CN109626414B - Method for recovering thallium and rhenium from smelting waste acid - Google Patents
Method for recovering thallium and rhenium from smelting waste acid Download PDFInfo
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- CN109626414B CN109626414B CN201910098339.2A CN201910098339A CN109626414B CN 109626414 B CN109626414 B CN 109626414B CN 201910098339 A CN201910098339 A CN 201910098339A CN 109626414 B CN109626414 B CN 109626414B
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- C01G15/00—Compounds of gallium, indium or thallium
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Abstract
The invention belongs to the field of production of metal products, and particularly relates to a method for recovering thallium and rhenium from smelting waste acid. The invention finds that the special ion exchange resin for recovering molybdenum and rhenium, namely RCX-5143 resin, has a specific selective adsorption function on trivalent thallium complex anions, adopts RCX-5143 resin to directly adsorb and extract scattered metal thallium and rhenium under the condition that the pH value is higher than 1 without using alkali to neutralize acidity, takes the raw material as acid wastewater of a smelting plant, adds the adsorption material which is commercially available RCX-5143 resin in the whole process, and has the advantages of simple process, low cost, thallium recovery rate of 83.4-85.7 percent and rhenium recovery rate of 82.2-86.6 percent.
Description
Technical Field
The invention belongs to the field of production of metal products, and particularly relates to a method for recovering thallium and rhenium from smelting waste acid.
Background
Thallium and rhenium are both rare earth metals. The rare metal has very important application, is an important component of modern high-tech new materials, can be combined with nonferrous metals to form a series of compound semiconductors, electronic optical materials, special alloys, novel functional materials, organic metal compounds and the like, and is widely applied to modern communication technology, electronic computers, space navigation development, medicine and health, photosensitive materials, photoelectric materials, energy sources, catalytic materials and the like.
Thallium and rhenium are often present in some mineral resources (e.g., non-ferrous copper sulfide ores). In the desulfurization link in the non-ferrous metal smelting process, thallium and rhenium are mainly volatilized into flue gas, and the flue gas is washed to enter acidic waste water (namely waste acid), for example, the accumulated content of thallium and rhenium in copper smelting waste acid can reach dozens of mg/L. Acid waste water is usually neutralized and settled with lime to remove heavy metals, so that a large amount of solid waste is generated, thallium mainly exists as monovalent ions, and hydroxide (TlOH) of thallium is dissolved in water. On one hand, the thallium-containing wastewater poses threat to the environment if not treated in time; on the other hand, the scattered metal resources are extremely limited, the content of the scattered metal resources in the crust is very low, and the waste of the resources is caused by the fact that the scattered metal resources are not recycled in the smelting process.
The invention patent application with publication number CN 10379005A discloses a method for preparing thallium chloride from lead-zinc smelting wastewater, which comprises the steps of adding lead-zinc ore smelting waste residues and lime into the lead-zinc smelting wastewater, collecting precipitated bottom mud, adding the lead-zinc ore smelting waste residues and sulfuric acid into the bottom mud to obtain a thallium extracting solution, and then adding sodium chloride into the thallium extracting solution to obtain precipitate thallium chloride. The solution of the above patent application has the advantage of "treating waste with waste", but thallium recovery is low.
