CN109706329A - A kind of method that extracting vanadium from stone coal prepares ammonium metavanadate - Google Patents
A kind of method that extracting vanadium from stone coal prepares ammonium metavanadate Download PDFInfo
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Abstract
The present invention provides a kind of method that extracting vanadium from stone coal prepares ammonium metavanadate, comprising the following steps: mixes bone coal miberal powder, high-carbon powder containing vanadium raw materials and conch meal, water is added to be granulated to obtain pellet containing vanadium；Grinding after vanadium pellet-roasting will be contained, leached, leaching slurry filter and washs to obtain contain vanadium leachate, washing lotion and tailings；It is stood what is obtained containing vanadium leachate, separation of solid and liquid obtains liquid before potassium alum and tower；Liquid before tower is purified and is enriched with by ion exchange resin, liquid after loaded resin and tower is obtained；Loaded resin is desorbed using NaOH solution, ammonium metavanadate is prepared in stripping liquid precipitation.The method that extracting vanadium from stone coal of the present invention prepares ammonium metavanadate makes full use of high-carbon containing the organic carbon in vanadium raw materials as fuel, the energy consumption during stone coal mine calcification baking can not only be reduced, high-carbon can also be made full use of containing the vanadium resource in vanadium raw materials, improve the yield of vanadium；Use conch meal for activator simultaneously, effectively save cost.
Description
Technical field
The present invention relates to a kind of methods that extracting vanadium from stone coal technology more particularly to extracting vanadium from stone coal prepare ammonium metavanadate.
Background technique
Vanadium be it is a kind of have important defense strategy resource, can be rated as " industrial vitamin ", be widely used in steel, close
The fields such as gold, chemical industry, medicine, atomic energy and vanadium cell.Vanadium mineral has more than 70 kinds in nature, is mainly total to other metallic ores
Raw, so far without finding independent vanadium mineral, the 88% of vanadium annual output is from vanadium titano-magnetite ore.The v-ti magnetite in China
Though ore resources are relatively abundant, Rock coal containing alum is also the navajoite resource of the other one big characteristic in China, V contained by bone coal2O5China is accounted for always to store up
The 87% of amount, is V in China's vanadium titano-magnetite2O56.7 times of reserves.Currently, the method for the extracting vanadium from stone coal used both at home and abroad is main
There are several types of: direct process for extracting vanadium by acid leaching, sodium-salt calcination-water logging technique, calcium salt roasting-acidleach (alkali leaching) technique, salt-free roasting
Burn (blank roasting)-acid leaching process and sulfating roasting-water logging technique etc..Wherein calcium salt roasting-acidleach (alkali leaching) technique is roasting
Toxic gas is not generated during burning, and belongs to environment-friendly type process for extracting vanadium.Calcium salt roasting-acidleach (alkali leaching) technique is in mixing process
A certain amount of CaO, CaCO is added in middle needs into bone coal according to a certain percentage3Or Ca (OH)2Equal calcium containing compounds, mix laggard
Row roasting, huge in consumption of this process for calcium salt, production cost is higher.
The content containing organic carbon in vanadium raw materials such as petroleum flying dust, oil shale and tar sand is higher, calorific value with higher,
In content of vanadium it is lower, but by burning after, be enriched in the residue of vanadium after combustion, content can increase substantially, highest
Up to 40% (with V2O5Meter) left and right, while these high-carbon are containing there is some elements for being beneficial to vanadium extraction in vanadium raw materials, such as potassium, sodium, magnesium
With calcium etc., the consumption of roasting reagent can be reduced.If calorific value and beneficial element therein can be made full use of, and vanadium therein is provided
Source extracts, not only can be energy saving, while also complying with the target that China develops a circular economy with energy-saving and emission-reduction.
China is shellfish culture big country, until the cultured output of shellfish in 2016 reaches 1529.41 ten thousand tons, accounts for world shellfish and supports
Grow 60% or more of total amount.After shellfish is processed, account for shellfish weight 60% or more shell often become waste abandon by with
Meaning abandons and topples over, this is a kind of waste of resource and the improper disposition for polluting environment, and resource utilization is the pass of shell disposition
Key.Waste shell pollution has become coastal area environmental problem urgently to be resolved, and accumulates caused environmental problem year by year
Increasingly severe, the resource utilization of waste shell is imperative.
In shell containing 95% or more calcium carbonate and a small amount of organic matter.
