CN104278148A - Environmentally friendly bastnaesite wet-process smelting process - Google Patents
Environmentally friendly bastnaesite wet-process smelting process Download PDFInfo
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- CN104278148A CN104278148A CN201310293704.8A CN201310293704A CN104278148A CN 104278148 A CN104278148 A CN 104278148A CN 201310293704 A CN201310293704 A CN 201310293704A CN 104278148 A CN104278148 A CN 104278148A
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Abstract
The invention relates to an environmentally friendly bastnaesite wet-process smelting process. The environmentally friendly bastnaesite wet-process smelting process takes the current technology as a research object, three unit technologies, namely'double salt precipitation separation', 'hydrochloric acid prior dissolution Fe and Th removing' and 'alkaline transfer', with maximum waste discharge amount in the current technology system are taken as waste recycling research breakthrough points, a 'necessary and sufficient condition' and an 'environmental load minimization' principle in green chemistry are combined for carrying out greenization reform study on the technological process, and the aims of reducing pollution load and realizing environmental friendliness are realized.
Description
Technical field
The present invention relates to hydrometallurgy field, be specifically related to a kind of eco-friendly hamartite wet method smelting process.
Background technology
The smelting technology of the existing most main flow of hamartite is " oxidizing roasting---sulfuric acid to leach---double salt precipitation separation method ", and it is mainly realized by a series of chemical reaction, and principle is as follows:
(1) roasting of hamartite
ReFCO3+O2 → ReFO+CO2 ↑ (Re represents non-Ce rare earth, and Re is La, Pr, Nd, Sm, Eu etc.）
CeFCO3+O2→CeO2+CO2↑
Refuse: a small amount of HF and CO2 waste gas enters air.
(2) sulfuric acid to leach
ReFO+H2SO4 → Re2 (SO4) 3+HF+*H2SO4 (unnecessary)
CeO2+H2SO4 → Ce (SO4) 2+H2O+*H2SO4 (unnecessary)
Refuse: slag
Occur except the H2SO4 that consumes except with rare earth generation replacement(metathesis)reaction, unnecessary H2SO4 is used as medium, and sulfuric acid to leach liquid consists of: 80g (REO)/L, H2SO4 concentration is 1mol/L.Leach with than being ReO:H2SO4-1:1.7
(3) double salt precipitation is separated
Re2(SO4)3+Na2SO4+H2O→Re2(SO4)3·Na2SO4·xH2O↓
Ce (SO4) 2 is still dissolved in sulfuric acid medium.
(4) reduction of Ce4+ and precipitation
Ce (SO4) 2+FeSO4 → Ce2 (SO4) 30 Fe2 (SO4) 3
Ce2(SO4)3+Na2SO4+H2O→Ce2(SO4)3·Na2SO4·yH2O↓
Refuse: containing the sulfuric acid waste of Na2SO4, HF, FeSO4 and Fe2 (SO4) 3 etc.
(5) alkali transforms
Ce2(SO4)3·Na2SO4·yHzO+NaOH→Ce(OH)3↓+Ce(OH)4↓+Na2SO4
Refuse: containing the waste lye of Na2SO4, NaOH etc.
(6) the excellent molten deironing of hydrochloric acid, thorium
Ce(OH)3+Ce(OH)4+HCl+Th(OH)4↓→CeCl3+Ce(OH)4↓+Th(OH)4↓+H2O
Because the Ksp of Fe (OH) 3, Th (OH) 4 and Ce (OH) 4 is very little, still be removed for precipitated form in the acidic solution of pH >=3, but Ce (OH) 4 is also with Fe, Th removes, which increases the rate of loss of CeO2, account for more than 5% of total cerium amount.
Refuse: containing the waste residue of Fe, Th and Ce.Because Th has low-activity, further special disposal will be done by producer.
(7) carbonate deposition
CeC13+(NH4)2CO3→Ce2(CO3)↓+NH4CI
Refuse: containing (NH4) 2CO3 and NH4Cl waste liquid
(8) oxidizing roasting generates CeO2
O2+Ce2(CO3)3→CeO2+CO2↑
Although this technique can produce CeO2 and the lanthanum concentrate rare earth chloride of 99% purity, there is less investment, easily the feature of grasp and upper detective.But can see from above technological principle, in the leaching of CeO2, separation, conversion and purge process, H2SO4, Na2SO4, FeSO4, NaOH of adding, HCl and (NH4) 2CO3 fails to enter end product, all enter aqueous phase with the form of ortho states or conversion state, be discharged into environment and these materials'uses once after be all thrown into environment as waste with water, problem that this technique has typically " three high ".Produce the reason mainly factor such as technological principle, chemical material kind and chemical material consumption of a large amount of refuse.
