed through is 1.2MPa, reaction Time is 3h, and mixing speed 250r/min, reaction temperature is 80 DEG C.
(5) leachate adjusts pH to 3 with sulfuric acid, hydrolyzes precipitation 1h, filtering, obtains thick vanadium and except vanadium extraction raffinate.Thick vanadium is through alkali After molten, ammonia is blasted, obtains ammonium metavanadate precipitate；It is filtrated to get ammonium metavanadate and filtrate；
(6) carry out substep evaporation after being well mixed obtained by (5) except vanadium extraction raffinate and filtrate and obtain potash and soda.
In the present embodiment, the V rate of recovery is 97%, the rate of recovery of element silicon is 92%, the rate of recovery of aluminium element is 94%, Potassium, the rate of recovery of sodium are respectively 92%, 93%.
Embodiment 3
The raw material siliceous rock containing vanadium in Sichuan somewhere, color are white, and each composition predominant amount is V2O5：0.98%, SiO2：66.75%, CaO：0.34%, Al2O3：18.53%, K2O：1.33%, Na2O：0.26%, MgO：0.49%, TFe： 1.67%.
(1) siliceous vanadium-containing shale is crushed into ore grinding to -200 mesh first and accounts for 55% fineness, obtained ore pulp to be selected, treat ore dressing Starch into secondary roughing of passing through, scan desiliconization three times, obtain vanadium concentrate and gangue；Collecting agent used in flotation is trimethyl The mixture of ammonium chloride and lauryl amine, the collecting agent, the ratio that 68g is added in ore per ton add；It is fluorine silicon that flotation is used Sour sodium；The ratio that dispersant is added 300g in ore per ton adds.The pH of the ore pulp to be selected is 3.
(2) aluminum oxide, the amount of silica in the gained vanadium concentrate of measuring process one, according to mol ratio, sodium carbonate：Vanadium concentrate Middle aluminum oxide=1.3:1 with taking sodium carbonate；According to mol ratio, Ca：Silica=2.0 in ore, with taking lime stone；It will match somebody with somebody and take Sodium carbonate, lime stone and gained vanadium concentrate it is well mixed after, carry out high-temperature roasting 1.5h at 850 DEG C, obtain production to be leached Thing and carbon dioxide.
(3) sintered product is subjected to dissolution in dilute alkaline soln, diluted alkaline concentration used is 80g/L during dissolution, leaching temperature For 85 DEG C, liquid-solid ratio 1:1, extraction time 2h, leached mud is as cement raw material.
(4) dissolution fluid is passed through carbon dioxide in closed container and carries out carburizing reagent, now after desiliconization purifies Carbon dioxide is caused by calcification baking process, and the carbon dioxide gas pressure that carbonization decomposable process is passed through is 1.5MPa, reaction Time is 2h, and mixing speed 300r/min, reaction temperature is 65 DEG C.
(5) leachate adjusts pH to 2.5 with hydrochloric acid, hydrolyzes precipitation 1.5h, filtering, obtains thick vanadium and except vanadium extraction raffinate.Thick vanadium After alkali soluble, ammonia is blasted, obtains ammonium metavanadate precipitate；It is filtrated to get ammonium metavanadate and filtrate；
(6) carry out substep evaporation after being well mixed obtained by (5) except vanadium extraction raffinate and filtrate and obtain potash and soda.
In the present embodiment, the V rate of recovery is 98%, the rate of recovery of element silicon is 92%, the rate of recovery of aluminium element is 94%, Potassium, the rate of recovery of sodium are respectively 92%, 94%.
Comparative example 1
The uniform embodiment 1 of other conditions is consistent, and difference is：Without the flotation of step 1, ore matter is directly used The calcium carbonate of amount 8% is calcined.In the comparative example, the V rate of recovery be only the rate of recovery of 72%, element silicon be 55%, aluminium The rate of recovery of element is that 40%, potassium, the rate of recovery of sodium are respectively 70%, 84% (when calculating the rate of recovery of sodium, it is contemplated that carbon used The dosage of sour sodium).
Comparative example 2
The uniform embodiment 1 of other conditions is consistent, and difference is：According to mol ratio, Ca：Silica in ore= 1.5, with taking lime stone.In the comparative example, the V rate of recovery is only that the rate of recovery of 68%, element silicon is time of 90%, aluminium element Yield is that 62%, potassium, the rate of recovery of sodium are respectively 72%, 88% (when calculating the rate of recovery of sodium, it is contemplated that the use of sodium carbonate used Amount).

