CN104843790A - Method for preparing sodium chromate from chromite by acid dissolution oxygenation - Google Patents
Method for preparing sodium chromate from chromite by acid dissolution oxygenation Download PDFInfo
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Abstract
The invention discloses a method for preparing sodium chromate from chromite by acid dissolution oxygenation. The method comprises the following steps of adding sulfuric acid into chromite ground into mineral powder, controlling reaction temperature, pressure and time, performing filtration after reaction, adding calcium-containing ores into filtrate to regulate the pH value to 2 to 5.5, performing filtration, adding an alkaline matter into filtrate to regulate the pH value to 4 to 6.5, performing filtration, adding an alkaline matter into filtrate to regulate the pH value to 6.5 to 9.5, and performing filtration to obtain solid chromium hydroxide; beating chromium hydroxide, adding an alkaline matter into beaten fluid to regulate the pH value to 8 to 14, controlling reaction temperature, pressure and time, adding an alkaline matter to regulate the pH value to 9 to 14 after reaction, performing filtration, adding an alkaline matter into filtrate to regulate the pH value to 6 to 9, performing filtration, and concentrating filtrate and crystallizing to obtain sodium chromate. According to the method, an oxidant can be added into chromite for reaction in a pressure strong-acid environment to damage a spinel structure of chromite and increase the dissolution rate of chromite, and the pH value can be regulated to effectively separate chromium ions from impurities.
Description
Technical field
The invention belongs to technical field of mineral processing, be specifically related to the method that Sodium chromate is prepared in the acid-soluble oxidation of a kind of chromite.
Background technology
Current Sodium chromate prepare large be raw material mainly with chromite, substantially adopt several method: have calcium roasting, few calcium or calcium-free roasting, the oxidizing method of ferrochrome alkali, the tower Continuous Liquid Phase oxidation technology of Pneumatic fluidized, potassium system sub-molten salt liquid phase oxidation etc., by the roasting of chromite or add alkali high temperature oxidation and obtain Sodium chromate.
The main drawback of calcium roasting is had to be that deslagging is many, slag contains sexavalent chrome up to 1% ~ 1.5% (in chromium trioxide), particularly containing the acid-soluble sexavalent chrome existed with sosoloid form, be difficult to removing toxic substances or utilize, cause larger environmental pollution, the chromium recovery ratio therefore in chromite is 75% ~ 80%.
The grog of few calcium or calcium-free roasting does not have acid-soluble chromium, and oxidation ratio is consistent with the numerical value of transformation efficiency, and on the other hand, because the technique return slag amount of adding is large, chrome content is high.A chromium slag part is as chromium salt production, and another part, as producing the starting material of ferrochrome, also has a small amount of untreated chromium slag, goes down for a long time, contaminate environment and increase loss.
The chromium slag that the tower Continuous Liquid Phase oxidation technology of Pneumatic fluidized, potassium system sub-molten salt liquid phase oxidation produce can be used for as the additive producing cement after smelt iron or high-temperature detoxification, but the limited and secondary pollution easily produced environment that has high input of the amount of process.
The technology of the acid-soluble process chromite of current use, Problems existing mainly trivalent chromium is separated with ferric.Trivalent chromium is with ferric to be separated conventional be first ferrous iron by ferric iron back, then add oxalic acid to be separated, this separation method mesoxalic acid cost is high, separating effect is general, the high efficiency separation of chromium and iron cannot be realized, thus cause the content overproof of iron in the chromium product prepared to cause chromium product not meet the demands.
Patent documentation CN101979679A discloses " a kind of method for the treatment of chromite by sulfuric acid leaching ", chromite " is ground to form breeze by the method, sulfuric acid is added in breeze, stir, add oxygenant, oxygenant is chromic trioxide, Potcrate or ammonium persulphate, its add-on is 0.2% ~ 7% of powdered ore quality, heating, Heating temperature is 120 ~ 190 DEG C, control reaction pressure is 0.2 ~ 1.2MPa, reaction times is 30 ~ 90min, react rear filtration, carry out solid-liquid separation, filter residue is directly as the raw material of smelting duriron, chromium sulfate solution is obtained by carrying out deironing process to filtrate, method further by direct crystallization prepares chromium sulphate ".This method after completion of the reaction, only carry out deironing process, and there is no detailed deironing treatment process, but containing impurity such as a certain amount of magnesium, aluminium in chromite, if do not processed, the purity of the product obtained can not improve, affect the quality of product, therefore need to carry out reasonably processing these impurity, in addition, the reaction pressure that the method adopts is lower, causes its reaction effect poor.Academic dissertation " chromite sulfuric acid leaching prepares the research of basic chromium sulfate process for cleanly preparing, Shi Peiyang, Northeastern University; 2002 " discloses the method adopting vitriolization chromite, but adopt synthesis under normal pressure in the method, its reaction effect is poor, and adopt complicated deironing treatment process.
Summary of the invention
As the result of various extensive and careful research and experiment, the present inventor has been found that, the reaction that chromite adds oxygenant under the environment of pressurization, strong acid can destroy chromite spinel structure, the solubility rate of chromite can be improved, and regulate pH can make effectively being separated of iron, aluminium, magnesium etc. and chromium, make the rate of recovery of chromite 85% ~ 90%, the high Sodium chromate of purity can be obtained simultaneously, based on this discovery, complete the present invention.
An object of the present invention is to solve at least the problems referred to above and/or defect, and the advantage will illustrated at least is below provided.
A further object of the invention is to provide the method that Sodium chromate is prepared in the acid-soluble oxidation of a kind of chromite, comprises the following steps:
Step one, chromite being ground to form granularity is 100 ~ 200 object breezes, then breeze to be added in reactor and to add sulfuric acid, stir with the speed of 300 ~ 800 revs/min, reacting by heating, and control reaction pressure and reaction times, resultant feed liquid is obtained after having reacted, resultant feed liquid is filtered and carries out solid-liquid separation, calcic ore adjust ph is added to 2-5.5 in filtrate, cross and filter calcium sulfate precipitation, then in filtrate, alkaline matter adjust ph is added to 4-6.5, cross and filter precipitation, and in filtrate, add alkaline matter adjust ph to 6.5-9.5, filtration obtains solid hydrogen chromic oxide,
Step 2, get the solid hydrogen chromic oxide obtained in 1 weight part step one, pull an oar after adding 0.5 ~ 1.5 weight parts water, obtain liquid of pulling an oar, making beating liquid is added in reactor, and add alkaline matter adjust ph to 8 ~ 14, reacting by heating, and control reaction pressure and reaction times, after having reacted, obtain resultant feed liquid, in resultant feed liquid, add alkaline matter adjust ph to 9-14, cross and filter precipitation, and in filtrate, add alkaline matter adjust ph to 6-9, cross and filter precipitation, filtrate obtains Sodium chromate after concentrated, crystallization.
