CN104195346A - Clean process method for efficiently extracting chromium in extracted vanadium tailings - Google Patents
Clean process method for efficiently extracting chromium in extracted vanadium tailings Download PDFInfo
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Abstract
The invention discloses a clean process method for efficiently extracting chromium in extracted vanadium tailings. For the extracted vanadium tailings, a silicon fixing agent is added while silicon is leached with low-concentration sodium hydroxide; the silicon is converted into an inert compound in the alkaline leaching and chromium extracting process; the inert compound is subjected to alkaline leaching and chromium extracting to obtain sodium chromate alkali solution with lower silicon content and iron-enriched tailings, so that high-efficiency extraction of the chromium in the extracted vanadium tailings and comprehensive utilization of valuable components are realized. According to the clean process method disclosed by the invention, the high-efficiency extraction of the chromium in the extracted vanadium tailings can be realized, the extraction rate of the chromium is larger than 85 percent, and the content of the silicon in the obtained sodium chromate alkali solution is lower.
Description
Technical field
The invention belongs to hydrometallurgy and chromium chemical technology field, particularly, the present invention relates to a kind of from tailings in vanadium extraction the clean process method of high efficiency extraction chromium.
Background technology
Vanadium and chromium are the important strategic resources of country, and vanadium product and the position of chromium product in national economy are irreplaceable.By smelting into molten iron containing vanadium minerals (as vanadium titano-magnetite), reoxidizing the higher vanadium slag of content of vanadium obtaining that blows is the main raw material of the current vanadium extraction of China.Different larger containing the blow vanadium slag component difference that obtains of vanadium minerals, but all can accompany simultaneously and deposit the valuable metal such as chromium, iron component with vanadium, very high utilization of resources value there is.After several different methods is extracted the vanadium in vanadium slag, obtain the tailings in vanadium extraction of the metals such as iron content, silicon, chromium.Cr0～2wt% in gained tailings after common Leaching of Vanadium from Vanadium slag, Si4～16wt%, TFe25～30wt% also has the metals such as a small amount of Al, Ca, Mg simultaneously.Smelt after vanadium extraction Cr4～15wt% in gained tailings taking the vanadium titano-magnetite in the red lattice of Flos Bombacis Malabarici area as raw material, Si6～15wt%, TFe15～37wt%.Add that the tailings in vanadium extraction scale of construction is huge, in exploitation tailings in vanadium extraction, the high efficiency extraction utilization of chromium, significant.
The method that current recovery valuable element chromium is prepared chromic salts product mainly comprises roasting method and the large class of liquid phase oxidation two.Owing to containing a certain amount of silicon in tailings in vanadium extraction simultaneously, directly adopt liquid phase oxidation to carry chromium, silicon also consumes alkali, and the leaching rate of chromium under identical alkali concn is significantly reduced.Carry chromium as CN 101817561B adopts liquid phase oxidation, with the leaching of 30wt%～80wt% sodium hydroxide solution, leach liquor adds cleaner removal of impurities, and this leach liquor alkali concn is high, and the decreasing ratio of silicon is lower, affects chromic salts quality product.Therefore, adopt liquid-phase oxidation vanadium to carry removing of the front silicon of chromium significant.
When tailings in vanadium extraction leaches with low-concentration sodium hydroxide, chromium can not enter liquid phase, and silicon can enter liquid phase, thereby can reach the object of pre-desiliconizing.By after liquid-solid alkali immersion liquid separation, then add silicon fixing agent in filtrate, when after desiliconization, filter residue is carried chromium with liquid phase oxidation again, the leaching yield of chromium can increase substantially.If CN101591023A and CN102249253A are aluminous fly-ash desiliconization, employing be exactly that first alkali soaks desiliconization, then reinforce silicea and carry out the two-step approach of solid silicon.But this method needs the liquid-solid separation of two steps, and obtains calcium silicate hydrate, need to process flow process complexity again.
The present invention adopts the leaching of silicon and is fixedly combined into a step, when leaching silicon with low-concentration sodium hydroxide, tailings in vanadium extraction adds silicon fixing agent, silicon is converted into the inert compound in alkali lixiviate chromium process, not only eliminate the impact of carrying chromium process silicon, improved the extraction yield of chromium, and flow process is easier.
Summary of the invention
For overcoming the defect of prior art, the object of the present invention is to provide the clean process method of chromium in a kind of high efficiency extraction tailings in vanadium extraction, can realize the high efficiency extraction of chromium in tailings in vanadium extraction.
