CN109554554A - A method of the Ti recovery from sulfate liquor - Google Patents
A method of the Ti recovery from sulfate liquor Download PDFInfo
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- CN109554554A CN109554554A CN201811602584.4A CN201811602584A CN109554554A CN 109554554 A CN109554554 A CN 109554554A CN 201811602584 A CN201811602584 A CN 201811602584A CN 109554554 A CN109554554 A CN 109554554A
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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
- C22B41/00—Obtaining germanium
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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
- C22B3/28—Amines
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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
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- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The method of the present invention relates to a kind of from sulfate liquor Ti recovery, includes the following steps: in acid condition, iron powder to be added by the ferric iron back in sulfate liquor into ferrous iron, adds complexing agent, is uniformly mixed and forms water phase, adjusts water phase pH；The modification agent for inhibiting arsenic co-extraction is added in tertiary amine-kerosene of acidification, is uniformly mixed and forms organic phase, water phase and organic phase mixing are extracted, and germanic organic phase is obtained；Germanic organic phase is stripped using sodium hydroxide, obtains the germanium solution of high concentration.The shortcomings that the present invention overcomes traditional tannin precipitation method, zinc replacement, ion-exchange and traditional tertiary amine extractions, substantially increases the separative efficiency of germanium, has saved production cost.The processes such as arsenic co-extraction modification agent are inhibited using the reduction of Fe powder, organic phase addition, realize tertiary amine extractant to the selective extraction of germanium in germanic more metal sulfate solution.This method step is simple, works well, and is easy to industrialize.
Description
Technical field
The present invention relates to dissipated metal recycling and hazardous waste processing technology fields, more particularly, to one kind from sulfuric acid
The method of Ti recovery in salting liquid.
Background technique
Germanium is a kind of important dissipated metal, is widely used in the fields such as semiconductor, catalyst and optical device.From
For germanium seldom individually at mine, the general association of germanium is in copper, lead and zinc ores and Part Coal Mine and its content is often extremely low, causes in right boundary
The extraction of germanium and separating difficulty are larger.Currently, germanium is classified as important strategic resource, thus the metallurgical extraction of germanium by many countries
It is still extremely important research direction.
The industrially Ti recovery generally from lead-zinc smelting system and partial fuel coal cigarette ash.Either handle lead-zinc smelting system
By-product or coal-fired cigarette ash, when using hydrometallurgic recovery, certain Ore Leaching is generally first used, then again from germanic leachate
Middle Ti recovery.The main method of Ti recovery has from solution: solvent extraction, the tannin precipitation method, ion exchange, zinc dust precipitation
Deng.The recycling of germanium generallys use the tannin precipitation method in solution, and this method has many advantages, such as that heavy germanium is high-efficient, easy to operate, but its
There are tannin consumption big (every precipitating 1mol germanium need to be consumed greater than the tannin of 25mol), deteriorate solution, not recyclable, at high cost
The deficiencies of, it needs to carry out Ti recovery using new separation method.
Extraction can be with the slave germanium-containing solution extraction separating Ge of relative efficiency, and extractant can recycle, extractant
Loss is smaller, and efficient, the single-minded recycling of germanium may be implemented.But all there is certain deficiency in most extraction system, such as extract
Take required acidity excessively high (60-100g/L), the selling at exorbitant prices of extractant and synthesis difficulty, the co-extraction of impurity element, back extraction difficult
Deng.
Under given conditions, amine extractant is used alone from arsenic containing solution when extracted germanium, the co-extraction of As commonly reaches
The co-extraction of 10% or so, Fe are up to 10% or more.The back extraction of Fe needs to increase extraction procedure using individual stripping agent, into
And increase production cost.And co-extraction arsenic can enter in strip liquor when NaOH back extraction is used only with germanium, in production germanium essence
During mine, a part of arsenic is caused also to enter in germanium concentrate, not only will affect germanium concentrate grade, but also in the subsequent chlorine of germanium concentrate
Change distillation production GeCl4In the process, arsenic-containing waste residue can be also generated, environment is polluted.To sum up, tertiary amine extraction needs to make under certain condition
Ferric iron, arsenic, germanium are separated respectively with individual stripping agent, trivial operations are with high costs, it is necessary to take certain means
To inhibit the co-extraction of ferric iron and arsenic during this.
