CN108559842B - A kind of method that low-concentration hcl Ore Leaching calcium strontium selects Weishan Lake rare earth ore concentrate - Google Patents
A kind of method that low-concentration hcl Ore Leaching calcium strontium selects Weishan Lake rare earth ore concentrate Download PDFInfo
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- CN108559842B CN108559842B CN201810759681.8A CN201810759681A CN108559842B CN 108559842 B CN108559842 B CN 108559842B CN 201810759681 A CN201810759681 A CN 201810759681A CN 108559842 B CN108559842 B CN 108559842B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The present invention provides a kind of method that low-concentration hcl Ore Leaching calcium strontium selects Weishan Lake rare earth ore concentrate, it is characterised in that: is impregnated with low-concentration hcl to Weishan Lake rare earth ore concentrate, and heats and reacted.It is described to filter, then Weishan Lake rare earth ore concentrate is added again into the leachate filtered out after the reaction was completed, and heat and reacted, the liquid discharge obtained after separation of solid and liquid, solid phase utilizes again.The present invention can improve Weishan Lake rare earth ore concentrate grade to 50% by 40%, 90% calcium carbonate in Weishan Lake rare earth ore concentrate and 85% strontium carbonate can efficiently be leached, and guarantee rare earth loss late less than 1%, containing only calcium chloride, strontium chloride and a small amount of iron chloride in the spent picking solution being discharged, it is easy to wastewater treatment.
Description
Technical field
The present invention relates to a kind of methods that low concentration of salt Ore Leaching calcium strontium selects Weishan Lake rare earth ore concentrate, belong to rare-earth wet method
Metallurgical technology field.
Background technique
Weishan Lake Rare Earth Mine is the famous light rare earth mineral reserve in China, is all the big light rare earth in China three with baotite and Sichuan Mine
Mine.As the raw material site of Shandong rare-earth smelting separation production line, Weishan Lake Rare Earth Mine is big with rare earth reserves, impure mineral is numerous
Lead to difficult the characteristics of smelting more.
Existing 40% grade Weishan Lake rare earth ore concentrate treatment process, that there are process flows is long, rare-earth yield is low, the three wastes are dirty
Serious problem is contaminated, the development of art technology is no longer adapted to.
Summary of the invention
The technical problem to be solved in the present invention, is lower to grade and the higher Weishan Lake of calcium carbonate, Strontium carbonate contents is dilute
Native concentrate carries out chemical mineral processing, to remove a large amount of calcium strontium elements therein, improves the grade of Weishan Lake rare earth ore concentrate.
To solve the above problems, this invention takes following technical schemes:
A kind of method that low-concentration hcl Ore Leaching calcium strontium selects Weishan Lake rare earth ore concentrate, it is characterised in that: use low concentration
Hydrochloric acid impregnates Weishan Lake rare earth ore concentrate, and heats and reacted.
After the reaction was completed, it filters, then Weishan Lake rare earth ore concentrate is added again into the leachate filtered out, and heat progress
It reacts, the liquid discharge obtained after separation of solid and liquid, solid phase utilizes again.
The Weishan Lake rare earth ore concentrate: grade is 35% -40%；The low-concentration hcl: molar concentration is
0.5mol/L—3mol/L。
The low-concentration hcl reacts Weishan Lake rare earth ore concentrate: temperature is 80 DEG C -95 DEG C, and the reaction time is 30 points
Clock -90 minutes.
The leachate is reacted with Weishan Lake rare earth ore concentrate: temperature be 90 DEG C -95 DEG C, the reaction time be 60 minutes -
120 minutes.
It is 3:1 that the liquid that the low-concentration hcl is reacted with Weishan Lake rare earth ore concentrate, which consolidates mass ratio,.
The low-concentration hcl is reacted with Weishan Lake rare earth ore concentrate, and the leaching rate of calcium carbonate reaches 90%, the leaching of strontium carbonate
Extracting rate reaches 85%.
The leachate is reacted with Weishan Lake rare earth ore concentrate: pH value is 4.5-6.0 at the end of reaction.