For reaching above-mentioned purpose, the present invention adopts following technical scheme:
A clean process method that extracts chromium in tailings in vanadium extraction, comprises the following steps:
(1) by tailings in vanadium extraction and sodium hydroxide solution Hybrid Heating, add the solid silicon of silicon fixing agent simultaneously, after liquid-solid separation, obtain immersion liquid and desiliconization slag containing sodium hydroxide;
(2) step (1) gained desiliconization slag mixes with sodium hydroxide solution, and then alkali lixiviate chromium under oxygenant effect, obtains alkali immersion liquid and alkali and soak slag after liquid-solid separation;
(3) step (2) gained alkali soak slag mix with alcohol and continue stir carry out alcohol wash dealkalize, after liquid-solid separation, obtain alcohol washing lotion and alkali and soak slag;
(4) step (3) gained alkali soaks slag and carries out the water-soluble chromium of carrying, and obtains chromium acid sodium alkaline liquid and slag after liquid-solid separation;
(5) step (4) gained slag obtains carrying chromium tailings after countercurrent washing;
(6) treatment step (4) gained chromium acid sodium alkaline liquid makes the female product of sodium dichromate 99 (sodium dichromate).
Tailings in vanadium extraction adds silicon fixing agent when leaching silicon with low-concentration sodium hydroxide, silicon is converted into the inert compound in alkali lixiviate chromium process, obtain through alkali lixiviate chromium chromium acid sodium alkaline liquid and the Fu Tie tailings that silicone content is lower again, thereby realize the high efficiency extraction of chromium and the comprehensive utilization of valuable component in tailings in vanadium extraction.
As optimal technical scheme, method of the present invention, the described tailings in vanadium extraction of step (1) is through ball milling or fragmentation.
Preferably, the granularity of described tailings in vanadium extraction is 100～250 orders, is preferably 200～250 orders.
Preferably, the concentration of described sodium hydroxide solution is 10～20wt%, is preferably 10～15wt%.
Preferably, the mass volume ratio of described tailings in vanadium extraction and sodium hydroxide solution (g:mL) is 1:8～1:20g/mL, is preferably 1:15～1:20g/mL.
Preferably, described silicon fixing agent is unslaked lime and/or by the unslaked lime milk of lime making of pulling an oar.
Preferably, the addition of described silicon fixing agent is make Ca wherein and contain SiO in chrome alum slag
2mol ratio be 0.7:1～1.5:1, be preferably 1:1～1.2:1.
Preferably, in described milk of lime, the mass ratio of unslaked lime CaO and water is 1:4～1:6.
Preferably, the temperature of described heating is 90～150 DEG C, is preferably 90～100 DEG C.
Preferably, the reaction times of described solid silicon is 0.5～4h, is preferably 1～2h.
Preferably, the described immersion liquid containing sodium hydroxide is returned for preparation steps (1) sodium hydroxide solution.
The solid silicea that method of the present invention is selected can make silicon form Calucium Silicate powder compounds, this compounds is inert component in alkali lixiviate chromium process, avoid the shortcomings such as the alkaline consumption that brings because silicone content is high in direct alkali lixiviate chromium process is large, amount of liquid phase is many, chromium acid sodium alkaline liquid is siliceous, also helped the extraction yield that improves chromium.By the leaching of silicon with fixedly be combined into a step, when tailings in vanadium extraction leaches with low-concentration sodium hydroxide, add silicon fixing agent, flow process is shorter, and can regulate molecular balance, reduces the silicon concentration in solution, reaches and better consolidates silicon effect.
As optimal technical scheme, method of the present invention, described in step (2), alkali lixiviate chromium carries out in closed reactor.
Preferably, the concentration of described sodium hydroxide solution is 30～60wt%, is preferably 30～50wt%.
Preferably, the mass volume ratio of described desiliconization slag and sodium hydroxide solution (g:mL) is 1:10～1:20g/mL, is preferably 1:10～1:15g/mL.
Preferably, the temperature of reaction of described alkali lixiviate chromium is 240～300 DEG C, is preferably 240～260 DEG C.
Preferably, the reaction times of described alkali lixiviate chromium is 2～6h, is preferably 2～4h.
Preferably, described oxygenant is one or more the mixture in air, oxygen, oxygen-rich air, ozone, clorox, potassium permanganate, potassium pyrosulfate.
