A method for purifying crude ammonium perrhenate from copper smelting

Abstract

The invention discloses a purification method of crude ammonium perrhenate from copper smelting, which belongs to the technical field of ammonium perrhenate purification. The specific process is: slurrying crude ammonium perrhenate to leach, obtain leaching residue and leachate, and part of the leachate is returned to the acid production adsorption process in an open circuit; slurrying the leaching residue obtained in the previous step, heating and leaching, solid-liquid separation, obtain leaching residue and leachate, and the leaching residue returns to the system; adding oxidant A to the leachate in the previous step, heating and oxidizing, fine filtering, and returning the oxidized residue to the system; freezing and crystallizing the oxidized liquid, solid-liquid separation, obtain primary crystals and liquid after primary crystallization; adding primary crystals to the solution, heating and dissolving, and then controlling the temperature of the filtrate for crystallization, separating the crystals and returning them to dissolve, freezing and crystallizing the liquid after crystallization, and then filtering and washing to obtain secondary crystals and liquid after secondary crystallization, and drying the secondary crystals to obtain the final product ammonium perrhenate. The direct yield of ammonium perrhenate of the invention is greater than 96%, the recovery rate is greater than 99%, and the ammonium perrhenate content is greater than 99.99%.

Description

Technical Field

[0001] The invention belongs to the field of ammonium rhenate purification, and in particular relates to a method for purifying crude ammonium perrhenate from copper smelting. Background Art

[0002] Rhenium is a rare and insoluble metal with high melting point, high strength, good plasticity and excellent mechanical stability, as well as excellent properties such as catalytic, high temperature resistance and corrosion resistance. Therefore, it is widely used in aerospace, petrochemical catalysts, thermoelectric alloys, electronic tube structural materials, environmental protection and other fields.

[0003] Rhenium does not have a separate deposit, so the main raw materials for extracting rhenium are copper rhenium ore and molybdenite. During the flotation of copper ore, 60%~80% of the rhenium is transferred to the copper concentrate. Therefore, pyrometallurgy is one of the two important industries for extracting rhenium. During the pyrometallurgical smelting process, copper rhenium ore is oxidized by rhenium sulfide to generate volatile Re2O7, which enters the flue gas. During the purification process of the flue gas in the acid production system, Re2O7 enters the waste acid to generate HReO4. Since the rhenium content in the waste acid is very low, chelated anion resin is used for adsorption. After ammonia water analysis, the analysis liquid is evaporated to obtain crude ammonium perrhenate containing 40%~65% rhenium, which is used as a product or a raw material for the next step of rhenium extraction.

[0004] Aiming at the current status of ammonium perrhenate purification in the copper smelting industry, the invention proposes a simple method and process for ammonium perrhenate purification to solve the problems of incomplete separation of potassium, lead, arsenic and the like in ammonium perrhenate or overly complicated process. Summary of the invention

[0005] The present invention aims at the problem that the separation of potassium, lead, arsenic and the like in ammonium perrhenate produced by copper smelting acid production is not thorough or the process is too complicated. The present invention proposes a method for purifying ammonium perrhenate produced by copper smelting. The method uses simple methods of dissolution, filtration and crystallization to make full use of the characteristics of each element to separate or remove elements such as potassium, lead, arsenic and the like from the leachate. The method has the advantages of simple operation, mild and controllable reaction of the entire process, good operating environment, no introduction of new elements in the process, and good connection with the original ammonium perrhenate recovery system.

[0006] In order to achieve the above-mentioned purpose, the main technical solutions provided by the present invention are as follows:

[0007] A method for purifying crude ammonium perrhenate from copper smelting, wherein the specific processing steps are as follows:

[0008] (1) The crude ammonium perrhenate is slurried according to a solid-liquid mass ratio of 1:(1-3), stirred and leached at 0°C-5°C for 0.5h-2h, and then the solid and liquid are separated to obtain leaching residue and leaching liquid. The leaching residue is further dissolved and recovered, and part of the leaching liquid is returned to the adsorption process in an open circuit;

[0009] (2) the leached residue obtained in step (1) is slurried according to a solid-liquid mass ratio of 1:(1-5), stirred and leached at 70°C-95°C for 0.5h-2h, and then the solid and liquid are separated to obtain leached residue and leaching liquid, and the leached residue is returned to the system;

[0010] (3) adding oxidant A to the leaching solution obtained in step (2), stirring and oxidizing at a temperature of 70°C to 95°C for 0.5h to 2h, fine filtering, and returning the oxidized residue to the system; freezing and crystallizing the oxidized liquid at -5°C to 5°C for 4h to 12h, and then filtering to obtain primary crystals and liquid after primary crystallization;

[0011] (4) Add the primary crystallization solution and stir at 70℃~95℃ for 0.5h~2h. Then cool the solution and control the temperature at 45~60℃ for crystallization for 0.5h-1h. Separate the crystals and return them for next dissolution. Continue to cool the crystallization solution to -5~5℃, freeze crystallize for 4h~12h, and then filter to obtain secondary crystals and secondary crystallization liquid. Dry the secondary crystals to obtain ammonium perrhenate.