Preferably, also need to add oxygenant after adding sulfuric acid in described step one.
Preferably, described oxygenant is the combination of one or more in sodium dichromate, oxygen, chromic trioxide, superoxide, persulphate, and its add-on is 0 ~ 50% of powdered ore quality.
Preferably, described superoxide is the one in sodium peroxide or hydrogen peroxide; Described persulphate is the one in Sodium Persulfate or ammonium persulphate.
Preferably, in described step one, the mass concentration of sulfuric acid is 1 ~ 90%, and its add-on is 0.3 ~ 0.9 times of powdered ore quality.
Preferably, described alkaline matter is the combination of one or more in sodium bicarbonate, sodium carbonate and oxygen sodium oxide; Described calcic ore is the combination of one or more in unslaked lime, white lime, rhombspar.
Preferably, in described step one, temperature of reaction is 50 ~ 360 DEG C, and reaction pressure is 0.3 ~ 8MPa, and the reaction times is 10 ~ 400min.
Preferably, also need before reacting by heating in described step 2 to add oxygen, its add-on is 0 ~ 99% of chromium hydroxide quality.
Preferably, in described step 2, temperature of reaction is room temperature ~ 360 DEG C, and reaction pressure is 0.01 ~ 8MPa, and the reaction times is 1 ~ 400min.
Preferably, the reacting by heating in described step one and step 2 all adopts microwave heating, and the microwave frequency of microwave heating is 2450 ± 50MHz.
The composition of the chromite described in the present invention is as shown in table 1:
Table 1
The main chemical reactions formula of the composition in step one of the present invention in chromite and sulfuric acid reaction is as follows:
Fe(CrO
2)
2+4H
2SO
4→FeSO
4+Cr
2(SO
4)
3+4H
2O
(Mg，Fe)Cr
2O
4+5H
2SO
4→FeSO
4+Cr
2(SO
4)
3+MgSO
4+5H
2O
MgCr
2O
4+4H
2SO
4→MgSO
4+Cr
2(SO
4)
3+4H
2O
(Mg，Fe)
7Si
8O
22(OH)
2+7H
2SO
4→7FeSiO
3↓+7MgSO
4↓+SiO
2↓+8H
2O
Wherein preferred oxygenant sodium dichromate dissolves Fe (CrO
2)
2master equation as follows:
Na
2Cr
2O
7+2Fe(CrO
2)
2+10H
2SO
4→Fe
2(SO
4)
3+2Cr
2(SO
4)
3+Na
2SO
4+10H
2O
Preferred oxygenant oxygen and Fe (CrO
2)
2the master equation of reaction is as follows:
O
2+4Fe(CrO
2)
2+18H
2SO
4→2Fe
2(SO
4)
3+4Cr
2(SO
4)
3+18H
2O
Preferred oxygenant chromic trioxide and Fe (CrO
2)
2the master equation of reaction is as follows:
2CrO
3+6Fe(CrO
2)
2+30H
2SO
4→3Fe
2(SO
4)
3+7Cr
2(SO
4)
3+30H
2O
Preferred oxygenant persulphate dissolves Fe (CrO
2)
2the master equation of reaction is as follows:
S
2O
8 2-+2Fe(CrO
2)
2+8H
2SO
4→Fe
2(SO
4)
3+2Cr
2(SO
4)
3+8H
2O+SO
4 2-
Preferred oxygenant superoxide dissolves Fe (CrO
2)
2the master equation of reaction is as follows:
O
2 2-+2Fe(CrO
2)
2+9H
2SO
4→Fe
2(SO
4)
3+2Cr
2(SO
4)
3+9H
2O+O
2-
After oxidizing reaction completes in the present invention, filter and carry out solid-liquid separation, the main component of the filter residue obtained is FeSiO
3, SiO
2deng, these filter residues can be used as the raw material of smelting duriron; Calcic ore adjust ph is added to 2-5.5 in the filtrate obtained, in filtrate, excess sulfuric acid generates calcium sulfate precipitation with the calcium ion added, cross and filter calcium sulfate precipitation, filter residue calcium sulfate can do gypsum, then in filtrate, alkaline matter adjust ph is added to 4-6.5, in this process, part magnesium ion, iron ion and aluminum ion in filtrate can produce with alkaline matter and precipitate, cross and filter precipitation, and in filtrate, add alkaline matter adjust ph to 6.5-9.5, chromium ion can produce with alkaline matter and precipitate in this process, i.e. solid hydrogen chromic oxide.
In the present invention oxygenant add the solubility rate that can improve chromite, the kind of oxygenant is the combination of one or more in sodium dichromate, oxygen, chromic trioxide, superoxide, persulphate, the use of these oxygenants can not bring other impurity into, ensure that the purity of the finished product.
Alkaline matter is the combination of one or more in sodium bicarbonate, sodium carbonate and oxygen sodium oxide in the present invention, the alkaline matter used is not when bringing other impurity into, iron ion, magnesium ion and aluminum ion effectively can be made to precipitate, achieve being separated of foreign ion and chromium ion.
In step 2 of the present invention, preferably can add oxygen promote that reaction is carried out, trivalent chromium oxidation is generated sexavalent chrome, after having reacted, alkaline matter adjust ph is added to 9-14 in resultant feed liquid, impurity iron ion and alkaline matter produce and precipitate in this process, cross and filter precipitation, realize being separated of hexavalent chromium and iron ion, and in filtrate, add alkaline matter adjust ph to 6-9, impurity aluminum ion and alkaline matter produce and precipitate in this process, cross and filter precipitation, realize hexavalent chromium to be separated with aluminum ions, filtrate is through concentrated, Sodium chromate is obtained after crystallization.
In the present invention, reacting by heating in step one and step 2 all adopts microwave heating, and microwave is a kind of hertzian wave with special property, and its frequency is between radiowave and light wave, its heating rate is fast, can make raw material in short-term, reach reaction temperature required, therefore energy consumption is lower, simultaneously in microwave heating process, material is self-heating, relative to the mode of existing air conduction, the projecting envrionment temperature of temperature of charge, can make reaction more abundant.