Preferably, described alkali immersion liquid and step (3) alcohol washing lotion rectifying gained alkali lye return to the sodium hydroxide solution required for preparation steps (2).
As optimal technical scheme, method of the present invention, the described alcohol of step (3) is the mixture of alcohol or alcohol and water, is preferably methyl alcohol and/or ethanol, or the mixture of methyl alcohol and/or ethanol and water.
Preferably, the mass volume ratio (g:mL) that described alkali soaks slag and alcohol is 1:2～1:6g/mL, is preferably 1:2～1:3g/mL.
Preferably, the temperature of described alcohol wash dealkalize is 30～60 DEG C, is preferably 30～40 DEG C; Time is 0.5～3h, is preferably 0.5～1h.
Preferably, described alcohol washing lotion is carried alkali through rectifying.
Preferably, to put forward alkali process be normal pressure or rectification under vacuum in described rectifying.
Preferably, the temperature of described rectifying is 65～85 DEG C, is preferably 65～70 DEG C.
Preferably, recycle being back to step (3) after the alcohol component condensation steaming.
As optimal technical scheme, method of the present invention, described in step (4), the water-soluble liquid-solid ratio of carrying chromium is 3:1～6:1mL/g, is preferably 3:1～4:1mL/g.
Preferably, the described water-soluble temperature of carrying chromium is 20～95 DEG C, is preferably 60～80 DEG C; Time is 20min～1h, is preferably 20～30min.
As optimal technical scheme, method of the present invention, the described countercurrent washing of step (5) is multi-stage countercurrent washing, is preferably 2～5 grades, more preferably 3～4 grades.
Preferably, the liquid-solid ratio of described washing is 3:1～6:1mL/g, is preferably 3:1～4:1mL/g.
Preferably, the temperature of described washing is 20～90 DEG C, is preferably 40～80 DEG C.
Preferably, gained washings returns to step (4) and carries out the water-soluble chromium of carrying.
As optimal technical scheme, method of the present invention, step is treated to described in (6): step (4) gained chromium acid sodium alkaline liquid through in and after the product step of converting such as removal of impurities, acidifying, transpiration cooling crystallization, make the female product of sodium dichromate 99 (sodium dichromate).
Chromium after the solid silicon of method selection liquid phase oxidation extraction of the present invention in slag, obtains chromium acid sodium alkaline liquid and Fu Tie tailings that silicone content is lower.Compared with prior art scheme, the present invention has following beneficial effect:
(1) resource utilization is high: the extraction yield of chromium of the present invention is greater than 85%, and sodium hydroxide alkalescence liquid recycles, and rich iron tailings is easy to follow-up comprehensive utilization;
(2) chromium acid sodium alkaline liquid silicone content is lower;
(3) short, the cleanliness without any pollution of flow process: waste water is realized near zero release, and finishing slag is realized resource utilization, produces cleanliness without any pollution.
Brief description of the drawings
Fig. 1 is process flow sheet of the present invention.
Embodiment
For the present invention is described better, be convenient to understand technical scheme of the present invention, below the present invention is described in more detail.But following embodiment is only simple and easy example of the present invention, does not represent or limit the scope of the present invention, and protection scope of the present invention is as the criterion with claims.Embodiment of the present invention are as follows:
A clean process method that extracts chromium in tailings in vanadium extraction, comprises the following steps:
(1) ball milling or broken tailings in vanadium extraction and 10～20wt% sodium hydroxide solution are mixed and heated to 90～150 DEG C taking the mass volume ratio of tailings in vanadium extraction and sodium hydroxide solution as 1:8～1:20g/mL, add the solid pasc reaction of silicon fixing agent is 0.5～4h simultaneously, after liquid-solid separation, obtain immersion liquid and desiliconization slag containing sodium hydroxide, the addition of described silicon fixing agent is make Ca wherein and contain SiO in chrome alum slag
2mol ratio be 0.7:1～1.5:1, return for preparing sodium hydroxide solution containing the immersion liquid of sodium hydroxide;
(2) step (1) gained desiliconization slag and 30～60wt% sodium hydroxide solution mix taking the mass volume ratio of desiliconization slag and sodium hydroxide solution as 1:10～1:20g/mL, then in closed reactor under oxygenant effect 240～300 DEG C of alkali lixiviate chromium 2h～6h, after liquid-solid separation, obtain alkali immersion liquid and alkali and soak slag, alkali immersion liquid and step (3) alcohol washing lotion rectifying gained alkali lye returns for the required sodium hydroxide solution of preparation steps (2);
(3) step (2) gained alkali soak slag and alcohol soaks slag and alcohol mass volume ratio taking alkali as 1:2～1:6g/mL mix and continue to stir 30～60 DEG C at carry out alcohol wash dealkalize 0.5～3h, after liquid-solid separation, obtain alcohol washing lotion and alkali and soak slag, alcohol washing lotion is carried alkali through rectifying;
(4) step (3) gained alkali soaks at 20～95 DEG C of slags and carries out the water-soluble chromium 20min～1h that carries, and obtains chromium acid sodium alkaline liquid and slag after liquid-solid separation, and the water-soluble liquid-solid ratio of carrying chromium is 3:1～6:1mL/g;
(5) step (4) gained slag obtains carrying chromium tailings after multi-stage countercurrent washing, and the liquid-solid ratio of washing is 3:1～6:1mL/g, and the temperature of washing is 20～90 DEG C, and gained washings returns to step (4) and carries out the water-soluble chromium of carrying;
(6) step (4) gained chromium acid sodium alkaline liquid through in and after removal of impurities, acidifying, transpiration cooling crystallisation step, make the female product of sodium dichromate 99.