Claims (9)

  1. A kind of 1. selecting smelting combination technique of vanadium, aluminium, potassium, silicon in synthetical recovery siliceous shale containing vanadium；It is characterized in that；Including following Step：
    The preliminary desiliconization of step 1
    Siliceous vanadium-containing shale is crushed into ore grinding to -200 mesh and accounts for 45%-55% fineness, obtains ore pulp to be selected, ore dressing slurry is treated and carries out Flotation, obtain vanadium concentrate and gangue；The pH of the ore pulp to be selected is 2-5, and solid-liquid mass ratio is 1 in the ore pulp to be selected：2.5- 1:3.5, collecting agent used is cation-collecting agent during flotation, and dispersant used is selected from calgon, prodan, waterglass At least one of；
    Step 2 high calcium basic roasting
    Aluminum oxide, the amount of silica in the gained vanadium concentrate of measuring process one, according to mol ratio, sodium carbonate：Aoxidized in vanadium concentrate Aluminium=0.7-1.3:1 with taking sodium carbonate；According to according to mol ratio, Ca：Silica=1.8-2.1 in ore, with take lime and/ Or lime stone；After with vanadium concentrate is well mixed obtained by the sodium carbonate, lime and/or the lime stone that take and step 1, in 850- 950 DEG C of progress high-temperature roasting at least 2h, obtain product to be leached；
    Step 3 desiliconization again
    Product to be leached obtained by step 2 is placed in aqueous slkali and leached；Obtain leachate and leach residue；During leaching, control Extraction temperature processed is 80-85 DEG C, the solid mass ratio of liquid is 1:1-3:1st, extraction time is more than or equal to 0.5h,
    Step 4 carbonization treatment
    Leachate obtained by step 3 is placed in container, in confined conditions, carbon dioxide is blasted, is 1- in air pressure Stirring reaction at least 2 hours, stands under conditions of 1.2MPa, temperature are 60-80 DEG C, filtering, obtains be carbonized extraction raffinate and hydroxide Aluminum precipitation；
    Step 5 analyses vanadium
    The pH value of adjustment carbonization extraction raffinate separates out thick vanadium, filters, obtain thick vanadium and except vanadium extraction raffinate to 2-3；Thick vanadium adds after alkali soluble Enter ammonia radical ion, obtain ammonium metavanadate precipitate；It is filtrated to get ammonium metavanadate and filtrate；
    Step 6 separation sodium, potassium
    Substep evaporation is carried out after being well mixed by filtrate obtained by step 5 and except vanadium extraction raffinate and obtains potash and soda.
  2. 2. vanadium, aluminium, potassium, the selecting smelting combination technique of silicon in a kind of synthetical recovery siliceous shale containing vanadium according to claim 1；Its It is characterised by：Cation-collecting agent described in step 1 is at least one in lauryl amine, DTAC, ether amines Kind.Preferably, the cation-collecting agent, the ratio that 50-80g is added in ore per ton adds.
  3. 3. vanadium, aluminium, potassium, the selecting smelting combination technique of silicon in a kind of synthetical recovery siliceous shale containing vanadium according to claim 1；Its It is characterised by：The ratio that dispersant is added 200-400g in ore per ton adds.
  4. 4. vanadium, aluminium, potassium, the selecting smelting combination technique of silicon in a kind of synthetical recovery siliceous shale containing vanadium according to claim 1；Its It is characterised by：In step 1, through roughing three times, desiliconization is scanned twice, obtains vanadium concentrate and gangue.
  5. 5. vanadium, aluminium, potassium, the selecting smelting combination technique of silicon in a kind of synthetical recovery siliceous shale containing vanadium according to claim 1；Its It is characterised by：In step 2, aluminum oxide, the amount of silica in the gained vanadium concentrate of measuring process one, according to mol ratio, carbonic acid Sodium：Aluminum oxide=0.7-1.3 in vanadium concentrate:1 with taking sodium carbonate；According to mol ratio, Ca：Silica=1.8-2.1 in ore, With taking lime stone；After with vanadium concentrate is well mixed obtained by the sodium carbonate, lime stone and step 1 taken, enter at 850-950 DEG C Row high-temperature roasting 2-3h, obtain product and carbon dioxide to be leached；Carbon dioxide is used for step 4.
  6. 6. vanadium, aluminium, potassium, the selecting smelting combination technique of silicon in a kind of synthetical recovery siliceous shale containing vanadium according to claim 1；Its It is characterised by：In step 3, product to be leached obtained by step 2 is placed in aqueous slkali and leached；Obtain leachate and leaching Residue；During leaching, it is 80-85 DEG C to control extraction temperature, mass ratio is 1 to liquid admittedly:1-3:1st, extraction time 0.5-1h, the alkali The concentration of alkali is 50-100g/L in solution.
  7. 7. vanadium, aluminium, potassium, the selecting smelting combination technique of silicon in a kind of synthetical recovery siliceous shale containing vanadium according to claim 1；Its It is characterised by：In step 4, leachate obtained by step 3 is placed in container, in confined conditions, blasts carbon dioxide, The stirring reaction 2-3 hours under conditions of air pressure is 1-1.2MPa, temperature is 60-80 DEG C, stand, filtering, obtain the extraction raffinate that is carbonized And aluminum hydroxide precipitation, during stirring, it is 200-300r/min to control mixing speed.
  8. 8. vanadium, aluminium, potassium, the selecting smelting combination technique of silicon in a kind of synthetical recovery siliceous shale containing vanadium according to claim 1；Its It is characterised by：In step 5, the pH value for adjusting carbonization extraction raffinate with acid solution separates out thick vanadium, filters, obtain thick vanadium and except vanadium to 2-3 Extraction raffinate；The acid solution is selected from least one of hydrochloric acid, sulfuric acid, phosphoric acid.
  9. 9. vanadium, aluminium, potassium, the selecting smelting combination technique of silicon in a kind of synthetical recovery siliceous shale containing vanadium according to claim 1；Its It is characterised by：The rate of recovery that the V rate of recovery is more than or equal to 97%, element silicon is more than or equal to more than the 90%, rate of recovery of aluminium element 94%th, the rate of recovery of potassium point is more than or equal to 93% more than or equal to the rate of recovery of 92%, sodium.
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CN110592400A (en) * 2019-08-15 2019-12-20 中南大学 Novel vanadium extraction and dressing combined method for high-silicon low-calcium stone coal
CN111020231A (en) * 2019-12-04 2020-04-17 杨秋良 Method for precipitating vanadium from sodium vanadium-rich liquid without ammonia
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