The present invention at least comprises following beneficial effect:
(1) reaction that in the present invention, chromite adds oxygenant under the environment of pressurization, strong acid can destroy chromite spinel structure, improves the solubility rate of chromite, and by adjust ph, iron, aluminium, silicon, magnesium plasma is effectively separated with chromium ion;
(2) in the filter residue produced in preparation process of the present invention, chromic content is for being less than 0.01%, total chrome content is less than 0.3%, the rate of recovery of chromite is 85% ~ 90%, compared with preparing the method for Sodium chromate with existing chromite process, there is technical process feature that is short, that discharge without " three wastes ", filter residue content is few and not containing sexavalent chrome, as smelting duriron, the raw material preparing gypsum etc., can improve the recycle of resource.
Part is embodied by explanation below by other advantage of the present invention, target and feature, part also will by research and practice of the present invention by those skilled in the art is understood.
Accompanying drawing illustrates:
Fig. 1 is the process flow sheet that step one in Sodium chromate method is prepared in the acid-soluble oxidation of chromite of the present invention;
Fig. 2 is the process flow sheet that step 2 in Sodium chromate method is prepared in the acid-soluble oxidation of chromite of the present invention;
Embodiment:
Below in conjunction with accompanying drawing, the present invention is described in further detail, can implement according to this with reference to specification sheets word to make those skilled in the art.
Should be appreciated that used hereinly such as " to have ", other element one or more do not allotted in " comprising " and " comprising " term or the existence of its combination or interpolation.
Embodiment 1:
A method for Sodium chromate is prepared in the acid-soluble oxidation of chromite, comprises the following steps:
Step one, chromite is ground to form granularity is 200 object breezes, then being added by breeze in reactor and adding mass concentration is 20% sulfuric acid, sulphuric acid is 0.9 times of powdered ore quality, then stir with the speed of 500 revs/min and add oxygenant sodium dichromate, sodium dichromate add-on is 10% of powdered ore quality, reacting by heating temperature is 50 DEG C, and to control reaction pressure be 1.0MPa and reaction times 100min;
Above-mentioned technological process main chemical reactions is as follows:
Fe(CrO
2)
2+4H
2SO
4→FeSO
4+Cr
2(SO
4)
3+4H
2O
(Mg，Fe)Cr
2O
4+5H
2SO
4→FeSO
4+Cr
2(SO
4)
3+MgSO
4+5H
2O
MgCr
2O
4+4H
2SO
4→MgSO
4+Cr
2(SO
4)
3+4H
2O
(Mg，Fe)
7Si
8O
22(OH)
2+7H
2SO
4→7FeSiO
3↓+7MgSO
4↓+SiO
2↓+8H
2O
Oxygenant sodium dichromate dissolves Fe (CrO
2)
2master equation as follows:
Na
2Cr
2O
7+2Fe(CrO
2)
2+10H
2SO
4→Fe
2(SO
4)
3+2Cr
2(SO
4)
3+Na
2SO
4+10H
2O
Resultant feed liquid is obtained after having reacted, resultant feed liquid is filtered and carries out solid-liquid separation, filter residue can be used as the raw material of smelting duriron, unslaked lime adjust ph to 2 is added in filtrate, generate calcium sulfate precipitation, cross and filter calcium sulfate precipitation, filter residue calcium sulfate can do gypsum, then in filtrate, add sodium bicarbonate and sodium hydroxide adjust ph to 4 that weight ratio is 1:1, in this process, part magnesium ion in filtrate, iron ion and aluminum ion can produce with alkaline matter and precipitate, cross and filter precipitation, and in filtrate, add the sodium bicarbonate and sodium hydroxide adjust ph to 8 that weight ratio is 1:1, chromium ion can produce with alkaline matter and precipitate in this process, filtration obtains solid hydrogen chromic oxide,
Step 2, get the solid hydrogen chromic oxide obtained in 1 weight part step one, pull an oar after adding 1 weight parts water, obtain liquid of pulling an oar, making beating liquid is added in reactor, and add the sodium bicarbonate and sodium hydroxide adjust ph to 8 that weight ratio is 1:1, then oxygen is added, the amount of oxygen is 60% of chromium hydroxide quality, reacting by heating temperature is 90 DEG C, and control reaction pressure 2MPa and reaction times 100min, after having reacted, obtain resultant feed liquid, the sodium bicarbonate that weight ratio is 1:1 and sodium hydroxide adjust ph to 9 is added in resultant feed liquid, impurity iron ion and alkaline matter produce and precipitate in this process, cross and filter precipitation, realize being separated of hexavalent chromium and iron ion, and in filtrate, add the sodium bicarbonate and sodium hydroxide adjust ph to 6 that weight ratio is 1:1, impurity aluminum ion and alkaline matter produce and precipitate in this process, cross and filter precipitation, realize hexavalent chromium to be separated with aluminum ions, filtrate is through concentrated, Sodium chromate is obtained after crystallization.Detect the impurity in this technological process, find that chromic content is for being less than 0.01%, the content of total chromium is for being less than 0.3%, and the rate of recovery of chromite reaches 90%.