Chinese patent (Publication No. CN106367618A) is described using waste PVC and bone coal according to certain ratio
Example progress is baking mixed, not only takes full advantage of the calorific value of waste plastics, improves waste plastics resource utilization rate, and improve vanadium
Leaching rate, but the process can generate a certain amount of HCl gas, will cause the pollution of environment.And the high-carbon that this patent uses contains
Vanadium raw materials, bone coal raw material and calcination activation agent are roasted according to a certain percentage, and roasting process not only takes full advantage of high-carbon and contains
The calorific value of vanadium raw materials improves its resource utilization rate, and improves the yield of vanadium, while roasting process is generated without pernicious gas,
It is analyzed the patent and environment is caused centainly to pollute, be not suitable for high-carbon containing vanadium raw materials, bone coal raw material and calcination activation agent mixing
Roast vanadium extraction.Chinese patent (Publication No. CN101240376A) describes using bone coal to be roasting as raw material, calcium oxide
Additive, cement and accelerator mix according to a certain percentage as binder, three, the calcification baking technique for bone coal.And
This patent replaces calcium oxide as roasting additive using waste shell powder, not only can be with save the cost, but also will discard
Conch meal comprehensive utilization of resources, is analyzed that the patent calcium salt consumption is larger, and production cost is higher, is not suitable for high-carbon containing vanadium
Raw material, bone coal raw material and the baking mixed vanadium extraction of calcination activation agent.Chinese patent (Publication No. CN108217708A) describes
Using waste shell as raw material, through washing, alkali cleaning, crushing, acidolysis, filtering, adjusting pH, reaction, yield, washing, drying, add
Add auxiliary material, tabletting granulating process to prepare nano microbeam calcium carbonate, realizes the comprehensive utilization of resources of waste shell, but this is specially
Sharp preparation process is complicated, and there is no come waste shell as calcination activation agent using being analyzed the patent and be not suitable for high-carbon
Containing vanadium raw materials, bone coal raw material and the baking mixed vanadium extraction of calcination activation agent.
Summary of the invention
It is an object of the present invention to for current bone coal calcium salt roasting process calcium salt energy-output ratio big, waste shell and
The problem of high-carbon can not be rationally and efficiently used containing vanadium raw materials, proposes a kind of method that extracting vanadium from stone coal prepares ammonium metavanadate, this method
While solving to extract the vanadium in bone coal, it is attached to realize height of the high-carbon containing organic carbon, vanadium resource and waste shell in vanadium raw materials
Value added resource utilization, not only can energy saving and cost, while also complying with China and developing a circular economy and energy-saving and emission-reduction
Target has great importance for sustainable development and environmental protection.
To achieve the above object, the technical solution adopted by the present invention is that: a kind of method that extracting vanadium from stone coal prepares ammonium metavanadate,
The following steps are included:
Bone coal miberal powder, high-carbon powder containing vanadium raw materials and conch meal (calcination activation agent) are mixed, and water are added to be granulated by step 1
To pellet containing vanadium；
Step 2 will contain vanadium pellet 4~36h of constant temperature calcining at 550~950 DEG C and must contain vanadium roasting material；
Step 3, will contain vanadium roasting abrasive lapping must contain vanadium calcining, calcining containing vanadium is leached, leaching slurry is filtered
It is (described containing V in vanadium leachate to vanadium leachate is contained2O5: 2~10g/L) and intermediate slag；
Step 4 washs intermediate slag using detergent twice, and primary wash liquor, secondary cleaning water and tailings is obtained by filtration；
Step 5, will be placed in containing vanadium leachate in 0~10 DEG C of thermostat stand 8~for 24 hours, be separated by solid-liquid separation that obtain potassium bright
Liquid before alum and tower；
Liquid before tower is purified and is enriched with by ion exchange resin by step 6, obtains liquid after loaded resin and tower；
Step 7 desorbs loaded resin using NaOH solution, by stripping liquid (V in the stripping liquid2O5: 60~100g/L, pH
Value 7~8) ammonium metavanadate is prepared in precipitation；Using the resin tower after dilution heat of sulfuric acid washing desorption, in case next time uses.
Further, the high-carbon is in oil shale mine containing vanadium, the flying dust of oil containing scherbinaite and tar sand containing vanadium containing vanadium raw materials
One or more mixing.The oil content of the oil shale containing vanadium is 5~40%wt, the phosphorus content of the flying dust of oil containing scherbinaite is 20~
50%wt, the phosphorus content of the tar sand containing vanadium are 20~40%wt.
Further, the mass ratio of the bone coal miberal powder, high-carbon powder containing vanadium raw materials and conch meal is 1:0.01~1:0.01
~0.5, preferably 1:0.05~0.8:0.05~0.3.The bone coal powder particle size is 80~200 mesh, and the high-carbon is former containing vanadium
Feed powder granularity is 80~200 mesh, and shell Powder Particle Size is 80~200 mesh.