Therefore, eco-friendly hamartite wet method smelting process is continued at present.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of eco-friendly hamartite wet method smelting process.Described technique take current technology as research object, 3 cell process that waste discharge gurry amount is maximum from current technology system, namely " double salt precipitation separation ", " hydrochloric acid is excellent molten except Fe; Th " and " alkali turns " technique study point of penetration as changing rejected material to useful resource, " necessary and sufficient condition " and " environmental loads minimizes " principle of combining with green chemistry carries out the greenization reform research of this technical process, reaches and can realize eco-friendly object by decreasing pollution load.
The technical solution adopted in the present invention is:
A kind of hamartite wet method smelting process, comprising:
The roasting of hamartite, sulfuric acid to leach, double salt precipitation are separated, the reduction of Ce4+ and precipitation, deironing and thorium, alkali transform, oxidizing roasting generates CeO2, it is characterized in that:
The reduction of Ce4+ and precipitation: adopt hydrogen peroxide to make reductive agent, hydrogen peroxide consumption is the 90-100% of theoretical amount, reduction temperature 50-60 DEG C, recovery time 50-70min, obtains cerium double salt precipitation thing
Deironing and thorium: this technique is carried out after the reduction and precipitation of Ce4+, technical process is: add the complexing agent alkaline solution containing NaOH in the cerium double salt precipitation thing that the reduction of Ce4+ and precipitation obtain, 1-2h is stirred under the condition of pH1-2, add sodium sulfate subsequently and stir 0.5h under 75-85 DEG C of condition, filter, obtain sulfuric acid liquid and the precipitation of iron content and thorium complex, throw out carries out alkali conversion; The sulfuric acid liquid of iron content and thorium complex adds Waste Sulfuric Acid makes its acidity be 0.1-0.4mol/L, and complexing agent is lived again; Wherein amount of complex is 2.5-3.5 times of theoretical amount, and complexing agent is diethyl pentetic acid;
Alkali transforms: processing parameter is: ReO:NaOH=1:0.9-1.1; NaOH concentration 65-75%; Alkali turns temperature 140-160 DEG C, and alkali turns time 0.5-1.5h.
Wherein preferred:
The reduction of Ce4+ and precipitation: adopt hydrogen peroxide to make reductive agent, hydrogen peroxide consumption is 95% of theoretical amount, reduction temperature 55 DEG C, and recovery time 60min obtains cerium double salt precipitation thing
Deironing and thorium: this technique is carried out after the reduction and precipitation of Ce4+, technical process is: add the complexing agent alkaline solution containing NaOH in the cerium double salt precipitation thing that the reduction of Ce4+ and precipitation obtain, 1.5h is stirred under the condition of pH1-2, add sodium sulfate subsequently and stir 0.5h under 80 DEG C of conditions, filter, obtain sulfuric acid liquid and the precipitation of iron content and thorium complex, throw out carries out alkali conversion; The sulfuric acid liquid of iron content and thorium complex adds Waste Sulfuric Acid makes its acidity be 0.1-0.4mol/L, and complexing agent is lived again; Wherein amount of complex is 3 times of theoretical amount, and complexing agent is diethyl pentetic acid;
Alkali transforms: processing parameter is: ReO:NaOH=1:1; NaOH concentration 70%; Alkali turns temperature 150 DEG C, and alkali turns time 1h.
The present invention is described in detail below:
(1) reduction of Ce4+ and precipitation
Need by the design of Ce4+, product during its reduction does not preferably introduce new impurity.To this, we select H2O2 to make reductive agent.The product that H2O2 makes reductive agent is O2 and H+, does not all affect the abstraction and purification of rare earth.
(2) deironing and thorium
The present invention selects complex scheme to remove Fe, Th, and the cardinal principle of foundation has 3 points:
, in the solid phase of double salt precipitation, its material existing forms is also different for one: Ce3 ten and Fe3+, Th4+ (reductive agent used can not reduce Fe3+, Th4+).Fe3+ is precipitated absorption and enters solid phase, and Th4+ is mainly mixed in solid phase with ThF4 precipitation, and Ce3+ is present in solid phase with the form of vitriol.
Its two: Ce3+ and the hardness of Fe3+, Th4+ acid have different, select suitable complexing agent only with Fe3+, Th4+ complexing, utilize the common-ion effcet adding a certain amount of sodium sulfate simultaneously, make Ce3+ not easily by complexing, and then increase the selectivity of complexing agent.