Embodiment 2:
A method for Sodium chromate is prepared in the acid-soluble oxidation of chromite, comprises the following steps:
Step one, chromite is ground to form granularity is 200 object breezes, then being added by breeze in reactor and adding mass concentration is 40% sulfuric acid, sulphuric acid is 0.7 times of powdered ore quality, then stir with the speed of 500 revs/min and add oxygenant oxygen, oxygen add-on is 20% of powdered ore quality, reacting by heating temperature is 140 DEG C, and to control reaction pressure be 2.0MPa and reaction times 150min;
Above-mentioned technological process main chemical reactions is as follows:
Fe(CrO
2)
2+4H
2SO
4→FeSO
4+Cr
2(SO
4)
3+4H
2O
(Mg，Fe)Cr
2O
4+5H
2SO
4→FeSO
4+Cr
2(SO
4)
3+MgSO
4+5H
2O
MgCr
2O
4+4H
2SO
4→MgSO
4+Cr
2(SO
4)
3+4H
2O
(Mg，Fe)
7Si
8O
22(OH)
2+7H
2SO
4→7FeSiO
3↓+7MgSO
4↓+SiO
2↓+8H
2O
Oxygenant oxygen and Fe (CrO
2)
2the master equation of reaction is as follows:
O
2+4Fe(CrO
2)
2+18H
2SO
4→2Fe
2(SO
4)
3+4Cr
2(SO
4)
3+18H
2O
Resultant feed liquid is obtained after having reacted, resultant feed liquid is filtered and carries out solid-liquid separation, filter residue can be used as the raw material of smelting duriron, rhombspar adjust ph to 5.5 is added in filtrate, generate calcium sulfate precipitation, cross and filter calcium sulfate precipitation, filter residue calcium sulfate can do gypsum, then in filtrate, add the sodium bicarbonate that weight ratio is 1:1:1, sodium hydroxide and sodium carbonate adjust ph to 6.5, in this process, part magnesium ion in filtrate, iron ion and aluminum ion can produce with alkaline matter and precipitate, cross and filter precipitation, and in filtrate, add the sodium bicarbonate that weight ratio is 1:1:1, sodium hydroxide and sodium carbonate adjust ph to 9, chromium ion can produce with alkaline matter and precipitate in this process, filtration obtains solid hydrogen chromic oxide,
Step 2, get the solid hydrogen chromic oxide obtained in 1 weight part step one, pull an oar after adding 1.5 weight parts waters, obtain liquid of pulling an oar, making beating liquid is added in reactor, and add the sodium bicarbonate that weight ratio is 1:1:1, sodium hydroxide and sodium carbonate adjust ph to 14, then oxygen is added, the amount of oxygen is 70% of chromium hydroxide quality, reacting by heating temperature is 180 DEG C, and control reaction pressure 4MPa and reaction times 200min, after having reacted, obtain resultant feed liquid, the sodium bicarbonate that weight ratio is 1:1:1 is added in resultant feed liquid, sodium hydroxide and sodium carbonate adjust ph to 14, impurity iron ion and alkaline matter produce and precipitate in this process, cross and filter precipitation, realize being separated of hexavalent chromium and iron ion, and in filtrate, add the sodium bicarbonate that weight ratio is 1:1:1, sodium hydroxide and sodium carbonate adjust ph to 9, impurity aluminum ion and alkaline matter produce and precipitate in this process, cross and filter precipitation, realize hexavalent chromium to be separated with aluminum ions, filtrate is through concentrated, Sodium chromate is obtained after crystallization.Detect the impurity in this technological process, find that chromic content is for being less than 0.01%, the content of total chromium is for being less than 0.3%, and the rate of recovery of chromite reaches 88%.
Embodiment 3:
A method for Sodium chromate is prepared in the acid-soluble oxidation of chromite, comprises the following steps:
Step one, chromite is ground to form granularity is 200 object breezes, then being added by breeze in reactor and adding mass concentration is 50% sulfuric acid, sulphuric acid is 0.6 times of powdered ore quality, then stir with the speed of 500 revs/min and add oxygenant oxygen, oxygen add-on is 30% of powdered ore quality, reacting by heating temperature is 200 DEG C, and to control reaction pressure be 4.0MPa and reaction times 200min;
Above-mentioned technological process main chemical reactions is as follows:
Fe(CrO
2)
2+4H
2SO
4→FeSO
4+Cr
2(SO
4)
3+4H
2O
(Mg，Fe)Cr
2O
4+5H
2SO
4→FeSO
4+Cr
2(SO
4)
3+MgSO
4+5H
2O
MgCr
2O
4+4H
2SO
4→MgSO
4+Cr
2(SO
4)
3+4H
2O
(Mg，Fe)
7Si
8O
22(OH)
2+7H
2SO
4→7FeSiO
3↓+7MgSO
4↓+SiO
2↓+8H
2O
Oxygenant oxygen and Fe (CrO
2)
2the master equation of reaction is as follows:
O
2+4Fe(CrO
2)
2+18H
2SO
4→2Fe
2(SO
4)
3+4Cr
2(SO4)
3+18H
2O
Resultant feed liquid is obtained after having reacted, resultant feed liquid is filtered and carries out solid-liquid separation, filter residue can be used as the raw material of smelting duriron, rhombspar adjust ph to 4 is added in filtrate, generate calcium sulfate precipitation, cross and filter calcium sulfate precipitation, filter residue calcium sulfate can do gypsum, then in filtrate, add the sodium bicarbonate that weight ratio is 1:2:1, sodium hydroxide and sodium carbonate adjust ph to 6, in this process, part magnesium ion in filtrate, iron ion and aluminum ion can produce with alkaline matter and precipitate, cross and filter precipitation, and in filtrate, add the sodium bicarbonate that weight ratio is 1:2:1, sodium hydroxide and sodium carbonate adjust ph to 8, chromium ion can produce with alkaline matter and precipitate in this process, filtration obtains solid hydrogen chromic oxide,
Step 2, get the solid hydrogen chromic oxide obtained in 1 weight part step one, pull an oar after adding 1 weight parts water, obtain liquid of pulling an oar, making beating liquid is added in reactor, and add the sodium bicarbonate that weight ratio is 1:2:1, sodium hydroxide and sodium carbonate adjust ph to 10, then oxygen is added, the amount of oxygen is 80% of chromium hydroxide quality, reacting by heating temperature is 240 DEG C, and control reaction pressure 6MPa and reaction times 300min, after having reacted, obtain resultant feed liquid, the sodium bicarbonate that weight ratio is 1:2:1 is added in resultant feed liquid, sodium hydroxide and sodium carbonate adjust ph to 12, impurity iron ion and alkaline matter produce and precipitate in this process, cross and filter precipitation, realize being separated of hexavalent chromium and iron ion, and in filtrate, add the sodium bicarbonate that weight ratio is 1:2:1, sodium hydroxide and sodium carbonate adjust ph to 8, impurity aluminum ion and alkaline matter produce and precipitate in this process, cross and filter precipitation, realize hexavalent chromium to be separated with aluminum ions, filtrate is through concentrated, Sodium chromate is obtained after crystallization.Detect the impurity in this technological process, find that chromic content is for being less than 0.01%, the content of total chromium is for being less than 0.3%, and the rate of recovery of chromite reaches 90%.