The invention patent application with publication number CN108611496A discloses a method for extracting come from copper smelting waste acid, which utilizes RCX-5143 macroporous anion exchange resin to recover rhenium in the waste acid, but does not relate to thallium recovery.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the invention aims to provide a method for recovering thallium and rhenium from smelting waste acid, in particular to a method for recovering thallium and rhenium from waste acid with pH value less than 1, which has the advantages of recovering scattered metals thallium and rhenium simultaneously and having high recovery rate.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for recovering thallium and rhenium from smelting waste acid comprises the following steps:
(1) pretreatment of resins
Soaking RCX-5143 anion exchange resin in sodium hydroxide solution, washing with water to neutrality, soaking in hydrochloric acid to convert into chlorine type, and washing with water to neutrality to obtain pretreated resin;
(2) recovery of rhenium
Collecting metallurgical plant thallium and rhenium-containing waste acid, filtering to remove insoluble substances, adding bromine water under stirring until the waste acid is yellow, and keeping for 10min to prevent color fading+) Fully oxidizing to form trivalent thallium complex anion, adding pretreated resin, stirring to adsorb ReO4 -Mixing with thallium complex anion, filtering, collecting resin, adding ammonia water containing EDTA or DTPA, stirring to elute ReO4 -Obtaining eluent, evaporating, concentrating, cooling to obtain precipitate, and drying to obtain ammonium rhenate (NH)4ReO4)；
(3) Thallium recovery
Collecting and eluting ReO4 -Adding Na into the resin2SO3Solution, agitation elution of Tl3+Ion to obtain Tl-rich+Adding sodium sulfide into the filtrate, precipitating, and drying to obtain thallium sulfide precipitate (Tl)2S)。
Preferably, the pH of the contaminated acid described in step (2) is < 1.
Preferably, the sodium hydroxide soaking condition in the step (1) is to soak the resin with 1mol/L sodium hydroxide solution with 4 times volume amount for 40-60 min.
Preferably, the hydrochloric acid soaking condition in the step (1) is to soak the resin with 4 times of volume of 1-2 mol/L hydrochloric acid solution for 40-60 min.
Preferably, the bromine water in the step (2) has a mass percentage concentration of 3%.
Preferably, when the pretreated resin is added in the step (2), the solid-to-liquid ratio of the resin to the wastewater is 0.005-0.01 g/ml.
Preferably, the agitation adsorption of ReO in step (2)4 -And the duration of the thallium-coordinated anion is 40-60 min.
Preferably, in the ammonia water containing EDTA or DTPA in the step (2), the mass percentage concentration of the ammonia water is 5-8%.
Preferably, in the ammonia water containing EDTA or DTPA in the step (2), the mass percentage concentration of EDTA or DTPA is 0.05-0.1%.
Preferably, when the ammonia water containing EDTA or DTPA is added in the step (2), the solid-to-liquid ratio of the resin to the ammonia water is 1:2 g/ml.
Preferably, the agitation elution of ReO in step (2)4 -The time duration is 30-50 min.
Preferably, the temperature for the evaporative concentration in step (2) is 90 ℃.
Preferably, the drying in step (2) and step (3) is vacuum drying.
Preferably, Na is as described in step (3)2SO3The mass percentage concentration of the solution is 0.5-1%.
Preferably, Na is added as described in step (3)2SO3In solution, the resin is mixed with Na2SO3The solid-to-liquid ratio of the solution is 1:2 g/ml.
Preferably, the agitation elution Tl described in the step (3)+The duration of the ions is 30-50 min.
Preferably, the amount of the added sodium sulfide in the step (3) is 1.2-1.5 times of the amount of the added theoretical amount of the sodium sulfide.
In the above method, the DTPA is named diethylenetriaminepentaacetic acid, and is named ethylenediethylenetriaminepentaacetic acid and diethylenetriaminepentaacetic acid, and its chemical structural formula is as follows:
in the method, the EDTA has the Chinese name of Ethylene Diamine Tetraacetic Acid (EDTA), the other names of EDTA are tetraacetic acid diaminoethylene and tolterone, and the chemical structural formula of the EDTA is as follows:
because the acid wastewater of the smelting industry contains SO4 2-、Cl-Plasma anions, the complex anion formed in step (2) comprising ReO4 -、TlBr4 -、TlBr5 2-、TlBr6 3-、TlCl4 -、Tl(SO4)2 -An isogenic anion; adding a reducing agent Na in the step (3)2SO3The purpose of (A) is to make Tl in the resin3+Reduction to Tl+Thus destroying the trivalent thallium coordinate anion and desorbing and eluting the thallium.