Further, calcium carbonate content is 94~97%wt in the conch meal, as adding for bone coal calcium salt roasting
Add agent, can not only have great importance with save the cost for sustainable development and environmental protection.
Further, the solid-to-liquid ratio of bone coal miberal powder, the mixture of high-carbon powder containing vanadium raw materials and conch meal and water described in step 1
It (g:mL) is 2.5~5:1, pellet partial size is 10~15mm.
Further, pellet-roasting temperature described in step 2 is 600~900 DEG C, lower constant temperature calcining 4~for 24 hours, and it obtains containing vanadium
Roasting material.
Further, the partial size of calcining containing vanadium described in step 3 is 80~200 mesh.
Further, described in step 3 leach: leaching agent is added in leaching tanks, according to liquid-solid ratio (mL:g) be 1.2~
Calcining containing vanadium is added into leaching tanks by 3.0:1, is 0.01~0.1:1 according to sulfuric acid and the mass ratio of calcining containing vanadium, and preferably 0.02
~0.08:1, it is 92~98% concentrated sulfuric acids that mass fraction is added into leaching tanks, under normal temperature conditions 2~4h of leaching, instead
The final ph that slurries should be controlled in the process is 1.5~3.0.
Further, pH adjusting method is as follows in step 3: pH value is higher than limit value and adds sulfuric acid, pH lower than restriction value complement
Add calcining containing vanadium.
Further, leaching agent described in step 3 is one of liquid and pickling solution or a variety of after water, tower.
Further, detergent described in step 4 is one of liquid and water or a variety of after secondary cleaning water, tower, is cleaned every time
Tailings water consumption is 0.3~2.0 times of tailings quality, respectively obtains primary wash liquor and secondary cleaning water, it is described obtain once wash
It is 1.5~3.0 as liquid before tower that liquid, which uses the concentrated sulfuric acid to adjust pH value, and the obtained secondary cleaning water returns to step as detergent
4 for cleaning intermediate slag.
Further, amberlite described in step 6 be Success 996, D296, D314, D301, D201, D202,
201 × 7, one or more in JD404 and JD501.Liquid can return to step 3 as leaching agent after tower described in step 6.
Further, NaOH solution concentration described in step 7 is 4~10%wt, preferably 6~10%wt.
Further, step 7 uses concentration to wash the pH that resin tower is discharged to resin tower for the sulfuric acid solution of 3~5%wt
Value is 1.5~3.0, obtains pickling solution, and the pickling solution is used as leaching agent back to step 3.
A kind of method that extracting vanadium from stone coal prepares ammonium metavanadate of the present invention, for current bone coal calcium salt roasting process energy consumption
The problem of big, waste shell and high-carbon can not be rationally and efficiently used containing vanadium raw materials is measured, proposes that a kind of extracting vanadium from stone coal prepares metavanadic acid
The method of ammonium realizes high-carbon containing organic carbon, vanadium resource and discarded shellfish in vanadium raw materials while solving to extract the vanadium in bone coal
The high added value resource utilization of shell.Specifically, it has the advantage that compared with prior art
1) present invention is carried out containing vanadium raw materials with bone coal raw material baking mixed using high-carbon: using high-carbon containing having in vanadium raw materials
Machine carbon can reduce the consumption of the energy in roasting stone coal mine roasting process as fuel；High-carbon can also be made full use of to contain simultaneously
Vanadium and other beneficial elements in vanadium raw materials, improve the yield of vanadium.
2) present invention makes full use of the carbonic acid in shell in high-carbon containing conch meal can also be added in vanadium raw materials and bone coal raw material
Calcium source of the calcium as calcification baking also turns waste into wealth shell while reducing calcium source cost, realizes that the height of waste shell is attached
Value added resource utilization.
3) present invention uses calcium salt roasting technique, is destroyed in bone coal using the calcium carbonate in shell in high-temperature calcination process
Mineral structure containing vanadium mineral will be exposed containing the vanadium in vanadium mineral so that leaching process only with lower acidity just
Vanadium in bone coal can be extracted.
4) present invention uses calcium salt roasting technique, two generated using the Decomposition of Calcium Carbonate in shell in high-temperature calcination process
Carbonoxide makes roasting material containing vanadium become loose porous, is conducive to coming into full contact with for material and air, will be containing the Low Valent Vanadium in vanadium mineral
Complete oxidation carries out oxidizing lower vanadium without adding oxidant to highest valence state, therefore in subsequent leaching process, at the same time,
The calcium oxide generated during Decomposition of Calcium Carbonate has certain sulfur fixation.