Embodiment 4:
A method for Sodium chromate is prepared in the acid-soluble oxidation of chromite, comprises the following steps:
Step one, chromite is ground to form granularity is 200 object breezes, then being added by breeze in reactor and adding mass concentration is 60% sulfuric acid, sulphuric acid is 0.53 times of powdered ore quality, then stir with the speed of 500 revs/min and add oxygenant persulphate, persulphate add-on is 35% of powdered ore quality, reacting by heating temperature is 240 DEG C, and to control reaction pressure be 5.0MPa and reaction times 250min;
Above-mentioned technological process main chemical reactions is as follows:
Fe(CrO
2)
2+4H
2SO
4→FeSO
4+Cr
2(SO
4)
3+4H
2O
(Mg，Fe)Cr
2O
4+5H
2SO
4→FeSO
4+Cr
2(SO
4)
3+MgSO
4+5H
2O
MgCr
2O
4+4H
2SO
4→MgSO
4+Cr
2(SO
4)
3+4H
2O
(Mg，Fe)
7Si
8O
22(OH)
2+7H
2SO
4→7FeSiO
3↓+7MgSO
4↓+SiO
2↓+8H
2O
Oxygenant persulphate and Fe (CrO
2)
2the master equation of reaction is as follows:
S
2O
8 2-+2Fe(CrO
2)
2+8H
2SO
4→Fe
2(SO
4)
3+2Cr
2(SO
4)
3+8H
2O+SO
4 2-
Resultant feed liquid is obtained after having reacted, resultant feed liquid is filtered and carries out solid-liquid separation, filter residue can be used as the raw material of smelting duriron, unslaked lime adjust ph to 3.5 is added in filtrate, generate calcium sulfate precipitation, cross and filter calcium sulfate precipitation, filter residue calcium sulfate can do gypsum, then hydro-oxidation sodium adjust ph to 5 in filtrate, in this process, part magnesium ion in filtrate, iron ion and aluminum ion can produce with alkaline matter and precipitate, cross and filter precipitation, and in filtrate hydro-oxidation sodium adjust ph to 8.5, chromium ion can produce with alkaline matter and precipitate in this process, filtration obtains solid hydrogen chromic oxide,
Step 2, get the solid hydrogen chromic oxide obtained in 1 weight part step one, pull an oar after adding 0.5 weight parts water, obtain liquid of pulling an oar, making beating liquid is added in reactor, and add sodium hydroxide adjust ph to 11, then oxygen is added, the amount of oxygen is 90% of chromium hydroxide quality, reacting by heating temperature is 360 DEG C, and control reaction pressure 8MPa and reaction times 400min, after having reacted, obtain resultant feed liquid, sodium hydroxide adjust ph to 13 is added in resultant feed liquid, impurity iron ion and alkaline matter produce and precipitate in this process, cross and filter precipitation, realize being separated of hexavalent chromium and iron ion, and in filtrate hydro-oxidation sodium adjust ph to 9, impurity aluminum ion and alkaline matter produce and precipitate in this process, cross and filter precipitation, realize hexavalent chromium to be separated with aluminum ions, filtrate is through concentrated, Sodium chromate is obtained after crystallization.Detect the impurity in this technological process, find that chromic content is for being less than 0.01%, the content of total chromium is for being less than 0.3%, and the rate of recovery of chromite reaches 85%.
Embodiment 5:
A method for Sodium chromate is prepared in the acid-soluble oxidation of chromite, comprises the following steps:
Step one, chromite is ground to form granularity is 200 object breezes, then being added by breeze in reactor and adding mass concentration is 70% sulfuric acid, sulphuric acid is 0.7 times of powdered ore quality, then stir with the speed of 500 revs/min and add oxygenant superoxide, peroxide charge is 40% of powdered ore quality, reacting by heating temperature is 300 DEG C, and to control reaction pressure be 6.0MPa and reaction times 310min;
Above-mentioned technological process main chemical reactions is as follows:
Fe(CrO
2)
2+4H
2SO
4→FeSO
4+Cr
2(SO
4)
3+4H
2O
(Mg，Fe)Cr
2O
4+5H
2SO
4→FeSO
4+Cr
2(SO
4)
3+MgSO
4+5H
2O
MgCr
2O
4+4H
2SO
4→MgSO
4+Cr
2(SO
4)
3+4H
2O
(Mg，Fe)
7Si
8O
22(OH)
2+7H
2SO
4→7FeSiO
3↓+7MgSO
4↓+SiO
2↓+8H
2O
Oxygenant superoxide and Fe (CrO
2)
2the master equation of reaction is as follows:
O
2 2-+2Fe(CrO
2)
2+9H
2SO
4→Fe
2(SO
4)
3+2Cr
2(SO
4)
3+9H
2O+O
2-
Resultant feed liquid is obtained after having reacted, resultant feed liquid is filtered and carries out solid-liquid separation, filter residue can be used as the raw material of smelting duriron, white lime adjust ph to 3 is added in filtrate, generate calcium sulfate precipitation, cross and filter calcium sulfate precipitation, filter residue calcium sulfate can do gypsum, then hydro-oxidation sodium adjust ph to 6 in filtrate, in this process, part magnesium ion in filtrate, iron ion and aluminum ion can produce with alkaline matter and precipitate, cross and filter precipitation, and in filtrate hydro-oxidation sodium adjust ph to 7, chromium ion can produce with alkaline matter and precipitate in this process, filtration obtains solid hydrogen chromic oxide,
Step 2, get the solid hydrogen chromic oxide obtained in 1 weight part step one, pull an oar after adding 1 weight parts water, obtain liquid of pulling an oar, making beating liquid is added in reactor, and add sodium hydroxide adjust ph to 9, then oxygen is added, the amount of oxygen is 99% of chromium hydroxide quality, reacting by heating temperature is 180 DEG C, and control reaction pressure 4MPa and reaction times 200min, after having reacted, obtain resultant feed liquid, sodium hydroxide adjust ph to 12 is added in resultant feed liquid, impurity iron ion and alkaline matter produce and precipitate in this process, cross and filter precipitation, realize being separated of hexavalent chromium and iron ion, and in filtrate hydro-oxidation sodium adjust ph to 8, impurity aluminum ion and alkaline matter produce and precipitate in this process, cross and filter precipitation, realize hexavalent chromium to be separated with aluminum ions, filtrate is through concentrated, Sodium chromate is obtained after crystallization.Detect the impurity in this technological process, find that chromic content is for being less than 0.01%, the content of total chromium is for being less than 0.3%, and the rate of recovery of chromite reaches 89%.