The main reaction processes of the process according to the invention are briefly described below:
adding bromine water into thallium-containing acidic waste water to ensure that Tl+Oxidation to form a trivalent thallium complex anion;
Tl+(thallium-containing acidic wastewater) + bromine water → trivalent thallium complex anion (1)
② RCX-5143 resin exchange adsorption ReO4 -、TlBr4 -、TlBr5 2-、TlBr6 3-、TlCl4 -、Tl(SO4)2 -Plasma anions;
resin-Cl-+ thallium-containing rhenium anion → resin-thallium-containing rhenium complex anion + Cl- (2)
③ eluting ReO with ammonia water containing EDTA or DTPA4 -And prevent trivalent thallium from eluting (hydrolyzing) under alkaline conditions;
resin-thallium-containing rhenium anion + ammonia → resin-trivalent thallium complex anion + ReO4 - (3)
The reacted resin-trivalent thallium complex anion also includes Tl (EDTA)-Or Tl (DTPA)2-A complex anion.
Fourthly, using reducing agent Na2SO3Desorbing and eluting to remove Tl in the resin3+Reduction to Tl+Destroying the trivalent thallium complex anion;
resin-trivalent thallium Complex anion + SO3 2-→ resin-SO4 2-+Tl+ (4)
Fifthly, rich in Tl+Adding sodium sulfide into the filtrate to obtain a thallium sulfide precipitate;
Tl++S2-→Tl2S↓ (5)
compared with the prior art, the invention has the following advantages and beneficial effects:
the invention finds that the special ion exchange resin for recovering molybdenum and rhenium, namely RCX-5143 resin, has a specific selective adsorption function on trivalent thallium complex anions, adopts RCX-5143 resin to directly adsorb and extract scattered metal thallium and rhenium under the condition that the pH value is higher than 1 without using alkali to neutralize acidity, takes the raw material as acid wastewater of a smelting plant, adds the adsorption material which is commercially available RCX-5143 resin in the whole process, and has the advantages of simple process, low cost, thallium recovery rate of 83.4-85.7 percent and rhenium recovery rate of 82.2-86.6 percent.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. For process parameters not specifically noted, reference may be made to conventional techniques.
Example 1
This example provides a method for recovering thallium and rhenium from metallurgical contaminated acids.
The used contaminated acid comes from a certain smelter, the thallium content is 41mg/L, the rhenium content is 15mg/L, and the pH value is less than 1.
1. Thallium and rhenium recovery
(1) Taking 25g of RCX-5143 resin (commercial Dusheng RCX-5143 resin) with the granularity of 100 meshes, soaking for 40min by using 1mol/L sodium hydroxide solution with the volume of 4 times, washing to be neutral by using water, soaking for 40min by using 1mol/L hydrochloric acid solution with the volume of 4 times, and washing to be neutral by using water to obtain pretreated resin;
(2) taking 5L of thallium and rhenium-containing waste acid from a certain smeltery, filtering out insoluble substances, dripping 3% bromine water under stirring to orange yellow, and keeping for 10min to prevent fading, so as to obtain monovalent thallium (Tl) in the waste acid+) Fully oxidizing and forming trivalent thallium complex anion, adding pretreated CX-5143 resin according to solid-to-liquid ratio of 0.005g/ml to adsorb ReO4 -Stirring the trivalent thallium complex anion for 40min, filtering and collecting the resin;
(3) adsorbing ReO according to the solid-to-liquid ratio of 1:2g/ml4 -Adding 50ml of ammonia water containing DTPA and having the mass percentage concentration of 5% into the resin of the trivalent thallium complex anion to elute ReO4 -Stirring for 30 min; wherein the mass percentage concentration of DTPA is 0.05%;
(4) containing ReO4 -Evaporating and concentrating the eluent at 90 ℃, cooling, crystallizing, and drying in vacuum to obtain ammonium rhenate (NH)4ReO4)0.095g；
(5) Collecting and eluting ReO4 -Adding 0.5 percent of reducing agent Na into the resin according to the solid-to-liquid ratio of 1:2g/ml2SO3Eluting with 100ml of solution to obtain Tl-rich solution+Stirring the filtrate for 30min, filtering and collecting the Tl-rich liquid+The filtrate of (1);
(6) to be rich in Tl+Adding sodium sulfide 1.2 times of the theoretical amount into the filtrate, precipitating, collecting precipitate, and vacuum drying to obtain thallium sulfide precipitate (Tl)2S)0.19g。
2. Detection of purity
The purity of the thallium sulfide detected by atomic absorption spectrophotometry is 97.1%, and the purity of the ammonium rhenate detected by ICP-MS is 98.5%
3. And (3) calculating the recovery rate:
the thallium recovery and rhenium recovery for the process described in this example were 83.4% and 86.6% as calculated by the following equations.