[0012] Furthermore, in step (3), the oxidant A is hydrogen peroxide, oxygen or ozone, and the mass ratio of the leaching solution to the oxidant A is (10-20):1.

[0013] Furthermore, the solution used for slurry adjustment in step (1) and step (2) is the liquid after the first crystallization or the liquid after the second crystallization; and the solution used for dissolving the first crystal in step (4) is the liquid after the second crystallization or pure water.

[0014] Furthermore, the content of rhenium in the crude ammonium perrhenate is 40-65wt%.

[0015] Furthermore, the filtration accuracy during the fine filtration is 600 meshes.

[0016] The positive beneficial effects of the present invention are as follows: the method fully utilizes the characteristics of each element through a simple method of dissolution, filtration and crystallization to separate or remove elements such as potassium, lead, arsenic and the like from the leachate, and most of the solution is returned to the next operation of the same level for reuse. The method has the advantages of simple operation, mild and controllable reaction in the entire process, good operating environment, no introduction of new elements in the process, and good connectivity with the original ammonium perrhenate system.

[0017] The direct recovery rate of ammonium perrhenate is greater than 96%, the recovery rate is greater than 99%, and the content of ammonium perrhenate is greater than 99.99%. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 It is a process flow chart of the present invention. DETAILED DESCRIPTION

[0019] The present invention will be further described below in conjunction with the accompanying drawings and specific embodiments:

[0020] Example 1

[0021] A method for purifying crude ammonium perrhenate from copper smelting, such as Figure 1 (Process to primary crystallization sample detection, comparison of full process results) as shown, the specific processing steps are as follows:

[0022] Take 100g of crude ammonium perrhenate from acid making, with a rhenium content of 48.39wt%, put it into a 500mL beaker, add 100mL of the first crystallization liquid returned from the previous time, stir at 0℃ for 1 hour for leaching, filter, and return part of the filtrate to the acid making adsorption process. Add 400mL of the first crystallization liquid returned from the previous time to the leached residue, stir at 85℃~90℃ for 2 hours, filter, and return the leached residue to this level for the next dissolution. Add 10mL of hydrogen peroxide (30wt%) to the filtrate, stir and oxidize at 85℃~90℃ for 1 hour, use a 600-mesh filter for fine filtration, and freeze and crystallize the filtrate at -1℃~1℃ for 4 hours to obtain the first crystal and the first crystal liquid. The first crystal is dried to obtain the ammonium perrhenate comparison sample, and its chemical composition is (wt%):

[0023]

[0024] Example 2

[0025] A method for purifying crude ammonium perrhenate from copper smelting, such as Figure 1 As shown, the specific processing steps are as follows:

[0026] Take 100g of crude ammonium perrhenate for acid making, with a rhenium content of 48.39wt%, put it into a 500mL beaker, add 100mL of the first or second crystallization liquid returned from the previous time (a saturated solution of ammonium perrhenate can reduce the dissolution of rhenium, but does not affect the dissolution of impurities), control the temperature at 0℃, stir for 1 hour for leaching, filter, and return the filtrate to the acid making adsorption process. Add 400mL of the crystallization liquid returned in the next step to the leaching residue, control the temperature at 85℃~90℃, stir for 2 hours, filter, return the filter residue to this stage for the next dissolution, add 10mL of commercially available hydrogen peroxide (30wt%) to the filtrate, control the temperature at 85℃~90℃, stir for 1 hour, and use a 600-mesh filter to filter. Fine filtration, the oxidized slag after fine filtration is returned to this stage for the next dissolution, the oxidized liquid after fine filtration is frozen and crystallized at -5~5℃ for 4 hours, filtered to obtain primary crystals and primary crystallization liquid, the primary crystal is added to the previous secondary crystallization liquid and stirred and heated to 85℃~90℃, the temperature is kept at 85℃~90℃ and stirred for 2 hours, then the solution is cooled to 45~50℃ and crystallized at 45~50℃ for 0.5 hours, the crystal is separated and returned to the next dissolution, the crystal liquid is frozen and crystallized at -1℃~1℃ for 4 hours and then filtered to obtain secondary crystals and secondary crystallization liquid, the secondary crystal is dried to obtain ammonium perrhenate product, and its chemical composition is (wt%):

[0027]

[0028] Example 3

[0029] A method for purifying crude ammonium perrhenate from copper smelting, such as Figure 1 As shown, the specific processing steps are as follows:

[0030] Take 100g of crude ammonium perrhenate for acid making, with a rhenium content of 41.79wt%, put it into a 500mL beaker, add 100mL of the first or second crystallization liquid returned from the previous time (a saturated solution of ammonium perrhenate can reduce the dissolution of rhenium, but does not affect the dissolution of impurities), control the temperature at 0℃, stir for 1 hour for leaching, filter, and return the filtrate to the acid making adsorption process. Add 400mL of the crystallization liquid returned in the next step to the leaching residue, control the temperature at 85℃~90℃, stir for 2 hours, filter, return the filter residue to this stage for the next dissolution, add 10mL of commercially available hydrogen peroxide (30wt%) to the filtrate, control the temperature at 85℃~90℃, stir for 1 hour, and use a 600-mesh filter to filter. Fine filtration, the oxidized slag after fine filtration is returned to this stage for the next dissolution, the filtrate after oxidation filtration is frozen and crystallized at -5~5℃ for 4 hours, filtered to obtain primary crystals and primary crystallization liquid, the primary crystal is added with the secondary crystallization liquid returned from the previous time, stirred and heated to 85℃~90℃, the temperature is kept at 85℃~90℃ and stirred for 2 hours, then the solution is cooled to 50~55℃ and crystallized at 50~55℃ for 1 hour, the crystal is separated and returned for the next dissolution, the crystallization liquid is frozen and crystallized at -1℃~1℃ for 4 hours, and then filtered to obtain secondary crystals and secondary crystallization liquid, the secondary crystal is dried to obtain ammonium perrhenate product, and its chemical composition is (wt%):

[0031]

[0032] The above implementation cases are only used to illustrate the preferred implementation modes of the present invention, but the present invention is not limited to the above implementation modes. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention within the scope of knowledge possessed by ordinary technicians in the field shall be deemed to be within the scope of protection of this application.

Claims

1. A method for purifying crude ammonium perrhenate from copper smelting, characterized in that: Here are the steps: (1) The crude ammonium perrhenate is slurried according to a solid-liquid mass ratio of 1:(1-3), stirred and leached at 0°C-5°C for 0.5h-2h, and then the solid and liquid are separated to obtain leaching residue and leaching liquid. The leaching residue is further dissolved and recovered, and part of the leaching liquid is open-circuited and returned to the adsorption process; the rhenium content in the crude ammonium perrhenate is 40-65wt%; (2) the leached residue obtained in step (1) is slurried according to a solid-liquid mass ratio of 1:(1-5), stirred and leached at 70°C-95°C for 0.5h-2h, and then the solid and liquid are separated to obtain leached residue and leaching liquid, and the leached residue is returned to the system; (3) adding oxidant A to the leachate obtained in step (2), stirring and oxidizing at a temperature of 70°C to 95°C for 0.5h to 2h, fine filtering, and returning the oxidized residue to the system; freezing and crystallizing the oxidized liquid at -5 to 5°C for 4h to 12h and then filtering to obtain a primary crystal and a liquid after the primary crystal; the oxidant A is hydrogen peroxide, oxygen or ozone, and the mass ratio of the leachate to the oxidant A is (10 to 20):1; (4) Add the primary crystallization solution and stir at 70°C~95°C for 0.5h~2h, then cool the solution and control the temperature at 45~60°C for crystallization for 0.5h-1h, separate the crystals and return them for the next dissolution, and continue to cool the crystallization solution to -5~5°C, freeze the crystallization solution for 4h~12h, and then filter it to obtain secondary crystals and secondary crystallization solution, and dry the secondary crystals to obtain ammonium perrhenate; The solution used for slurry adjustment in step (1) and step (2) is the liquid after the first crystallization or the liquid after the second crystallization; the solution used for dissolving the first crystal in step (4) is the liquid after the second crystallization or pure water.

2. The method for purifying crude ammonium perrhenate from copper smelting according to claim 1, characterized in that: The filtration accuracy during the fine filtration is 600 meshes.

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