5) it is 1.5~3.0 that the present invention controls the pH value of slurries in leaching process by addition bone coal calcining and sulfuric acid,
It can effectively avoid being introduced into lime etc. to enter in slurries rich in the substance of calcium constituent, the CaO in lime can be sent out in slurries
Raw following precipitation reaction, and then reduce V2O5Leaching rate, 4H++5nCaO+[H2V10O28]4-=5 [nCaOV2O5]+3H2O draws
Also the increase of tailings amount can be caused while entering lime indirectly.
In addition, the pH value for controlling slurries by addition bone coal calcining and sulfuric acid in leaching process is 1.5~3.0, it can
Effectively to avoid being introduced into sulfuric acid in the alkaline matters such as lime, sodium hydroxide and potassium hydroxide and superfluous, the wave of sulfuric acid is caused
Take.
6) present invention leaches at normal temperature, under the high temperature conditions (50 DEG C of T >), when pH=1.5~2.5, can promote to hydrolyze
Precipitation: 6 [H2V10O28]4-+24H+=6V2O5·H2O↓+13H2O
Make the V in solution2O5Precipitating enters in solid phase, reduces V2O5Leaching rate, and with the raising of extraction temperature,
Precipitation rate increases therewith；And the precipitating of hydration vanadic anhydride can be effectively reduced in (20~30 DEG C) leachings under normal temperature conditions
Rate improves V in roasting material2O5Leaching rate, while room temperature leaches can reduce the dissolution rate of impurity element, improves leachate
Degree of purity.
Detailed description of the invention
Fig. 1 is the process flow chart that extracting vanadium from stone coal of the present invention prepares ammonium metavanadate method.
Specific embodiment
The present invention is further described with reference to embodiments:
Stone coal mine employed in following embodiment is identical with the type of conch meal, wherein the testing result of stone coal mine such as table
Shown in 1, calcium carbonate content is 96%wt in conch meal.
1 bone coal raw material testing result of table
Embodiment 1
Present embodiment discloses a kind of methods that extracting vanadium from stone coal prepares ammonium metavanadate, as shown in Figure 1, comprising the following steps:
(1) stone coal mine, oil shale mine containing vanadium and shell are crushed using jaw crusher, wherein the oil shale containing vanadium
Oil content 30%, V2O5Content is 0.51%.Using ball mill by broken stone coal mine, oil shale mine containing vanadium and grinding shells
To 100 mesh, bone coal miberal powder, the miberal powder of oil shale containing vanadium and conch meal are obtained；Bone coal miberal powder, the miberal powder of oil shale containing vanadium and conch meal are pressed
It is that 1:0.3:0.06 is mixed according to mass ratio, is that water is added in 1:4 according to liquid-solid ratio (mL:g), mixing is granulated, and preparing partial size is
The pelletizing of 10~15mm；
(2) pellet of preparation is placed in Muffle furnace, constant temperature calcining 15h must contain vanadium roasting at being 900 DEG C in maturing temperature
Imitation frosted glass；
(3) vanadium roasting material will be contained using ball mill and is milled to 100 mesh, and obtain calcining containing vanadium；It adds water in leaching tanks, according to
Liquid-solid ratio (mL:g) is 2.0:1, and calcining containing vanadium is added into leaching tanks, is 0.04:1 according to sulfuric acid and the mass ratio of calcining containing vanadium,
It is 98% concentrated sulfuric acid that mass fraction is added into leaching tanks, under normal temperature conditions leaching 2h, controls slurries in reaction process
Final ph be 2.0~2.5.V containing vanadium leachate is obtained by filtration2O5: 5.8g/L and intermediate slag；
(4) intermediate slag is washed with water twice and filters, cleans 1.2 times that intermediate slag water consumption is intermediate slag amount every time,
Respectively obtain primary wash liquor, secondary cleaning water and tailings；
(5) 18h will be stood in the obtained thermostat for being placed in 5 DEG C containing vanadium leachate, it is bright through being separated by solid-liquid separation available potassium
Liquid before alum and tower；
(6) liquid before obtained tower is directly passed through ion exchange resin Success 996 to be purified and be enriched with, is born
Liquid after load resin and tower；
(7) it uses concentration to desorb loaded resin for 8% NaOH solution, obtains stripping liquid (V2O5: 90g/L, pH value 7~
8), direct precipitation prepares AMV；
(8) using concentration to wash resin tower to the pH value that resin tower is discharged for 5% sulfuric acid solution again is 2.0~2.5, with
Standby next time uses.
Wherein the testing result of liquid and stripping liquid is as shown in table 2 after acquired leachate, primary wash liquor, secondary cleaning water, tower,
The ammonium metavanadate testing result of preparation is as shown in table 3.
