CN100465307C

CN100465307C - Stone-like coal gas phase vanadium extracting method

Info

Publication number: CN100465307C
Application number: CNB2007100352585A
Authority: CN
Inventors: 黎吉星
Original assignee: Individual
Current assignee: Individual
Priority date: 2007-06-29
Filing date: 2007-06-29
Publication date: 2009-03-04
Anticipated expiration: 2027-06-29
Also published as: CN101078064A

Abstract

A method to extract vanadium with stone coal gas phase, the technology steps are as following: the stone coal or the stone material prepared with the ore containing alum will be broke, and milled to produce the powder, the size of which is 60-80 eyes, the powder will be delivered into the furnace in fluid bed to degrade at high temperature and be aerified by burning. They will be burned for 8-30 seconds at 900-1250deg.C, and at the same time, will be oxygen aerified by inputting air containing 30-50% oxygen, the vanadic oxide in the material will become burner gas. The burner gas enters the deposition room, and it will be cooled to 500deg.C by heat exchanger, and will be flushed of f by two-stage whirlwind according to dry method. The burner gas after deslagging will enter the electrostatic dust catcher from the deposition room to enrich. The enriched material will be dipped by alkali solution and dipping solution containing alum can be gained. The remained burned gas will enter the two-stage apray tower to make the vanadic oxide in gas phase become spray solution containing vanadic. Vitriol will be added into the two solution containing alum, the raw vanadic oxide will be deposit out by neutralized with acid. This patent can widely take advantage of the stone coal resource with low caloric value and low grade, the reclaim rate is high, and it can save energy, it does not need flux and the cost of it is low, the exhaust of the three wastes, and it is helpful to protect environment.

Description

Stone-like coal gas phase vanadium extracting method

Technical field

The present invention relates to a kind of method of from bone coal, refining Vanadium Pentoxide in FLAKES.

Background technology

Vanadium (V) is V in the periodic table of elements _BFamily's element, antimony (Sb) belongs to V _AElement has similarity on chemical physical property.The fusing point of Vanadium Pentoxide in FLAKES is 658 ℃, and the fusing point of antimonous oxide is 655 ℃, and antimony pyrometallurgical smelting nearly all adopts the method for the heavy antimony of gas phase.Antimony is about 5 * 10 in the earth's crust ^-5%, and vanadium reaches 1.5 * 10 ^-2%, much abundanter than antimony, but very disperse, the rich navajoite of 1% content is difficult to find.Vanadium in mineral deposits such as association titanomagnetite, magnetite, bauxite, uranium ore, phosphorus ore, has the Pan Xi in Sichuan, the Chengde in Hebei, several places such as Ma'an Mountain in Anhui mostly in China's vanadium titano-magnetite, but the stone coal vanadium-containing reserves surpass external navajoite summation.Stone coal vanadium-containing is that 500,000,000 year ancient times in Precambrian bacterium algae biomagnification deposition forms, and mineralogical composition mainly is roscoelite; Charcoal greying or semi-graphited mostly in the bone coal, and calorific value is not high.The bone coal reserves in Hunan Province are very abundant, V ₂O ₅Content is generally 0.2-1.0%, low grade ore in the genus.Industrially acquire a certain degree of difficulty with extracting vanadium from stone coal, the ton product consumes ore up to 200-400 tons.The vanadium titano-magnetite vanadium extraction is salt and an alkali (caustic soda or soda ash) of the vanadium slag after smelting being pulverized back adding 10%, balling-up oven dry back in rotary kiln through 750-850 ℃ of temperature roastings 3 hours, allow vanadium be converted into the sodium metavanadate of solubility, the levigate back of grog cooling of burning till is added the leaching of water multi-stage countercurrent with mother liquor, use acid (H again ₂SO ₄Or HCI) remove impurity, the ammonium meta-vanadate crystal of gained gets the Vanadium Pentoxide in FLAKES product at 500 ℃ of calcining deaminations.

But the solution of sodium metavanadate is spent ion exchange resin also, and methods such as organic solvent extraction are purified.

