CN104726689B - Method for decomposing chromite by low-temperature atmospheric-pressure fluidization - Google Patents
Method for decomposing chromite by low-temperature atmospheric-pressure fluidization Download PDFInfo
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Abstract
The invention relates to a method for decomposing chromite by low-temperature atmospheric-pressure fluidization, which comprises the following steps: adding potassium hydroxide and an optionally added mixed water solution of potassium carbonate and/or potassium metaaluminate into a reactor, preheating, adding chromite and/or pretreated chromite, and introducing oxidizing gas to perform oxidizing reaction while heating; diluting the reaction slurry with a diluter to obtain a solution containing potassium chromate, potassium hydroxide, potassium carbonate, potassium metaaluminate and other water-soluble impurity components and an iron-rich tailing solid-liquid mixed slurry; and carrying out solid-liquid separation on the mixed slurry at 80-130 DEG C to obtain the iron-rich tailings and chromium-containing alkali liquor. The reaction temperature of the method is below the boiling point of the solution, and the process is performed under atmospheric pressure; and thus, the method has the advantages of low equipment cost, high safety and high chromium extraction yield (up to 95% above), and is easy to operate, and the operating temperature is much lower than the temperature of the traditional chromium extraction technique.
Description
Technical field
The invention belongs to chromite hydrometallurgy and chromium chemical field, more particularly to a kind of low-temperature atmosphere-pressure fluidisation decomposition ferrochrome
The method of ore deposit.
Background technology
Chromium resource is national grand strategy resource, and chromic salts is important inorganic chemical product, can as chemical industry-light industry-
The important foundation raw material of senior alloy material, is a class chemical industry metallurgical raw material that China gives priority to, is widely used in metallurgy, system
In the industry such as leather, pigment, dyestuff, spices, the process of metal surface, wood preservation, military project, it is most competitive to be listed in
One of 8 kinds of resource raw material products.
Chromite is a kind of mineral of spinelle configuration, is the currently the only chrome ore for being available for and exploiting, and is mainly used in metallurgy
In industry, refractory material and chemical industry.In metallurgical industry, chromite is the raw material for producing ferrochrome and crome metal；Chromium
Iron ore can also be used to manufacture chrome brick, chromium and magnesium brick and other special refractories；In chemical industry, chromite is mainly used in life
Sodium dichromate is produced, and then produces other chromium compounds.Chromite is widely used in the industry such as pigment, weaving, plating, process hides, also
Catalyst and catalyzer contact agent etc. can be made.
Mainly there are calcium roasting method and calcium-free roasting method by the method that raw material produces chromic salts product of chromite.Chromite is used
It is traditional that chromium conversion ratio is low when having calcium roasting method technique to smelt, and only 75%, three wastes discharge amount is big, and sodium dichromate product per ton is about arranged
2.5-3.0 ton high poison chromium slags are put, chromium slag chrome content is high（For 4-5%）, it is difficult to detoxify and comprehensively utilize, intermediate product calcium chromate is
Carcinogenic substance, additionally discharges a large amount of chromium-containing waste gas, and environmental pollution is serious.Optimization tradition has the calcium-free roasting method that calcium roasting method is formed
Chromium conversion ratio up to 90%, chromium slag discharge rate is 0.8 ton/ton sodium dichromate, and content of 6-valence Cr ions is low in slag, pollutes little, while control
The generation of carcinogenic substance calcium chromate, but calcium-free roasting does not thoroughly solve chromium slag contaminated problem, and equipment investment is big, roasting
Body of heater ring formation is serious in journey, and the country not yet realizes large-scale industrial production.
To solve the above problems, CN102643977A is proposed and will be included chromite, selected from soda ash, sodium acid carbonate, sulfuric acid
One or more in sodium and NaOH and the compound of optional sodium chromate in horizontal revolving kiln in the presence of oxygen in
Liquid phase roasting is melted at 350-1500 DEG C, sodium chromate is obtained.The method makes chromite in molten salt system in liquid phase is melted, significantly
Improve chromium conversion ratio, increased yield, fundamentally solve the problems, such as that calcium-free roasting technique easily ties wall, but method operation
Temperature is high, and equipment is complicated, and investment is big.
