CN1059762A - The novel process of V 2 O 5 production by chloric acid chlorination method - Google Patents

Abstract

The novel process of V 2 O 5 production by chloric acid chlorination method.The present invention utilizes aqueous hydrochloric acid to feed chlorine and changes the vanadium in the vanadium slag over to solution, adds alkali again and makes vanadium ion generate the vanadium hydroxide precipitation, thereby make V ₂O ₅Recovery rate reach more than 96%.It has solved the difficult problem of impurity such as removing silicon, calcium, magnesium from vanadium raw materials, makes process for extracting vanadium produce the major transformation that updates.

Description

The novel process of V 2 O 5 production by chloric acid chlorination method

The invention belongs to the extracting method of the compound of vanadium.

Known to the applicant, the technique for producing vanadium pentoxide of widespread usage is the Wet-smelting method of vanadium slag through the oxidation sodium roasting both at home and abroad at present.That is: vanadium slag → broken ball milling magnetic separation → oxidation sodium roasting → water logging → purification and impurity removal → many vanadium ammonium precipitation → oven dry → deamination oxidation → finished product.Contain the vanadium rate in order to improve in the raw material, the vanadium slag that often blew before steel-making makes the vanadium rate that contains of raw material be enriched to 10-20% from 1%.But because SiO ₂Can not thoroughly remove with the compound of calcium, the recovery rate of vanadium is still not high, and general iron and steel enterprise's recovery rate is less than 70%, and best in the world recovery rate is 92%.

Want to have breakthrough on process for extracting vanadium, obtain high recovery rate high benefit, complicated current technology is become simply, key issue is how the SiO that is present in a large number in the vanadium raw materials ₂, CaO, MgO etc. remove, this is the brainstorm project of listing China Ministry of Metallurgical Industry the enforcement period of the seventh five-year plan.The present invention has successfully solved this difficult problem.

The present invention is achieved in that vanadium raw materials (containing the high silicon steel slag of high calcium, coal gangue, vanadium slag, inferior vanadium slag of vanadium etc.) and admixes aqueous solution of hydrochloric acid after levigate, in reaction tower, carry out chemical reaction (being called for short the acidleach chlorination reaction), make the vanadium in the raw material all change acidic solution over to ionic species with the chlorine that feeds.Use the filtering separation method then and remove a large amount of SiO ₂With other materials (as insoluble substances such as C in the coal gangue or intermediate product FeOCl) that do not participate in reacting on a small quantity.Again with acid dip solution NH ₃H ₂O or NaOH, Ca(OH) ₂, Na ₂CO ₃Neutralize, make vanadium ion and OH ^-Effect generates V(OH) ₃↓, V(OH) ₄↓ precipitation.Here the pH value that needs strict control solution is between 6.5～.07, otherwise Ca ²⁺, Mg ²⁺Under the situation of PH＞7, also can generate Ca(OH) ₂, Mg(OH) ₂Precipitation.With the filtering separation method insoluble vanadium hydroxide is separated again at last, promptly got thick vanadium product.This thick vanadium can be used as finished product and sells iron and steel enterprise and smelt the high vanadium pig iron, also can be with conventional oxidation sodium roasting method (being commonly called as pyrogenic process) or with " oxidation alkali solution technique " (being commonly called as water law) further processing high-purity high-quality Vanadium Pentoxide in FLAKES.Utilize the vanadium extraction of this novel process, V ₂O ₅Recovery rate can reach more than 96%.

This novel process Production Flow Chart signal as figure:

Compare with existing process for extracting vanadium, this novel process has following advantage: 1, this novel process vanadium slag that need not blow, can utilize the direct vanadium extraction of steel-making refuse-slag, and not only reduce the vanadium extraction cost greatly, simultaneously can improve iron and steel output, can the say so major reform of update of process for extracting vanadium of this law.2, this novel process is not only applicable to the raw material-vanadium slag of the oxidation sodium roasting method vanadium extraction of present widespread use, but also is applicable to the raw material such as slag, coal gangue, vanadium slag, inferior vanadium slag of high silicon high calcium, the source of having widened vanadium raw materials greatly.3, this law step is simple, and facility investment is few, has saved and has invested huge roasting kiln or vertical multiple hearth furnace.With 40 tons of V of current methods investment monthly output ₂O ₅Expense be 1600～1,700 ten thousand yuan, and with 4,000,000 yuan of the expense deficiencies of 40 tons of this novel process investment monthly outputs.4, the recovery rate of current methods coal gangue is 35～40%, and the recovery rate of this novel process coal gangue can reach 90%.Is 55～75% with current methods from the recovery rate of Leaching of Vanadium from Vanadium slag, adopts this novel process vanadium extraction recovery rate from vanadium slag to reach more than 96%.5, adopt this novel process not have waste substantially, intermediate product SiO ₂Can make road-making material, filtered liquid can be used H ₂SO ₄Displace HCl and reuse CaSO ₄System cement or sulfuric acid, residue CaO makes material of construction, but iron contamination production red iron oxide, Mn impurity can be made the additive of polynary fertilizer ... no toxic and harmful and dust produce in the production process, and is low in the pollution of the environment.

Produce embodiment for one below: aqueous solution of hydrochloric acid with being pumped into (5 meters of reaction tower heights penetrate pressure 0.5kg) in the tower, is adjusted solution with soft water and made PH=2, will contain V again ₂O ₅Be that 6 tons of (solid-to-liquid ratio is 1: 2) liftings of 4.8% slag (flush slags of Ma Gang company three steel) are gone in the reaction tower, the reinforced liquid adding hole of cat head is built.Cat head has an outlet pipe to feed gas trap interior (returning application in order to absorb sour gas).Open the chlorine valve, adjust air feed and press 0.6kg, violent chemical reaction takes place in the tower in this moment, and temperature is controlled at 60～70 ℃, and reaction was kept 4～8 hours.After treating that substance reaction fully in the tower, be chilled to room temperature, open the tower bottom valve, thing in the tower by filtering basin, is added slag in the water purge column from cat head again.The slag that filters out is most of to be SiO ₂, can make road-making material.The logical ammoniacal liquor of leach liquor in settling tank stirs again, and control pH value 6.5～7.0 bleeds off the settling tank supernatant liquid, with lower floor's slurries suction drier, and dehydration, oven dry.The product that obtains be thick barium [V(OH) ₃, V(OH) ₄Deng] weight is 0.598 ton.Through sodium oxide roasting or the molten further refinement of alkali oxide, can get high-purity high-quality V again ₂O ₅0.281 ton, recovery rate is 97.43%.

Claims (1)

1, a kind of novel process of extracting Vanadium Pentoxide in FLAKES from raw materials such as coal gangue or v-bearing steel slag is characterized in that earlier aqueous hydrochloric acid being mixed and stirred vanadium raw materials and feeds chlorine react insoluble SlO in the chlorination tower ₂Deng being separated with the various vanadium ions that enter solution, calcium ion etc.; And then in leach liquor, add alkali lye [NH ₃H ₂O or Na ₂CO ₃, Ca (OH) ₂, NaOH etc.] the control pH value is 6.5～7, vanadium ion generates insoluble precipitation of hydroxide, filters and separates out thick vanadium (vanadium hydroxide), uses oxidation sodium roasting method or oxidation alkali solution technique again, further processing can get high-quality V ₂O ₅Its principles of chemistry are:

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