Summary of the invention
Based on this, the present invention is complicated for operation for iron arsenic co-extraction bring in the prior art, and environmental hazard is larger, cost
Higher technical problem provides a kind of method of co-extraction that can inhibit ferric iron and arsenic in extraction process, carrys out Ti recovery.
A method of from sulfate liquor Ti recovery, include the following steps:
(1) in acid condition, iron powder is added by the ferric iron back in sulfate liquor into ferrous iron, adds complexing
Agent is uniformly mixed and forms water phase, adjusts the pH of water phase；
(2) modification agent for inhibiting arsenic co-extraction is added in tertiary amine-kerosene of acidification, is uniformly mixed and forms organic phase, water phase
It is extracted with organic phase mixing, obtains germanic organic phase；
(3) germanic organic phase is stripped using sodium hydroxide, obtains the germanium solution of high concentration.
The pH of the acidity is 0.0-1.0 in one of the embodiments,.
The additional amount of the iron powder is 0.5-2 times of ferric iron content in sulfate liquor in one of the embodiments,.
The complexing agent is selected from one kind of tartaric acid, citric acid, oxalic acid in one of the embodiments,.
The additional amount of the complexing agent is 1-10 times of sulfate liquor Ge content in one of the embodiments,.
The pH of water phase is adjusted in one of the embodiments, and the pH is 0.2-2.0.
The tertiary amine is N235 or TOA in one of the embodiments,.
The modification agent is TOP (trioctyl phosphate) in one of the embodiments,.
In one of the embodiments, in the sulfate Ge content be greater than 0.01g/L, ferric iron, arsenic content be greater than
0.1g/L。
The concentration of NaOH is 0.5-5mol/L in one of the embodiments,.
The principle of the present invention: in PH≤7, germanic is in aqueous sulfuric acid with Ge (OH)4Molecular forms exist, and do not add
When adding complexing agent, the germanium in solution is not extracted substantially.The addition of complexing agent can not only make germanic acid be changed into yin from molecular state
Ionic state, and the complex compound radius generated is greater than germanic acid molecular radius, so that the germanic species in solution be made to be easier by uncle
Amine extractant extraction.Using iron powder by ferric iron back at inextractable ferrous iron, to eliminate ferric iron to extracting
The influence of journey.The combination for inhibiting arsenious acid proton and tertiary amine by the way that modification agent is added, to be played to the co-extraction of arsenic certain
Inhibiting effect.
Compared with prior art, the invention has the advantages that: by presetting pH, iron powder be added, complexing agent addition, contain
The presetting pH of germanium sulfate liquor, extractant extraction, load organic oppositing back-extraction technical process overcome traditional tannin heavy germanium method, zinc
The shortcomings that powder substitution method, ion-exchange and traditional tertiary amine extraction, the separative efficiency of germanium is substantially increased, has saved and has been produced into
This.The processes such as arsenic co-extraction modification agent are inhibited using the reduction of Fe powder, organic phase addition, realize tertiary amine extractant to germanic mostly gold
Belong to the selective extraction of germanium in sulfuric acid solution, the rate of recovery of germanium is high, effectively realizes the impurity member such as germanium and zinc, arsenic, iron, cadmium, silicon
The separation of element.This method step is relatively simple, works well, and is easy to industrialize.
Detailed description of the invention
Fig. 1 is the flow diagram of the method for the Ti recovery disclosed by the invention from sulfate liquor.