Extracting vanadium from stone coal has still been continued to use this traditional processing technology basically since the seventies in last century, just a little improvement have been done in the part.There are several significant drawback in this production technique: one, subsidiary material (lyonium salt, alkali) consumption is many, nearly 20 tons of ton product consumption; Two, the heat energy of carbon does not have fine utilization, wastes energy; Three, environmental pollution is serious, and the chlorine in the gas phase, sulphur, the alkali salt in slag, the liquid are difficult to get rid of, and cause the deforestation crop, the harm human and livestock health.Four, can not use low-grade (V ₂O ₅Content＜0.5% ore); And, because technical process is long, equipment is many, causing that investment is big, cost is high, little factory incompetence is done environmental protection well, the factory of getting on the job with indigenous methods chaotic state in which corrupt practices prevail especially.

In recent years, because the high speed development of Iron And Steel Industry, some extraordinary industry increases the needs of vanadium are anxious, cause spurt in prices, and broke through 150,000 yuan per ton already, once short-term reached 400,000 yuan.Domesticly once organized scientific and technical personnel to tackle key problems, attended to one thing and lose sight of another, and be much to seek so far that investment is little, cost is low, the three wastes are handled well, can utilize the production technique of low grade ore.

Summary of the invention

The purpose of this invention is to provide a kind of stone-like coal gas phase vanadium extracting method, accomplish not add flux (salt, alkali) roasting, save energy, three waste discharge and be up to state standards, can utilize low heat value, low-grade stone coal resource simultaneously.

Processing step of the present invention is as follows:

1, fragmentation contains navajoite stone

Containing the scherbinaite coal is meant and contains carbonaceous shale, spoil, roscoelite, vanadium phosphorus ore or the vanadium green ore deposit of Vanadium Pentoxide in FLAKES more than 0.3%.Broken process is the pellet that the ore palate is broken into particle diameter＜20mm.

2, preparation bone coal raw material

At first chemically examine the carbon content of ore, when carbon content is lower than 15%, then in ore, add coal, be mixed with carbon content and be 15% bone coal raw material.

3, grinding

Raw material is worn into 60-80 purpose powder.

4, roasting gasification

Powder stock is sent into Pintsch process in the fluidizing furnace, and 900-1250 ℃ of roasting temperatures 8-30 seconds, the air that feeds oxygen level 30-50% simultaneously carried out oxygen-rich gasification, makes the Vanadium Pentoxide in FLAKES in the raw material become furnace gas.

5, dry cinder discharging

Furnace gas goes into to be equipped with the settling pocket of interchanger and inertial dust separator from the fluidizing furnace jacking, is cooled to 500 ℃ and separate through two stage cyclone, removes the powder of particle diameter more than 20 microns.

6, static enrichment and dipping dissolving

Furnace gas behind the deslagging enters electrostatic precipitator by settling pocket, and the following dust of micron order will enrichment in electrostatic precipitator in the furnace gas, and enriched substance is flooded with alkali lye, obtains containing the vanadium dipping solution.

7, spray absorbs and filter cleaner

Remaining dust enters the secondary spray column in the furnace gas, and first step absorption agent is water, rare ammonia or rare magnesium liquid, and second stage absorption agent contains NH ₄ ⁺, Mg ²⁺Or K ⁺Ionic alkali lye makes the Vanadium Pentoxide in FLAKES in the gas phase change liquid phase over to, refilters slagging-off.

8, acid neutralization

Sulfuric acid adding with 40-60% concentration contains the vanadium dipping solution and contains in the vanadium spray solution, goes out Vanadium Pentoxide in FLAKES through sour neutralization precipitation, filters and obtains the Vanadium Pentoxide in FLAKES crude product.