In recent years, Chinese Academy Of Sciences Process Engineering Research Institute has made to grind in a large number to the liquid phase method process for cleanly preparing of chromic salts
Study carefully, develop sub-molten salt method and molten-salt growth method series chromium-salt clean production process.Such as CN1410358A using KOH fused salts in oxidant
In the presence of, chromite is decomposed in liquid phase oxidation, and high conversion rate, bed drain purge is little, and reaction temperature is at 250～400 DEG C, at present the work
The built ton demonstration project of skill.But its alkali lye circulating and evaporating concentration link energy consumption is larger.
Also CN101659444A and CN101481144A are proposed respectively by preparing sodium chromate from chromite（Potassium）Cleaning side
Method, chromite is in NaOH-NaNO3-H2O or KOH-KNO3-H2React with oxidizing gas in O media, sodium nitrate（Potassium）As urging
Change medium, be not consumed in the reaction；Alkali lye, sodium chromate are obtained after reaction（Potassium）And the reaction product mixture of scum.It is blended
The leaching of product, solid-liquor separation, evaporation crystallisation by cooling obtains sodium chromate（Potassium）, after scrubbed and drying, finally give
Qualified sodium chromate（Potassium）Product；Crystalline mother solution is circulated together with alkali lye, for decomposing chromite.Chromium turns in above method
Rate is all higher than 99%, and rate containing chromium is less than 0.5% in slag.But introduce NaNO in the normal direction system3, complicate later separation.
And CN101817561A proposes a kind of method of pollution-free production of sodium chromate by pressure leaching of chromite.The method include with
Lower step：1) chromite carries out heated oxide reaction in NaOH solution with oxidizing gas；2) dilution step 1) product that obtains
Thing, the sodium chromate for making partially crystallizable fully enters liquid phase；3) by step 2) Solid-liquid mixture that obtains slurry carries out separation of solid and liquid；4)
To step 3) calcium oxide removal of impurities is added in the dilution that obtains；5) by step 4) obtain except mixture solution evaporative crystallization, obtain chromium
Sour sodium crystal and crystalline mother solution, crystals of sodium chromate saturation chromium acid sodium solution drip washing, is obtained after drying after separation of solid and liquid
Qualified sodium chromate product.The method reaction system composition is simple, and difficult separation phase is not introduced in system, is conducive to the efficient of sodium chromate
Separate.But the method hypertonia, equipment investment is big.
The content of the invention
It is an object of the invention to provide a kind of method of potassium hydroxide solution low-temperature decomposition chromite at ambient pressure.The party
Method adds potassium carbonate and potassium metaaluminate, because potassium metaaluminate is the product that aluminium leaches out by potassium hydroxide in chromite, carbonic acid
Potassium is the product of Carbon Dioxide in Air and potassium hydroxide in course of reaction, so the addition of potassium carbonate and potassium metaaluminate is not
Affect the circulation of evaporative crystallization liquid in technique.The addition of another aspect potassium carbonate and potassium metaaluminate improves and boiled under identical alkali concn
Point, reduces the alkali concn of reaction.Below solution boiling point, process is carried out at ambient pressure the method reaction temperature, equipment cost
It is low, it is easy to operate and security is good.
The present invention principle be chromite in the reactor added with longitudinal guide shell and/or transverse baffle with finite concentration
Potassium hydroxide, potassium carbonate, potassium metaaluminate solution in react at 150～350 DEG C with oxidizing gas, make trivalent chromium by oxygen
Chemical conversion Cr VI generates sodium chromate.