Embodiment 6:
A method for Sodium chromate is prepared in the acid-soluble oxidation of chromite, comprises the following steps:
Step one, chromite is ground to form granularity is 200 object breezes, then being added by breeze in reactor and adding mass concentration is 80% sulfuric acid, sulphuric acid is 0.7 times of powdered ore quality, then stir with the speed of 500 revs/min and add oxygenant chromic trioxide, chromic trioxide add-on is 50% of powdered ore quality, reacting by heating temperature is 360 DEG C, and to control reaction pressure be 8.0MPa and reaction times 400min;
Above-mentioned technological process main chemical reactions is as follows:
Fe(CrO
2)
2+4H
2SO
4→FeSO
4+Cr
2(SO
4)
3+4H
2O
(Mg，Fe)Cr
2O
4+5H
2SO
4→FeSO
4+Cr
2(SO
4)
3+MgSO
4+5H
2O
MgCr
2O
4+4H
2SO
4→MgSO
4+Cr
2(SO
4)
3+4H
2O
(Mg，Fe)
7Si
8O
22(OH)
2+7H
2SO
4→7FeSiO
3↓+7MgSO
4↓+SiO
2↓+8H
2O
Oxygenant chromic trioxide and Fe (CrO
2)
2the master equation of reaction is as follows:
2CrO
3+6Fe(CrO
2)
2+30H
2SO
4→3Fe
2(SO
4)
3+7Cr
2(SO
4)
3+30H
2O
Resultant feed liquid is obtained after having reacted, resultant feed liquid is filtered and carries out solid-liquid separation, filter residue can be used as the raw material of smelting duriron, unslaked lime and rhombspar adjust ph to 4.5 is added in filtrate, generate calcium sulfate precipitation, cross and filter calcium sulfate precipitation, filter residue calcium sulfate can do gypsum, then in filtrate, sodium bicarbonate adjust ph to 5 is added, in this process, part magnesium ion in filtrate, iron ion and aluminum ion can produce with alkaline matter and precipitate, cross and filter precipitation, and in filtrate, add sodium bicarbonate adjust ph to 8, chromium ion can produce with alkaline matter and precipitate in this process, filtration obtains solid hydrogen chromic oxide,
Step 2, get the solid hydrogen chromic oxide obtained in 1 weight part step one, pull an oar after adding 1.5 weight parts waters, obtain liquid of pulling an oar, making beating liquid is added in reactor, and add sodium bicarbonate adjust ph to 13, then oxygen is added, the amount of oxygen is 70% of chromium hydroxide quality, reacting by heating temperature is 180 DEG C, and control reaction pressure 4MPa and reaction times 200min, after having reacted, obtain resultant feed liquid, sodium bicarbonate adjust ph to 9 is added in resultant feed liquid, impurity iron ion and alkaline matter produce and precipitate in this process, cross and filter precipitation, realize being separated of hexavalent chromium and iron ion, and in filtrate, add sodium bicarbonate adjust ph to 9, impurity aluminum ion and alkaline matter produce and precipitate in this process, cross and filter precipitation, realize hexavalent chromium to be separated with aluminum ions, filtrate is through concentrated, Sodium chromate is obtained after crystallization.Detect the impurity in this technological process, find that chromic content is for being less than 0.01%, the content of total chromium is for being less than 0.3%, and the rate of recovery of chromite reaches 87%.
Embodiment 7:
A method for Sodium chromate is prepared in the acid-soluble oxidation of chromite, comprises the following steps:
Step one, chromite is ground to form granularity is 200 object breezes, then being added by breeze in reactor and adding mass concentration is 50% sulfuric acid, sulphuric acid is 0.7 times of powdered ore quality, then stir with the speed of 500 revs/min, reacting by heating temperature is 340 DEG C, and to control reaction pressure be 7.0MPa and reaction times is 300min;
Above-mentioned technological process main chemical reactions is as follows:
Fe(CrO
2)
2+4H
2SO
4→FeSO
4+Cr
2(SO
4)
3+4H
2O
(Mg，Fe)Cr
2O
4+5H
2SO
4→FeSO
4+Cr
2(SO
4)
3+MgSO
4+5H
2O
MgCr
2O
4+4H
2SO
4→MgSO
4+Cr
2(SO
4)
3+4H
2O
(Mg，Fe)
7Si
8O
22(OH)
2+7H
2SO
4→7FeSiO
3↓+7MgSO
4↓+SiO
2↓+8H
2O
Resultant feed liquid is obtained after having reacted, resultant feed liquid is filtered and carries out solid-liquid separation, filter residue can be used as the raw material of smelting duriron, rhombspar adjust ph to 4 is added in filtrate, generate calcium sulfate precipitation, cross and filter calcium sulfate precipitation, filter residue calcium sulfate can do gypsum, then hydro-oxidation sodium adjust ph to 6 in filtrate, in this process, part magnesium ion in filtrate, iron ion and aluminum ion can produce with alkaline matter and precipitate, cross and filter precipitation, and in filtrate hydro-oxidation sodium adjust ph to 9, chromium ion can produce with alkaline matter and precipitate in this process, filtration obtains solid hydrogen chromic oxide,
Step 2, get the solid hydrogen chromic oxide obtained in 1 weight part step one, pull an oar after adding 1 weight parts water, obtain liquid of pulling an oar, making beating liquid is added in reactor, and add sodium hydroxide adjust ph to 9, then oxygen is added, the amount of oxygen is 70% of chromium hydroxide quality, reacting by heating temperature is 180 DEG C, and control reaction pressure 4MPa and reaction times 200min, after having reacted, obtain resultant feed liquid, sodium hydroxide adjust ph to 14 is added in resultant feed liquid, impurity iron ion and alkaline matter produce and precipitate in this process, cross and filter precipitation, realize being separated of hexavalent chromium and iron ion, and in filtrate hydro-oxidation sodium adjust ph to 9, impurity aluminum ion and alkaline matter produce and precipitate in this process, cross and filter precipitation, realize hexavalent chromium to be separated with aluminum ions, filtrate is through concentrated, Sodium chromate is obtained after crystallization.Detect the impurity in this technological process, find that chromic content is for being less than 0.01%, the content of total chromium is for being less than 0.3%, and the rate of recovery of chromite reaches 89%.
Embodiment 8:
A method for Sodium chromate is prepared in the acid-soluble oxidation of chromite, comprises the following steps:
Step one, chromite is ground to form granularity is 100 object breezes, then being added by breeze in reactor and adding mass concentration is 10% sulfuric acid, sulphuric acid is 0.7 times of powdered ore quality, then stir with the speed of 500 revs/min and add oxygenant chromic trioxide, chromic trioxide add-on is 50% of powdered ore quality, microwave heating temperature of reaction is 100 DEG C, and microwave frequency is 2450 ± 50MHz, and to control reaction pressure be 8.0MPa and reaction times 100min, resultant feed liquid is obtained after having reacted, resultant feed liquid is filtered and carries out solid-liquid separation, filter residue can be used as the raw material of smelting duriron, unslaked lime and rhombspar adjust ph to 4 is added in filtrate, generate calcium sulfate precipitation, cross and filter calcium sulfate precipitation, filter residue calcium sulfate can do gypsum, then in filtrate, sodium bicarbonate adjust ph to 5 is added, in this process, part magnesium ion in filtrate, iron ion and aluminum ion can produce with alkaline matter and precipitate, cross and filter precipitation, and in filtrate, add sodium bicarbonate adjust ph to 9, chromium ion can produce with alkaline matter and precipitate in this process, filtration obtains solid hydrogen chromic oxide,
Step 2, get the solid hydrogen chromic oxide obtained in 1 weight part step one, pull an oar after adding 1 weight parts water, obtain liquid of pulling an oar, making beating liquid is added in reactor, and add sodium bicarbonate adjust ph to 12, then oxygen is added, the amount of oxygen is 70% of chromium hydroxide quality, microwave heating temperature of reaction is 180 DEG C, microwave frequency is 2450 ± 50MHz, and control reaction pressure 8MPa and reaction times 100min, after having reacted, obtain resultant feed liquid, sodium bicarbonate adjust ph to 12 is added in resultant feed liquid, impurity iron ion and alkaline matter produce and precipitate in this process, cross and filter precipitation, realize being separated of hexavalent chromium and iron ion, and in filtrate, add sodium bicarbonate adjust ph to 8, impurity aluminum ion and alkaline matter produce and precipitate in this process, cross and filter precipitation, realize hexavalent chromium to be separated with aluminum ions, filtrate is through concentrated, Sodium chromate is obtained after crystallization.Detect the impurity in this technological process, find that chromic content is for being less than 0.01%, the content of total chromium is for being less than 0.3%, and the rate of recovery of chromite reaches 90%.
