CN107287421B - A kind of process from hydrochloric acid leaching system extracting and refining molysite - Google Patents
A kind of process from hydrochloric acid leaching system extracting and refining molysite Download PDFInfo
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- CN107287421B CN107287421B CN201710369816.5A CN201710369816A CN107287421B CN 107287421 B CN107287421 B CN 107287421B CN 201710369816 A CN201710369816 A CN 201710369816A CN 107287421 B CN107287421 B CN 107287421B
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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
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/402—Mixtures of acyclic or carbocyclic compounds of different types
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a kind of processes from hydrochloric acid leaching system extracting and refining molysite, method includes the following steps: 1) oxidizing agent solution is added dropwise in the solution of Xiang Hanyou divalent iron salt, it is fully oxidized ferrous ion, obtains the water phase containing trivalent iron salt；2) extractant organic phase is prepared；3) by water phase that step 1) obtains and step 2) obtain it is organic mix, extracted, separate organic phase: 4) being stripped the obtained organic phase of step 3) using strippant, after split-phase, collect anti-stripping agent.
Description
Technical field
The invention belongs to chemical extraction purification technique fields, and in particular to a kind of from hydrochloric acid leaching system extracting and refining molysite
Process.
Background technique
Applied to the resource utilization of aluminous fly-ash, red mud and other ferrous metal wastes, covering object includes high alumina
Flyash, red mud, ferrous metal waste and grade are lower than the iron ore that blast furnace process requires.According to statistics, the height of China's accumulation
Aluminium powder coal ash reaches 300,000,000 tons, and reserves reach 5,000,000,000 tons.Aluminum oxide content is 35%~55% in aluminous fly-ash
Between, it is calculated by this, the total content of aluminium oxide is between 17.5~27.5 hundred million tons in China's aluminous fly-ash.If by these oxygen
Change aluminium to use, it, can by the annual aluminium oxide demand in current China (consuming 40,000,000 tons of aluminium oxide every year on average) estimation
Needed for meeting China 125 years, it is possible thereby to which it is externally interdependent and avoidable domestic due to exploiting bauxite to greatly reduce bauxite
Bring environment and ecological disruption.
Aluminium oxide is extracted from flyash, there are two kinds of techniques of alkaline process and acid system.Alkaline process is more direct, and product purity is high.But
Because a large amount of consumption lime stones bring the destruction of another environment and ecology, have also drawn high list while solid waste utilizes
The production cost of position product.It compares with alkaline process, acid system process is short, advantage of lower cost.But the because intrinsic spy of acid leaching process
Point, in leachate other than aluminium oxide, other metals, such as metallic iron are worth in high rare metal gallium and flyash
Contained other heavy metal coppers, zinc, lead, mercury etc. are all leached and enter leachate.When sulfuric acid leaching, alumina recovery rate is low,
And it is thermodynamically not dominant.Salt Ore Leaching thermodynamics is dominant, and because the coordination ability of chloride ion is strong, oxidation
Aluminium recovery is high.But just because of the coordination ability of chloride ion is strong, in~30% salt Ore Leaching, almost 100% iron is also immersed
Out.If iron not removed, it is off quality to will lead to alumina product.How de-iron is removed, is the one of salt Ore Leaching flyash
A production bottleneck.Iron is separated from hydrochloric acid leachate, never molding technique emerges, therefore provides in flyash high added value
Source field, the acid-hatching of young eggs are under a cloud always.To find out its cause, be exactly that acid leaching process can leach together iron and other impurities metal,
And separation is difficult.If being able to capture this problem, the bottleneck problem of flyash high added value recycling will disappear, especially
It is hydrochloric acid leaching process, industrially realizing will become feasible.Chinese patent CN104946889A is disclosed with N, N- diformazan heptyl
Acetamide (amine extractant, industrial code name N503) and tributyl phosphate (TBP) make extractant separated in hydrochloric acid medium iron and
Aluminium, but this extraction system has following problem: 1.N, N- diformazan heptyl acetamide expensive, about 150,000 yuan of people of price per ton
People's coin causes operating cost high, and the practicability is poor；2.TBP belongs to phosphoric acid ester extractant, and N503 belongs to amine extractant, and two
Person's synergistic effect is poor, is easy emulsification and causes split-phase difficult；3. loading capacity is small, saturation extraction capacity is less than 50 grams per liters (with three
Valence iron meter), cause the concentration of iron in anti-stripping agent lower than 80 grams per liters, certain difficulty is caused to subsequent processing；4.N, N- diformazan
Heptyl acetamide has stronger extracting power to divalent subgroup element such as copper etc., leads to the iron tramp content for being extracted into organic phase
Height, product purity are limited.Other similar technology, is also never shown in and has been reported that.