Specific embodiment
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, with reference to the accompanying drawing to the present invention
Specific embodiment be described in detail.Many details are explained in the following description in order to fully understand this hair
It is bright.But the invention can be embodied in many other ways as described herein, those skilled in the art can be not
Similar improvement is done in the case where violating intension of the present invention, therefore the present invention is not limited to the specific embodiments disclosed below.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.
Embodiment one
(1) under the conditions of pH=1.0, be added 0.8 times of iron powder of ferric iron mole by the ferric iron in sulfate liquor also
Original is at ferrous iron, wherein each element content in solution after iron powder reducing are as follows: germanium 0.05-0.06g/L, zinc 40g/L, arsenic 0.75g/
L, ferric iron 0.2g/L, cadmium 0.2g/L, silicon 0.1g/L add tartaric acid, and additional amount is 5 times of germanium mole, and mixing is equal
Even formation water phase adjusts the pH to 1.2 of water phase；
(2) contain 25%N235,10%TOP and 65% sulfonated kerosene in organic phase, water phase is mixed by 1:1 is compared with organic phase
It closes and carries out single-stage extraction, obtain germanic organic phase.The extraction yield of each element is as shown in table 1.
Table 1
| Element | Ge(IV) | Zn(II) | As(III) | Fe(III) | Cd(II) | Si(IV) |
| Extraction yield | 93.8% | 0.0% | 1.3% | 0.9% | 0.0% | 0.0% |
(3) using 0.5mol/L sodium hydroxide, to germanic organic phase, the single-stage when being comparably 1:1 is stripped 10min, and germanium is anti-
Extraction rate is up to 100%.
Embodiment two
(1) under the conditions of pH=0.8,0.8 times of ferric iron mole of iron powder is added by the ferric iron in sulfate liquor
It is reduced into ferrous iron, wherein each element content in solution after iron powder reducing are as follows: germanium 0.05-0.06g/L, zinc 40g/L, arsenic
0.75g/L, iron 0.15g/L, cadmium 0.2g/L, silicon 0.1g/L, add tartaric acid, and additional amount is 7 times of germanium mole, mixing
It is formed uniformly water phase, adjusts the pH to 1.2 of water phase；
(2) contain 25%N235,10%TOP and 65% sulfonated kerosene in organic phase, water phase is mixed by 1:1 is compared with organic phase
It closes and carries out single-stage extraction, obtain germanic organic phase；The extraction yield of each element is as shown in table 2.
Table 2
| Element | Ge(IV) | Zn(II) | As(III) | Fe(III) | Cd(II) | Si(IV) |
| Extraction yield | 95.7% | 3.7% | 3.7% | 0.9% | 0.5% | 0.1% |
(3) using 0.8mol/L sodium hydroxide, to germanic organic phase, the single-stage when being comparably 1:1 is stripped 10min, germanium
Back extraction ratio is 98%.
Embodiment three
(1) under the conditions of pH=1.0,1.0 times of ferric iron mole of iron powder is added will be by the trivalent in sulfate liquor
Iron is reduced into ferrous iron, wherein each element content in solution after iron powder reducing are as follows: germanium 0.05-0.06g/L, zinc 40g/L, arsenic
0.75g/L, iron 0.1g/L, cadmium 0.2g/L, silicon 0.1g/L, add tartaric acid, and additional amount is 5 times of germanium mole, mixing
It is formed uniformly water phase, adjusts the pH to 1.2 of water phase；
(2) contain 10%N235,10%TOP and 80% sulfonated kerosene in organic phase, water phase is mixed by 1:1 is compared with organic phase
It closes and carries out single-stage extraction, obtain germanic organic phase；The extraction yield of each element is as shown in table 3.
Table 3
| Element | Ge(IV) | Zn(II) | As(III) | Fe(III) | Cd(II) | Si(IV) |
| Extraction yield | 90.1% | 0.1% | 0.0% | 0.4% | 0.0% | 2.3% |
(3) 10min, germanium back extraction ratio are stripped when being comparably 1:1 to germanic organic phase using 2.0mol/L sodium hydroxide
It is 100%.
