CN104726689A - Method for decomposing chromite by low-temperature atmospheric-pressure fluidization - Google Patents
Method for decomposing chromite by low-temperature atmospheric-pressure fluidization Download PDFInfo
- Publication number
- CN104726689A CN104726689A CN201310722901.7A CN201310722901A CN104726689A CN 104726689 A CN104726689 A CN 104726689A CN 201310722901 A CN201310722901 A CN 201310722901A CN 104726689 A CN104726689 A CN 104726689A
- Authority
- CN
- China
- Prior art keywords
- chromite
- potassium hydroxide
- potassium
- reaction
- metaaluminate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
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, particularly relate to a kind of method that low-temperature atmosphere-pressure fluidisation decomposes chromite.
Background technology
Chromium resource is national grand strategy resource, chromic salts is important inorganic chemical product, can be used as the important foundation raw material of chemical industry-light industry-senior alloy material, it is the class chemical industry metallurgical raw material that China gives priority to, be widely used in the industry such as process, wood preservation, military project of metallurgy, process hides, pigment, dyestuff, spices, metallic surface, being listed in is one of competitive 8 kinds of resource raw material product of most.
Chromite is a kind of mineral of spinel configuration, is uniquely for the chrome ore of exploitation, to be mainly used in metallurgical industry, refractory materials and chemical industry at present.In metallurgical industry, chromite is the starting material producing ferrochrome and chromium metal; Chromite can also be used to manufacture chrome brick, magnesite chrome brick and other special refractories; In chemical industry, chromite is mainly used in production sodium dichromate 99, and then produces other chromium cpds.Chromite is widely used in the industry such as pigment, weaving, plating, process hides, also can make catalyzer and activator etc.
Be that the method for raw material production chromic salts product mainly contains calcium roasting method and calcium-free roasting method with chromite.When what chromite use was traditional has calcium roasting method technique to smelt, chromium low conversion rate, be only 75%, three wastes discharge amount is large, and sodium dichromate product per ton about discharges the high malicious chromium slag of 2.5-3.0 ton, chromium slag chrome content high (for 4-5%), be difficult to removing toxic substances and comprehensive utilization, intermediate product yellow ultramarine is carcinogens, and discharge is a large amount of containing chromium waste gas in addition, and environmental pollution is serious.The chromium transformation efficiency optimizing the calcium-free roasting method that tradition has calcium roasting method to be formed can reach 90%, chromium slag output is 0.8 ton of/ton of sodium dichromate, in slag, content of 6-valence Cr ions is low, pollute little, control the generation of carcinogens yellow ultramarine, but calcium-free roasting does not thoroughly solve chromium slag contaminated problem, and facility investment is large simultaneously, in roasting process, body of heater ring formation is serious, domesticly not yet realizes large-scale industrial production.
For solving the problem, CN102643977A proposes and will comprise chromite, be selected from compound melting liquid phase roasting at 350-1500 DEG C in the presence of oxygen in horizontal revolving kiln of one or more and the optional Sodium chromate in soda ash, sodium bicarbonate, sodium sulfate and sodium hydroxide, obtain Sodium chromate.The method makes chromite in melting liquid phase in molten salt system, and greatly increase chromium transformation efficiency, add output, fundamentally solve the problem that calcium-free roasting technique easily ties wall, but this method service temperature is high, equipment is complicated, and investment is large.
In recent years, the liquid phase method process for cleanly preparing of Chinese Academy Of Sciences Process Engineering Research Institute to chromic salts has made large quantity research, develops sub-molten salt method and molten-salt growth method series chromium-salt clean production process.As CN1410358A utilizes KOH fused salt under the effect of oxygenant, chromite is decomposed in liquid-phase oxidation, and transformation efficiency is high, and bed drain purge is little, and temperature of reaction is at 250 ~ 400 DEG C, and this technique builds ton demonstration project at present.But it is larger that its alkali lye circulating and evaporating concentrates link energy consumption.
Also have CN101659444A and CN101481144A to propose respectively by the cleaning method of preparing sodium chromate from chromite (potassium), chromite is at NaOH-NaNO
3-H
2o or KOH-KNO
3-H
2react with oxidizing gas in O medium, SODIUMNITRATE (potassium), as catalytic media, is not consumed in the reaction; The reaction product mixture of alkali lye, Sodium chromate (potassium) and scum is obtained after reaction.Through the leaching of reaction product mixture, solid-liquor separation, transpiration cooling crystallization obtains Sodium chromate (potassium), after drip washing and drying, finally obtains qualified Sodium chromate (potassium) product; Crystalline mother solution circulates together with alkali lye, for decomposing chromite.In above method, chromium transformation efficiency is all greater than 99%, is less than 0.5% in slag containing chromium rate.But introduce NaNO in this normal direction system
3, make later separation complicated.