Note that: wherein the atomic weight of 2Tl or Re means the atomic weight of 2Tl or 1 Re
Example 2
This example provides a method for recovering thallium and rhenium from metallurgical contaminated acids.
The used contaminated acid comes from a certain smelter, the thallium content is 35mg/L, the rhenium content is 24mg/L, and the pH value is less than 1.
1. Thallium and rhenium recovery
(1) Taking 30g of RCX-5143 resin (commercially available Dusheng RCX-5143 resin) with the granularity of 100 meshes, soaking for 50min by using 1mol/L sodium hydroxide solution with the volume of 4 times, washing to be neutral by using water, soaking for 50min by using 1mol/L hydrochloric acid solution with the volume of 4 times, and washing to be neutral by using water to obtain pretreated resin;
(2) taking 5L of thallium and rhenium-containing waste acid from a certain smeltery, filtering out insoluble substances, dripping 3% bromine water under stirring to orange yellow, and keeping for 10min to prevent fading, so as to obtain monovalent thallium (Tl) in the waste acid+) Fully oxidizing and forming trivalent thallium complex anion, adding pretreated RCX-5143 resin according to solid-to-liquid ratio of 0.006g/ml for adsorbing ReO4 -Stirring the trivalent thallium complex anion for 50min, filtering and collecting the resin;
(3) adsorbing ReO according to the solid-to-liquid ratio of 1:2g/ml4 -Adding 60ml of ammonia water containing EDTA and having the mass percentage concentration of 6% to elute ReO4 -Stirring for 40 min; wherein the mass percentage concentration of the EDTA is 0.05 percent;
(4) containing ReO4 -Evaporating and concentrating the eluent at 90 ℃, cooling, crystallizing, and drying in vacuum to obtain ammonium rhenate (NH)4ReO4)0.15g；
(5) Collecting and eluting ReO4 -Adding 0.7 mass percent of reducing agent Na into the resin according to the solid-to-liquid ratio of 1:2g/ml2SO3Eluting with 60ml of solution to obtain Tl-rich solution+Stirring the filtrate for 40min, filtering and collecting the Tl-rich liquid+The filtrate of (1);
(6) to be rich in Tl+Adding sodium sulfide 1.3 times of the theoretical amount into the filtrate, precipitating, collecting precipitate, and vacuum drying to obtain thallium sulfide precipitate (Tl)2S)0.16g。
2. Detection of purity
The purity of the thallium sulfide detected by atomic absorption spectrophotometry is 99.3%, and the purity of the rhenium acid ammonia detected by ICP-MS is 98.3%
3. And (3) calculating the recovery rate:
the thallium recovery for the process described in this example was 84.0% and rhenium recovery was 85.2% as calculated by the formula in example 1.
Example 3
This example provides a method for recovering thallium and rhenium from metallurgical contaminated acids.
The waste acid comes from a smelting plant, the thallium content is 26mg/L, the rhenium content is 35mg/L, and the pH value is less than 1.