Example IV
(1) under the conditions of pH=1.0, be added 0.8 times of iron powder of ferric iron mole by the ferric iron in sulfate liquor also
Original is at ferrous iron, wherein each element content in solution after iron powder reducing are as follows: germanium 0.05-0.06g/L, zinc 40g/L, arsenic 0.75g/
L, ferric iron 0.2g/L, cadmium 0.2g/L, silicon 0.1g/L add tartaric acid, and additional amount is 5 times of germanium mole, and mixing is equal
Even formation water phase adjusts the pH to 1.2 of water phase；
(2) contain 5%N235,10%TOP and 85% sulfonated kerosene in organic phase, water phase is mixed by 1:1 is compared with organic phase
It closes and carries out single-stage extraction, obtain germanic organic phase.The extraction yield of each element is as shown in table 4.
Table 4
| Element | Ge(IV) | Zn(II) | As(III) | Fe(III) | Cd(II) | Si(IV) |
| Extraction yield | 83.9% | 0.0% | 0.0% | 0.0% | 0.0% | 0.0% |
(3) using 0.5mol/L sodium hydroxide, to germanic organic phase, the single-stage when being comparably 1:1 is stripped 10min, and germanium is anti-
Extraction rate is up to 100%.
Embodiment five
(1) under the conditions of pH=1.0, be added 0.8 times of iron powder of ferric iron mole by the ferric iron in sulfate liquor also
Original is at ferrous iron, wherein each element content in solution after iron powder reducing are as follows: germanium 0.05-0.06g/L, zinc 40g/L, arsenic 0.75g/
L, ferric iron 0.2g/L, cadmium 0.2g/L, silicon 0.1g/L add tartaric acid, and additional amount is 5 times of germanium mole, and mixing is equal
Even formation water phase adjusts the pH to 1.2 of water phase；
(2) contain 15%N235,10%TOP and 75% sulfonated kerosene in organic phase, water phase is mixed by 1:1 is compared with organic phase
It closes and carries out single-stage extraction, obtain germanic organic phase.The extraction yield of each element is as shown in table 5.
Table 5
| Element | Ge(IV) | Zn(II) | As(III) | Fe(III) | Cd(II) | Si(IV) |
| Extraction yield | 92.2% | 0.0% | 0.4% | 0.0% | 0.0% | 0.0% |
(3) using 0.5mol/L sodium hydroxide, to germanic organic phase, the single-stage when being comparably 1:1 is stripped 10min, and germanium is anti-
Extraction rate is up to 100%.
Embodiment six
(1) under the conditions of pH=1.0, be added 0.8 times of iron powder of ferric iron mole by the ferric iron in sulfate liquor also
Original is at ferrous iron, wherein each element content in solution after iron powder reducing are as follows: germanium 0.05-0.06g/L, zinc 40g/L, arsenic 0.75g/
L, ferric iron 0.2g/L, cadmium 0.2g/L, silicon 0.1g/L add tartaric acid, and additional amount is 5 times of germanium mole, and mixing is equal
Even formation water phase adjusts the pH to 1.2 of water phase；
(2) contain 20%N235,10%TOP and 70% sulfonated kerosene in organic phase, water phase is mixed by 1:1 is compared with organic phase
It closes and carries out single-stage extraction, obtain germanic organic phase.The extraction yield of each element is as shown in table 6.
Table 6
| Element | Ge(IV) | Zn(II) | As(III) | Fe(III) | Cd(II) | Si(IV) |
| Extraction yield | 93.1% | 0.0% | 1.7% | 0.2% | 0.0% | 0.0% |
(3) using 0.5mol/L sodium hydroxide, to germanic organic phase, the single-stage when being comparably 1:1 is stripped 10min, and germanium is anti-
Extraction rate is up to 100%.