And CN101817561A proposes a kind of method of pollution-free production of sodium chromate by pressure leaching of chromite.The method comprises the following steps: 1) chromite carries out heated oxide reaction with oxidizing gas in NaOH solution; 2) dilution step 1) product that obtains, make the Sodium chromate of partial crystallization all enter liquid phase; 3) by step 2) Solid-liquid mixture that obtains slurry carries out solid-liquid separation; 4) to step 3) add calcium oxide removal of impurities in the diluent that obtains; 5) by step 4) the removal of impurities solution evaporation crystallization that obtains, obtain crystals of sodium chromate and crystalline mother solution, after solid-liquid separation, the saturated chromium acid sodium solution drip washing of crystals of sodium chromate, can obtain qualified Sodium chromate product after drying.This method reaction system composition is simple, does not introduce difficult separation phase, be conducive to the high efficiency separation of Sodium chromate in system.But this method hypertonia, facility investment is large.
Summary of the invention
The object of the present invention is to provide the method for a kind of potassium hydroxide solution low-temperature decomposition chromite at ambient pressure.The method adds salt of wormwood and potassium metaaluminate, because potassium metaaluminate is the product that in chromite, aluminium is leached out by potassium hydroxide, salt of wormwood is the reaction product of Carbon Dioxide in Air and potassium hydroxide in reaction process, thus salt of wormwood and potassium metaaluminate add the circulation not affecting evaporative crystallization liquid in technique.On the other hand the interpolation of salt of wormwood and potassium metaaluminate improves boiling point under identical alkali concn, reduces the alkali concn of reaction.The method temperature of reaction is below solution boiling point, and process is carried out at ambient pressure, and equipment cost is low, easy handling and security is good.
Principle of the present invention is that chromite reacts at 150 ~ 350 DEG C with oxidizing gas in the reactor being added with longitudinal guide shell and/or transverse baffle with certain density potassium hydroxide, salt of wormwood, potassium metaaluminate solution, makes trivalent chromium be oxidized to sexavalent chrome and generates Sodium chromate.
For reaching above-mentioned purpose, the present invention adopts following technical scheme:
Low-temperature atmosphere-pressure fluidisation decomposes a method for chromite, comprises the following steps:
(1) add in reactor by potassium hydroxide and the salt of wormwood of optional interpolation and/or the mixed aqueous solution of potassium metaaluminate, preheating, then adds chromite and/or pretreated chromite, passes into oxidizing gas and carry out oxidizing reaction under heating; Salt of wormwood and/or the potassium metaaluminate of optional interpolation wherein can both add, or only add one wherein, also can both all not add;
Wherein, reactor is added with guide shell and/or baffle plate, and the mass ratio of potassium hydroxide and chromite is 2:1 ~ 10:1, such as, be 2.5:1,4:1,5.5:1,7:1,9.5:1 etc.;
(2) the reaction paste thinner that step (1) obtains is diluted, obtain starching containing the solution of potassiumchromate, potassium hydroxide, salt of wormwood, potassium metaaluminate and other water-soluble impurity components and the Solid-liquid mixture of Fu Tie tailings;
(3) mixed slurry obtained step (2) at 80 ~ 130 DEG C, such as, is carry out solid-liquid separation under 85 DEG C, 98 DEG C, 102 DEG C, 110 DEG C, 116 DEG C, 124 DEG C etc. to obtain rich iron tailings and containing chromium alkali lye.
Wherein, it is identical that Posterior circle liquid proportioning is reacted by the present invention's potassium hydroxide used, salt of wormwood, potassium aluminate mixing solutions and factory, therefore can directly use circulation fluid and without the need to removal of impurities, make the present invention be easy to realize industrialization; In addition, add salt of wormwood and potassium aluminate can improve reaction solution boiling point, greatly can reduce operation pressure, reduce facility investment.
In method of the present invention, pre-treatment described in step (1) is mechanical activation and/or calcination activation.