It is that, up to above-mentioned purpose, the present invention is adopted the following technical scheme that：
A kind of method that low-temperature atmosphere-pressure fluidisation decomposes chromite, comprises the following steps：
(1) mixed aqueous solution of the potassium carbonate and/or potassium metaaluminate of potassium hydroxide and optional addition is added in reactor,
Preheating, is subsequently adding chromite and/or pretreated chromite, and oxidizing gas are passed through under heating carries out oxidation reaction；Its
In optional addition potassium carbonate and/or potassium metaaluminate can both add, or one kind being only added thereto, it is also possible to both
Without；
Wherein, added with guide shell and/or baffle plate, potassium hydroxide is 2 with the mass ratio of chromite to reactor:1～10:1, example
Such as it is 2.5:1、4:1、5.5:1、7:1、9.5:1 etc.；
(2) reaction paste that step (1) is obtained is diluted with diluent, is obtained containing potassium chromate, potassium hydroxide, carbonic acid
The Solid-liquid mixture slurry of potassium, the solution of potassium metaaluminate and other water-solubility impurity components and iron-rich tailings；
(3) mixed slurry obtained to step (2) is at 80～130 DEG C, for example, 85 DEG C, 98 DEG C, 102 DEG C, 110 DEG C, 116
DEG C, carry out separation of solid and liquid under 124 DEG C etc. and obtain iron-rich tailings and alkali lye containing chromium.
Wherein, used by the present invention Posterior circle liquid proportioning is reacted by potassium hydroxide, potassium carbonate, potassium aluminate mixed solution and factory
It is identical, therefore circulation fluid can be used directly and without the need for removal of impurities, makes the present invention be easily achieved industrialization；Additionally, add potassium carbonate and
Potassium aluminate can improve reactant liquor boiling point, can substantially reduce operation pressure, reduce equipment investment.
In method of the present invention, pretreatment described in step (1) is mechanical activation and/or calcination activation.
Preferably, the mechanical activation is the one kind or two or more combination of roller ball mill, planetary ball mill or stirring ball-milling.
In method of the present invention, the concentration of potassium hydroxide described in step (1) is 40wt%～80wt%, for example,
42wt%, 46wt%, 55wt%, 62wt%, 70wt%, 73wt%, 78wt% etc., concentration of potassium carbonate is 0wt%～20wt%, for example,
2wt%, 5wt%, 9wt%, 13wt%, 16wt%, 19wt% etc., potassium metaaluminate concentration be 0wt%～20wt%, for example, 2wt%, 5wt%,
9wt%, 13wt%, 16wt%, 19wt% etc..
Preferably, the temperature of the preheating be 80-120 DEG C, for example, 85 DEG C, 92 DEG C, 102 DEG C, 110 DEG C, 115 DEG C etc.,
Preferably 100 DEG C.
In method of the present invention, potassium hydroxide and the mass ratio of chromite are 2.5 in step (1):1～8:1, preferably
For 3:1～5:1.
In method of the present invention, oxidizing gas described in step (1) are air, oxygen, oxygen-enriched air or ozone
One kind or two or more mixing in gas.
In method of the present invention, the temperature of heating is 150～350 DEG C in step (1), for example, 160 DEG C, 175 DEG C,
192 DEG C, 210 DEG C, 240 DEG C, 280 DEG C, 300 DEG C, 315 DEG C, 330 DEG C, 345 DEG C etc., preferably 190～250 DEG C；Reaction time is
0.5～10h, for example, 1.1h, 2h, 4h, 7h, 9h etc., preferably 1～5h.
In method of the present invention, reactor is the reactor added with longitudinal guide shell or transverse baffle, and liquid mixes admittedly
By the way of Gas Stirring, agitating mode such as Fig. 2 can greatly promote the haptoreaction of chromite and reaction medium, improve chromium
Iron ore leaching rate.
In method of the present invention, in step (2) slurry after dilution the content of potassium hydroxide be 100～500g/L, example
Such as it is 110g/L, 140g/L, 180g/L, 250g/L, 310g/L, 390g/L, 420g/L, 460g/L, 480g/L.
In method of the present invention, step (2) diluent is water or concentration in below 300g/L, for example, 10g/
The potassium hydroxide aqueous solution of L, 40g/L, 80g/L, 150g/L, 210g/L, 250g/L, 290g/L etc..
Used as optimal technical scheme, method of the present invention comprises the steps：
(1) mixed aqueous solution of the potassium carbonate and/or potassium metaaluminate of potassium hydroxide and optional addition is added in reactor,
80-120 DEG C is preheated to, chromite and/or pretreated chromite is subsequently adding, oxidation is passed through at being heated to 150～350 DEG C
Property gas carries out 0.5～10h of oxidation reaction；
Wherein, added with guide shell and/or baffle plate, potassium hydroxide is 2 with the mass ratio of chromite to reactor:1～10:1, hydrogen
The concentration of potassium oxide is 40wt%～80wt%, and concentration of potassium carbonate is 0wt%～20wt%, and potassium metaaluminate concentration is 0wt%～20wt%,
Oxidizing gas are the one kind or two or more mixing in air, oxygen, oxygen-enriched air or ozone gas；
(2) reaction paste for obtaining step (1) is carried out with water or concentration in the potassium hydroxide aqueous solution of below 300g/L
Dilution, obtains the solution containing potassium chromate, potassium hydroxide, potassium carbonate, potassium metaaluminate and other water-solubility impurity components and Fu Tie tails
The Solid-liquid mixture slurry of slag, the content of potassium hydroxide is 100～500g/L in slurry after dilution；
(3) separation of solid and liquid is carried out at 80～130 DEG C to the mixed slurry that step (2) is obtained and obtains iron-rich tailings and containing chromium
Alkali lye.
Compared with prior art, the present invention has following superiority：
1st, from reaction system, ammonium acetate is simple, other hardly possiblies is not introduced in system and separates phase, additionally, used
Potassium hydroxide, potassium carbonate, potassium aluminate mixed solution and factory reaction Posterior circle liquid proportioning is identical, therefore circulation fluid can be used directly
And without the need for removal of impurities, make the present invention be easily achieved industrialization；The addition of another aspect potassium carbonate and/or potassium metaaluminate can improve identical
Boiling point under alkali concn, reduces the alkali concn of reaction, improves the security of reaction.
2nd, from terms of reaction condition, the reaction temperature of the technique is low, and alkali concn is low, less energy consumption, and the corrosion to equipment is little, reduces
Generate the production cost of potassium chromate.
3rd, from reaction pressure, the reaction process reaction pressure be normal pressure, equipment needed thereby before and after reaction process flow process
For normal pressure, equipment cost is low, it is easy to operation and security is good, advantageously reduces cost of labor.
4th, the reaction process is carried out under pilot plant, has been taken into full account the flowing in multiplying arrangement and has been heated and has asked
Topic, optimizes contact of the reaction medium with chromite.Evaporative crystallization liquid carries out experimental result in using industrial processes
Well, may be directly applied to production.
Description of the drawings
Fig. 1 is the schematic flow sheet of the inventive method；
Fig. 2 is inside reactor structure chart.
Specific embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the enforcement
Example is used only for help and understands the present invention, is not construed as the concrete restriction to the present invention.
Fig. 1 is the schematic flow sheet of the inventive method.Fig. 2 is inside reactor structure chart.
Embodiment 1
A kind of method that low-temperature atmosphere-pressure fluidisation decomposes chromite, comprises the following steps：
1）Certain density potassium hydroxide, potassium carbonate, the potassium metaaluminate aqueous solution are configured, fluidized-bed reactor, preheating is added
To 100 DEG C.The solution potassium hydroxide, potassium carbonate, the content of potassium metaaluminate are respectively 40%, 10%, 5%.Will screening for 200 mesh with
Under chromite mix with the solution, wherein the mass ratio of potassium hydroxide and chromite is 10:1, i.e. chromite 7kg, hydroxide
Potassium mixed solution 120L；
2）Continue heated fluidized bed reactor, open compressed air, control throughput is in 10m3/ h, maintains at 240 DEG C
10h, air mass flow is not less than 12m3/h；
3）Cooling sampling dilution, is diluted to reaction slurry concentration of potassium hydroxide 300g/L, by mixing slurry under 80 DEG C or so
Material is separated by filtration, and respectively obtains iron-rich tailings and alkali lye containing chromium, and Jing titration after tailings cyclic washing, drying is measured into chromium content,
Chromium dissolution rate is calculated for 95.05%.
Embodiment 2
1）Certain density potassium hydroxide, potassium carbonate, the potassium metaaluminate aqueous solution are configured, fluidized-bed reactor, preheating is added
To 100 DEG C, the solution potassium hydroxide, potassium carbonate, the content of potassium metaaluminate are respectively 50%, 10%, 0%.Will screening for 200 mesh with
Under chromite mix with the solution, wherein the mass ratio of potassium hydroxide and chromite is 5:1, i.e. chromite 18kg, hydroxide
Potassium mixed solution 120L；
2）Continue heated fluidized bed reactor, and open compressed air, control throughput is in 10m3/ h, maintain at 255 DEG C
8h, air mass flow is not less than 12m3/h；
3）Cooling sampling dilution, is diluted to reaction slurry concentration of potassium hydroxide 300g/L, by mixing slurry under 80 DEG C or so
Material is separated by filtration, and respectively obtains iron-rich tailings and alkali lye containing chromium, and Jing titration after tailings cyclic washing, drying is measured into chromium content,
Chromium dissolution rate is calculated for 96.11%.
Embodiment 3
1）Certain density potassium hydroxide, potassium carbonate, the potassium metaaluminate aqueous solution are configured, fluidized-bed reactor, preheating is added
To 100 DEG C, the solution potassium hydroxide, potassium carbonate, the content of potassium metaaluminate are respectively 50%, 10%, 5%..Will screening for 200 mesh with
Under chromite mix with the solution, wherein the mass ratio of potassium hydroxide and chromite is 3:1, i.e. chromite 30kg, hydroxide
Potassium mixed solution 120L；
2）Continue heated fluidized bed reactor, and open compressed air, control throughput is in 10m3/ h, maintains at 285 DEG C
6h, air mass flow is not less than 16m3/h；
3）Cooling sampling dilution, is diluted to reaction slurry concentration of potassium hydroxide 120g/L, by mixing slurry under 100 DEG C or so
Material is separated by filtration, and respectively obtains iron-rich tailings and alkali lye containing chromium, and Jing titration after tailings cyclic washing, drying is measured into chromium content,
Chromium dissolution rate is calculated for 98.52%.
Embodiment 4
1）Certain density potassium hydroxide, potassium carbonate, the potassium metaaluminate aqueous solution are configured, fluidized-bed reactor, preheating is added
To 80 DEG C, the solution potassium hydroxide, potassium carbonate, the content of potassium metaaluminate are respectively 60%, 10%, 5%.By screening for below 200 mesh
Chromite mix with the solution, wherein the mass ratio of potassium hydroxide and chromite is 5:1, i.e. chromite 22kg, potassium hydroxide
Mixed solution 120L；
2）Continue heated fluidized bed reactor, and open compressed air, control throughput is in 10m3/ h, maintains at 340 DEG C
0.5h, control air mass flow is not less than 16m3/h；
3）Cooling sampling dilution, is diluted to reaction slurry concentration of potassium hydroxide 450g/L, by mixing slurry under 130 DEG C or so
Material is separated by filtration, and respectively obtains iron-rich tailings and alkali lye containing chromium, and Jing titration after tailings cyclic washing, drying is measured into chromium content,
Chromium dissolution rate is calculated for 95.7%.
Embodiment 5
1）Certain density potassium hydroxide, potassium carbonate, the potassium metaaluminate aqueous solution are configured, fluidized-bed reactor, preheating is added
To 120 DEG C, the solution potassium hydroxide, potassium carbonate, the content of potassium metaaluminate are respectively 50%, 10%, 5%.Will screening for 200 mesh with
Under chromite mix with the solution, wherein the mass ratio of potassium hydroxide and chromite is 4:1, i.e. chromite 23kg, hydroxide
Potassium mixed solution 120L；
2）Continue heated fluidized bed reactor, and open compressed air, control throughput is in 10m3/ h, maintains at 270 DEG C
6h, control air mass flow is not less than 16m3/h；
3）Cooling sampling dilution, is diluted to reaction slurry concentration of potassium hydroxide 300g/L, by mixing slurry under 90 DEG C or so
Material is separated by filtration, and respectively obtains iron-rich tailings and alkali lye containing chromium, and Jing titration after tailings cyclic washing, drying is measured into chromium content,
Chromium dissolution rate is calculated for 97%.
Embodiment 6
1）Certain density potassium hydroxide, potassium carbonate, the potassium metaaluminate aqueous solution are configured, fluidized-bed reactor, preheating is added
To 100 DEG C, the solution potassium hydroxide, potassium carbonate, the content of potassium metaaluminate are respectively 50%, 5%, 10%.Will screening for 200 mesh with
Under chromite mix with the solution, wherein the mass ratio of potassium hydroxide and chromite is 3.5:1, i.e. chromite 26kg, hydrogen-oxygen
Change potassium mixed solution 120L；
2）Continue heated fluidized bed reactor, and open compressed air, control throughput is in 10m3/ h, maintains at 280 DEG C
6h, control air mass flow is not less than 16m3/h；
3）Cooling sampling dilution, is diluted to reaction slurry concentration of potassium hydroxide 300g/L, by mixing slurry under 80 DEG C or so
Material is separated by filtration, and respectively obtains iron-rich tailings and alkali lye containing chromium, and Jing titration after tailings cyclic washing, drying is measured into chromium content,
Chromium dissolution rate is calculated for 96.99%.
Embodiment 7
1）Potassium hydroxide, potassium carbonate, the potassium metaaluminate aqueous solution are added into fluidized-bed reactor, 90 DEG C is preheated to, the solution
It is that potassium hydroxide, potassium carbonate, the content of potassium metaaluminate are respectively 70%, 5%, 5% from industrial evaporative crystallization mother liquor.Will sieve
It is divided into the chromite below 200 mesh to mix with the solution, wherein potassium hydroxide and the mass ratio of chromite are 2:1, i.e. chromite
60kg, potassium hydroxide mixed solution 120L；
2）Continue heated fluidized bed reactor, and open oxygen, control throughput is in 10m3/ h, 6h at maintaining 300 DEG C, control
Oxygen flow processed is not less than 20m3/h；
3）Cooling sampling dilution, is diluted to reaction slurry concentration of potassium hydroxide 350g/L, by mixing slurry under 80 DEG C or so
Material is separated by filtration, and respectively obtains iron-rich tailings and alkali lye containing chromium, and Jing titration after tailings cyclic washing, drying is measured into chromium content,
Chromium dissolution rate is calculated for 95.34%.
Embodiment 8
1）Certain density potassium hydroxide, potassium carbonate, the potassium metaaluminate aqueous solution are configured, fluidized-bed reactor, preheating is added
To 100 DEG C, the solution potassium hydroxide, potassium carbonate, the content of potassium metaaluminate are respectively 50%, 20%, 5%.Will screening for 200 mesh with
Under chromite mix with the solution, wherein the mass ratio of potassium hydroxide and chromite is 3.3:1, i.e. chromite 27kg, hydrogen-oxygen
Change potassium mixed solution 120L；
2）Continue heated fluidized bed reactor, and open compressed air, control throughput is in 10m3/ h, maintains at 280 DEG C
6h, control air mass flow is not less than 16m3/h；
3）Cooling sampling dilution, is diluted to reaction slurry concentration of potassium hydroxide 300g/L, by mixing slurry under 80 DEG C or so
Material is separated by filtration, and respectively obtains iron-rich tailings and alkali lye containing chromium, and Jing titration after tailings cyclic washing, drying is measured into chromium content,
Chromium dissolution rate is calculated for 98.1%.
Embodiment 9
1）Certain density potassium hydroxide, potassium carbonate, the potassium metaaluminate aqueous solution are configured, fluidized-bed reactor, preheating is added
To 100 DEG C, the solution potassium hydroxide, potassium carbonate, the content of potassium metaaluminate are respectively 50%, 5%, 20%.Will screening for 200 mesh with
Under chromite mix with the solution, wherein the mass ratio of potassium hydroxide and chromite is 3.3:1, i.e. chromite 27kg, hydrogen-oxygen
Change potassium mixed solution 120L；
2）Continue heated fluidized bed reactor, and open compressed air, control throughput is in 10m3/ h, maintains at 280 DEG C
6h, control air mass flow is not less than 16m3/h；
3）Cooling sampling dilution, is diluted to reaction slurry concentration of potassium hydroxide 300g/L, by mixing slurry under 80 DEG C or so
Material is separated by filtration, and respectively obtains iron-rich tailings and alkali lye containing chromium, and Jing titration after tailings cyclic washing, drying is measured into chromium content,
Chromium dissolution rate is calculated for 96.4%.
Embodiment 10
1）Certain density potassium hydroxide, potassium carbonate, the potassium metaaluminate aqueous solution are configured, fluidized-bed reactor, preheating is added
To 100 DEG C, the solution potassium hydroxide, potassium carbonate, the content of potassium metaaluminate are respectively 80%, 0%, 0%.By screening for below 200 mesh
Chromite mix with the solution, wherein the mass ratio of potassium hydroxide and chromite is 3.3:1, i.e. chromite 42kg, hydroxide
Potassium solution 120L；
2）Continue heated fluidized bed reactor, and open compressed air, control throughput is in 10m3/ h, maintains at 250 DEG C
6h, control air mass flow is not less than 16m3/h；
3）Cooling sampling dilution, is diluted to reaction slurry concentration of potassium hydroxide 300g/L, by mixing slurry under 80 DEG C or so
Material is separated by filtration, and respectively obtains iron-rich tailings and alkali lye containing chromium, and Jing titration after tailings cyclic washing, drying is measured into chromium content,
Chromium dissolution rate is calculated for 98.5%.
Embodiment 11
1）The circulation fluid plus fluidized bed of the filtrate Jing evaporative crystallizations that Jing after industrial reaction chromite is separated by filtration is anti-
Answer device, be preheated to 100 DEG C, the main component in solution potassium hydroxide, potassium carbonate, the content of potassium metaaluminate are respectively 48%, 10%,
5%, screening is mixed for the chromite below 200 mesh with the solution, wherein potassium hydroxide and the mass ratio of chromite are 3.5:1,
That is chromite 27kg, industrial stoste 120L；
2）Continue heated fluidized bed reactor, and open compressed air, control throughput is in 10m3/ h, maintains at 160 DEG C
6h, control air mass flow is not less than 16m3/h；
3）Cooling sampling dilution, is diluted to reaction slurry concentration of potassium hydroxide 300g/L, by mixing slurry under 80 DEG C or so
Material is separated by filtration, and respectively obtains iron-rich tailings and alkali lye containing chromium, and Jing titration after tailings cyclic washing, drying is measured into chromium content,
Chromium dissolution rate is calculated for 97.6%.
Applicant states that the present invention illustrates the detailed process equipment of the present invention and technological process by above-described embodiment,
But above-mentioned detailed process equipment and technological process are the invention is not limited in, that is, does not mean that the present invention has to rely on above-mentioned detailed
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within the present invention's
Within the scope of protection domain and disclosure.
Claims (15)
1. a kind of method that low-temperature atmosphere-pressure fluidisation decomposes chromite, comprises the following steps：
(1) mixed aqueous solution of potassium hydroxide, potassium carbonate and potassium metaaluminate is added in reactor, preheating is subsequently adding ferrochrome
Ore deposit and/or pretreated chromite, oxidizing gas are passed through under heating carries out oxidation reaction；
Wherein, added with guide shell and/or baffle plate, potassium hydroxide is 2 with the mass ratio of chromite to reactor:1～10:1；
(2) reaction paste that step (1) is obtained is diluted with diluent, obtain containing potassium chromate, potassium hydroxide, potassium carbonate,
The Solid-liquid mixture slurry of the solution and iron-rich tailings of potassium metaaluminate and other water-solubility impurity components；
(3) separation of solid and liquid is carried out at 80～130 DEG C to the mixed slurry that step (2) is obtained and obtains iron-rich tailings and alkali containing chromium
Liquid；
Wherein, the concentration of potassium hydroxide described in step (1) be 40wt%～80wt%, concentration of potassium carbonate be 0wt%～
20wt%, potassium metaaluminate concentration is not 0wt% for the concentration of 0wt%～20wt%, the potassium carbonate and potassium metaaluminate.
2. method according to claim 1, it is characterised in that pretreatment described in step (1) is mechanical activation and/or roasting
Burn activation.
3. method according to claim 2, it is characterised in that the mechanical activation is roller ball mill, planetary ball mill or stirs
Mix the one kind or two or more combination of ball milling.
4. method according to claim 1, it is characterised in that the temperature of the preheating is 80-120 DEG C.
5. method according to claim 4, it is characterised in that the temperature of the preheating is 100 DEG C.
6. method according to claim 1, it is characterised in that potassium hydroxide is with the mass ratio of chromite in step (1)
2.5:1～8:1.
7. method according to claim 6, it is characterised in that potassium hydroxide is with the mass ratio of chromite in step (1)
3:1～5:1.
8. method according to claim 1, it is characterised in that oxidizing gas described in step (1) be air, oxygen,
One kind or two or more mixing in oxygen-enriched air or ozone gas.
9. method according to claim 1, it is characterised in that the temperature of heating is 150～350 DEG C in step (1), reaction
Time is 0.5～10h.
10. method according to claim 9, it is characterised in that the temperature of heating is 190～250 DEG C in step (1).
11. methods according to claim 9, it is characterised in that the reaction time is 1～5h in step (1).
12. methods according to claim 1, it is characterised in that reactor is added with longitudinal guide shell or transverse baffle
Reactor, liquid mixes by the way of Gas Stirring admittedly.
13. methods according to claim 1, it is characterised in that the content of potassium hydroxide is in step (2) slurry after dilution
100～500g/L.
14. methods according to claim 1, it is characterised in that step (2) diluent is water or concentration in 300g/L
Following potassium hydroxide aqueous solution.
15. methods according to claim 1, it is characterised in that comprise the steps：
(1) mixed aqueous solution of potassium hydroxide and potassium carbonate and potassium metaaluminate is added in reactor, is preheated to 80-120 DEG C, so
Chromite and/or pretreated chromite are added afterwards, and oxidizing gas are passed through at being heated to 150～350 DEG C to carry out aoxidizing instead
Answer 0.5～10h；
Wherein, added with guide shell and/or baffle plate, potassium hydroxide is 2 with the mass ratio of chromite to reactor:1～10:1, hydroxide
The concentration of potassium be 40wt%～80wt%, concentration of potassium carbonate be 0wt%～20wt%, potassium metaaluminate concentration be 0wt%～
The concentration of 20wt%, the potassium carbonate and potassium metaaluminate is not 0wt%, and oxidizing gas are air, oxygen, oxygen-enriched air or smelly
One kind or two or more mixing in carrier of oxygen；
(2) the reaction paste water or concentration for obtaining step (1) is diluted in the potassium hydroxide aqueous solution of below 300g/L,
Obtain containing potassium chromate, potassium hydroxide, potassium carbonate, potassium metaaluminate and the solution of other water-solubility impurity components and consolidating for iron-rich tailings
Liquid mixed slurry, the content of potassium hydroxide is 100～500g/L in slurry after dilution；
(3) separation of solid and liquid is carried out at 80～130 DEG C to the mixed slurry that step (2) is obtained and obtains iron-rich tailings and alkali containing chromium
Liquid.
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