Typical but non-limiting embodiment of the present invention is as follows:
Embodiment 1
The present embodiment uses tailings in vanadium extraction containing Cr1.35wt%, Si7.03wt%, TFe26.30wt%.
(1) 50g tailings in vanadium extraction is carried out to ball-milling processing, then mix with the sodium hydroxide solution of 10wt%, slag alkali mass volume ratio is 1:20, is heated to 90 DEG C; Press Ca and contain SiO in chrome alum slag
2mol ratio be 0.7:1 preparing quick lime, and stir and make milk of lime as 1:4 adds water by unslaked lime (taking CaO) and the mass ratio of water, milk of lime is joined to stirring reaction 4h in solution, carry out liquid-solid separation, obtain immersion liquid and desiliconization slag containing sodium hydroxide; Immersion liquid containing sodium hydroxide is returned for preparing sodium hydroxide solution;
(2) sodium hydroxide solution of preparation 30wt%, it is joined in reactor and mixed with desiliconization slag in step (1), slag alkali mass ratio is 1:20, be heated to 300 DEG C, use oxygen as oxygenant, liquid phase alkali lixiviate chromium, reaction 2h, liquid-solid separation, obtains chromium acid sodium alkaline liquid and alkali soaks slag;
(3) alkali soaks slag with methanol mixed is carried out alcohol wash dealkalize in step (2), and slag alcohol mass volume ratio is 1:2, is heated to 40 DEG C, reacts 1h, carries out liquid-solid separation, obtains alcohol washing lotion and alkali and soaks slag;
(4) alcohol washing lotion is carried out rectifying and is carried alkali under normal pressure in step (3), and rectification temperature is 65 DEG C, is back to step (3) and recycles after the alcohol component condensation steaming;
(5) alkali soaks slag and carries out the water-soluble chromium of carrying at 95 DEG C in step (3), and liquid-solid ratio is 6:1mL/g, and the time is 20min, and liquid-solid separation obtains chromium acid sodium alkaline liquid and slag; Slag obtains rich iron tailings after 2 grades of countercurrent washings under 20 DEG C, liquid-solid ratio 6:1mL/g condition, and washings returns for the water-soluble chromium of carrying; Chromium acid sodium alkaline liquid through in and after the product step of converting such as removal of impurities, acidifying, transpiration cooling crystallization, make the female product of sodium dichromate 99 (sodium dichromate).
Can obtain after testing, the extraction yield of chromium is 87%, and in chromium acid sodium alkaline liquid, silicone content is 0.05g/L.
Embodiment 2
The present embodiment uses tailings in vanadium extraction containing Cr5.34wt%, Si12.74wt%, TFe18.49wt%.