Embodiment 9:
A method for Sodium chromate is prepared in the acid-soluble oxidation of chromite, comprises the following steps:
Step one, chromite is ground to form granularity is 200 object breezes, then being added by breeze in reactor and adding mass concentration is 40% sulfuric acid, sulphuric acid is 0.7 times of powdered ore quality, then stir with the speed of 500 revs/min and add the compound oxidant of sodium dichromate, oxygen and the chromic trioxide that weight ratio is 1:1:1, its add-on is 20% of powdered ore quality, reacting by heating temperature is 140 DEG C, and to control reaction pressure be 2.0MPa and reaction times 150min;
Resultant feed liquid is obtained after having reacted, resultant feed liquid is filtered and carries out solid-liquid separation, filter residue can be used as the raw material of smelting duriron, rhombspar adjust ph to 5.5 is added in filtrate, generate calcium sulfate precipitation, cross and filter calcium sulfate precipitation, filter residue calcium sulfate can do gypsum, then in filtrate, add the sodium bicarbonate that weight ratio is 1:1:1, sodium hydroxide and sodium carbonate adjust ph to 6.5, in this process, part magnesium ion in filtrate, iron ion and aluminum ion can produce with alkaline matter and precipitate, cross and filter precipitation, and in filtrate, add the sodium bicarbonate that weight ratio is 1:1:1, sodium hydroxide and sodium carbonate adjust ph to 9, chromium ion can produce with alkaline matter and precipitate in this process, filtration obtains solid hydrogen chromic oxide,
Step 2, get the solid hydrogen chromic oxide obtained in 1 weight part step one, pull an oar after adding 1.5 weight parts waters, obtain liquid of pulling an oar, making beating liquid is added in reactor, and add the sodium bicarbonate that weight ratio is 1:1:1, sodium hydroxide and sodium carbonate adjust ph to 14, reacting by heating temperature is 180 DEG C, and control reaction pressure 4MPa and reaction times 200min, after having reacted, obtain resultant feed liquid, the sodium bicarbonate that weight ratio is 1:1:1 is added in resultant feed liquid, sodium hydroxide and sodium carbonate adjust ph to 14, impurity iron ion and alkaline matter produce and precipitate in this process, cross and filter precipitation, realize being separated of hexavalent chromium and iron ion, and in filtrate, add the sodium bicarbonate that weight ratio is 1:1:1, sodium hydroxide and sodium carbonate adjust ph to 9, impurity aluminum ion and alkaline matter produce and precipitate in this process, cross and filter precipitation, realize hexavalent chromium to be separated with aluminum ions, filtrate is through concentrated, Sodium chromate is obtained after crystallization.Detect the impurity in this technological process, find that chromic content is for being less than 0.01%, the content of total chromium is for being less than 0.3%, and the rate of recovery of chromite reaches 85%.
In order to effect of the present invention is described, contriver provides contrast experiment as follows:
Comparative example 1:
In step one of the present invention, the reaction pressure of employing is 0.2MPa, and it is less than scope of the present invention, and identical with embodiment 6 of all the other parameters, technological process is also identical.Detect the impurity in this technological process, find that chromic content is 0.05%, the content of total chromium is 0.6%, and the rate of recovery of chromite is 70%.
Comparative example 2:
In step one of the present invention, the reaction pressure of employing is 9MPa, and it is greater than scope of the present invention, and identical with embodiment 6 of all the other parameters, technological process is also identical.Detect the impurity in this technological process, find that chromic content is for being less than 0.01%, the content of total chromium is for being less than 0.3%, and the rate of recovery of chromite reaches 87%.
Can find out from above-mentioned, when the reaction pressure adopted in comparative example 1 step one is less than scope of the present invention, find in impurity that chromic content is 0.05%, the content of total chromium is 0.6%, and the rate of recovery of chromite is 70%, and effect is poor.The reaction pressure adopted in comparative example 2 step one is greater than scope of the present invention, its experiment effect is identical with embodiment 6, when the pressure adopted higher than scope of the present invention is described, experiment effect can not be improved further, and higher requirement can be produced to equipment.
Comparative example 3:
In step 2 of the present invention, after having reacted, in resultant feed liquid, add sodium hydroxide adjust ph to 8, it is not in scope of the present invention, and identical with embodiment 6 of all the other parameters, technological process is also identical.Detect the Sodium chromate prepared, compared with embodiment 6, in the Sodium chromate of comparative example 3, the content of iron is higher than embodiment 6.Illustrate and only can prepare the high Sodium chromate of purity in the regulation range of pH of the present invention.
Comparative example 4:
In step 2 of the present invention, after having reacted, second time adjust ph to 5, it is less than the scope of pH value 6 ~ 9 of the present invention, and identical with embodiment 6 of all the other parameters, technological process is also identical.Detect the Sodium chromate prepared, compared with embodiment 6, in the Sodium chromate of comparative example 4, the content of aluminium is higher than embodiment 6.
Comparative example 5:
In step 2 of the present invention, after having reacted, second time adjust ph to 10, it is greater than the scope of pH value 6 ~ 9 of the present invention, and identical with embodiment 6 of all the other parameters, technological process is also identical.Detect the Sodium chromate prepared, compared with embodiment 6, in the Sodium chromate of comparative example 4, the content of aluminium is higher than embodiment 6.
As can be seen from comparative example 4 and comparative example 5, in step 2 of the present invention, after having reacted, second time adjust ph only can prepare the high Sodium chromate of purity in the regulation range of pH of the present invention.