Embodiment seven
1) under the conditions of pH=1.0,0.8 times of iron powder of ferric iron mole is added by the ferric iron back in sulfate liquor
At ferrous iron, wherein each element content in solution after iron powder reducing are as follows: germanium 0.05-0.06g/L, zinc 40g/L, arsenic 0.75g/L,
Ferric iron 0.2g/L, cadmium 0.2g/L, silicon 0.1g/L add tartaric acid, and additional amount is 5 times of germanium mole, are uniformly mixed
Water phase is formed, the pH to 1.2 of water phase is adjusted；
(2) contain 25%N235,15%TOP and 60% sulfonated kerosene in organic phase, water phase is mixed by 1:1 is compared with organic phase
It closes and carries out single-stage extraction, obtain germanic organic phase.The extraction yield of each element is as shown in table 7.
Table 7
| Element | Ge(IV) | Zn(II) | As(III) | Fe(III) | Cd(II) | Si(IV) |
| Extraction yield | 94.5% | 1.6% | 1.1% | 0.9% | 0.0% | 0.0% |
(3) using 0.5mol/L sodium hydroxide, to germanic organic phase, the single-stage when being comparably 1:1 is stripped 10min, and germanium is anti-
Extraction rate is up to 100%.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of method of the Ti recovery from sulfate liquor, which comprises the steps of:
(1) in acid condition, iron powder is added by the ferric iron back in sulfate liquor into ferrous iron, adds complexing agent,
It is uniformly mixed and forms water phase, adjust the pH of water phase；
(2) modification agent for inhibiting arsenic co-extraction is added in the tertiary amine of acidification-kerosene phase, is uniformly mixed and forms organic phase, water phase and
Organic phase mixing is extracted, and germanic load organic phases are obtained；
(3) germanic load organic phases are stripped using sodium hydroxide, obtain the germanium solution of high concentration.
2. the method according to claim 1, wherein the pH of the acidity is 0.0-1.0.
3. the method according to claim 1, wherein the additional amount of the iron powder is ferric iron in sulfate liquor
0.5-2 times of mole.
4. the method according to claim 1, wherein the complexing agent is in tartaric acid, citric acid, oxalic acid
It is a kind of.
5. the method according to claim 1, wherein the additional amount of the complexing agent is sulfate liquor Ge content
1-10 times.
6. the pH is 0.2-2.0 the method according to claim 1, wherein adjusting the pH of water phase.
7. the method according to claim 1, wherein the tertiary amine is three pungent/decyl tertiary amines or trioctylamine.
8. the method according to claim 1, wherein the modification agent is trioctyl phosphate.
9. the method according to claim 1, wherein Ge content is greater than 0.01g/L, trivalent in the sulfate
Iron, arsenic content be greater than 0.1g/L.
10. the method according to claim 1, wherein the concentration of NaOH is 0.5-5mol/L.
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Cited By (3)
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| CN110791648A (en) * | 2019-11-07 | 2020-02-14 | 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 | Method for extracting and recovering germanium from sulfuric acid leaching solution |
| CN112695212A (en) * | 2020-12-10 | 2021-04-23 | 衢州华友钴新材料有限公司 | Method for separating germanium from high-iron high-arsenic sulfate solution through ternary co-extraction |
| CN114277264A (en) * | 2021-12-28 | 2022-04-05 | 广东先导稀材股份有限公司 | Method for extracting and recovering germanium |
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| CN110791648A (en) * | 2019-11-07 | 2020-02-14 | 深圳市中金岭南有色金属股份有限公司丹霞冶炼厂 | Method for extracting and recovering germanium from sulfuric acid leaching solution |
| CN112695212A (en) * | 2020-12-10 | 2021-04-23 | 衢州华友钴新材料有限公司 | Method for separating germanium from high-iron high-arsenic sulfate solution through ternary co-extraction |
| CN114277264A (en) * | 2021-12-28 | 2022-04-05 | 广东先导稀材股份有限公司 | Method for extracting and recovering germanium |
| CN114277264B (en) * | 2021-12-28 | 2023-10-24 | 广东先导稀材股份有限公司 | Method for extracting and recycling germanium |
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