Preferably, described 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, described in step (1), the concentration of potassium hydroxide is 40wt% ~ 80wt%, be such as 42wt%, 46wt%, 55wt%, 62wt%, 70wt%, 73wt%, 78wt% etc., concentration of potassium carbonate is 0wt% ~ 20wt%, be such as 2wt%, 5wt%, 9wt%, 13wt%, 16wt%, 19wt% etc., potassium metaaluminate concentration is 0wt% ~ 20wt%, such as, be 2wt%, 5wt%, 9wt%, 13wt%, 16wt%, 19wt% etc.
Preferably, the temperature of described preheating is 80-120 DEG C, such as, be 85 DEG C, 92 DEG C, 102 DEG C, 110 DEG C, 115 DEG C etc., is preferably 100 DEG C.
In method of the present invention, in step (1), the mass ratio of potassium hydroxide and chromite is 2.5:1 ~ 8:1, is preferably 3:1 ~ 5:1.
In method of the present invention, oxidizing gas described in step (1) is the one kind or two or more mixing in air, oxygen, oxygen-rich air or ozone gas.
In method of the present invention, the temperature of heating is 150 ~ 350 DEG C in step (1), such as, be 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., be preferably 190 ~ 250 DEG C; Reaction times is 0.5 ~ 10h, such as, be 1.1h, 2h, 4h, 7h, 9h etc., is preferably 1 ~ 5h.
In method of the present invention, reactor is the reactor being added with longitudinal guide shell or transverse baffle, and liquid-solid mixing adopts the mode of gas stirring, and alr mode, as Fig. 2, can promote the contact reacts of chromite and reaction medium greatly, improves chromite leaching yield.
In method of the present invention, in step (2) slurry after dilution, the content of potassium hydroxide is 100 ~ 500g/L, such as, be 110g/L, 140g/L, 180g/L, 250g/L, 310g/L, 390g/L, 420g/L, 460g/L, 480g/L etc.
In method of the present invention, step (2) described thinner be water or concentration at below 300g/L, be such as the potassium hydroxide aqueous solution of 10g/L, 40g/L, 80g/L, 150g/L, 210g/L, 250g/L, 290g/L etc.
As optimal technical scheme, method of the present invention, comprises the steps:
(1) potassium hydroxide and the salt of wormwood of optional interpolation and/or the mixed aqueous solution of potassium metaaluminate are added in reactor, be preheated to 80-120 DEG C, then add chromite and/or pretreated chromite, pass into oxidizing gas at being heated to 150 ~ 350 DEG C and carry out oxidizing reaction 0.5 ~ 10h;
Wherein, reactor is added with guide shell and/or baffle plate, the mass ratio of potassium hydroxide and chromite is 2:1 ~ 10:1, the concentration of potassium hydroxide is 40wt% ~ 80wt%, concentration of potassium carbonate is 0wt% ~ 20wt%, potassium metaaluminate concentration is 0wt% ~ 20wt%, and oxidizing gas is the one kind or two or more mixing in air, oxygen, oxygen-rich air or ozone gas;
(2) reaction paste water step (1) obtained or concentration are diluted at the potassium hydroxide aqueous solution of below 300g/L, obtain starching containing the solution of potassiumchromate, potassium hydroxide, salt of wormwood, potassium metaaluminate and other water-soluble impurity components and the Solid-liquid mixture of Fu Tie tailings, in slurry after dilution, the content of potassium hydroxide is 100 ~ 500g/L;
(3) mixed slurry obtained step (2) carries out solid-liquid separation and obtains rich iron tailings and contain chromium alkali lye at 80 ~ 130 DEG C.
Compared with prior art, the present invention has following superiority:
1, from reaction system, leach liquor composition is simple, other difficult separation phases are not introduced in system, in addition, it is identical that Posterior circle liquid proportioning is reacted by potassium hydroxide used, salt of wormwood, potassium aluminate mixing solutions and factory, therefore can directly use circulation fluid and without the need to removal of impurities, make the present invention be easy to realize industrialization; On the other hand the interpolation of salt of wormwood and/or potassium metaaluminate can improve the boiling point under identical alkali concn, reduces the alkali concn of reaction, improves the security of reaction.
2, from reaction conditions, the temperature of reaction of this technique is low, and alkali concn is low, less energy consumption, little to the corrosion of equipment, reduces the production cost generating potassiumchromate.
3, from reaction pressure, this reaction process reaction pressure is normal pressure, and before and after reaction process flow process, required equipment is also normal pressure, and equipment cost is low, easy handling and security is good, is conducive to reducing cost of labor.