Visible, the reaction that in the present invention, chromite adds oxygenant under the environment of pressurization, strong acid can destroy chromite spinel structure, improves the solubility rate of chromite, and by adjust ph, iron, aluminium, silicon, magnesium plasma is effectively separated with chromium ion.
Although embodiment of the present invention are open as above, but it is not restricted to listed in specification sheets and embodiment utilization, it can be applied to various applicable the field of the invention completely, for those skilled in the art, can easily realize other amendment, therefore do not deviating under the universal that claim and equivalency range limit, the present invention is not limited to specific details and illustrates here and the legend described.
Claims (10)
1. a method for Sodium chromate is prepared in the acid-soluble oxidation of chromite, it is characterized in that, comprises the following steps:
Step one, chromite being ground to form granularity is 100 ~ 200 object breezes, then breeze to be added in reactor and to add sulfuric acid, stir with the speed of 300 ~ 800 revs/min, reacting by heating, and control reaction pressure and reaction times, resultant feed liquid is obtained after having reacted, resultant feed liquid is filtered and carries out solid-liquid separation, calcic ore adjust ph is added to 2-5.5 in filtrate, generate calcium sulfate precipitation, cross and filter calcium sulfate precipitation, then in filtrate, alkaline matter adjust ph is added to 4-6.5, cross and filter precipitation, and in filtrate, add alkaline matter adjust ph to 6.5-9.5, filtration obtains solid hydrogen chromic oxide,
Step 2, get the solid hydrogen chromic oxide obtained in 1 weight part step one, pull an oar after adding 0.5 ~ 1.5 weight parts water, obtain liquid of pulling an oar, making beating liquid is added in reactor, and add alkaline matter adjust ph to 8 ~ 14, reacting by heating, and control reaction pressure and reaction times, after having reacted, obtain resultant feed liquid, in resultant feed liquid, add alkaline matter adjust ph to 9-14, cross and filter precipitation, and in filtrate, add alkaline matter adjust ph to 6-9, cross and filter precipitation, filtrate obtains Sodium chromate after concentrated, crystallization.
2. the method for Sodium chromate is prepared in the acid-soluble oxidation of chromite as claimed in claim 1, it is characterized in that, also needs to add oxygenant in described step one after adding sulfuric acid.
3. the method for Sodium chromate is prepared in the acid-soluble oxidation of chromite as claimed in claim 2, it is characterized in that, described oxygenant is the combination of one or more in sodium dichromate, oxygen, chromic trioxide, superoxide, persulphate, and its add-on is 0 ~ 50% of powdered ore quality.
4. the method for Sodium chromate is prepared in the acid-soluble oxidation of chromite as claimed in claim 3, it is characterized in that, described superoxide is the one in sodium peroxide or hydrogen peroxide; Described persulphate is the one in Sodium Persulfate or ammonium persulphate.
5. the method for Sodium chromate is prepared in the acid-soluble oxidation of chromite as claimed in claim 1, and it is characterized in that, in described step one, the mass concentration of sulfuric acid is 1 ~ 90%, and its add-on is 0.3 ~ 0.9 times of powdered ore quality.
6. the method for Sodium chromate is prepared in the acid-soluble oxidation of chromite as claimed in claim 1, and it is characterized in that, described alkaline matter is the combination of one or more in sodium bicarbonate, sodium carbonate and oxygen sodium oxide; Described calcic ore is the combination of one or more in unslaked lime, white lime, rhombspar.
7. the method for Sodium chromate is prepared in the acid-soluble oxidation of chromite as claimed in claim 1, and it is characterized in that, in described step one, temperature of reaction is 50 ~ 360 DEG C, and reaction pressure is 0.3 ~ 8MPa, and the reaction times is 10 ~ 400min.
8. the method for Sodium chromate is prepared in the acid-soluble oxidation of chromite as claimed in claim 1, and it is characterized in that, also need before reacting by heating in described step 2 to add oxygen, its add-on is 0 ~ 99% of chromium hydroxide quality.
9. the method for Sodium chromate is prepared in the acid-soluble oxidation of chromite as claimed in claim 1, and it is characterized in that, in described step 2, temperature of reaction is room temperature ~ 360 DEG C, and reaction pressure is 0.01 ~ 8MPa, and the reaction times is 1 ~ 400min.
10. the method for Sodium chromate is prepared in the acid-soluble oxidation of chromite as claimed in claim 1, it is characterized in that, the reacting by heating in described step one and step 2 all adopts microwave heating, and the microwave frequency of microwave heating is 2450 ± 50MHz.
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| CN107128975A (en) * | 2017-03-30 | 2017-09-05 | 昆明理工大学 | A kind of method that chromite in microwave field prepares potassium bichromate crystal |
| CN107399763A (en) * | 2017-06-28 | 2017-11-28 | 昆明理工大学 | A kind of ultrasonic microwave combines the method for preparing sodium dichromate |
| CN111977700A (en) * | 2020-08-31 | 2020-11-24 | 湖北振华化学股份有限公司 | Method for separating and recovering chromium, iron, aluminum and magnesium from mixed solution |
| CN112048619A (en) * | 2020-08-31 | 2020-12-08 | 湖北振华化学股份有限公司 | Method for separating and recovering chromium, iron, aluminum and magnesium from mixed solution |
| CN112299427A (en) * | 2020-10-29 | 2021-02-02 | 王庆乐 | Extraction process of vanadium extraction tailings |
| WO2023150855A3 (en) * | 2022-02-14 | 2023-11-02 | Lorintech Tecnologia S.A. | Method for obtaining a nickel ore concentrate, method for processing a nickel ore concentrate, and method for recovering materials derived from nickel ore |
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| CN112048619A (en) * | 2020-08-31 | 2020-12-08 | 湖北振华化学股份有限公司 | Method for separating and recovering chromium, iron, aluminum and magnesium from mixed solution |
| CN112299427A (en) * | 2020-10-29 | 2021-02-02 | 王庆乐 | Extraction process of vanadium extraction tailings |
| WO2023150855A3 (en) * | 2022-02-14 | 2023-11-02 | Lorintech Tecnologia S.A. | Method for obtaining a nickel ore concentrate, method for processing a nickel ore concentrate, and method for recovering materials derived from nickel ore |
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Denomination of invention: A method for preparing sodium chromate by acid soluble oxidation of ferrochrome ore Effective date of registration: 20220413 Granted publication date: 20161130 Pledgee: China Construction Bank Corporation Mianyang Branch Pledgor: SICHUAN YINHE CHEMICAL Co.,Ltd. Registration number: Y2022980004215 |
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