1. Thallium and rhenium recovery
(1) Taking 40g RCX-5143 resin (commercial Dusheng RCX-5143 resin) with the granularity of 100 meshes, soaking for 50min by using 1mol/L sodium hydroxide solution with the volume of 4 times, washing to be neutral by using water, soaking for 50min by using 2mol/L hydrochloric acid solution with the volume of 4 times, and washing to be neutral by using water to obtain pretreated resin;
(2) taking 5L of thallium and rhenium-containing waste acid from a certain smeltery, filtering out insoluble substances, dripping 3% bromine water under stirring to orange yellow, and keeping for 10min to prevent fading, so as to obtain monovalent thallium (Tl) in the waste acid+) Fully oxidizing and forming trivalent thallium complex anion, adding pretreated RCX-5143 resin according to solid-to-liquid ratio of 0.008g/ml for adsorbing ReO4 -Stirring the trivalent thallium complex anion for 50min, filtering and collecting the resin;
(3) adsorbing ReO according to the solid-to-liquid ratio of 1:2g/ml4 -Adding 80ml of ammonia water containing DTPA and having the mass percentage concentration of 7% into the resin of the trivalent thallium complex anion to elute ReO4 -Stirring for 50 min; wherein the mass percentage concentration of DTPA is 0.1%;
(4) containing ReO4 -Evaporating and concentrating the eluent at 90 ℃, cooling, crystallizing, and drying in vacuum to obtain ammonium rhenate (NH)4ReO4)0.22g；
(5) Collecting and eluting ReO4 -Adding 0.8 mass percent of reducing agent Na into the resin according to the solid-to-liquid ratio of 1:2g/ml2SO3Eluting with 80ml of solution to obtain Tl-rich solution+Stirring the filtrate for 50min, filtering and collecting the Tl-rich liquid+The filtrate of (1);
(6) to be rich in Tl+Adding sodium sulfide 1.4 times of the theoretical amount into the filtrate, precipitating, collecting precipitate, and vacuum drying to obtain thallium sulfide precipitate (Tl)2S)0.12g。
2. Detection of purity
The purity of the thallium sulfide detected by atomic absorption spectrophotometry is 98.1%, and the purity of the rhenic acid ammonia detected by ICP-MS is 99.1%
3. And (3) calculating the recovery rate:
the thallium recovery for the process described in this example was 83.8% and rhenium recovery was 86.5% as calculated by the formula in example 1.
Example 4
The used contaminated acid comes from a certain smelter, the thallium content is 32mg/L, the rhenium content is 43mg/L, and the pH value is less than 1.
1. Thallium and rhenium recovery
(1) Taking 50g RCX-5143 resin (commercial Dusheng RCX-5143 resin) with the granularity of 100 meshes, soaking for 60min by using 1mol/L sodium hydroxide solution with the volume of 4 times, washing to be neutral by using water, soaking for 60min by using 2mol/L hydrochloric acid solution with the volume of 4 times, and washing to be neutral by using water to obtain pretreated resin;
(2) 5L of thallium and rhenium-containing waste acid in a certain smeltery is taken, insoluble substances are filtered out, bromine water with the mass percentage concentration of 3 percent is added dropwise under the stirring condition until the waste acid is orange yellow, and the color is kept for 10min without fading, so that univalent thallium in the waste acid(Tl+) Fully oxidizing and forming trivalent thallium complex anion, adding pretreated RCX-5143 resin according to solid-to-liquid ratio of 0.01g/ml to adsorb ReO4 -Stirring the trivalent thallium complex anion for 60min, filtering and collecting the resin;
(3) adsorbing ReO according to the solid-to-liquid ratio of 1:2g/ml4 -Adding 100ml of aqueous ammonia containing EDTA with the mass percentage concentration of 8% into the resin of the trivalent thallium complex anion to elute ReO4 -Stirring for 50 min; wherein the mass percentage concentration of the EDTA is 0.1 percent;
(4) containing ReO4 -Evaporating and concentrating the eluent at 90 ℃, cooling, crystallizing, and drying in vacuum to obtain ammonium rhenate (NH)4ReO4)0.26g；
(5) Collecting and eluting ReO4 -Adding 1% reducing agent Na into the resin according to the solid-to-liquid ratio of 1:2g/ml2SO3Eluting with 100ml of solution to obtain Tl-rich solution+Stirring the filtrate for 50min, filtering and collecting the Tl-rich liquid+The filtrate of (1);
(6) to be rich in Tl+Adding sodium sulfide 1.5 times of the theoretical amount into the filtrate, precipitating, collecting precipitate, and vacuum drying to obtain thallium sulfide precipitate (Tl)2S)0.15g。