4, this reaction process carries out under pilot plant, has taken into full account flowing in zoom facility and by heat problem, has optimized the contact of reaction medium and chromite.Through adopting evaporative crystallization liquid in Industrial processes to carry out experimental result well, production can be directly applied to.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the inventive method;
Fig. 2 is inside reactor structure iron.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment only understands the present invention for helping, and should not be considered as concrete restriction of the present invention.
Fig. 1 is the schematic flow sheet of the inventive method.Fig. 2 is inside reactor structure iron.
Embodiment 1
Low-temperature atmosphere-pressure fluidisation decomposes a method for chromite, comprises the following steps:
1) configure certain density potassium hydroxide, salt of wormwood, the potassium metaaluminate aqueous solution, add fluidized-bed reactor, be preheated to 100 DEG C.The content of this solution potassium hydroxide, salt of wormwood, potassium metaaluminate is 40%, 10%, 5% respectively.The chromite being below 200 orders by screening mixes with this solution, and wherein the mass ratio of potassium hydroxide and chromite is 10:1, i.e. chromite 7kg, potassium hydroxide mixing solutions 120L;
2) continue heated fluidized bed reactor, open pressurized air, control airshed at 10m
3/ h, 10h at maintaining 240 DEG C, air flow quantity is not less than 12m
3/ h;
3) cooling sampling dilution, be diluted to reaction slurry concentration of potassium hydroxide 300g/L, by mixed slurry filtering separation under about 80 DEG C, obtain rich iron tailings respectively and contain chromium alkali lye, record chromium content by after tailings repetitive scrubbing, drying through titration, calculating chromium solubility rate is 95.05%.
Embodiment 2
1) configure certain density potassium hydroxide, salt of wormwood, the potassium metaaluminate aqueous solution, add fluidized-bed reactor, be preheated to 100 DEG C, the content of this solution potassium hydroxide, salt of wormwood, potassium metaaluminate is 50%, 10%, 0% respectively.The chromite being below 200 orders by screening mixes with this solution, and wherein the mass ratio of potassium hydroxide and chromite is 5:1, i.e. chromite 18kg, potassium hydroxide mixing solutions 120L;
2) continue heated fluidized bed reactor, and open pressurized air, control airshed at 10m
3/ h, 8h at maintaining 255 DEG C, air flow quantity is not less than 12m
3/ h;
3) cooling sampling dilution, be diluted to reaction slurry concentration of potassium hydroxide 300g/L, by mixed slurry filtering separation under about 80 DEG C, obtain rich iron tailings respectively and contain chromium alkali lye, record chromium content by after tailings repetitive scrubbing, drying through titration, calculating chromium solubility rate is 96.11%.
Embodiment 3
1) configure certain density potassium hydroxide, salt of wormwood, the potassium metaaluminate aqueous solution, add fluidized-bed reactor, be preheated to 100 DEG C, the content of this solution potassium hydroxide, salt of wormwood, potassium metaaluminate is 50%, 10%, 5% respectively.。The chromite being below 200 orders by screening mixes with this solution, and wherein the mass ratio of potassium hydroxide and chromite is 3:1, i.e. chromite 30kg, potassium hydroxide mixing solutions 120L;
2) continue heated fluidized bed reactor, and open pressurized air, control airshed at 10m
3/ h, 6h at maintaining 285 DEG C, air flow quantity is not less than 16m
3/ h;
3) cooling sampling dilution, be diluted to reaction slurry concentration of potassium hydroxide 120g/L, by mixed slurry filtering separation under about 100 DEG C, obtain rich iron tailings respectively and contain chromium alkali lye, record chromium content by after tailings repetitive scrubbing, drying through titration, calculating chromium solubility rate is 98.52%.
Embodiment 4
1) configure certain density potassium hydroxide, salt of wormwood, the potassium metaaluminate aqueous solution, add fluidized-bed reactor, be preheated to 80 DEG C, the content of this solution potassium hydroxide, salt of wormwood, potassium metaaluminate is 60%, 10%, 5% respectively.The chromite being below 200 orders by screening mixes with this solution, and wherein the mass ratio of potassium hydroxide and chromite is 5:1, i.e. chromite 22kg, potassium hydroxide mixing solutions 120L;
2) continue heated fluidized bed reactor, and open pressurized air, control airshed at 10m
3/ h, 0.5h at maintaining 340 DEG C, control air flow quantity and be not less than 16m
3/ h;
3) cooling sampling dilution, be diluted to reaction slurry concentration of potassium hydroxide 450g/L, by mixed slurry filtering separation under about 130 DEG C, obtain rich iron tailings respectively and contain chromium alkali lye, record chromium content by after tailings repetitive scrubbing, drying through titration, calculating chromium solubility rate is 95.7%.