The testing result of liquid and stripping liquid after 2 leachate of table, primary wash liquor, secondary cleaning water, tower
3 ammonium metavanadate testing result of table
| Title | V2O5 (%) | K (%) | Na (%) | Fe (%) | Al (%) | Mo (%) | Cr (%) | Mn (%) | Ca (%) | Mg (%) |
| AMV | 76.85 | 0.0027 | 0.0110 | 0.0013 | 0.0064 | 0.0052 | 0.0000 | 0.0000 | 0.0041 | 0.0005 |
V2O5Yield: 88.78%, AMV impurity are controllable.
Embodiment 2
Present embodiment discloses a kind of methods that extracting vanadium from stone coal prepares ammonium metavanadate, comprising the following steps:
(1) stone coal mine, the flying dust of oil containing scherbinaite and shell are crushed using jaw crusher, wherein the flying dust of oil containing scherbinaite
Phosphorus content 26%, V2O5Content is 1.2%.Using ball mill by broken stone coal mine, the flying dust of oil containing scherbinaite and grinding shells
To 100 mesh, bone coal miberal powder, the flying dust of oil containing scherbinaite and conch meal are obtained；By bone coal miberal powder, the miberal powder of oil shale containing vanadium and conch meal according to
Mass ratio is that 1:0.1:0.08 is mixed, and is that water is added in 1:4 according to liquid-solid ratio (mL:g), mixing is granulated, and preparing partial size is 10
The pelletizing of~15mm；
(2) pellet of preparation is placed in Muffle furnace, constant temperature calcining 18h must contain vanadium roasting at being 880 DEG C in maturing temperature
Imitation frosted glass；
(3) vanadium roasting material will be contained using ball mill and is milled to 100 mesh, and obtain calcining containing vanadium；Liquid after tower is added in leaching tanks,
It is 2.0:1 according to liquid-solid ratio (mL:g), calcining containing vanadium is added into leaching tanks, is according to sulfuric acid and the mass ratio of calcining containing vanadium
0.05:1, it is 98% concentrated sulfuric acid that mass fraction is added into leaching tanks, under normal temperature conditions leaching 3h, is controlled in reaction process
The final ph of slurrying liquid is 2.0~2.5.V containing vanadium leachate is obtained by filtration2O5: 5.65g/L and intermediate slag；
(4) intermediate slag is washed twice with detergent (liquid and water after tower) and filtered, clean intermediate slag dosage of scour every time
It is 1.1 times of intermediate slag amount, respectively obtains primary wash liquor, secondary cleaning water and tailings；
(5) 12h will be stood in the obtained thermostat for being placed in 3 DEG C containing vanadium leachate, it is bright through being separated by solid-liquid separation available potassium
Liquid before alum and tower；
(6) liquid before obtained tower is directly passed through ion exchange resin D296 to be purified and be enriched with, obtains loaded resin
With liquid after tower；
(7) it uses concentration to desorb loaded resin for 10% NaOH solution, obtains stripping liquid (V2O5: 95g/L, pH value 7~
8), direct precipitation prepares AMV；
(8) using concentration to wash resin tower to the pH value that resin tower is discharged for 5% sulfuric acid solution again is 2.0~2.5, with
Standby next time uses.
Wherein the testing result of liquid and stripping liquid is as shown in table 4 after acquired leachate, primary wash liquor, secondary cleaning water, tower,
The ammonium metavanadate testing result of preparation is as shown in table 5.
The testing result of liquid and stripping liquid after 4 leachate of table, primary wash liquor, secondary cleaning water, tower
| Title | V2O5(g/L) | K(g/L) | Na(g/L) | Fe(g/L) | Al(g/L) | Mo(g/L) | Cr(g/L) | Mn(g/L) | Ca(g/L) | Mg(g/L) |
| Leachate | 5.65 | 0.3249 | 0.1899 | 0.3524 | 3.0680 | 0.0201 | 0.0026 | 0.0333 | 0.6522 | 1.5970 |
| Primary wash liquor | 2.11 | 0.1899 | 0.1414 | 0.0484 | 1.3110 | 0.0088 | 0.0006 | 0.0174 | 0.6020 | 0.9024 |
| Secondary cleaning water | 0.42 | 0.1650 | 0.1352 | 0.0855 | 1.4170 | 0.0008 | 0.0011 | 0.0159 | 0.5809 | 0.8394 |
| Liquid after tower | 0.12 | 0.2703 | 0.1438 | 0.2110 | 2.4310 | 0.0007 | 0.0020 | 0.0276 | 0.6500 | 1.359 |
| Stripping liquid | 95.0 | 0.0430 | 54.2660 | 0.0021 | 0.0121 | 0.2462 | 0.0000 | 0.0000 | 0.0076 | 0.0098 |
5 ammonium metavanadate testing result of table
| Title | V2O5 (%) | K (%) | Na (%) | Fe (%) | Al (%) | Mo (%) | Cr (%) | Mn (%) | Ca (%) | Mg (%) |
| AMV | 76.77 | 0.0024 | 0.0120 | 0.0014 | 0.0058 | 0.0042 | 0.0000 | 0.0000 | 0.0040 | 0.0004 |
V2O5Yield: 89.75%, AMV impurity are controllable.