The leachate is reacted with Weishan Lake rare earth ore concentrate: in the liquid phase after reaction, rare earth oxide loss late is less than
1%。
The present invention carries out a salt Ore Leaching to the calcium strontium mineral in Weishan Lake rare earth ore concentrate with low-concentration hcl, has reacted
Weishan Lake rare earth ore concentrate is added in Xiang Yici leachate after being separated by solid-liquid separation again by Cheng Bingjing, using in remaining salt Ore Leaching concentrate
Part calcium, strontium mineral, while will be under rare-earth precipitation in a leachate using excessive carbonic acid class calcium, strontium mineral in concentrate
Come, after separation of solid and liquid, then with low-concentration hcl salt Ore Leaching is carried out to solid phase, thoroughly to leach calcium therein, strontium mineral, solid-liquid
After separation, concentrate enters subsequent processing to solid phase as a purpose, and concentrate is added again and recycles rare earth therein for liquid phase.In this way, two steps
Acidleach alternately, forms continuous two-stage countercurrent and leaches.
The present invention by adopting the above technical scheme, is leached by two-stage, can by 90% calcium carbonate in Weishan Lake rare earth ore concentrate and
85% strontium carbonate efficiently leaches, and REO content in the rare earth ore concentrate of 40% grade is improved to 50% or so, simultaneously, it is ensured that rare earth
Loss late is lower than 1%, realizes the high efficiency choosing to Weishan Lake rare earth ore concentrate.It is contained only in the secondary leachate of output in the process
Calcium chloride and strontium chloride, pH value are conducive to processing discharge close to 6.0, and environmentally friendly.
Related chemical equation has in the process:
CaCO3+2HCl=CaCl2+H2O+CO2↑
SrCO3+2HCl=SrCl2+H2O+CO2↑
RE2(CO3)3+6HCl=2RECl3+3H2O+3CO2↑
3 CaCO3+2RECl3=3 CaCl2 + RE2(CO3)3↓
3 SrCO3+2RECl3= SrCl2 + RE2(CO3)3↓
Compared with prior art, the invention has the following advantages:
(1) present invention can improve Weishan Lake rare earth ore concentrate grade to 50% by 40%, can will be in Weishan Lake rare earth ore concentrate
90% calcium carbonate and 85% strontium carbonate efficiently leach, and guarantee rare earth loss late less than 1%, containing only chlorine in the spent picking solution being discharged
Change calcium, strontium chloride and a small amount of iron chloride, is easy to wastewater treatment.
(2) the oxidizing roasting process in original technique is reduced in present invention process, shortens process, is improved alkali and is turned effect, and
The final rare-earth yield that improves realizes that zero waste gas emission, soda wastewater flow rate reduce by 30% than original technique, waste residue amount ratio to 88% or more
Originally reduce 30%-40%.
Detailed description of the invention
A kind of low concentration of salt Ore Leaching calcium strontium of attached drawing 1 selects the process flow chart of the method for Weishan Lake rare earth ore concentrate
Wherein, concentrate is raw material Weishan Lake rare earth ore concentrate.
Specific embodiment
A kind of method that low concentration of salt Ore Leaching calcium strontium selects Weishan Lake rare earth ore concentrate of the present invention is a kind of continuous concentrate
Impurity removal process is selected in change, therefore embodiment is stated with continuous several groups of test processes.
A kind of method that low concentration of salt Ore Leaching calcium strontium selects Weishan Lake rare earth ore concentrate of embodiment 1
The raw material Weishan Lake rare earth ore concentrate grade of use is lower than 40%.
1,11.8m3 hydrochloric acid is measured, is injected in reactor tank, concentration of hydrochloric acid (equivalent concentration) is 2.6N, puts into the Weishan 3.73t
Lake rare earth ore concentrate is warming up to 90 DEG C and is stirred to react 2 hours, and rare earth concentration no longer changes at this time, is considered as reaction terminating.
Filtering, obtains filtrate, steeps liquid as a hypo acid, injects in another tank, amounts to 14.2m3；
Filter residue 2.2t is obtained by filtration, the filter residue: moisture content 15.90%, rare earth oxide content 50.81%；
It is purpose solid phase.
One hypo acid steeps component content in liquid:
The REO is rare earth oxide.