Summary of the invention
The present invention has the technique of specific extraction ability using a kind of pair of iron, and iron is only extracted into organic phase, is then used
Ferric chloride solution is obtained after water back extraction.Because extraction process selectivity is very strong, other impurities metal such as aluminium is (for extraction
Process, aluminium are foreign metals), gallium, copper, zinc, lead, mercury etc., all stay in water phase.Water phase is further processed, purity can be obtained
Reach the alumina product of requirement.Extraction system of the invention is by specific ferric iron, methylisobutylketone, tributyl phosphate and phase
Regulator n-octyl alcohol and 2-Ethyl Hexanol composition, and do split-phase promotor with a small amount of n-amyl alcohol and (reduce the shape of foam-like third phase
At the quick separating with promotion organic phase and water phase).There are many workable oxidant species, such as hydrogen peroxide, sodium hypochlorite, chlorine
Gas, ammonium persulfate, sodium chlorate etc..From the point of view of economy, sodium chlorate obtains 5 electronics during the reaction, and ferrous iron
It is changed into ferric iron and provides an electronics, that is to say, that 106 grams of sodium chlorate can aoxidizes 280 grams of ferrous irons, than other oxidants
Efficiency it is much higher (such as chlorine, 71 grams of chlorine oxidations, 112 grams of ferrous irons), therefore the preferred sodium chlorate of the present invention can also select double
Oxygen water makees oxidant, and (34 grams of hydrogen peroxide oxidations, 112 grams of ferrous irons, the efficiency than chlorine double, even if considering dividing certainly for hydrogen peroxide
Solution, also more much more cost effective than using chlorine).
The specific technical solution of the present invention is a kind of process from hydrochloric acid leaching system extracting and refining molysite, including
Following steps:
1) oxidizing agent solution is added dropwise in the solution of Xiang Hanyou divalent iron salt, is fully oxidized ferrous ion, is contained
There is the water phase of trivalent iron salt；
2) extractant organic phase is prepared；
3) by water phase that step 1) obtains and step 2) obtain it is organic mix, extracted, separate organic phase:
4) the obtained organic phase of step 3) is stripped using strippant, after split-phase, collects anti-stripping agent.
Further, the oxidizing agent solution in the step 1) is sodium chlorate solution.
Further, the oxidizing agent solution in the step 1) is hydrogen peroxide, sodium hypochlorite, chlorine or ammonium persulfate.
Further, the organic phase composition of extractant in the step 1) is following (volume %):
Methylisobutylketone: 15~35%
Tributyl phosphate: 35~70%
N-octyl alcohol: 5~30%
2-Ethylhexyl Alcohol: 5~30%
N-amyl alcohol: 1~5%
Diluent 0~20%.
Further, the diluent in the extractant is sulfonated kerosene.
Further, water phase and organic volume ratio mixed are 1:1 in the step 3).
Further, extraction temperature is room temperature in the step 3), and incorporation time is 1 minute, and the split-phase time is 30 seconds.
Further, in the water phase of the step 1) in make concentration of hydrochloric acid not less than 40 grams per liters by adding concentrated hydrochloric acid.
Further, the step 3) uses tandem counter-current extraction technique, and when saturation extracts, the concentration of organic phase iron reaches
140 grams per liters.
Further, strippant is distilled water in the step 4), using tandem countercurrent reextraction taking technique.
Beneficial effects of the present invention
It will be ferrous oxidising at ferric iron in salt acid leach solution.It, will since the difficulty that ferrous iron is extracted is big
Ferrous iron is first converted into ferric iron and is extracted again, is stripped by water, obtains the ferric chloride solution that purity is greater than 99.5%, three-level
After back extraction, the concentration of iron be can achieve or more than 120 grams per liters, significant effect in ferric chloride solution.In addition, inverse using tandem
Extraction process is flowed, advantageous condition has all been opened up to subsequent any treatment process, such as produces iron pigment or burns production
Croci etc..Process flow of the invention is easily achieved industrialized production.
Detailed description of the invention
Fig. 1 is flyash hydrochloric acid leachate process flow diagram of the present invention.
Fig. 2 is that ferric iron counter-current extraction of the present invention and countercurrent reextraction take schematic diagram.
Fig. 3 is that laboratory simulation level Four cascade extraction tests schematic diagram.
0 represents initial water phase or organic phase in figure, water 0 added with 0 indicate initial water phase and it is initial it is organic mix after by
First order extraction, isolates organic phase 1 and water phase 1, wherein the water 1 isolated continues and new organic phase 0 mixes, carries out second
Grade extraction, and so on.
Specific embodiment
The present invention will be further described in detail below with reference to the embodiments and the accompanying drawings.
Embodiment 1
500 grams of aluminous fly-ash are placed in polytetrafluoro container, which is placed in autoclave, and 25% salt is added
400 milliliters of acid stirs 2 hours in 160 DEG C.When reactor temperature is cooled to room temperature, reaction vessel is taken out, is filtered, is collected
Filtrate obtains 200 milliliters of filtrate.Filtrate composition is as follows: Fe2+37 grams per liters, Al3+80 grams per liters, other metal ions do not detect.It is molten
150 grams per liter of concentration of hydrochloric acid in liquid.Liquor capacity is adjusted to 500 milliliters with distilled water.Under conditions of being stirred continuously into solution
Sodium chlorate solution is added dropwise, until being fully oxidized with sodium bromate detection ferrous ion.100 milliliters of solution are taken every time.