Principle of work of the present invention is to utilize Vanadium Pentoxide in FLAKES (V ₂O ₅) be easy to evaporable characteristics (similar) more than 700 ℃ to antimonous oxide, when the ore in sand form roasting, do not allow v element be converted into the vanadate of melt and dissolved attitude, but fully oxidation gasification, be steam-like and break away from slag, enter gas phase, furnace gas removes the dust removal slag through cooling-sedimentation, cyclonic separation, dissolves to such an extent that contain the vanadium dipping solution through static enrichment, dipping again.Remaining furnace gas is through rare ammonium, alkali lye spray, and wherein the Vanadium Pentoxide in FLAKES more than 98% becomes and contains the vanadium spray solution.Contain vanadium solution acid (H with above-mentioned two kinds ₂SO ₄Or HCI) handles, get V ₂O ₅Crude product.

Compared with the prior art, the present invention has following characteristics:

1, extensively utilizes low heat value, low-grade bone coal resource, rate of recovery height

Low heat value, low-grade scherbinaite coal that contains can be gasified, make the Vanadium Pentoxide in FLAKES of low levels directly enter gas phase, change liquid phase over to again through Pintsch process, oxidation, the rate of recovery improves a lot.

2, save energy

The carbon that contains on the one hand in the scherbinaite coal obtains utilizing, and the waste hot steam of Chan Shenging can be used for generating, save energy on the other hand.

3, few without flux, saline and alkaline usage quantity, removed production cost low.

The present invention has saved salt, alkali fusion agent, adds dry cinder discharging, and the dust more than 95% is without dipping, is not stained with saline and alkalinely, has only 5% dust to need to handle with alkali lye, and therefore saline and alkaline usage quantity is few, and production cost can reduce about 40%.

4, three wastes discharge amount is little, and the waste water waste vapour recycles, and helps environment protection.

The present invention does not use saline and alkaline flux, from production technique control with reduced source of pollution, adds the used heat steam and can be used for generating, and waste water is extracting K, Mg, NH ₃Make reusable edible behind the chemical fertilizer, so three wastes discharge amount is little, helps environment protection.

Embodiment

Embodiment one

With carbon content more than 15%, V ₂O ₅The bone coal of content more than 0.3% breaks through the secondary palate and is the pellet of particle diameter＜20mm, in the 3R2615 Raymond mill, wear into 60 orders-80 order fine powder, send in the fluidized-bed roaster with dish feeder, temperature is 1200-1250 ℃ in the operation stove, regulate the air inlet amount of oxygen level 30-50%, oxygen-rich gasification makes the Vanadium Pentoxide in FLAKES vaporization rate reach more than 98% in 8-30 seconds.Furnace gas temperature after the heat exchange of settling pocket interchanger is reduced to about 500 ℃, deslagging on time, and under the normal circumstances, the settling pocket deslagging accounts for 60%.Afterwards, furnace gas is sent into secondary cyclone, makes grit reduce to 50g/m ³, bed drain purge accounts for 35%.Furnace gas enters the electrostatic precipitator enrichment, enriched substance is flooded with KOH alkali lye, obtain containing the vanadium dipping solution, remaining furnace gas then enters the secondary spray column and absorbs, the absorption agent of one-level is a water, the absorption agent of secondary is an alkali lye, it is 10% that alkali lye contains the KOH amount, make the Vanadium Pentoxide in FLAKES in the gas phase be absorbed dissolving by alkali lye rapidly, and be converted into potassium metavanadate with the spray of fine mist multilayer down,, behind the filter cleaner, with concentration is the neutralization of 40% sulfuric acid, and the vanadium dipping solution that contains that is obtained by the enriched substance dipping carries out acid neutralization simultaneously, and filtration obtains the Vanadium Pentoxide in FLAKES crude product.

Embodiment two

Basic identical with embodiment one, different is that temperature is 900-950 ℃, enriched substance NH in the stove ₄OH alkali lye dipping, one-level spray column absorption agent is rare ammonium, secondary spray column absorption agent is to contain 10% NH ₄The alkali lye of OH.

Embodiment three

Basic identical with example one, different is that temperature is 1000-1050 ℃ in the stove, and used bone coal carbon content is lower than 15%, needs to add coal and makes carbon content reach 15%.