Embodiment 3
Present embodiment discloses a kind of methods that extracting vanadium from stone coal prepares ammonium metavanadate, comprising the following steps:
(1) stone coal mine, tar sand containing vanadium and shell are crushed using jaw crusher, wherein the tar sand containing vanadium contains
Carbon amounts 35%, V2O5Content is 0.86%.Using ball mill by broken stone coal mine, tar sand containing vanadium and grinding shells to 100
Mesh obtains bone coal miberal powder, the emery dust of pitch containing vanadium and conch meal；By bone coal miberal powder, the emery dust of pitch containing vanadium and conch meal according to mass ratio
It is mixed for 1:0.2:0.12, is that water is added in 1:4 according to liquid-solid ratio (mL:g), mixing is granulated, and preparing partial size is 10~15mm
Pelletizing；
(2) pellet of preparation is placed in Muffle furnace, constant temperature calcining must contain vanadium roasting for 24 hours at being 850 DEG C in maturing temperature
Imitation frosted glass；
(3) vanadium roasting material will be contained using ball mill and is milled to 100 mesh, and obtain calcining containing vanadium；Liquid after tower is added in leaching tanks,
It is 2.0:1 according to liquid-solid ratio (mL:g), calcining containing vanadium is added into leaching tanks, is according to sulfuric acid and the mass ratio of calcining containing vanadium
0.038:1, it is 98% concentrated sulfuric acid that mass fraction is added into leaching tanks, under normal temperature conditions leaching 2.5h, reaction process
The final ph of middle control slurries is 2.0~2.5.V containing vanadium leachate is obtained by filtration2O5: 5.74g/L and intermediate slag；
(4) intermediate slag is washed twice with detergent (liquid and water after tower) and filtered, clean intermediate slag dosage of scour every time
It is 1.5 times of intermediate slag amount, respectively obtains primary wash liquor, secondary cleaning water and tailings；
(5) 10h will be stood in the obtained thermostat for being placed in 4 DEG C containing vanadium leachate, it is bright through being separated by solid-liquid separation available potassium
Liquid before alum and tower；
(6) liquid before obtained tower is directly passed through ion exchange resin JD404 to be purified and be enriched with, obtains loaded resin
With liquid after tower；
(7) it uses concentration to desorb loaded resin for 10% NaOH solution, obtains stripping liquid (V2O5: 85g/L, pH value 7~
8), direct precipitation prepares AMV；
(8) using concentration to wash resin tower to the pH value that resin tower is discharged for 5% sulfuric acid solution again is 2.0~2.5, with
Standby next time uses.
Wherein the testing result of liquid and stripping liquid is as shown in table 6 after acquired leachate, primary wash liquor, secondary cleaning water, tower,
The ammonium metavanadate testing result of preparation is as shown in table 7.
The testing result of liquid and stripping liquid after 6 leachate of table, primary wash liquor, secondary cleaning water, tower
| Title | V2O5(g/L) | K(g/L) | Na(g/L) | Fe(g/L) | Al(g/L) | Mo(g/L) | Cr(g/L) | Mn(g/L) | Ca(g/L) | Mg(g/L) |
| Leachate | 5.74 | 0.1260 | 0.0589 | 0.1234 | 1.1690 | 0.0168 | 0.0010 | 0.0102 | 0.4658 | 0.5309 |
| Primary wash liquor | 1.53 | 0.0532 | 0.0624 | 0.0036 | 0.2577 | 0.0055 | 0.0001 | 0.0033 | 0.4575 | 0.1851 |
| Secondary cleaning water | 0.13 | 0.0112 | 0.0564 | 0.0014 | 0.0140 | 0.0005 | 0.0000 | 0.0002 | 0.4135 | 0.0120 |
| Liquid after tower | 0.14 | 0.0897 | 0.0461 | 0.0718 | 0.7191 | 0.0001 | 0.0006 | 0.0076 | 0.7009 | 0.4214 |
| Stripping liquid | 85.0 | 0.0330 | 48.2660 | 0.0018 | 0.0125 | 0.2512 | 0.0000 | 0.0000 | 0.0072 | 0.0096 |
7 ammonium metavanadate testing result of table
| Title | V2O5 (%) | K (%) | Na (%) | Fe (%) | Al (%) | Mo (%) | Cr (%) | Mn (%) | Ca (%) | Mg (%) |
| AMV | 76.68 | 0.0022 | 0.0118 | 0.0012 | 0.0038 | 0.0036 | 0.0000 | 0.0000 | 0.0042 | 0.0003 |
V2O5Yield: 91.45%, AMV impurity are controllable.