(1) 50g tailings in vanadium extraction is carried out to ball-milling processing, then mix with the sodium hydroxide solution of 12wt%, slag alkali mass ratio is 1:18, is heated to 100 DEG C; Press Ca and contain SiO in chrome alum slag
2mol ratio be 0.9:1 preparing quick lime, and stir and make milk of lime as 1:4.5 adds water by unslaked lime (taking CaO) and the mass ratio of water, milk of lime is joined to stirring reaction 3h in solution, carry out liquid-solid separation, obtain immersion liquid and desiliconization slag containing sodium hydroxide; Immersion liquid containing sodium hydroxide is returned for preparing sodium hydroxide solution;
(2) sodium hydroxide solution of preparation 40wt%, it is joined in reactor and mixed with desiliconization slag in step (1), slag alkali mass ratio is 1:18, be heated to 280 DEG C, use oxygen as oxygenant, liquid phase alkali lixiviate chromium, reaction 4h, liquid-solid separation, obtains chromium acid sodium alkaline liquid and alkali soaks slag;
(3) alkali soaks slag and mixes with ethanol and carry out alcohol wash dealkalize in step (2), and slag alcohol mass volume ratio is 1:3, is heated to 60 DEG C, reacts 0.5h, carries out liquid-solid separation, obtains alcohol washing lotion and alkali and soaks slag;
(4) alcohol washing lotion is carried out rectifying and is carried alkali under normal pressure in step (3), and rectification temperature is 70 DEG C, is back to step (3) and recycles after the alcohol component condensation steaming;
(5) alkali soaks slag and carries out the water-soluble chromium of carrying at 85 DEG C in step (3), and liquid-solid ratio is 5:1mL/g, and the time is 30min, and liquid-solid separation obtains chromium acid sodium alkaline liquid and slag; Slag obtains rich iron tailings after 4 grades of countercurrent washings under 80 DEG C, liquid-solid ratio 3:1mL/g condition, and washings returns for the water-soluble chromium of carrying; Chromium acid sodium alkaline liquid through in and after the product step of converting such as removal of impurities, acidifying, transpiration cooling crystallization, make the female product of sodium dichromate 99 (sodium dichromate).
Can obtain after testing, the extraction yield of chromium is 90%, and in chromium acid sodium alkaline liquid, silicone content is 0.09g/L.
Embodiment 3
The present embodiment uses tailings in vanadium extraction containing Cr5.34wt%, Si12.74wt%, TFe18.49wt%.
(1) 50g tailings in vanadium extraction is carried out to ball-milling processing, then mix with the sodium hydroxide solution of 14wt%, slag alkali mass ratio is 1:16, is heated to 110 DEG C; Press Ca and contain SiO in chrome alum slag
2mol ratio be 1:1 preparing quick lime, and stir and make milk of lime as 1:5 adds water by unslaked lime (taking CaO) and the mass ratio of water, milk of lime is joined to stirring reaction 2h in solution, carry out liquid-solid separation, obtain immersion liquid and desiliconization slag containing sodium hydroxide; Immersion liquid containing sodium hydroxide is returned for preparing sodium hydroxide solution;
(2) sodium hydroxide solution of preparation 50wt%, it is joined in reactor and mixed with desiliconization slag in step (1), slag alkali mass ratio is 1:10, be heated to 250 DEG C, use oxygen as oxygenant, liquid phase alkali lixiviate chromium, reaction 5h, liquid-solid separation, obtains chromium acid sodium alkaline liquid and alkali soaks slag;
(3) alkali soaks slag with methanol mixed is carried out alcohol wash dealkalize in step (2), and slag alcohol mass volume ratio is 1:4, is heated to 30 DEG C, reacts 3h, carries out liquid-solid separation, obtains alcohol washing lotion and alkali and soaks slag;
(4) alcohol washing lotion is carried out rectifying and is carried alkali under normal pressure in step (3), and rectification temperature is 75 DEG C, is back to step (3) and recycles after the alcohol component condensation steaming;
(5) alkali soaks slag and carries out the water-soluble chromium of carrying at 20 DEG C in step (3), and liquid-solid ratio is 4:1mL/g, and the time is 40min, and liquid-solid separation obtains chromium acid sodium alkaline liquid and slag; Slag obtains rich iron tailings after 3 grades of countercurrent washings under 20 DEG C, liquid-solid ratio 6:1mL/g condition, and washings returns for the water-soluble chromium of carrying; Chromium acid sodium alkaline liquid through in and after the product step of converting such as removal of impurities, acidifying, transpiration cooling crystallization, make the female product of sodium dichromate 99 (sodium dichromate).
Can obtain after testing, the extraction yield of chromium is 92.5%, and in chromium acid sodium alkaline liquid, silicone content is 0.13g/L.
Embodiment 4
The present embodiment uses tailings in vanadium extraction containing Cr1.35wt%, Si7.03wt%, TFe26.30wt%.