Embodiment 5
1) configure certain density potassium hydroxide, salt of wormwood, the potassium metaaluminate aqueous solution, add fluidized-bed reactor, be preheated to 120 DEG C, the content of this solution potassium hydroxide, salt of wormwood, potassium metaaluminate is 50%, 10%, 5% respectively.The chromite being below 200 orders by screening mixes with this solution, and wherein the mass ratio of potassium hydroxide and chromite is 4:1, i.e. chromite 23kg, potassium hydroxide mixing solutions 120L;
2) continue heated fluidized bed reactor, and open pressurized air, control airshed at 10m
3/ h, 6h at maintaining 270 DEG C, control air flow quantity and be not less than 16m
3/ h;
3) cooling sampling dilution, be diluted to reaction slurry concentration of potassium hydroxide 300g/L, by mixed slurry filtering separation under about 90 DEG C, obtain rich iron tailings respectively and contain chromium alkali lye, record chromium content by after tailings repetitive scrubbing, drying through titration, calculating chromium solubility rate is 97%.
Embodiment 6
1) configure certain density potassium hydroxide, salt of wormwood, the potassium metaaluminate aqueous solution, add fluidized-bed reactor, be preheated to 100 DEG C, the content of this solution potassium hydroxide, salt of wormwood, potassium metaaluminate is 50%, 5%, 10% respectively.The chromite being below 200 orders by screening mixes with this solution, and wherein the mass ratio of potassium hydroxide and chromite is 3.5:1, i.e. chromite 26kg, potassium hydroxide mixing solutions 120L;
2) continue heated fluidized bed reactor, and open pressurized air, control airshed at 10m
3/ h, 6h at maintaining 280 DEG C, control air flow quantity and be not less than 16m
3/ h;
3) cooling sampling dilution, be diluted to reaction slurry concentration of potassium hydroxide 300g/L, by mixed slurry filtering separation under about 80 DEG C, obtain rich iron tailings respectively and contain chromium alkali lye, record chromium content by after tailings repetitive scrubbing, drying through titration, calculating chromium solubility rate is 96.99%.
Embodiment 7
1) potassium hydroxide, salt of wormwood, the potassium metaaluminate aqueous solution are added fluidized-bed reactor, be preheated to 90 DEG C, this solution is from industrial evaporative crystallization mother liquor, and the content of potassium hydroxide, salt of wormwood, potassium metaaluminate is 70%, 5%, 5% respectively.The chromite being below 200 orders by screening mixes with this solution, and wherein the mass ratio of potassium hydroxide and chromite is 2:1, i.e. chromite 60kg, potassium hydroxide mixing solutions 120L;
2) continue heated fluidized bed reactor, and open oxygen, control airshed at 10m
3/ h, 6h at maintaining 300 DEG C, control oxygen flow and be not less than 20m
3/ h;
3) cooling sampling dilution, be diluted to reaction slurry concentration of potassium hydroxide 350g/L, by mixed slurry filtering separation under about 80 DEG C, obtain rich iron tailings respectively and contain chromium alkali lye, record chromium content by after tailings repetitive scrubbing, drying through titration, calculating chromium solubility rate is 95.34%.
Embodiment 8
1) configure certain density potassium hydroxide, salt of wormwood, the potassium metaaluminate aqueous solution, add fluidized-bed reactor, be preheated to 100 DEG C, the content of this solution potassium hydroxide, salt of wormwood, potassium metaaluminate is 50%, 20%, 5% respectively.The chromite being below 200 orders by screening mixes with this solution, and wherein the mass ratio of potassium hydroxide and chromite is 3.3:1, i.e. chromite 27kg, potassium hydroxide mixing solutions 120L;
2) continue heated fluidized bed reactor, and open pressurized air, control airshed at 10m
3/ h, 6h at maintaining 280 DEG C, control air flow quantity and be not less than 16m
3/ h;
3) cooling sampling dilution, be diluted to reaction slurry concentration of potassium hydroxide 300g/L, by mixed slurry filtering separation under about 80 DEG C, obtain rich iron tailings respectively and contain chromium alkali lye, record chromium content by after tailings repetitive scrubbing, drying through titration, calculating chromium solubility rate is 98.1%.