It prepares extraction organic phase: it is following (volume ratio) to extract organic phase composition: methylisobutylketone: 17%；Tributyl phosphate:
38%；N-octyl alcohol: 11%；2-Ethylhexyl Alcohol: 14%；N-amyl alcohol: 3%；Sulfonated kerosene 17%.
When extraction, 100 milliliters of organic phase are taken, every time 100 milliliters of phase of water intaking.100 milliliters of organic phase is successively to 4 100 millis
Water phase is risen to be extracted.When extraction, incorporation time 1 minute, the split-phase time 30 seconds.
After separating organic phase, organic phase is stripped with 100 milliliters of distilled water, stands 3 minutes split-phases.After split-phase,
Anti-stripping agent is collected, metal ion species each in anti-stripping agent are detected with ICP.As a result as follows:
1. anti-stripping agent of table analyzes result
From table 1 it can be calculated that in anti-stripping agent, the purity of iron is greater than 99.9%, reaches the requirement of high purity iron.
Embodiment 2
Certain factory of table 2. provide iron content waste water composition approximately as:
Using the iron content waste water that certain factory provides as research object.The group of extractant becomes 20% methylisobutylketone, 47%
TBP, 5% n-octyl alcohol, 13% 2- ethylhexyl alcohol, 2% n-amyl alcohol and 13% sulfonated kerosene.Extraction experiments are level Four tandem extraction
It takes.Experimental implementation is as shown in Figure 3.Wherein, 0 initial water phase or organic phase are represented, water 0 indicates initial water phase added with 0 and initially has
Machine extracts after mixing by the 1st grade, isolates organic phase 1 and water phase 1, wherein the water 1 isolated continues and new organic phase 0
Mixing carries out the 2nd grade of extraction, and so on.
Each extraction experiments all take 100 milliliters of organic phase, 100 milliliters of water phase.According to the path in figure, it gets out organic phase
1~4.Then organic phase is stripped from 1~4 sequence with 100 milliliters of distilled water.Metal ion in anti-stripping agent is dense
Degree is analyzed with ICP.As a result as follows:
After the iron content waste water that table 3. provides certain factory carries out extraction and separation, tandem back extraction carried out to organic phase, in strip liquor
The concentration of each metal ion
It can be calculated from the data of table 3, the purity of iron ion is greater than 99.9%.
The present invention mainly emphasizes that high purity iron is separated and obtained in hydrochloric acid system, can although being directed to Ash Utilization
To extend in the production technology that other use salt Ore Leaching or dissolution, such as red mud recycling and other serious corrosion ironwork salt
The recycling of iron in acid leaching liquor.
Claims (7)
1. a kind of process from hydrochloric acid leaching system extracting and refining molysite, which comprises the following steps:
1) oxidizing agent solution is added dropwise in the solution of Xiang Hanyou divalent iron salt, is fully oxidized ferrous ion, obtains containing three
The water phase of valence molysite；
2) extractant organic phase is prepared；
3) by water phase that step 1) obtains and step 2) obtain it is organic mix, extracted, separate organic phase；Extraction temperature
It is room temperature, incorporation time is 1 minute, and the split-phase time is 30 seconds；
4) the obtained organic phase of step 3) is stripped using strippant, after split-phase, collects anti-stripping agent；
Organic phase composition of extractant described in step 2) is following (volume %):
Methylisobutylketone: 15~35%
Tributyl phosphate: 35~38%
N-octyl alcohol: 5~30%
2-Ethylhexyl Alcohol: 5~30%
N-amyl alcohol: 1~5%
Diluent sulfonated kerosene 13~17%.
2. method according to claim 1, which is characterized in that the oxidizing agent solution in the step 1) is sodium chlorate solution.
3. method according to claim 1, which is characterized in that the oxidizing agent solution in the step 1) is hydrogen peroxide, secondary chlorine
Sour sodium, chlorine or ammonium persulfate.
4. method according to claim 1, which is characterized in that water phase and organic volume ratio mixed in the step 3)
It is 1:1.
5. method according to claim 1, which is characterized in that make hydrochloric acid by adding concentrated hydrochloric acid in the water phase of the step 1)
Concentration is not less than 40 grams per liters.
6. method according to claim 1, which is characterized in that the step 3) uses tandem counter-current extraction technique, saturation extraction
When taking, the concentration of organic phase iron reaches 140 grams per liters.
7. method according to claim 1, which is characterized in that strippant is distilled water in the step 4), using tandem
Countercurrent reextraction taking technique.
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| CN108557791A (en) * | 2018-06-08 | 2018-09-21 | 武汉工程大学 | The method for preparing calcium dihydrogen phosphate using low-grade phosphate ore |
| CN109517983A (en) * | 2018-12-20 | 2019-03-26 | 清远市嘉禾稀有金属有限公司 | A kind of method that HoY solution removes ferrous ion |
| CN110844963A (en) * | 2019-11-21 | 2020-02-28 | 神华准能资源综合开发有限公司 | Method for separating and recovering aluminum-containing high-iron-salt-acid wastewater |
| CN113213547A (en) * | 2021-03-10 | 2021-08-06 | 斯瑞尔环境科技股份有限公司 | Method for recovering copper and iron from etching waste liquid |
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