(1) 50g tailings in vanadium extraction is carried out to ball-milling processing, then mix with the sodium hydroxide solution of 16wt%, slag alkali mass ratio is 1:14, is heated to 120 DEG C; Press Ca and contain SiO in chrome alum slag
2mol ratio be 1.2:1 preparing quick lime, and stir and make milk of lime as 1:5.5 adds water by unslaked lime (taking CaO) and the mass ratio of water, milk of lime is joined to stirring reaction 2h in solution, carry out liquid-solid separation, obtain immersion liquid and desiliconization slag containing sodium hydroxide; Immersion liquid containing sodium hydroxide is returned for preparing sodium hydroxide solution;
(2) sodium hydroxide solution of preparation 55wt%, it is joined in reactor and mixed with desiliconization slag in step (1), slag alkali mass ratio is 1:14, be heated to 260 DEG C, use oxygen as oxygenant, liquid phase alkali lixiviate chromium, reaction 6h, liquid-solid separation, obtains chromium acid sodium alkaline liquid and alkali soaks slag;
(3) alkali soaks methyl alcohol, the ethanol mixing that slag mixes with 1:1 and carries out alcohol wash dealkalize in step (2), and slag alcohol mass volume ratio is 1:5, is heated to 50 DEG C, reacts 2h, carries out liquid-solid separation, obtains alcohol washing lotion and alkali and soaks slag;
(4) alcohol washing lotion is carried out rectifying and is carried alkali under normal pressure in step (3), and rectification temperature is 80 DEG C, is back to step (3) and recycles after the alcohol component condensation steaming;
(5) alkali soaks slag and carries out the water-soluble chromium of carrying at 65 DEG C in step (3), and liquid-solid ratio is 5:1mL/g, and the time is 1h, and liquid-solid separation obtains chromium acid sodium alkaline liquid and slag; Slag obtains rich iron tailings after 5 grades of countercurrent washings under 90 DEG C, liquid-solid ratio 3:1mL/g condition, and washings returns for the water-soluble chromium of carrying; Chromium acid sodium alkaline liquid through in and after the product step of converting such as removal of impurities, acidifying, transpiration cooling crystallization, make the female product of sodium dichromate 99 (sodium dichromate).
Can obtain after testing, the extraction yield of chromium is 95.7%, and in chromium acid sodium alkaline liquid, silicone content is 0.16g/L.
Embodiment 5
The present embodiment uses tailings in vanadium extraction containing Cr1.35wt%, Si7.03wt%, TFe26.30wt%.
(1) 50g tailings in vanadium extraction is carried out to ball-milling processing, then mix with the sodium hydroxide solution of 18wt%, slag alkali mass ratio is 1:10, is heated to 130 DEG C; Press Ca and contain SiO in chrome alum slag
2mol ratio be 1.4:1 preparing quick lime, and stir and make milk of lime as 1:6 adds water by unslaked lime (taking CaO) and the mass ratio of water, milk of lime is joined to stirring reaction 1h in solution, carry out liquid-solid separation, obtain immersion liquid and desiliconization slag containing sodium hydroxide; Immersion liquid containing sodium hydroxide is returned for preparing sodium hydroxide solution;
(2) sodium hydroxide solution of preparation 60wt%, it is joined in reactor and mixed with desiliconization slag in step (1), slag alkali mass ratio is 1:15, be heated to 270 DEG C, use oxygen as oxygenant, liquid phase alkali lixiviate chromium, reaction 3h, liquid-solid separation, obtains chromium acid sodium alkaline liquid and alkali soaks slag;
(3) alkali soaks slag with methanol mixed is carried out alcohol wash dealkalize in step (2), and slag alcohol mass volume ratio is 1:6, is heated to 30 DEG C, reacts 1.5h, carries out liquid-solid separation, obtains alcohol washing lotion and alkali and soaks slag;
(4) alcohol washing lotion is carried out rectifying and is carried alkali under normal pressure in step (3), and rectification temperature is 85 DEG C, is back to step (3) and recycles after the alcohol component condensation steaming;
(5) alkali soaks slag and carries out the water-soluble chromium of carrying at 55 DEG C in step (3), and liquid-solid ratio is 4:1mL/g, and the time is 50min, and liquid-solid separation obtains chromium acid sodium alkaline liquid and slag; Slag obtains rich iron tailings after 3 grades of countercurrent washings under 50 DEG C, liquid-solid ratio 4:1mL/g condition, and washings returns for the water-soluble chromium of carrying; Chromium acid sodium alkaline liquid through in and after the product step of converting such as removal of impurities, acidifying, transpiration cooling crystallization, make the female product of sodium dichromate 99 (sodium dichromate).