The rising solubleness that its three: Ce2 (SO4) 3Na2SO4yH2O precipitates with temperature reduces, and the proper extension of the change of temperature and complexing action time can be utilized to reach the possibility of thorough removal of impurities.
(3) alkali transforms
In production CeO2 technique, sulfuric acid is adornd double salt precipitation Ce2 (SO4) 3Na2SO4yH2O alkali and transfer Ce (OH) 3 to, its objective is impurity such as removing SO42-, F-and SiO32-, is the important step obtaining high-purity C eO2 product.We find when the alkali studying hamartite rare earth turns, and the key factor that rare-earth alkali turns completeness and alkali rotary speed is the concentration of NaOH, instead of NaOH consumption.According to this principles of science, the parameter that we turn double salt alkali has re-started research, and the consumption and the alkali that greatly reduce NaOH turn the time.
The present invention has the following advantages: technique of the present invention take current technology as research object, 3 cell process that waste discharge gurry amount is maximum from current technology system, namely " double salt precipitation separation ", " hydrochloric acid is excellent molten except Fe; Th " and " alkali turns " technique study point of penetration as changing rejected material to useful resource, " necessary and sufficient condition " and " environmental loads minimizes " principle of combining with green chemistry carries out the greenization reform research of this technical process, reaches and can realize eco-friendly object by decreasing pollution load.
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 is only help to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment one
A kind of hamartite wet method smelting process, comprising:
The roasting of hamartite, sulfuric acid to leach, double salt precipitation are separated, the reduction of Ce4+ and precipitation, deironing and thorium, alkali transform, oxidizing roasting generates CeO2, it is characterized in that:
The reduction of Ce4+ and precipitation: adopt hydrogen peroxide to make reductive agent, hydrogen peroxide consumption is 95% of theoretical amount, reduction temperature 55 DEG C, and recovery time 60min obtains cerium double salt precipitation thing
Deironing and thorium: this technique is carried out after the reduction and precipitation of Ce4+, technical process is: add the complexing agent alkaline solution containing NaOH in the cerium double salt precipitation thing that the reduction of Ce4+ and precipitation obtain, 1.5h is stirred under the condition of pH1-2, add sodium sulfate subsequently and stir 0.5h under 80 DEG C of conditions, filter, obtain sulfuric acid liquid and the precipitation of iron content and thorium complex, throw out carries out alkali conversion; The sulfuric acid liquid of iron content and thorium complex adds Waste Sulfuric Acid makes its acidity be 0.1-0.4mol/L, and complexing agent is lived again; Wherein amount of complex is 3 times of theoretical amount, and complexing agent is diethyl pentetic acid;
Alkali transforms: processing parameter is: ReO:NaOH=1:1; NaOH concentration 70%; Alkali turns temperature 150 DEG C, and alkali turns time 1h.
Embodiment two
A kind of hamartite wet method smelting process, comprising:
The roasting of hamartite, sulfuric acid to leach, double salt precipitation are separated, the reduction of Ce4+ and precipitation, deironing and thorium, alkali transform, oxidizing roasting generates CeO2, it is characterized in that:
The reduction of Ce4+ and precipitation: adopt hydrogen peroxide to make reductive agent, hydrogen peroxide consumption is 90% of theoretical amount, reduction temperature 50 DEG C, and recovery time 50min obtains cerium double salt precipitation thing
Deironing and thorium: this technique is carried out after the reduction and precipitation of Ce4+, technical process is: add the complexing agent alkaline solution containing NaOH in the cerium double salt precipitation thing that the reduction of Ce4+ and precipitation obtain, 1h is stirred under the condition of pH1, add sodium sulfate subsequently and stir 0.5h under 75 DEG C of conditions, filter, obtain sulfuric acid liquid and the precipitation of iron content and thorium complex, throw out carries out alkali conversion; The sulfuric acid liquid of iron content and thorium complex adds Waste Sulfuric Acid makes its acidity be 0.1mol/L, and complexing agent is lived again; Wherein amount of complex is 2.5 times of theoretical amount, and complexing agent is diethyl pentetic acid;
Alkali transforms: processing parameter is: ReO:NaOH=1:0.9; NaOH concentration 65%; Alkali turns temperature 140 DEG C, and alkali turns time 0.5h.