Embodiment 9
1) configure certain density potassium hydroxide, salt of wormwood, the potassium metaaluminate aqueous solution, add fluidized-bed reactor, be preheated to 100 DEG C, the content of this solution potassium hydroxide, salt of wormwood, potassium metaaluminate is 50%, 5%, 20% respectively.The chromite being below 200 orders by screening mixes with this solution, and wherein the mass ratio of potassium hydroxide and chromite is 3.3:1, i.e. chromite 27kg, potassium hydroxide mixing solutions 120L;
2) continue heated fluidized bed reactor, and open pressurized air, control airshed at 10m
3/ h, 6h at maintaining 280 DEG C, control air flow quantity and be not less than 16m
3/ h;
3) cooling sampling dilution, be diluted to reaction slurry concentration of potassium hydroxide 300g/L, by mixed slurry filtering separation under about 80 DEG C, obtain rich iron tailings respectively and contain chromium alkali lye, record chromium content by after tailings repetitive scrubbing, drying through titration, calculating chromium solubility rate is 96.4%.
Embodiment 10
1) configure certain density potassium hydroxide, salt of wormwood, the potassium metaaluminate aqueous solution, add fluidized-bed reactor, be preheated to 100 DEG C, the content of this solution potassium hydroxide, salt of wormwood, potassium metaaluminate is 80%, 0%, 0% respectively.The chromite being below 200 orders by screening mixes with this solution, and wherein the mass ratio of potassium hydroxide and chromite is 3.3:1, i.e. chromite 42kg, potassium hydroxide solution 120L;
2) continue heated fluidized bed reactor, and open pressurized air, control airshed at 10m
3/ h, 6h at maintaining 250 DEG C, control air flow quantity and be not less than 16m
3/ h;
3) cooling sampling dilution, be diluted to reaction slurry concentration of potassium hydroxide 300g/L, by mixed slurry filtering separation under about 80 DEG C, obtain rich iron tailings respectively and contain chromium alkali lye, record chromium content by after tailings repetitive scrubbing, drying through titration, calculating chromium solubility rate is 98.5%.
Embodiment 11
1) fluidized-bed reactor is added through the filtrate of filtering separation through the circulation fluid of evaporative crystallization by after industrial reaction chromite, be preheated to 100 DEG C, the content of this main component in solution potassium hydroxide, salt of wormwood, potassium metaaluminate is 48%, 10%, 5% respectively, the chromite being below 200 orders by screening mixes with this solution, wherein the mass ratio of potassium hydroxide and chromite is 3.5:1, i.e. chromite 27kg, industrial stoste 120L;
2) continue heated fluidized bed reactor, and open pressurized air, control airshed at 10m
3/ h, 6h at maintaining 160 DEG C, control air flow quantity and be not less than 16m
3/ h;
3) cooling sampling dilution, be diluted to reaction slurry concentration of potassium hydroxide 300g/L, by mixed slurry filtering separation under about 80 DEG C, obtain rich iron tailings respectively and contain chromium alkali lye, record chromium content by after tailings repetitive scrubbing, drying through titration, calculating chromium solubility rate is 97.6%.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. low-temperature atmosphere-pressure fluidisation decomposes a method for chromite, comprises the following steps:
(1) add in reactor by potassium hydroxide and the salt of wormwood of optional interpolation and/or the mixed aqueous solution of potassium metaaluminate, preheating, then adds chromite and/or pretreated chromite, passes into oxidizing gas and carry out oxidizing reaction under heating;
Wherein, reactor is added with guide shell and/or baffle plate, and the mass ratio of potassium hydroxide and chromite is 2:1 ~ 10:1;
(2) the reaction paste thinner that step (1) obtains is diluted, obtain starching containing the solution of potassiumchromate, potassium hydroxide, salt of wormwood, potassium metaaluminate and other water-soluble impurity components and the Solid-liquid mixture of Fu Tie tailings;
(3) mixed slurry obtained step (2) carries out solid-liquid separation and obtains rich iron tailings and contain chromium alkali lye at 80 ~ 130 DEG C.
2. method according to claim 1, is characterized in that, pre-treatment described in step (1) is mechanical activation and/or calcination activation;
Preferably, described mechanical activation is the one kind or two or more combination of roller ball mill, planetary ball mill or stirring ball-milling.