Can obtain after testing, the extraction yield of chromium is 94.2%, and in chromium acid sodium alkaline liquid, silicone content is 0.18g/L.
Embodiment 6
The present embodiment uses tailings in vanadium extraction containing Cr5.09wt%, Si14.8wt%, TFe17.28wt%.
(1) 50g tailings in vanadium extraction is carried out to ball-milling processing, then mix with the sodium hydroxide solution of 20wt%, slag alkali mass ratio is 1:8, is heated to 150 DEG C; Press Ca and contain SiO in chrome alum slag
2mol ratio be 1.5:1 preparing quick lime, and stir and make milk of lime as 1:6 adds water by unslaked lime (taking CaO) and the mass ratio of water, milk of lime is joined to stirring reaction 0.5h in solution, carry out liquid-solid separation, obtain immersion liquid and desiliconization slag containing sodium hydroxide; Immersion liquid containing sodium hydroxide is returned for preparing sodium hydroxide solution;
(2) sodium hydroxide solution of preparation 45wt%, it is joined in reactor and mixed with desiliconization slag in step (1), slag alkali mass ratio is 1:15, be heated to 240 DEG C, use oxygen as oxygenant, liquid phase alkali lixiviate chromium, reaction 3h, liquid-solid separation, obtains chromium acid sodium alkaline liquid and alkali soaks slag;
(3) alkali soaks slag with methanol mixed is carried out alcohol wash dealkalize in step (2), and slag alcohol mass volume ratio is 1:3, is heated to 40 DEG C, reacts 1h, carries out liquid-solid separation, obtains alcohol washing lotion and alkali and soaks slag;
(4) alcohol washing lotion is carried out rectifying and is carried alkali under normal pressure in step (3), and rectification temperature is 70 DEG C, is back to step (3) and recycles after the alcohol component condensation steaming;
(5) alkali soaks slag and carries out the water-soluble chromium of carrying at 60 DEG C in step (3), and liquid-solid ratio is 3:1mL/g, and the time is 45min, and liquid-solid separation obtains chromium acid sodium alkaline liquid and slag; Slag obtains rich iron tailings after 4 grades of countercurrent washings under 70 DEG C, liquid-solid ratio 4:1mL/g condition, and washings returns for the water-soluble chromium of carrying; Chromium acid sodium alkaline liquid through in and after the product step of converting such as removal of impurities, acidifying, transpiration cooling crystallization, make the female product of sodium dichromate 99 (sodium dichromate).
Can obtain after testing, the extraction yield of chromium is 90.6%, and in chromium acid sodium alkaline liquid, silicone content is 0.19g/L.
Can find out from above-described embodiment, the inventive method flow process is simple, and exploitativeness is strong.The extraction yield of chromium is greater than 85%, and in chromium acid sodium alkaline liquid, silicone content is lower than 0.2g/L.
Applicant's statement, the present invention illustrates processing method of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned processing step, does not mean that the present invention must rely on above-mentioned processing step and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, and the selections of the equivalence replacement to the selected raw material of the present invention and the interpolation of ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, also can carry out arbitrary combination between various embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a clean process method that extracts chromium in tailings in vanadium extraction, comprises the following steps:
(1) by tailings in vanadium extraction and sodium hydroxide solution Hybrid Heating, add the solid silicon of silicon fixing agent simultaneously, after liquid-solid separation, obtain immersion liquid and desiliconization slag containing sodium hydroxide;
(2) step (1) gained desiliconization slag mixes with sodium hydroxide solution, and then alkali lixiviate chromium under oxygenant effect, obtains alkali immersion liquid and alkali and soak slag after liquid-solid separation;
(3) step (2) gained alkali soak slag mix with alcohol and continue stir carry out alcohol wash dealkalize, after liquid-solid separation, obtain alcohol washing lotion and alkali and soak slag;
(4) step (3) gained alkali soaks slag and carries out the water-soluble chromium of carrying, and obtains chromium acid sodium alkaline liquid and slag after liquid-solid separation;
(5) step (4) gained slag obtains carrying chromium tailings after countercurrent washing;
(6) treatment step (4) gained chromium acid sodium alkaline liquid makes the female product of sodium dichromate 99.