2,3.5t Weishan Lake rare earth ore concentrate is put into, 95 DEG C are stirred to react in gained mono- hypo acid of 14.2m3 bubble liquid one step up
It 1.5 hours, filters after the reaction was completed；
Filtrate is that quadratic acid steeps liquid, amounts to 16 cubic metres, arranges to waste water；
Filter residue is that a hypo acid steeps slag, amounts to 3.62t, moisture 19.37, rare earth oxide content 41.73%.
Sample examination quadratic acid steeps liquid, as a result as follows:
3,8.3 cubic metres of 3mol/L hydrochloric acid are prepared, is mixed with gained mono- hypo acid of 3.62t bubble slag in previous step, is heated to 90
DEG C, it stirs 2 hours, filtering；
Filtrate is that a hypo acid steeps liquid, amounts to 10m3；
Filter residue is that quadratic acid steeps slag, amounts to 1.86t, moisture 15.72%, rare earth oxide content 50.88%.
The ingredient of the one hypo acid bubble liquid is as follows:
4,3.76t concentrate is put into gained filtrate one step up, is heated to 95 DEG C, stirs 1.5 hours, filtering.Filter residue is
One hypo acid steeps slag, weight in wet base 4.6t, moisture 13.94%, REO content 40.35%.Filtrate is that quadratic acid steeps liquid, amounts to 12 m3, sampling
It is as follows to chemically examine ingredient:
5, the hydrochloric acid that configuration 11m3 concentration is 2.73N puts into the bubble slag of mono- hypo acid of 4.6t obtained by previous step in hydrochloric acid, 90 DEG C
It is heated with stirring to qualified (2 hours reaction time)；Filtering.
Filtrate is that a hypo acid steeps liquid, volume 12.5m3；
Filter residue is that quadratic acid steeps slag, slag weight 2.6t, moisture 18.2%, REO content 48.19%.
The composition detection result of above-mentioned hypo acid bubble liquid:
6,3.94t concentrate is put into resulting mono- hypo acid of 12.5m3 bubble liquid one step up, is heated to 95 DEG C, stirs 1 hour
Sampling, rare earth is slightly higher, stops heating and continues stirring 1 hour, qualified.Filtering, filtrate be quadratic acid steep liquid, 14 cubic metres of volume.
Filter residue steeps slag, weight in wet base 5.1t, moisture 16.16%, REO content 51.03% for a hypo acid.
The composition detection result of above-mentioned quadratic acid bubble liquid:
7,3.3N hydrochloric acid 10.5m3 is configured, by the bubble slag investment hydrochloric acid of a hypo acid obtained by previous step, is heated to 90 DEG C, stirring
2 hours, filtering.
Filtrate 2m3 is obtained by filtration, i.e. a hypo acid steeps liquid；
Filter residue 2.65t, moisture 15.78%, REO content 50.55% is obtained by filtration.
The composition detection result of above-mentioned hypo acid bubble liquid:
8,3.93t concentrate is put into gained mono- hypo acid of 12m3 bubble liquid one step up, (reaction time is to qualified for 95 DEG C of stirrings
1.5 hours), filtering.Filtrate 13m3 is obtained, i.e. quadratic acid steeps liquid.
Filter residue is obtained, steeps slag, weight in wet base 5.2t, moisture 21.21%, REO content 54.19% for a hypo acid.
The composition detection result of above-mentioned quadratic acid bubble liquid:
9,2.3N hydrochloric acid 13m3 is configured.The bubble slag of mono- hypo acid of 5.2t obtained by previous step is put into matched hydrochloric acid.It is heated to 90
DEG C, keep the temperature 0.5 hour.
Filtering, obtains filtrate 15.8m3, filter residue 4.2t, moisture 16.47%, REO content 53.52%.
Filtrate component testing result:
10,3.47t concentrate is put into gained filtrate one step up, is heated to 95 DEG C, keep the temperature, after stirring 3 hours,
REO concentration is 0.21g/L in solution, qualified.Filtering, filtrate 16m3, ingredient are as shown in the table.Filter residue 3.8t, moisture 16.42,
REO content 51.29%.
The composition detection result of filtrate:
In addition to specified otherwise, percentage of the present invention is mass percent, and the ratio is mass ratio.