2. Detection of purity
The purity of the thallium sulfide detected by atomic absorption spectrophotometry is 98.6%, and the purity of the rhenic acid ammonia detected by ICP-MS is 97.9%
3. And (3) calculating the recovery rate:
the thallium recovery and rhenium recovery for the process described in this example were 85.7% and 82.2% as calculated by the following equations.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A method for recovering thallium and rhenium from smelting waste acid is characterized by comprising the following steps:
(1) pretreatment of resins
Soaking RCX-5143 anion exchange resin in sodium hydroxide solution, washing with water to neutrality, soaking in hydrochloric acid to convert into chlorine type, and washing with water to neutrality to obtain pretreated resin;
(2) recovery of rhenium
Taking the pH of a smelting plant<1, filtering insoluble substances, dripping bromine water under stirring until the waste acid is yellow, keeping for 10min, fully oxidizing monovalent thallium in the waste acid to form trivalent thallium complex anion, adding pretreated resin, stirring to adsorb ReO4 -Mixing with thallium complex anion, filtering, collecting resin, adding ammonia water containing EDTA or DTPA, stirring to elute ReO4 -Obtaining eluent, evaporating, concentrating, cooling to obtain precipitate, and drying to obtain ammonium rhenate;
(3) thallium recovery
Collecting and eluting ReO4 -Adding Na into the resin2SO3Solution, agitation elution of Tl+Ion to obtain Tl-rich+And adding sodium sulfide into the filtrate, precipitating and drying to obtain a thallium sulfide precipitate.
2. The method for recovering thallium and rhenium from metallurgical contaminated acid as claimed in claim 1, wherein:
the condition for soaking the sodium hydroxide solution in the step (1) is that 1mol/L sodium hydroxide solution with 4 times of volume amount is used for soaking resin for 40-60 min;
the hydrochloric acid soaking condition in the step (1) is to soak the resin for 40-60 min by using a hydrochloric acid solution with 4 times of volume amount and the concentration of 1-2 mol/L.
3. The method for recovering thallium and rhenium from metallurgical contaminated acid as claimed in claim 1, wherein: the mass percentage concentration of the bromine water in the step (2) is 3%.
4. The method for recovering thallium and rhenium from metallurgical contaminated acid as claimed in claim 1, wherein:
when the pretreated resin is added in the step (2), the solid-to-liquid ratio of the resin to the wastewater is 0.005-0.01 g/mL;
stirring adsorption of ReO as described in step (2)4 -And the duration of the thallium-coordinated anion is 40-60 min.
5. The method for recovering thallium and rhenium from metallurgical contaminated acid as claimed in claim 1, wherein:
in the ammonia water containing EDTA or DTPA in the step (2), the mass percentage concentration of the ammonia water is 5-8%;
in the ammonia water containing EDTA or DTPA in the step (2), the mass percentage concentration of the EDTA or DTPA is 0.05-0.1%;
when the ammonia water containing EDTA or DTPA is added in the step (2), the solid-to-liquid ratio of the resin to the ammonia water is 1:2 g/mL;
stirring elution of ReO as described in step (2)4 -The time duration is 40-60 min.
6. The method for recovering thallium and rhenium from metallurgical contaminated acid as claimed in claim 1, wherein: the temperature for the evaporative concentration in step (2) was 90 ℃.
7. The method for recovering thallium and rhenium from metallurgical contaminated acid as claimed in claim 1, wherein:
na described in step (3)2SO3The mass percentage concentration of the solution is 0.5-1%;
adding Na as described in step (3)2SO3In solution, the resin is mixed with Na2SO3The solid-liquid ratio of the solution is 1:2 g/mL;
the agitation elution Tl described in the step (3)+The duration of the ions is 30-40 min.
8. The method for recovering thallium and rhenium from metallurgical contaminated acid as claimed in claim 1, wherein: and (4) adding sodium sulfide in the step (3) in an amount which is 1.2-1.5 times of the amount required by the theoretical amount.
9. The method for recovering thallium and rhenium from metallurgical contaminated acid as claimed in claim 1, wherein: and (3) drying in vacuum.
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