2. method according to claim 1, is characterized in that, the tailings in vanadium extraction described in step (1) is through ball milling or fragmentation;
Preferably, the granularity of described tailings in vanadium extraction is 100～250 orders, is preferably 200～250 orders;
Preferably, the concentration of described sodium hydroxide solution is 10～20wt%, is preferably 10～15wt%;
Preferably, the mass volume ratio of described tailings in vanadium extraction and sodium hydroxide solution is 1:8～1:20g/mL, is preferably 1:15～1:20g/mL.
3. method according to claim 1, is characterized in that, silicon fixing agent described in step (1) is unslaked lime and/or by the unslaked lime milk of lime making of pulling an oar;
Preferably, in described milk of lime, the mass ratio of unslaked lime CaO and water is 1:4～1:6;
Preferably, the addition of described silicon fixing agent is make Ca wherein and contain SiO in chrome alum slag
2mol ratio be 0.7:1～1.5:1, be preferably 1:1～1.2:1;
Preferably, the temperature of described heating is 90～150 DEG C, is preferably 90～100 DEG C;
Preferably, the reaction times of described solid silicon is 0.5～4h, is preferably 1～2h;
Preferably, the described immersion liquid containing sodium hydroxide is returned for preparation steps (1) sodium hydroxide solution.
4. method according to claim 1, is characterized in that, described in step (2), alkali lixiviate chromium carries out in closed reactor;
Preferably, the concentration of described sodium hydroxide solution is 30～60wt%, is preferably 30～50wt%;
Preferably, the mass volume ratio of described desiliconization slag and sodium hydroxide solution is 1:10～1:20g/mL, is preferably 1:10～1:15g/mL.
5. method according to claim 1, is characterized in that, described in step (2), the temperature of reaction of alkali lixiviate chromium is 240～300 DEG C, is preferably 240～260 DEG C;
Preferably, the reaction times of described alkali lixiviate chromium is 2～6h, is preferably 2～4h;
Preferably, described oxygenant is one or more the mixture in air, oxygen, oxygen-rich air, ozone, clorox, potassium permanganate, potassium pyrosulfate;
Preferably, after described alkali immersion liquid and the rectifying of step (3) alcohol washing lotion, gained alkali lye returns to the sodium hydroxide solution required for preparation steps (2).
6. method according to claim 1, is characterized in that, the alcohol described in step (3) is the mixture of alcohol or alcohol and water, is preferably methyl alcohol and/or ethanol, or the mixture of methyl alcohol and/or ethanol and water;
Preferably, the mass volume ratio that described alkali soaks slag and alcohol is 1:2～1:6g/mL, is preferably 1:2～1:3g/mL;
Preferably, the temperature of described alcohol wash dealkalize is 30～60 DEG C, is preferably 30～40 DEG C; Time is 0.5～3h, is preferably 0.5～1h.
7. method according to claim 1, is characterized in that, described in step (3), alcohol washing lotion is carried alkali through rectifying;
Preferably, to put forward alkali process be normal pressure or rectification under vacuum in described rectifying;
Preferably, the temperature of described rectifying is 65～85 DEG C, is preferably 65～70 DEG C;
Preferably, recycle being back to step (3) after the alcohol component condensation steaming.
8. method according to claim 1, is characterized in that, described in step (4), the water-soluble liquid-solid ratio of carrying chromium is 3:1～6:1mL/g, is preferably 3:1～4:1mL/g;
Preferably, the described water-soluble temperature of carrying chromium is 20～95 DEG C, is preferably 60～80 DEG C; Time is 20min～1h, is preferably 20～30min.
9. method according to claim 1, is characterized in that, countercurrent washing described in step (5) is multi-stage countercurrent washing, is preferably 2～5 grades, more preferably 3～4 grades;
Preferably, the liquid-solid ratio of described washing is 3:1～6:1mL/g, is preferably 3:1～4:1mL/g;
Preferably, the temperature of described washing is 20～90 DEG C, is preferably 40～80 DEG C;
Preferably, gained washings returns to step (4) and carries out the water-soluble chromium of carrying.
10. method according to claim 1, is characterized in that, step is treated to described in (6): step (4) gained chromium acid sodium alkaline liquid through in and after removal of impurities, acidifying, transpiration cooling crystallisation step, make the female product of sodium dichromate 99.
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