Finally, it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not intended to restrict the invention,
It, for those skilled in the art, still can be with although describing the invention in detail with reference to the foregoing embodiments
It modifies the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.It is all
Within the spirit and principles in the present invention, any modification, equivalent replacement, improvement and so on should be included in guarantor of the invention
Within the scope of shield.
Claims (4)
1. a kind of method that low-concentration hcl Ore Leaching calcium strontium selects Weishan Lake rare earth ore concentrate, it is characterised in that: use low concentration of salt
Acid impregnates Weishan Lake rare earth ore concentrate, and heats and reacted；
It is described after the reaction was completed, filtering then Weishan Lake rare earth ore concentrate is added into the leachate filtered out, and heat progress again
It reacts, the liquid discharge obtained after separation of solid and liquid, solid phase utilizes again；
The Weishan Lake rare earth ore concentrate: grade is 35% -40%；The low-concentration hcl: molar concentration is 0.5mol/L-
3mol/L；
It is 3:1 that the liquid that the low-concentration hcl is reacted with Weishan Lake rare earth ore concentrate, which consolidates mass ratio,；
The leachate is reacted with Weishan Lake rare earth ore concentrate: pH value is 4.5-6.0 at the end of reaction；In liquid phase after reaction,
Rare earth oxide loss late is less than 1%.
2. a kind of method that low-concentration hcl Ore Leaching calcium strontium selects Weishan Lake rare earth ore concentrate according to claim 1,
Be characterized in that: the low-concentration hcl reacts Weishan Lake rare earth ore concentrate: temperature is 80 DEG C -95 DEG C, and the reaction time is 30 points
Clock -90 minutes.
3. a kind of method that low-concentration hcl Ore Leaching calcium strontium selects Weishan Lake rare earth ore concentrate according to claim 2,
Be characterized in that: the leachate is reacted with Weishan Lake rare earth ore concentrate: temperature be 90 DEG C -95 DEG C, the reaction time be 60 minutes -
180 minutes.
4. a kind of method that low-concentration hcl Ore Leaching calcium strontium selects Weishan Lake rare earth ore concentrate according to claim 1,
Be characterized in that: the low-concentration hcl is reacted with Weishan Lake rare earth ore concentrate, and the leaching rate of calcium carbonate reaches 90%, strontium carbonate
Leaching rate reaches 85%.
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| CN109439931A (en) * | 2018-12-03 | 2019-03-08 | 包头稀土研究院 | A kind of method of awns court of a feudal ruler Paasche rare-earth ore resource comprehensive utilization |
| CN111850296B (en) * | 2020-07-16 | 2022-02-25 | 乐山盛和稀土股份有限公司 | Method for recovering and preparing high-purity strontium compound from rare earth ore |
| CN114836637B (en) * | 2022-05-20 | 2023-11-24 | 全南县新资源稀土有限责任公司 | Rare earth oxide acid-soluble grouping method |
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|---|---|---|---|---|
| CN1045812A (en) * | 1989-03-20 | 1990-10-03 | 甘肃稀土公司 | The processing method of silicon, calcium, lanthanum in the extracting and separating yttrium |
| CN1928131A (en) * | 2006-09-29 | 2007-03-14 | 东北大学 | Method for separating rare-earth element and fluorapatite, calcium chloraphosphate and calcium phosphate |
| CN105668888A (en) * | 2015-12-31 | 2016-06-15 | 包头稀土研究院 | Low-grade mixed rare earth ore concentrate chemical dressing and chemical dressing waste water resource comprehensively recycling method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045812A (en) * | 1989-03-20 | 1990-10-03 | 甘肃稀土公司 | The processing method of silicon, calcium, lanthanum in the extracting and separating yttrium |
| CN1928131A (en) * | 2006-09-29 | 2007-03-14 | 东北大学 | Method for separating rare-earth element and fluorapatite, calcium chloraphosphate and calcium phosphate |
| CN105668888A (en) * | 2015-12-31 | 2016-06-15 | 包头稀土研究院 | Low-grade mixed rare earth ore concentrate chemical dressing and chemical dressing waste water resource comprehensively recycling method |
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