Embodiment 4
Present embodiment discloses a kind of methods that extracting vanadium from stone coal prepares ammonium metavanadate, comprising the following steps:
(1) stone coal mine, high-carbon (oil shale mine containing vanadium, the flying dust of oil containing scherbinaite and are contained containing vanadium raw materials using jaw crusher
Vanadium tar sand) and shell be crushed, wherein the oil content of oil shale mine containing vanadium 30%, V2O5Content is that 0.51%, oil containing scherbinaite flies
Grey phosphorus content 26%, V2O5Content is the phosphorus content 35% of the 1.2%, tar sand containing vanadium, V2O5Content is 0.86%.Using ball milling
Broken stone coal mine, tar sand containing vanadium and grinding shells to 100 mesh are obtained bone coal miberal powder, high-carbon powder containing vanadium raw materials and shellfish by machine
Shell powder；Bone coal miberal powder, high-carbon are mixed containing vanadium raw materials and conch meal according to mass ratio for 1:0.4:0.11, wherein high-carbon
It is mixed containing oil shale mine containing vanadium, the flying dust of oil containing scherbinaite and tar sand containing vanadium in vanadium raw materials according to mass ratio for 1:1:2, according to
Liquid-solid ratio (mL:g) is that water is added in 1:4, and mixing is granulated, and prepares the pelletizing that partial size is 10~15mm；
(2) pellet of preparation is placed in Muffle furnace, constant temperature calcining 20h must contain vanadium roasting at being 900 DEG C in maturing temperature
Imitation frosted glass；
(3) vanadium roasting material will be contained using ball mill and is milled to 100 mesh, and obtain calcining containing vanadium；Liquid after tower is added in leaching tanks,
It is 2.0:1 according to liquid-solid ratio (mL:g), calcining containing vanadium is added into leaching tanks, is according to sulfuric acid and the mass ratio of calcining containing vanadium
0.044:1, it is 98% concentrated sulfuric acid that mass fraction is added into leaching tanks, under normal temperature conditions leaching 2h, in reaction process
The final ph for controlling slurries is 2.0~2.5.V containing vanadium leachate is obtained by filtration2O5: 5.92g/L and intermediate slag；
(4) intermediate slag is washed twice with detergent (liquid and water after tower) and filtered, clean intermediate slag dosage of scour every time
It is 1.2 times of intermediate slag amount, respectively obtains primary wash liquor, secondary cleaning water and tailings；
(5) 8h will be stood in the obtained thermostat for being placed in 5 DEG C containing vanadium leachate, through being separated by solid-liquid separation available potassium alum
With liquid before tower；
(6) liquid before obtained tower is directly passed through ion exchange resin JD501 to be purified and be enriched with, obtains loaded resin
With liquid after tower；
(7) it uses concentration to desorb loaded resin for 10% NaOH solution, obtains stripping liquid (V2O5: 92.3g/L, pH value 7
~8), direct precipitation prepares AMV；
(8) using concentration to wash resin tower to the pH value that resin tower is discharged for 5% sulfuric acid solution again is 2.0~2.5, with
Standby next time uses.
Wherein the testing result of liquid and stripping liquid is as shown in table 8 after acquired leachate, primary wash liquor, secondary cleaning water, tower,
The ammonium metavanadate testing result of preparation is as shown in table 9.