Embodiment four

To contain vanadium (V ₂O ₅) amount 0.8% roscoelite ore allocates 15% coal by weight into, through the palate crusher fragmentation, sends into fluidizing furnace with the powder that Raymond mill is worn into about 80 orders.Feed oxygen-rich air, about 20 seconds kinds of 1100-1250 ℃ of roasting temperatures in fluidizing furnace are removed the dirt that removes slag through sedimentation, cyclonic separation, the electrostatic precipitator enrichment, enriched substance obtains containing the vanadium dipping solution with Mg (OH) 2 rare magnesium liquid dippings, remaining furnace gas enters spray column, and the absorption agent of I level is Mg (OH) ₂Rare magnesium liquid, the absorption agent of II level are rare magnesium alkali lye of 15% concentration.Spray obtains contains the vanadium dipping solution that contains that vanadium spray solution and enrichment obtain and all enters neutralization tank.Neutralization tank under stirring state by acid accumulator storage (50%H ₂SO ₄Solution) inject acid solution, control PH1.0-1.6; Slowly inject ammoniacal liquor by ammonia vessel, transfer PH to 9.8, remove impurity such as silicon, aluminium; Transfer PH to 8.0-8.5 with acid again, add calcium solution, impurity such as dephosphorization, arsenic.Metavanadic acid magnesium solution after refining adds 5 times of ammonium liquid to vanadium, and precipitation, filtration, washing get the pure product of ammonium meta-vanadate.500 ℃ of calcining deaminations get the pure product of Vanadium Pentoxide in FLAKES, and ammonia then enters the ammonia absorber recycle.

Embodiment five

Basic identical with example four, different is that raw material is a vanadium phosphorus ore ore, and rare magnesium liquid is Mg (HCO ₃) rare magnesium liquid, the H in the acid accumulator storage ₂SO ₄Concentration is 60%.

Embodiment six

Basic identical with example four, different is that raw material is the green ore deposit of a vanadium ore.

Claims

1, a kind of stone-like coal gas phase vanadium extracting method is characterized in that processing step is as follows:

A, fragmentation contain navajoite stone

Containing navajoite stone is meant and contains carbonaceous shale, spoil, roscoelite, vanadium phosphorus ore or the vanadium green ore deposit of Vanadium Pentoxide in FLAKES more than 0.3%; Broken process is the pellet that the ore palate is broken into particle diameter＜20mm;

B, preparation bone coal raw material

At first chemically examine the carbon content of ore, when carbon content is lower than 15%, then in ore, add coal, be mixed with carbon content and be 15% bone coal raw material;

C, grinding

Raw material powder is worn into 60-80 purpose powder;

D, roasting gasification

Powder stock is sent into Pintsch process in the fluidizing furnace, and 900-1250 ℃ of roasting temperatures 8-30 seconds, the air that feeds oxygen level 30-50% simultaneously carried out oxygen-rich gasification, makes the Vanadium Pentoxide in FLAKES in the raw material become furnace gas;

E, dry cinder discharging

Furnace gas enters the settling pocket that mat-chaged device and inertial dust separator are housed from the fluidizing furnace item, is cooled to 500 ℃ and separate through two stage cyclone, removes the dust of particle diameter more than 20 microns;

F, static enrichment and dipping dissolving

Furnace gas behind the deslagging enters electrostatic precipitator by settling pocket, and the following dust of micron order will enrichment in electrostatic precipitator in the furnace gas, and enriched substance is flooded with alkali lye, obtains containing the vanadium dipping solution;

G, spray absorb and filter cleaner

Remaining dust enters the secondary spray column in the furnace gas, and the absorption agent of the first step is water, rare ammonia or rare magnesium liquid, and second stage water-retaining agent is to contain NH ₄ ⁺, Mg ²⁺Or K ⁺Ionic alkali lye becomes five oxygen, two vanadium in the gas phase and contains the vanadium spray solution, refilters slagging-off;

H, acid neutralization

Sulfuric acid adding with 40-60% concentration contains the vanadium dipping solution and contains the vanadium spray solution, goes out Vanadium Pentoxide in FLAKES through sour neutralization precipitation, filters and obtains five oxygen, two vanadium crude products.