3. method according to claim 1, is characterized in that, described in step (1), the concentration of potassium hydroxide is 40wt% ~ 80wt%, and concentration of potassium carbonate is 0wt% ~ 20wt%, and potassium metaaluminate concentration is 0wt% ~ 20wt%;
Preferably, the temperature of described preheating is 80-120 DEG C, is preferably 100 DEG C.
4. method according to claim 1, is characterized in that, in step (1), the mass ratio of potassium hydroxide and chromite is 2.5:1 ~ 8:1, is preferably 3:1 ~ 5:1.
5. method according to claim 1, is characterized in that, oxidizing gas described in step (1) is the one kind or two or more mixing in air, oxygen, oxygen-rich air or ozone gas.
6. method according to claim 1, is characterized in that, in step (1), the temperature of heating is 150 ~ 350 DEG C, is preferably 190 ~ 250 DEG C; Reaction times is 0.5 ~ 10h, is preferably 1 ~ 5h.
7. the method according to any one of claim 1-6, is characterized in that, reactor is the reactor being added with longitudinal guide shell or transverse baffle, and liquid-solid mixing adopts the mode of gas stirring.
8. method according to claim 1, is characterized in that, in step (2) slurry after dilution, the content of potassium hydroxide is 100 ~ 500g/L.
9. method according to claim 1, is characterized in that, step (2) described thinner is water or the concentration potassium hydroxide aqueous solution at below 300g/L.
10. method according to claim 1, is characterized in that, comprises the steps:
(1) potassium hydroxide and the salt of wormwood of optional interpolation and/or the mixed aqueous solution of potassium metaaluminate are added in reactor, be preheated to 80-120 DEG C, then add chromite and/or pretreated chromite, pass into oxidizing gas at being heated to 150 ~ 350 DEG C and carry out oxidizing reaction 0.5 ~ 10h;
Wherein, reactor is added with guide shell and/or baffle plate, the mass ratio of potassium hydroxide and chromite is 2:1 ~ 10:1, the concentration of potassium hydroxide is 40wt% ~ 80wt%, concentration of potassium carbonate is 0wt% ~ 20wt%, potassium metaaluminate concentration is 0wt% ~ 20wt%, and oxidizing gas is the one kind or two or more mixing in air, oxygen, oxygen-rich air or ozone gas;
(2) reaction paste water step (1) obtained or concentration are diluted at the potassium hydroxide aqueous solution of below 300g/L, obtain starching containing the solution of potassiumchromate, potassium hydroxide, salt of wormwood, potassium metaaluminate and other water-soluble impurity components and the Solid-liquid mixture of Fu Tie tailings, in slurry after dilution, the content of potassium hydroxide is 100 ~ 500g/L;
(3) mixed slurry obtained step (2) carries out solid-liquid separation and obtains rich iron tailings and contain chromium alkali lye at 80 ~ 130 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310722901.7A CN104726689B (en) | 2013-12-24 | 2013-12-24 | Method for decomposing chromite by low-temperature atmospheric-pressure fluidization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310722901.7A CN104726689B (en) | 2013-12-24 | 2013-12-24 | Method for decomposing chromite by low-temperature atmospheric-pressure fluidization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104726689A true CN104726689A (en) | 2015-06-24 |
| CN104726689B CN104726689B (en) | 2017-05-10 |
Family
ID=53451099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310722901.7A Active CN104726689B (en) | 2013-12-24 | 2013-12-24 | Method for decomposing chromite by low-temperature atmospheric-pressure fluidization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104726689B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107902699A (en) * | 2017-11-14 | 2018-04-13 | 中国科学院过程工程研究所 | A kind of decomposition method of continuous pressure self-heating liquid phase oxidation chromite |
| CN111850298A (en) * | 2020-07-16 | 2020-10-30 | 许裕金 | Method for extracting and purifying non-metallic ore by energy-gathering system equipment |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4045340A (en) * | 1975-08-28 | 1977-08-30 | Luigi Stoppani Di P Stoppani & C. | Method for recovering and exploiting waste of the chromic anhydride production |
| CN101481144A (en) * | 2008-01-09 | 2009-07-15 | 中国科学院过程工程研究所 | Clean production method for preparing potassium chromate from chromic iron |
| CN102320661A (en) * | 2011-09-06 | 2012-01-18 | 重庆民丰化工有限责任公司 | Three-phase catalytic oxidation preparation technology of soluble chromate |