The testing result of liquid and stripping liquid after 8 leachate of table, primary wash liquor, secondary cleaning water, tower
| Title | V2O5(g/L) | K(g/L) | Na(g/L) | Fe(g/L) | Al(g/L) | Mo(g/L) | Cr(g/L) | Mn(g/L) | Ca(g/L) | Mg(g/L) |
| Leachate | 5.92 | 0.6087 | 1.1430 | 0.9433 | 4.9690 | 0.0178 | 0.0065 | 0.0588 | 0.5421 | 2.0390 |
| Primary wash liquor | 1.870 | 0.5373 | 1.0790 | 0.7661 | 4.4370 | 0.0051 | 0.0054 | 0.0503 | 0.5083 | 1.7890 |
| Secondary cleaning water | 0.066 | 0.1104 | 0.3477 | 0.0251 | 0.3461 | 0.0003 | 0.0003 | 0.0049 | 0.4326 | 0.2161 |
| Liquid after tower | 0.13 | 0.5630 | 1.0780 | 0.8201 | 4.7340 | 0.0003 | 0.0058 | 0.0545 | 0.5861 | 1.8214 |
| Stripping liquid | 92.3 | 0.0320 | 58.2620 | 0.0018 | 0.0132 | 0.2212 | 0.0000 | 0.0000 | 0.0066 | 0.0086 |
9 ammonium metavanadate testing result of table
| Title | V2O5 (%) | K (%) | Na (%) | Fe (%) | Al (%) | Mo (%) | Cr (%) | Mn (%) | Ca (%) | Mg (%) |
| AMV | 76.71 | 0.0020 | 0.0130 | 0.0011 | 0.0028 | 0.0034 | 0.0000 | 0.0000 | 0.0044 | 0.0003 |
V2O5Yield: 90.24%, AMV impurity are controllable.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of method that extracting vanadium from stone coal prepares ammonium metavanadate, which comprises the following steps:
Step 1 mixes bone coal miberal powder, high-carbon powder containing vanadium raw materials and conch meal, and water is added to be granulated to obtain pellet containing vanadium；
Step 2 will contain vanadium pellet 4~36h of constant temperature calcining at 550~950 DEG C and must contain vanadium roasting material；
Step 3, will contain vanadium roasting abrasive lapping must contain vanadium calcining, calcining containing vanadium is leached, leaching slurry is obtained by filtration and is contained
Vanadium leachate and intermediate slag；
Step 4 washs intermediate slag using detergent twice, and primary wash liquor, secondary cleaning water and tailings is obtained by filtration；
Step 5, will be placed in containing vanadium leachate in 0~10 DEG C of thermostat stand 8~for 24 hours, through be separated by solid-liquid separation obtain potassium alum and
Liquid before tower；
Liquid before tower is purified and is enriched with by ion exchange resin by step 6, obtains liquid after loaded resin and tower；
Step 7 desorbs loaded resin using NaOH solution, and ammonium metavanadate is prepared in stripping liquid precipitation.
2. the method that extracting vanadium from stone coal prepares ammonium metavanadate according to claim 1, which is characterized in that the high-carbon contains vanadium raw materials
For one of oil shale mine containing vanadium, the flying dust of oil containing scherbinaite and vanadium tar sand or a variety of mixing.
3. the method that extracting vanadium from stone coal according to claim 1 or claim 2 prepares ammonium metavanadate, which is characterized in that the bone coal miberal powder,
The mass ratio of high-carbon powder containing vanadium raw materials and conch meal is 1:0.01~1.0:0.01~0.50.
4. the method that extracting vanadium from stone coal prepares ammonium metavanadate according to claim 4, which is characterized in that stone coal mine described in step 1
The solid-to-liquid ratio g:mL of powder, the mixture of high-carbon powder containing vanadium raw materials and conch meal and water be 2.5~5:1, pellet partial size be 10~
15mm。
5. the method that extracting vanadium from stone coal prepares ammonium metavanadate according to claim 1, which is characterized in that leached described in step 3: will
Leaching agent is added in leaching tanks, is 1.2~3.0:1 according to liquid-solid ratio, calcining containing vanadium is added into leaching tanks, according to sulfuric acid and
The mass ratio of calcining containing vanadium is 0.01~0.1:1, and it is 92~98% concentrated sulfuric acids that mass fraction is added into leaching tanks, in normal temperature condition
2~4h of lower leaching, the final ph that slurries are controlled in reaction process is 1.5~3.0.
6. the method that extracting vanadium from stone coal prepares ammonium metavanadate according to claim 5, which is characterized in that pH adjusting method is as follows:
PH value adds sulfuric acid, pH higher than limit value and adds calcining containing vanadium lower than limit value.
7. the method that extracting vanadium from stone coal prepares ammonium metavanadate according to claim 1, which is characterized in that in washing described in step 4
Between slag: the dosage for cleaning detergent during intermediate slag every time is 0.3~2.0 times of intermediate slag amount.
8. according to claim 1 or 4 extracting vanadium from stone coal method for preparing ammonium metavanadate, which is characterized in that ion described in step 6
It is one or more in Success 996, D296, D314, D301, D201, D202,201 × 7, JD404 and JD501 that exchange, which is set,.
9. according to claim 1 or 4 extracting vanadium from stone coal method for preparing ammonium metavanadate, which is characterized in that NaOH described in step 7
Solution concentration is 4~10%wt.
10. according to claim 1 or 4 extracting vanadium from stone coal method for preparing ammonium metavanadate, which is characterized in that step 7 is using dense
It is 1.5~3.0 that the sulfuric acid solution that degree is 3~5%wt, which washs resin tower to the pH value that resin tower is discharged,.
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