Embodiment three
A kind of hamartite wet method smelting process, comprising:
The roasting of hamartite, sulfuric acid to leach, double salt precipitation are separated, the reduction of Ce4+ and precipitation, deironing and thorium, alkali transform, oxidizing roasting generates CeO2, it is characterized in that:
The reduction of Ce4+ and precipitation: adopt hydrogen peroxide to make reductive agent, hydrogen peroxide consumption is 100% of theoretical amount, reduction temperature 60 DEG C, and recovery time 70min obtains cerium double salt precipitation thing
Deironing and thorium: this technique is carried out after the reduction and precipitation of Ce4+, technical process is: add the complexing agent alkaline solution containing NaOH in the cerium double salt precipitation thing that the reduction of Ce4+ and precipitation obtain, 2h is stirred under the condition of pH1-2, add sodium sulfate subsequently and stir 0.5h under 85 DEG C of conditions, filter, obtain sulfuric acid liquid and the precipitation of iron content and thorium complex, throw out carries out alkali conversion; The sulfuric acid liquid of iron content and thorium complex adds Waste Sulfuric Acid makes its acidity be 0.4mol/L, and complexing agent is lived again; Wherein amount of complex is 3.5 times of theoretical amount, and complexing agent is diethyl pentetic acid;
Alkali transforms: processing parameter is: ReO:NaOH=1:1.1; NaOH concentration 75%; Alkali turns temperature 160 DEG C, and alkali turns time 1.5h.
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 (4)
1. a hamartite wet method smelting process, comprising:
The roasting of hamartite, sulfuric acid to leach, double salt precipitation are separated, the reduction of Ce4+ and precipitation, deironing and thorium, alkali transform, oxidizing roasting generates CeO2, it is characterized in that:
The reduction of Ce4+ and precipitation: adopt hydrogen peroxide to make reductive agent, hydrogen peroxide consumption is the 90-100% of theoretical amount, reduction temperature 50-60 DEG C, recovery time 50-70min, obtains cerium double salt precipitation thing;
Deironing and thorium: this technique is carried out after the reduction and precipitation of Ce4+, technical process is: add the complexing agent alkaline solution containing NaOH in the cerium double salt precipitation thing that the reduction of Ce4+ and precipitation obtain, 1-2h is stirred under the condition of pH1-2, add sodium sulfate subsequently and stir 0.5h under 75-85 DEG C of condition, filter, obtain sulfuric acid liquid and the precipitation of iron content and thorium complex, throw out carries out alkali conversion; The sulfuric acid liquid of iron content and thorium complex adds Waste Sulfuric Acid makes its acidity be 0.1-0.4mol/L, and complexing agent is lived again; Wherein amount of complex is 2.5-3.5 times of theoretical amount, and complexing agent is diethyl pentetic acid;
Alkali transforms: processing parameter is: ReO:NaOH=1:0.9-1.1; NaOH concentration 65-75%; Alkali turns temperature 140-160 DEG C, and alkali turns time 0.5-1.5h.
2. technique according to claim 1, the reduction of preferred Ce4+ and precipitation: adopt hydrogen peroxide to make reductive agent, hydrogen peroxide consumption is 95% of theoretical amount, reduction temperature 55 DEG C, and recovery time 60min obtains cerium double salt precipitation thing.
3. technique according to claim 1, preferred deironing and thorium: this technique is carried out after the reduction and precipitation of Ce4+, technical process is: add the complexing agent alkaline solution containing NaOH in the cerium double salt precipitation thing that the reduction of Ce4+ and precipitation obtain, 1.5h is stirred under the condition of pH1-2, add sodium sulfate subsequently and stir 0.5h under 80 DEG C of conditions, filter, obtain sulfuric acid liquid and the precipitation of iron content and thorium complex, throw out carries out alkali conversion; The sulfuric acid liquid of iron content and thorium complex adds Waste Sulfuric Acid makes its acidity be 0.1-0.4mol/L, and complexing agent is lived again; Wherein amount of complex is 3 times of theoretical amount, and complexing agent is diethyl pentetic acid.
4. technique according to claim 1, preferred bases transforms: processing parameter is: ReO:NaOH=1:1; NaOH concentration 70%; Alkali turns temperature 150 DEG C, and alkali turns time 1h.
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| CN108913876A (en) * | 2018-07-26 | 2018-11-30 | 德昌县志能稀土有限责任公司 | A kind of method that Rare Earth Mine microwave decomposition-high acidic oils extract high-purity cerium |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108913876A (en) * | 2018-07-26 | 2018-11-30 | 德昌县志能稀土有限责任公司 | A kind of method that Rare Earth Mine microwave decomposition-high acidic oils extract high-purity cerium |
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Application publication date: 20150114 |