| CN103449522A (en) * | 2012-06-01 | 2013-12-18 | 中国科学院过程工程研究所 | Method for producing chromates through using chromium-containing waste residues |
-
2013
- 2013-12-24 CN CN201310722901.7A patent/CN104726689B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4045340A (en) * | 1975-08-28 | 1977-08-30 | Luigi Stoppani Di P Stoppani & C. | Method for recovering and exploiting waste of the chromic anhydride production |
| CN101481144A (en) * | 2008-01-09 | 2009-07-15 | 中国科学院过程工程研究所 | Clean production method for preparing potassium chromate from chromic iron |
| CN102320661A (en) * | 2011-09-06 | 2012-01-18 | 重庆民丰化工有限责任公司 | Three-phase catalytic oxidation preparation technology of soluble chromate |
| CN103449522A (en) * | 2012-06-01 | 2013-12-18 | 中国科学院过程工程研究所 | Method for producing chromates through using chromium-containing waste residues |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107902699A (en) * | 2017-11-14 | 2018-04-13 | 中国科学院过程工程研究所 | A kind of decomposition method of continuous pressure self-heating liquid phase oxidation chromite |
| CN107902699B (en) * | 2017-11-14 | 2019-09-27 | 中国科学院过程工程研究所 | A kind of decomposition method of continuous pressure self-heating liquid phase oxidation chromite |
| CN111850298A (en) * | 2020-07-16 | 2020-10-30 | 许裕金 | Method for extracting and purifying non-metallic ore by energy-gathering system equipment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104726689B (en) | 2017-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101817561B (en) | Method for pollution-free production of sodium chromate by pressure leaching of chromite | |
| CN104313361B (en) | A kind of Leaching of Vanadium from Vanadium slag containing chromium and the process of coproduction chromium-base alloy | |
| CN102251119B (en) | Method for recycling vanadium extraction tailings | |
| CN104726705B (en) | A kind of chromite leaches the method for carrying chromium | |
| CN101659444B (en) | Clean production method for preparing sodium chromate from chromite | |
| CN103060838B (en) | In a kind of potassium hydroxide solution, electrochemical decomposition chromite extracts the method for chromium | |
| CN106065435A (en) | A kind of method and system processing vanadium slag | |
| CN103668301B (en) | Electrolysis is utilized to prepare the apparatus and method of chromium acid sodium solution | |
| CN108315522B (en) | The method that microwave reinforced direct-reduction processing ilmenite produces reduced iron powder and rich-titanium material | |
| CN106148988A (en) | The molten electrolysis of ferrochrome acid produces chromic anhybride technique | |
| CN101481144B (en) | Clean production method for preparing potassium chromate from chromic iron | |
| CN108642276A (en) | A kind of method that acid decomposition scheelite prepares tungsten oxide and tungsten powder | |
| CN110055371A (en) | The method that molten iron production vanadium slag containing sodium directly leaches vanadium extraction | |
| CN108441629A (en) | A kind of method that acid decomposition Scheelite-Wolframite Mixed Mine prepares tungsten oxide and tungsten powder | |
| CN109971908A (en) | Converter molten iron adds the method for soda manufacture vanadium slag containing sodium | |
| CN104760997A (en) | Production method of sodium chromate with alkali liquid circulation and liquid phase oxidization | |
| CN105314679A (en) | Process for preparing chromic anhydride and dichromate by carbon ferrochrome liquid phase method | |
| CN104726689B (en) | Method for decomposing chromite by low-temperature atmospheric-pressure fluidization | |
| CN101328540B (en) | Method for reclaiming sodium molybdate solution from molybdenum-containing leached residue | |
| CN104973627A (en) | Method for producing chromic oxide from carbon ferrochrome | |
| CN103086433A (en) | Method for preparing sodium dichromate by sodium-based molten salt oxidation continuous carbonization | |
| CN103183384B (en) | The method that a kind of preroast strengthening sub-molten salt decomposes chromite | |
| CN104278152A (en) | Molten-alkali-method-leaching comprehensive utilization process for laterite-nickel ore | |
| CN105016388B (en) | The environmentally protective manufacture chromium compound technique of carbon ferrochrome clean energy-saving | |
| CN110042192A (en) | Converter adds the method for soda manufacture vanadium slag containing sodium and its Oxidation Leaching |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |