CN108707766B

CN108707766B - Method for separating and recycling uranium and molybdenum from stone coal pickle liquor

Info

Publication number: CN108707766B
Application number: CN201810514683.0A
Authority: CN
Inventors: 董玉明; 李会强; 张笛; 裴丽丽; 张红玲; 徐红彬; 张懿
Original assignee: Institute of Process Engineering of CAS
Current assignee: Institute of Process Engineering of CAS
Priority date: 2018-05-25
Filing date: 2018-05-25
Publication date: 2020-12-29
Anticipated expiration: 2038-05-25
Also published as: CN108707766A

Abstract

The invention relates to a method for separating and recycling uranium and molybdenum from stone coal pickle liquor, which comprises the following steps: adjusting the pH value of the stone coal pickle liquor, then adjusting the oxidation-reduction potential of the solution, and adjusting the concentration of sulfate in the solution; adsorbing the solution by using the extraction resin to obtain uranium-and molybdenum-rich resin and effluent; and desorbing the uranium-rich and molybdenum-rich resin in sequence to obtain a uranium-rich solution and a molybdenum-rich solution. The leaching resin is adopted as an adsorbent to adsorb the stone coal pickle liquor, the resin selectively adsorbs uranium and molybdenum without absorbing other elements such as vanadium, iron and the like by controlling the redox potential of the solution, and the recovery rate of the uranium and the molybdenum is high; and desorbing the uranium and the molybdenum step by step for efficient separation subsequently to obtain uranium and molybdenum products with low impurity content. The method not only efficiently recovers uranium and molybdenum resources in the stone coal pickle liquor, but also deeply purifies the vanadium extraction solution, is beneficial to obtaining high-purity vanadium products subsequently, and has the advantages of low cost, simple operation, cleanness, environmental protection and the like.

Description

Method for separating and recycling uranium and molybdenum from stone coal pickle liquor

Technical Field

The invention relates to the technical field of hydrometallurgy and vanadium chemical industry, in particular to a method for separating and recycling uranium and molybdenum from stone coal pickle liquor.

Background

The stone coal is a vanadium-containing polymetallic mineral resource, is one of main raw materials for extracting vanadium, and besides vanadium, the stone coal also contains various associated elements such as aluminum, potassium, iron, calcium, magnesium, molybdenum, nickel, cobalt, copper, titanium, chromium, uranium, selenium and the like. The existing method for extracting vanadium from stone coal mainly comprises two main types: roasting and acid leaching. Because the reasons of serious pollution, low vanadium recovery rate and the like of the roasting vanadium extraction process are gradually eliminated, the acid leaching process is adopted in the prior production, a plurality of metal impurities are inevitably generated in the acid leaching process, and the impurities have great influence on the subsequent vanadium enrichment process and the purity of the vanadium product.

At present, most production processes only treat and recover metal aluminum, iron, potassium and the like with high content of stone coal pickle liquor. Such as chinese patents CN102560115A, CN101289703A, CN103789560A, CN101538649A, CN105695738A, CN105603191A, CN102424914A, CN102127657A, CN102115105A, CN102126735A, CN101230419A, CN1049642A, CN104131180A, CN102002585A, etc.

The stone coal pickle liquor sometimes contains uranium and molybdenum, although the content of uranium and molybdenum is generally low, the properties of uranium and molybdenum in the stone coal pickle liquor are close to those of vanadium, and the uranium and molybdenum can be enriched in a vanadium enrichment process along with the operation of a vanadium extraction system, so that the normal operation of the vanadium enrichment process and the purity of a final vanadium product are seriously influenced, and therefore, the recovery should be considered. Wangming jade and the like (extracting and separating vanadium molybdenum [ J ] from stone coal pickle liquor]Nonferrous metal science and engineering, 2012,3(5):14-17) proposes a method for extracting, separating and recovering vanadium and molybdenum from stone coal pickle liquor, which adopts P204 as an extractant to synchronously extract vanadium and molybdenum from the stone coal pickle liquor and reversely extract the vanadium and the molybdenum step by step. Vanadium and molybdenum are separated in the same unit operation, and during back extraction, partial molybdenum and vanadium are inevitable to enter a water phase together, so that the purity of a vanadium product is only 98.6%. Van-Cai (research on extraction of vanadium, molybdenum and uranium from acid leaching solution of stone coal fluidized bed furnace slag, comprehensive utilization of mineral products, 1990,2:3-7) proposes a method for co-extracting vanadium, molybdenum and uranium from acid leaching solution of stone coal, then using sulfuric acid to back extract vanadium, using ammonium carbonate to back extract molybdenum and uranium, adjusting pH to 2-3 to precipitate ammonium polyvanadate, adjusting pH to 2-3, adding sodium sulfide to precipitate molybdenum trisulfide, and adding ammonia water to adjust pH to 7.5 to heavy ammonium uranate. According to the method, a small amount of molybdenum still remains during vanadium back extraction, so that the purity of vanadium products is easily low, uranium and molybdenum are subjected to back extraction, the uranium and molybdenum products are entrained by each other due to the fact that uranium and molybdenum are separated by a chemical method, and the efficiency of a co-extraction method is low because the concentration of vanadium in acid leaching liquid is far higher than that of uranium and molybdenum. The extraction method generally adopts vanadium, uranium and molybdenum for co-extraction, and is difficult to avoid mutual entrainment and prepare high-purity products. Chinese patent CN105385849A proposes a stone coal vanadium ore enriched U₃O₈In a method ofAdding an ammonium salt composite precipitator into the stone coal pickle liquor, adjusting and controlling the pH to be 3.0-6.5 to obtain poly-vanadate and mixed precipitates of uranium, aluminum, phosphorus and the like, adding alkali into the mixed precipitates to adjust the pH to be 8-9, and obtaining a vanadium solution and uranium-containing slag. The method firstly obtains mixed precipitates of vanadium, uranium, iron, aluminum, calcium, phosphorus and other elements, and then separates vanadium and uranium according to the condition that the solubility of vanadate in an alkali solution is higher and uranium and other metal elements are insoluble in an alkali solution.

In other uranium molybdenum ore pickle liquor, the separation of uranium and molybdenum generally comprises a precipitation method, an ion exchange method and an extraction method, wherein the precipitation method is suitable for the solution with high uranium and molybdenum concentration, and the ion exchange method and the extraction method are suitable for the solution with lower uranium and molybdenum concentration. The common methods of ion exchange and extraction are uranium and molybdenum simultaneous adsorption/extraction and fractional desorption/back extraction. The problem of the extraction method is that the dissolution of an extractant in a water phase causes water pollution and an emulsion layer is generated. The ion exchange method has the problems of small exchange capacity, chlorine or nitrate must be used during desorption, and new impurities are introduced into the system, such as Chinese patents CN103866122A, CN105567958A and the like. Different from other uranium molybdenum ore pickle liquors, the stone coal pickle liquor is as follows: the content of vanadium in the stone coal pickle liquor is relatively high, and the content of uranium and molybdenum is generally low; the situation is opposite in other uranium molybdenum ore pickle liquor. Aiming at the characteristics of the stone coal pickle liquor, reports that uranium and molybdenum are synchronously adsorbed by adopting extraction resin in the stone coal vanadium extraction pickle liquor and the uranium and molybdenum are desorbed step by step, and a desorbent does not contain chloride ions or nitrate radicals are not seen yet.

Disclosure of Invention

In view of the problems in the prior art, the invention provides a method for separating and recovering uranium and molybdenum from stone coal pickle liquor, wherein the method adopts extraction resin as an adsorbent to adsorb the stone coal pickle liquor, overcomes the defects of the traditional extraction and ion exchange resin, enables the resin to selectively adsorb the uranium and the molybdenum without absorbing other elements such as vanadium, iron and the like by controlling the oxidation-reduction potential of the solution, and has high recovery rate of the uranium and the molybdenum; and meanwhile, the uranium and the molybdenum are efficiently separated through subsequent step-by-step desorption, and the desorption liquid avoids the introduction of chloride ions and nitrate radicals, so that uranium and molybdenum products with low impurity content are obtained. The method not only efficiently recovers uranium and molybdenum resources in the stone coal pickle liquor, but also deeply purifies the vanadium extraction solution, is beneficial to obtaining high-purity vanadium products subsequently, and has the characteristics of low cost, simple operation, cleanness, environmental protection and the like.

In order to achieve the purpose, the invention adopts the following technical scheme:

the invention provides a method for separating and recovering uranium and molybdenum from stone coal pickle liquor, which comprises the following steps:

(1) adjusting the pH value of the stone coal pickle liquor, then adjusting the oxidation-reduction potential of the solution, and adjusting the concentration of sulfate in the solution;

(2) adsorbing the solution obtained in the step (1) by using extraction resin to obtain uranium-and molybdenum-rich resin and effluent liquid;

(3) and (3) desorbing the uranium-rich and molybdenum-rich resin obtained in the step (2) in sequence to obtain a uranium-rich solution and a molybdenum-rich solution.

According to the invention, the pH value of the stone coal pickle liquor is adjusted to-1-2, preferably 1-2 in the step (1); for example, -1, -0.8, -0.5, -0.3, 0, 0.2, 0.5, 0.8, 1, 1.3, 1.5, 1.8 or 2, etc., which are not intended to be exhaustive for the sake of brevity and clarity.

The invention controls the pH of the stone coal pickle liquor within the range, mainly aims to ensure that uranium and molybdenum exist in a sulfate radical complex form, and controls the oxidation-reduction potential of the solution under the pH condition to ensure that tetravalent vanadium, divalent iron and trivalent chromium all form cations VO²⁺、Fe²⁺、Cr³⁺The form exists in the solution, no precipitate is generated, and simultaneously the resin can be prevented from being damaged under the condition of high acidity, and HSO is prevented₄ ^-Thus, the pH favors adsorption of the resin.

In step (1) of the present invention, the pH is adjusted by using basic or acidic substances commonly used in the art, and sulfuric acid, sodium hydroxide, potassium hydroxide, ammonia water, etc. are preferable in order not to introduce new impurities into the system, but not limited thereto.

According to the invention, the concentration of the sulfate adjusted in step (1) is 0.1-5 mol/L, preferably 0.3-1 mol/L, and may be, for example, 0.1mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L or 5mol/L, and the specific values therebetween are limited to space and are not exhaustive for the sake of brevity.

The sulfate is added into the solution to adjust the sulfate concentration in the solution, and the sulfate can be any one or the combination of at least two of sodium sulfate, potassium sulfate, ammonium sulfate, sodium bisulfate, potassium bisulfate and ammonium bisulfate, and preferably is any one or the combination of at least two of sodium sulfate, potassium sulfate or ammonium sulfate.

The method controls the sulfate concentration in the solution mainly by controlling the composition proportion of uranium and molybdenum sulfate complex, wherein the main sulfate complex of uranium is UO₂(SO₄)₂ ^2-、UO₂(SO₄)₃ ^4-、UO₂SO₄The major sulfate complex of molybdenum is MoO₂(SO₄)₂ ^2-、MoO₂(SO₄)₃ ^4-、MoO₂SO₄High-charge polymer UO with uranium and molybdenum as much as possible₂(SO₄)₃ ^4-、MoO₂(SO₄)₃ ^4-The form exists, which is more beneficial to the adsorption of the resin.

According to the invention, the redox potential in step (1) is adjusted to 350 to 750mV, preferably 500 to 750mV, which may be 350mV, 400mV, 450mV, 500mV, 550mV, 600mV, 650mV, 700mV or 750mV, for example, and the particular values between these values are not exhaustive for reasons of brevity and simplicity.

The invention controls the oxidation-reduction potential of the solution within the range, can ensure that vanadium and iron are tetravalent and divalent respectively, and the tetravalent vanadium is VO under the condition that the pH value is-1-2²⁺Ferrous iron Fe²⁺And inProvided that chromium is present in trivalent form as Cr³⁺These cations are not adsorbed by the extraction resin. If the oxidation-reduction potential is not in the range, under the condition that the pH value is-1-2, vanadium and iron are respectively pentavalent and trivalent, chromium is hexavalent, and pentavalent vanadium is complexed with sulfate radical to generate VO₂SO₄ ^-、VO₂(SO₄)₂ ^3-Etc. complexing of ferric iron with sulfate to form Fe (SO)₄)₂ ^-、Fe(SO₄)₃ ^3-Etc. complexing hexavalent chromium with sulfate radicals to form CrO₃SO₄ ^2-The active substance of the levextrel resin has poor selectivity to these complexes, and the complex is adsorbed by the resin, and is difficult to separate because the complex is mixed with the complex of uranium and molybdenum. The invention selectively controls vanadium, iron and chromium in the solution to be tetravalent, divalent and trivalent through changing the oxidation-reduction potential of the solution so as to make the solution become VO²⁺、Fe²⁺、Cr³⁺The vanadium is in the form of vanadium (IV) which exists in the solution, thereby realizing the effective separation of vanadium from uranium and molybdenum.

According to the invention, the addition of the oxidizing agent and the reducing agent in step (1) adjusts the oxidation-reduction potential, and it is preferable to use the peroxide and/or the persulfate oxidizing agent and the low-valent sulfur reducing agent in order not to introduce new impurities into the system during the adjustment of the oxidation-reduction potential.

According to the invention, the oxidant is any one or a combination of at least two of chlorate, hypochlorite, perchlorate, nitrate, nitrite, manganese-containing compound with more than two valences, peroxide, ferrate, persulfate, oxygen, ozone or air, preferably peroxide and/or persulfate, and further preferably any one or a combination of at least two of hydrogen peroxide, ammonium persulfate, sodium persulfate or potassium persulfate.

According to the invention, the reducing agent is any one of sulfite, bisulfite, pyrosulfite, thiosulfate, sulfide, hydrosulfide, sulfur dioxide or sulfur powder or the combination of at least two of the above.

According to the invention, the extraction resin of step (2) is composed of an active substance and a polymer coated on the surface of the active substance, the content of the active substance in the extraction resin is 20-60 wt%, for example, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt% or 60 wt%, and the specific values between the above values are limited by space and for the sake of brevity, the invention is not exhaustive.

According to the invention, the active substance is a neutral and/or amine extractant, preferably an amine extractant.

The active substance of the leaching resin used in the invention is preferably an amine extractant, and the amine extractant has an ion exchange effect on an anion metal complex and an association effect on a neutral metal complex mainly by considering the existence form of sulfate radical complex anions of uranium and molybdenum in the stone coal pickle liquor. The pH value of the stone coal pickle liquor is controlled, and HSO is prevented₄ ^-The sulphate is added to control the metal to form stable anion uranium and molybdenum acyl complexes, and the ion exchange capacity is enhanced, so that the active substance has larger adsorption capacity

According to the invention, the neutral extractant is any one or a combination of at least two of carbon oxygen, phosphorus oxygen or sulfur-containing neutral extractants, and is preferably a phosphorus oxygen neutral extractant.

According to the invention, the amine extractant is any one or a combination of at least two of primary, secondary, tertiary amine or quaternary ammonium salt extractants, preferably any one or a combination of at least two of primary, secondary and tertiary amine extractants.

According to the invention, the polymer is styrene-divinylbenzene copolymer resin and is white spherical particle macroporous resin.

The extraction resin used in the invention adopts neutral and/or amine extractant as active substance, and the stone coal pickle liquor is equivalent to multi-stage extraction adsorption through macroporous extraction resin, thereby greatly increasing adsorption capacity and increasing adsorption rate. The active substance is embedded in the polymer, so that the loss of the active substance in the ion exchange process is prevented, the service life of the extraction resin is prolonged, and the extraction resin has the advantages of high capacity and high efficiency of solvent extraction, simple ion exchange operation, no pollution and the like.

According to the invention, the extraction resin is converted into sulfate-type extraction resin by using sulfuric acid before the adsorption in the step (2), so as to prevent other impurity anions from being introduced into the system.

According to the invention, the flow rate of the solution in the adsorption process in the step (2) is 0.5-30 BV/h, for example, 0.5BV/h, 1BV/h, 5BV/h, 10BV/h, 15BV/h, 20BV/h, 25BV/h or 30BV/h, and the specific values therebetween are not exhaustive for the sake of space and simplicity.

According to the invention, the flow rate of the solution in the adsorption process in the step (2) is preferably 1-20 BV/h, and more preferably 5-10 BV/h.

The invention adopts the extraction resin, the adsorption is different from the traditional resin, the adsorption liquid mainly acts on the active substance of the extractant in the resin, the adsorption balance can be achieved in a short time, the flow rate can be faster during the adsorption, the adsorption rate is higher, and the production efficiency is improved.

According to the invention, the penetration points of uranium and molybdenum in the effluent liquid in the step (2) are both 0.5ppm, and the penetration points refer to: the concentration of the element in the effluent at the end of adsorption stops when either uranium or molybdenum reaches the breakthrough point.

The method controls the low uranium and molybdenum content (less than 0.5ppm) in the effluent, and is beneficial to recycling vanadium in the subsequent working procedures of the effluent, thereby obtaining a high-purity vanadium product.

The extraction resin is adopted to efficiently adsorb the uranium and the molybdenum together, the uranium and the molybdenum content in effluent liquid is low (less than 0.5ppm), and the method is favorable for recycling the vanadium in subsequent working procedures of the effluent liquid and obtaining a high-purity vanadium product.

According to the present invention, the adsorption in step (2) is a multi-stage series adsorption, the number of adsorption stages is 2-8 stages, preferably 3-5 stages, such as 2 stages, 3 stages, 4 stages, 5 stages, 6 stages, 7 stages or 8 stages, and the specific values between the above values are limited by space and for simplicity, and the present invention is not exhaustive.

The invention adopts multistage series adsorption, can fully utilize the characteristic of large adsorption capacity of resin, takes three-stage series adsorption columns as an example, one adsorption column is always kept saturated and enters the working procedures of washing, desorption, transformation and the like, and the other two adsorption columns are circularly carried out in a state that the first adsorption column is nearly saturated and the second adsorption column is not penetrated.

According to the invention, the effluent obtained in step (2) is used for the recovery of vanadium.

According to the invention, the uranium desorption operation in step (3) is: and (3) desorbing the uranium-rich and molybdenum-rich resin obtained in the step (2) by using a uranium desorbent to obtain a uranium-rich solution and a molybdenum-rich resin.

According to the invention, the uranium desorbent is any one of or a combination of at least two of sulphuric acid, sulphate, oxalic acid or oxalate. The uranium desorbent provided by the invention is used for desorbing uranium-rich and molybdenum-rich resin in the form of solution.

According to the invention, the concentration of sulfuric acid in the uranium desorbent is 1-20 wt%, for example, 1 wt%, 3 wt%, 5 wt%, 8 wt%, 10 wt%, 13 wt%, 15 wt%, 18 wt% or 20 wt%, and the specific values therebetween are not limited to space and for brevity, and are not exhaustive.

According to the invention, the concentration of sulfate in the uranium desorbent is 1-15 wt%, for example, 1 wt%, 3 wt%, 5 wt%, 7 wt%, 10 wt%, 12 wt% or 15 wt%, and the specific values therebetween are not exhaustive for reasons of space and simplicity.

According to the present invention, the sulfate is any one or a combination of at least two of sodium sulfate, potassium sulfate, ammonium sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, and ammonium hydrogen sulfate, preferably any one or a combination of at least two of sodium sulfate, potassium sulfate, and ammonium sulfate, and more preferably ammonium sulfate.

The invention adopts the combination of sulfuric acid and/or sulfate solution as the desorbent, and no other impurity anions are introduced into the system, thereby being beneficial to obtaining high-purity vanadium products in the subsequent procedures. Because the affinity of the resin active substance and molybdenum is stronger, only uranium can be desorbed by using sulfuric acid and salts thereof with proper concentration as a desorbent, and molybdenum still remains on the resin, thereby achieving the purpose of separating uranium from molybdenum. The addition of the sulfate is increased, so that the use amount of sulfuric acid can be reduced, the ratio of the sulfate and the sulfate is controlled, uranium can be efficiently desorbed, the pH of a uranium-rich solution in the desorption process is in a proper range, the resin is not blocked by uranium hydrolysis precipitation, the use of the resin is not influenced, and the use amount of ammonia water in the subsequent uranium precipitation process can be reduced.

According to the invention, the concentration of oxalic acid in the uranium desorbent is 1-20 wt%, for example, 1 wt%, 3 wt%, 5 wt%, 8 wt%, 10 wt%, 13 wt%, 15 wt%, 18 wt% or 20 wt%, and the specific values therebetween are limited to space and for brevity, and the invention is not exhaustive.

According to the invention, the concentration of oxalate in the uranium desorbent is 1-15 wt%, for example 1 wt%, 3 wt%, 5 wt%, 7 wt%, 10 wt%, 12 wt% or 15 wt%, and the specific values therebetween are not exhaustive for reasons of space and simplicity.

According to the invention, the oxalate is any one or combination of at least two of sodium oxalate, potassium oxalate or ammonium oxalate, preferably ammonium oxalate.

The invention can use oxalic acid and/or oxalate solution as uranium desorbent, mainly because of C₂O₄ ^2-For UO₂ ²⁺Has strong complexation, and the first order stable constant of the oxalate complex of uranium reaches 3.7 multiplied by 10⁶And the primary stability constant of the uranium sulfate complex is only 50, so that the uranium is easily desorbed into the aqueous solution by using oxalic acid and the salt thereof as a desorbent, and the desorption efficiency is greatly improved. Because the affinity of the resin active substance and molybdenum is stronger, oxalic acid and salt thereof with proper concentration are used as a desorbent and only uranium can be desorbed, and molybdenum still remains on the resin, thereby achieving the purpose of separating uranium from molybdenum. The use amount of oxalic acid can be reduced by increasing the use amount of oxalate, so that uranium can be efficiently desorbed by controlling the proportion of the oxalate and the oxalate, the pH value of a uranium-rich solution is in a proper range in the desorption process, the resin is not blocked by uranium hydrolysis precipitation to influence the use of the resin, and the use amount of ammonia water in the subsequent uranium precipitation process can be reduced.

According to the invention, the flow rate of the solution in the uranium desorption process is 0.5-30 BV/h, for example, 0.5BV/h, 1BV/h, 5BV/h, 10BV/h, 15BV/h, 20BV/h, 25BV/h or 30BV/h, and the specific values between the above values are limited to space and for the sake of brevity, and the invention is not exhaustive.

According to the invention, the flow speed of the solution in the uranium desorption process is preferably 1-20 BV/h, and further preferably 2-10 BV/h.

The invention adopts the extraction resin, so that the desorption is different from the traditional resin desorption, the desorption liquid mainly acts on the extractant active substance in the resin, and the complete elution can be realized in a short time, so that the flow rate can be faster during desorption, the desorption rate is higher, and the production efficiency is improved.

According to the invention, the uranium concentration in the effluent at the end of the desorption is 2 to 10ppm, preferably 2 to 5ppm, and may be, for example, 2ppm, 3ppm, 4ppm, 5ppm, 6ppm, 7ppm, 8ppm, 9ppm or 10ppm, and the specific values between these values, which are not exhaustive for reasons of brevity and simplicity.

According to the invention, the effluent liquid with the uranium concentration more than or equal to 1g/L in the desorption process is qualified desorption liquid, and the effluent liquid with the uranium concentration less than 1g/L is lean desorption liquid.

According to the invention, the qualified desorption liquid is subjected to uranium precipitation, and the lean desorption liquid is used as a desorbent for desorbing uranium next time.

The method controls the lower uranium concentration in the effluent liquid at the desorption end point, and fully utilizes the characteristics of large adsorption capacity and high desorption speed of the resin to desorb the uranium loaded on the resin completely. High-concentration uranium desorption liquid (desorption qualified liquid) is used for precipitation, and low-concentration uranium desorption liquid (desorption barren liquor) returns and is used for desorption of resin next time, so that the recycling rate of uranium is improved.

The uranium product can be prepared by using the obtained uranium-rich solution, and the method can be used for example as follows: adding ammonia water into the obtained uranium-rich solution to adjust the pH value for uranium precipitation, and carrying out solid-liquid separation to obtain ammonium diuranate and filtrate.

According to the invention, the addition of ammonia to adjust the pH to 6-9, preferably 7-8, for example 6, 6.5, 7, 7.5, 8, 8.5 or 9, and the specific values therebetween, are not exhaustive for reasons of space and simplicity.

According to the invention, the temperature of the uranium precipitation process is 10-90 ℃, preferably 25 ℃ (room temperature) to 70 ℃, for example, 10 ℃,20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or 90 ℃, and the specific values between the above values are limited by space and for simplicity, and the invention is not exhaustive.

The invention returns the filtrate obtained after solid-liquid separation to the stone coal pickle liquor obtained in the step (1).

According to the invention, the operation of desorbing molybdenum in the step (3) is as follows: and desorbing the molybdenum-rich resin obtained after uranium desorption by using ammonia water and/or a carbonate solution to obtain a molybdenum-rich solution.

The reason why the ammonia water and/or carbonate solution is used as the desorbent of the molybdenum in the invention is mainly that the affinity of the molybdenum and the resin active substance is stronger, and the anion molybdenum acyl sulfate complex needs to be converted into alkaline monomolybdate radical anion by using the ammonia water and/or the carbonate, so that the affinity of the resin active substance and the molybdenum is reduced, and the molybdenum is desorbed into the aqueous solution. And the ammonia water and/or the carbonate solution are/is used as the desorption agent of the molybdenum, so that new impurities cannot be introduced into an acid system, and the molybdenum product with low impurity content can be easily prepared.

According to the invention, the concentration of the ammonia water is 1-20 wt%, for example, 1 wt%, 3 wt%, 5 wt%, 8 wt%, 10 wt%, 13 wt%, 15 wt%, 18 wt% and 20 wt%, and the specific values between the above values are limited to space and for simplicity, and the invention is not exhaustive.

According to the invention, the carbonate solution has a concentration of 1 to 20 wt%, which may be, for example, 1 wt%, 3 wt%, 5 wt%, 8 wt%, 10 wt%, 13 wt%, 15 wt%, 18 wt% and 20 wt%, and the specific values therebetween are not exhaustive for reasons of space and simplicity.

According to the invention, the carbonate is any one or combination of at least two of sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate or ammonium bicarbonate, preferably ammonium carbonate and/or ammonium bicarbonate.

According to the invention, the flow rate of the solution in the process of desorbing molybdenum is 0.5-30 BV/h, for example, 0.5BV/h, 1BV/h, 5BV/h, 10BV/h, 15BV/h, 20BV/h, 25BV/h or 30BV/h, and the specific values between the above values are limited to space and for the sake of brevity, and the invention is not exhaustive.

According to the invention, the flow rate of the solution in the molybdenum desorption process is preferably 1-20 BV/h, and more preferably 2-10 BV/h.

According to the invention, the molybdenum concentration in the effluent at the end of the desorption is 2 to 10ppm, preferably 2 to 5ppm, and may be, for example, 2ppm, 3ppm, 4ppm, 5ppm, 6ppm, 7ppm, 8ppm, 9ppm or 10ppm, and the specific values therebetween are not exhaustive for reasons of brevity and simplicity.

According to the invention, the effluent liquid with the molybdenum concentration more than or equal to 1g/L in the desorption process is qualified desorption liquid, and the effluent liquid with the molybdenum concentration less than 1g/L is lean desorption liquid;

the method controls the lower molybdenum concentration in the effluent liquid at the desorption end point, and fully utilizes the characteristics of large adsorption capacity and high desorption speed of the resin to completely desorb the molybdenum loaded on the resin. The high-concentration molybdenum desorption solution (desorption qualified solution) is used for precipitation, and the low-concentration molybdenum desorption solution (desorption lean solution) is returned for next resin desorption, so that the recovery rate of molybdenum is improved.

According to the invention, the molybdenum product can be prepared by using the obtained molybdenum-rich solution, preferably, when ammonia water is used for desorption, sulfuric acid is directly added into the obtained molybdenum-rich solution to adjust the pH value for molybdenum precipitation, and ammonium tetramolybdate and filtrate are obtained after solid-liquid separation; when a carbonate solution is used as the desorbent, molybdenum is precipitated at the above-mentioned pH adjustmentAdding NH into the obtained molybdenum-rich solution₄ ⁺。

According to the invention, the addition of sulfuric acid to adjust the pH to 1 to 4, preferably 2 to 3, for example 1, 1.5, 2, 2.5, 3, 3.5 or 4, and the specific values therebetween are not exhaustive for reasons of space and simplicity.

According to the present invention, the temperature of the molybdenum deposition process is 10-90 ℃, preferably 25 ℃ (room temperature) to 50 ℃, for example, 10 ℃,20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or 90 ℃, and the specific values therebetween are limited to space and for brevity, and the present invention is not exhaustive.

According to the invention, sulfuric acid is added in the molybdenum precipitation process to adjust the pH value to weak acidity, no new impurities are introduced into the system, the ammonium tetramolybdate is precipitated more completely, and the temperature is kept during molybdenum precipitation, so that the purity of the ammonium tetramolybdate is higher, and the impurity entrainment amount is less.

The resin after adsorption and the resin after desorption are washed by clean water for 1-3 times, and the obtained washing liquid can be returned to the stone coal pickle liquor in the step (1).

As a preferred technical solution, the method comprises the steps of:

(1) adjusting the pH value of the stone coal pickle liquor to-1-2, then adjusting the oxidation-reduction potential of the solution to 350-750 mV, and adjusting the concentration of sulfate in the solution to 0.1-5 mol/L;

(2) carrying out 2-8-stage series adsorption on the solution obtained in the step (1) by using extraction resin, wherein the flow speed of the solution in the adsorption process is 0.5-30 BV/h, the penetration points of uranium and molybdenum in the effluent liquid are both 0.5ppm, and the adsorption is stopped when either of the uranium and molybdenum in the effluent liquid reaches the penetration point, so that uranium-rich resin, molybdenum-rich resin and the effluent liquid are obtained; the extraction resin consists of 20-60 wt% of active substances and a polymer coated on the surface of the extraction resin, wherein the active substances are neutral and/or amine extractants, and the polymer is styrene-divinylbenzene copolymer resin;

(3) desorbing the uranium-rich and molybdenum-rich resin obtained in the step (2) by using at least one of sulfuric acid, sulfate, oxalic acid or oxalate as a uranium desorbent, wherein the solution flow rate is 0.5-30 BV/h, and the uranium concentration in the effluent liquid at the desorption end point is 2-10 ppm, so as to obtain a uranium-rich solution and a molybdenum-rich resin; adding ammonia water into the obtained uranium-rich solution to adjust the pH value to 6-9, sinking uranium at 10-90 ℃, performing solid-liquid separation to obtain ammonium diuranate and filtrate, and returning the filtrate to the stone coal pickle liquor in the step (1);

(4) desorbing the molybdenum-rich resin obtained after uranium desorption by using ammonia water and/or a carbonate solution, wherein the flow rate of the solution is 0.5-30 BV/h, and the concentration of molybdenum in an effluent liquid at the end of desorption is 2-10 ppm, so as to obtain a molybdenum-rich solution; when ammonia water is used for desorption, sulfuric acid is directly added into the obtained molybdenum-rich solution to adjust the pH value to 1-4, and when carbonate solution is used as a desorbent, NH is supplemented into the obtained molybdenum-rich solution₄ ⁺And (3) adjusting the pH value to 1-4, precipitating molybdenum at 10-90 ℃, performing solid-liquid separation to obtain ammonium tetramolybdate and filtrate, and returning the filtrate to the stone coal pickle liquor in the step (1).

Compared with the prior art, the invention at least has the following beneficial effects:

(1) the leaching resin is adopted as an adsorbent, and the resin selectively adsorbs uranium and molybdenum without adsorbing other elements such as vanadium, iron and the like by controlling the conditions such as oxidation-reduction potential, pH, sulfate radical concentration and the like of the stone coal pickle liquor.

(2) The extraction resin is adopted for adsorption, the adsorption capacity is large, the adsorption and desorption speed is high, the efficiency is high, the operation is simple, and the active substances are not easy to lose.

(3) Chloride ions and nitrate radicals are not introduced in the desorption process, and the process is clean and pollution-free.

(4) The recovery rate of uranium and molybdenum is high, the uranium and molybdenum are separated thoroughly, and the impurity content of uranium and molybdenum products is low.

(5) The effluent liquid has low uranium and molybdenum content, so that the subsequent stone coal pickle liquor can be conveniently prepared into a high-purity vanadium product.

Drawings

FIG. 1 is a process flow diagram provided by one embodiment of the present invention.

The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.

Detailed Description

The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.

To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:

example 1

The stone coal pickle liquor used in the embodiment contains: v1.72 g/L, U0.0146 g/L, Mo 0.1163g/L and Fe 0.59 g/L. As shown in fig. 1, uranium and molybdenum are separated and recovered from the stone coal pickle liquor according to the following steps:

(1) pretreating stone coal pickle liquor: firstly, adjusting the pH value of the solution to 2 by using alkali liquor, then adding sodium persulfate, potassium thiosulfate, potassium sulfide, potassium metabisulfite, sodium hydrosulfide, ammonium sulfide and ammonium bisulfite to adjust the oxidation-reduction potential of the solution to 550mV, and finally adding sodium bisulfate to adjust the sulfate concentration of the solution to 0.5 mol/L;

(2) adsorbing uranium and molybdenum: controlling the flow rate of the solution obtained after the pretreatment in the step (1) to be 10BV/h, and performing 6-stage series adsorption by using extraction resin of which the active substance is a carbon-oxygen-containing neutral extractant (the content is 30 wt%) to obtain uranium-rich resin, molybdenum-rich resin and effluent, wherein the uranium concentration in the effluent is less than 0.2ppm, and the molybdenum concentration in the effluent is less than 0.4 ppm;

(3) desorbing uranium and preparing ammonium diuranate: desorbing the uranium-rich and molybdenum-rich resin obtained in the step (2) by using a mixed solution of 5 wt% sulfuric acid and 10 wt% ammonium sulfate, controlling the flow rate of the solution to be 5.725BV/h, and controlling the final uranium concentration of the desorption to be less than 5ppm to obtain a uranium-rich solution and molybdenum-rich resin; wherein the concentration of uranium in the desorbed qualified liquid is 20.56g/L, ammonia water is added into the qualified liquid to adjust the pH value of the solution to 7, uranium precipitation is carried out at 10 ℃, ammonium diuranate and filtrate are obtained after filtration, and the obtained desorbed barren solution is used as a desorbent for desorbing uranium next time;

(4) desorption of molybdenum and preparation of ammonium tetramolybdate: desorbing the molybdenum-rich resin obtained in the step (3) by using an ammonia water solution with the concentration of 20 wt%, controlling the desorption flow rate to be 5BV/h, controlling the concentration of molybdenum in an effluent liquid at the desorption end point to be less than 8ppm, and obtaining a molybdenum-rich solution after the desorption is finished; wherein the concentration of molybdenum in the qualified desorption solution is 63.73g/L, sulfuric acid is added into the qualified desorption solution to adjust the pH value of the solution to 1, molybdenum is precipitated at 45 ℃, ammonium tetramolybdate and filtrate are obtained after filtration, and the obtained lean desorption solution is used as a desorbent for desorbing molybdenum next time;

(5) recycling product wastewater: and (4) returning the filtrate obtained in the steps (3) and (4) to the stone coal pickle liquor obtained in the step (1).

Through detection and calculation: the recovery rate of uranium is 96.42 percent, and the recovery rate of molybdenum is 97.37 percent; ammonium diuranate purity 96.12%, U: 72.99%, Mo: 0.0684%; the purity of ammonium tetramolybdate is 97.71%, and the content of Mo: 56.94%, containing U: 0.0069 percent.

The concentrations of vanadium and iron in the effluent are basically consistent with those of the stock solution except for residual trace uranium and molybdenum.

Example 2

The stone coal pickle liquor used in the embodiment contains: v2.38 g/L, U0.0093 g/L, Mo 0.1538g/L and Fe 1.62 g/L. Separating and recycling uranium and molybdenum from the stone coal pickle liquor according to the following steps:

(1) pretreating stone coal pickle liquor: firstly, adjusting the pH value of a solution to 1.8 by using an alkali liquor, then adding sodium persulfate, potassium persulfate, sodium thiosulfate, sodium sulfide, potassium sulfite, potassium hydrosulfide, ammonium hydrosulfide and potassium hydrosulfite to adjust the oxidation-reduction potential of the solution to 714.78mV, and finally adding ammonium sulfate and sodium sulfate to adjust the sulfate concentration of the solution to 0.3 mol/L;

(2) adsorbing uranium and molybdenum: controlling the flow rate of the solution obtained after the pretreatment in the step (1) to be 5BV/h, and performing 5-stage series adsorption by using extraction resin of which the active substance is a phosphorus-oxygen-containing neutral extractant (the content is 25 wt%) to obtain uranium-rich resin, molybdenum-rich resin and effluent, wherein the uranium concentration in the effluent is less than 0.3ppm, and the molybdenum concentration in the effluent is less than 0.5 ppm;

(3) desorbing uranium and preparing ammonium diuranate: desorbing the uranium-rich and molybdenum-rich resin obtained in the step (2) by using a mixed solution of oxalic acid with the concentration of 1 wt% and sodium oxalate with the concentration of 15 wt%, controlling the flow rate of the solution to be 2BV/h, and obtaining a uranium-rich solution and molybdenum-rich resin, wherein the final uranium concentration of the desorption is less than 2 ppm; wherein the concentration of uranium in the desorbed qualified liquid is 16.38g/L, ammonia water is added into the qualified liquid to adjust the pH of the solution to 9, uranium precipitation is carried out at 90 ℃, ammonium diuranate and filtrate are obtained after filtration, and the obtained desorbed barren solution is used as a desorbent for desorbing uranium next time;

(4) desorption of molybdenum and preparation of ammonium tetramolybdate: desorbing the molybdenum-rich resin obtained in the step (3) by using an ammonium carbonate solution with the concentration of 20 wt%, controlling the desorption flow rate to be 10BV/h, controlling the concentration of molybdenum in the effluent liquid at the desorption end point to be less than 10ppm, and obtaining a molybdenum-rich solution after the desorption is finished; wherein the concentration of molybdenum in the qualified desorption solution is 84.29g/L, sulfuric acid is added into the qualified desorption solution to adjust the pH value of the solution to 2, molybdenum is precipitated at 25 ℃, ammonium tetramolybdate and filtrate are obtained after filtration, and the obtained lean desorption solution is used as a desorbent for desorbing molybdenum next time;

Through detection and calculation: the recovery rate of uranium is 95.98%, and the recovery rate of molybdenum is 98.59%; ammonium diuranate purity 96.12%, U: 72.83%, Mo: 0.0795 percent; the purity of ammonium tetramolybdate is 98.63%, and the content of Mo: 57.19%, containing U: 0.0047 percent.

Example 3

The stone coal pickle liquor used in the embodiment contains: v1.72 g/L, U0.0146 g/L, Mo 0.1163g/L and Fe 0.59 g/L. Separating and recycling uranium and molybdenum from the stone coal pickle liquor according to the following steps:

(1) pretreating stone coal pickle liquor: firstly, adjusting the pH of a solution to 1 by using alkali liquor, then introducing sulfur dioxide, adding hydrogen peroxide to adjust the oxidation-reduction potential of the solution to 750mV, and finally adding potassium sulfate to adjust the sulfate concentration of the solution to 1 mol/L;

(2) adsorbing uranium and molybdenum: controlling the flow rate of the solution obtained after the pretreatment in the step (1) to be 1BV/h, and performing 4-stage series adsorption by using extraction resin of which the active substance is a sulfur-containing neutral extractant (the content is 25 wt%) to obtain uranium-and molybdenum-rich resin and effluent, wherein the uranium concentration in the effluent is less than 0.4ppm, and the molybdenum concentration in the effluent is less than 0.3 ppm;

(3) desorbing uranium and preparing ammonium diuranate: desorbing the uranium-rich and molybdenum-rich resin obtained in the step (2) by using a mixed solution of 1 wt% sulfuric acid, 1 wt% oxalic acid, 20 wt% ammonium oxalate and 20 wt% ammonium sulfate, controlling the flow rate of the solution to be 10BV/h, and controlling the desorption end point uranium concentration to be less than 5ppm to obtain a uranium-rich solution and molybdenum-rich resin; wherein the concentration of uranium in the desorbed qualified liquid is 28.39g/L, ammonia water is added into the qualified liquid to adjust the pH of the solution to 6, uranium precipitation is carried out at room temperature, ammonium diuranate and filtrate are obtained after filtration, and the obtained desorbed barren solution is used as a desorbent for desorbing uranium next time;

(4) desorption of molybdenum and preparation of ammonium tetramolybdate: desorbing the molybdenum-rich resin obtained in the step (3) by using an ammonium bicarbonate solution with the concentration of 20 wt%, controlling the desorption flow rate to be 20BV/h, controlling the concentration of molybdenum in an effluent liquid at the desorption end point to be less than 2ppm, and obtaining a molybdenum-rich solution after the desorption is finished; wherein the concentration of molybdenum in the desorbed qualified solution is 84.29g/L, sulfuric acid is added into the qualified solution to adjust the pH of the solution to 3, molybdenum is precipitated at room temperature, ammonium tetramolybdate and filtrate are obtained after filtration, and the obtained desorbed barren solution is used as a desorbent for desorbing molybdenum next time;

Through detection and calculation: the recovery rate of uranium is 96.84%, and the recovery rate of molybdenum is 97.83%; ammonium diuranate purity was 96.69%, containing U: 73.06%, Mo: 0.0514 percent; the purity of ammonium tetramolybdate is 98.01%, and the content of Mo: 57.24%, containing U: 0.0082%.

Example 4

(1) pretreating stone coal pickle liquor: firstly, adjusting the pH value of a solution to-1 by using an acid solution, then adding ammonium persulfate, potassium persulfate, ammonium thiosulfate, potassium sulfide, ammonium sulfite, ammonium metabisulfite and sodium bisulfite to adjust the redox potential of the solution to 750mV, and finally adding potassium sulfate to adjust the sulfate concentration of the solution to 1 mol/L;

(2) adsorbing uranium and molybdenum: controlling the flow rate of the solution obtained after the pretreatment in the step (1) to be 20BV/h, and performing 7-stage series adsorption by using extraction resin of which the active substance is a quaternary ammonium salt-containing extractant (the content is 40 wt%) to obtain uranium-rich resin, molybdenum-rich resin and effluent, wherein the uranium concentration in the effluent is less than 0.2ppm, and the molybdenum concentration in the effluent is less than 0.5 ppm;

(3) desorbing uranium and preparing ammonium diuranate: desorbing the uranium-rich and molybdenum-rich resin obtained in the step (2) by using an oxalic acid solution with the concentration of 20 wt%, controlling the flow rate of the solution to be 30BV/h, and obtaining a uranium-rich solution and a molybdenum-rich resin, wherein the final uranium concentration of the desorption is less than 4 ppm; wherein the concentration of uranium in the desorbed qualified liquid is 21.49g/L, ammonia water is added into the qualified liquid to adjust the pH value of the solution to 8, uranium precipitation is carried out at room temperature, ammonium diuranate and filtrate are obtained after filtration, and the obtained desorbed barren solution is used as a desorbent for desorbing uranium next time;

(4) desorption of molybdenum and preparation of ammonium tetramolybdate: desorbing the molybdenum-rich resin obtained in the step (3) by using a mixed solution of 20 wt% ammonia water, 1 wt% ammonium bicarbonate and 1 wt% ammonium carbonate, controlling the desorption flow rate to be 2BV/h, controlling the concentration of molybdenum in an effluent liquid at the desorption end to be less than 9ppm, and obtaining a molybdenum-rich solution after the desorption is finished; wherein the concentration of molybdenum in the desorbed qualified solution is 90.62g/L, sulfuric acid is added into the qualified solution to adjust the pH of the solution to 4, molybdenum is precipitated at room temperature, ammonium tetramolybdate and filtrate are obtained after filtration, and the obtained desorbed barren solution is used as a desorbent for desorbing molybdenum next time;

Through detection and calculation: the recovery rate of uranium is 96.38%, and the recovery rate of molybdenum is 97.89%; ammonium diuranate purity was 95.98%, containing U: 72.68%, Mo: 0.0729%; the purity of ammonium tetramolybdate is 98.52%, and the content of Mo: 57.13%, containing U: 0.0053%.

Example 5

The stone coal pickle liquor used in the embodiment contains: v3.38 g/L, U0.0066 g/L, Mo 0.0984g/L and Fe 1.25 g/L. Separating and recycling uranium and molybdenum from the stone coal pickle liquor according to the following steps:

(1) pretreating stone coal pickle liquor: firstly, adjusting the pH value of a solution to 0 by using an alkali liquor, then adding sodium persulfate and potassium sulfite to adjust the oxidation-reduction potential of the solution to 350mV, and finally adding sodium bisulfate, potassium bisulfate and ammonium sulfate to adjust the sulfate concentration of the solution to 3 mol/L;

(2) adsorbing uranium and molybdenum: controlling the flow rate of the solution obtained after the pretreatment in the step (1) to be 0.5BV/h, and performing 8-stage series adsorption by using extraction resin of which the active substance is a quaternary ammonium salt-containing extractant (the content is 20 wt%) to obtain uranium-rich resin, molybdenum-rich resin and effluent, wherein the uranium concentration in the effluent is less than 0.3ppm, and the molybdenum concentration in the effluent is less than 0.4 ppm;

(3) desorbing uranium and preparing ammonium diuranate: desorbing the uranium-rich and molybdenum-rich resin obtained in the step (2) by using a sulfuric acid solution with the concentration of 20 wt%, controlling the flow rate of the solution to be 20BV/h, and controlling the desorption end point uranium concentration to be less than 5ppm to obtain a uranium-rich solution and a molybdenum-rich resin; wherein the concentration of uranium in the desorbed qualified liquid is 24.51g/L, ammonia water is added into the qualified liquid to adjust the pH value of the solution to 7.5, uranium precipitation is carried out at 60 ℃, ammonium diuranate and filtrate are obtained after filtration, and the obtained desorbed barren solution is used as a desorbent for desorbing uranium next time;

(4) desorption of molybdenum and preparation of ammonium tetramolybdate: desorbing the molybdenum-rich resin obtained in the step (3) by using 1 wt% ammonia water solution, controlling the desorption flow rate to be 30BV/h, controlling the concentration of molybdenum in the effluent liquid at the desorption end point to be less than 7ppm, and obtaining a molybdenum-rich solution after the desorption is finished; wherein the concentration of molybdenum in the qualified desorption solution is 71.94g/L, sulfuric acid is added into the qualified desorption solution to adjust the pH value of the solution to be 2.7, molybdenum is precipitated at the temperature of 30 ℃, ammonium tetramolybdate and filtrate are obtained after filtration, and the obtained lean desorption solution is used as a desorbent for desorbing molybdenum next time;

Through detection and calculation: the recovery rate of uranium is 95.99 percent, and the recovery rate of molybdenum is 98.21 percent; the purity of ammonium diuranate is 97.02%, and the ammonium diuranate contains U: 73.24%, Mo: 0.0412 percent; the purity of ammonium tetramolybdate is 98.37%, and the content of Mo: 57.03%, containing U: 0.0032%.

Example 6

(1) pretreating stone coal pickle liquor: firstly, adjusting the pH value of the solution to 1.5 by using alkali liquor, then adding peroxide, persulfate, sulfite and pyrosulfite to adjust the oxidation-reduction potential of the solution to 550mV, and finally adding ammonium bisulfate to adjust the sulfate concentration of the solution to 0.9 mol/L;

(2) adsorbing uranium and molybdenum: controlling the flow rate of the solution obtained after the pretreatment in the step (1) to be 30BV/h, and performing 6-stage series adsorption by using extraction resin of which the active substances are carbon-oxygen-containing, phosphorus-oxygen-containing and sulfur-containing neutral extractant (the content is 25 wt%) to obtain uranium-and molybdenum-rich resin and effluent liquid, wherein the uranium concentration in the effluent liquid is less than 0.3ppm, and the molybdenum concentration in the effluent liquid is less than 0.4 ppm;

(3) desorbing uranium and preparing ammonium diuranate: desorbing the uranium-rich and molybdenum-rich resin obtained in the step (2) by using an ammonium oxalate solution with the concentration of 20 wt%, controlling the flow rate of the solution to be 1BV/h, and obtaining a uranium-rich solution and molybdenum-rich resin, wherein the final uranium concentration of the desorption is less than 3 ppm; wherein the concentration of uranium in the desorbed qualified liquid is 20.28g/L, ammonia water is added into the qualified liquid to adjust the pH value of the solution to 8.5, uranium precipitation is carried out at 30 ℃, ammonium diuranate and filtrate are obtained after filtration, and the obtained desorbed barren solution is used as a desorbent for desorbing uranium next time;

(4) desorption of molybdenum and preparation of ammonium tetramolybdate: carrying out mixed solution of ammonia water with the concentration of 1 wt%, sodium bicarbonate with the concentration of 1 wt% and potassium carbonate with the concentration of 20 wt% on the molybdenum-rich resin obtained in the step (3), controlling the desorption flow rate to be 1BV/h, controlling the concentration of molybdenum in the effluent liquid at the desorption end point to be less than 9ppm, and obtaining a molybdenum-rich solution after the desorption is finished; wherein the concentration of molybdenum in the qualified desorption solution is 69.01g/L, sulfuric acid is added into the qualified desorption solution to adjust the pH of the solution to 2.5, molybdenum is precipitated at 40 ℃, ammonium tetramolybdate and filtrate are obtained after filtration, and the obtained lean desorption solution is used as a desorbent for desorbing molybdenum next time;

Through detection and calculation: the recovery rate of uranium is 95.83 percent, and the recovery rate of molybdenum is 98.01 percent; ammonium diuranate purity was 96.83%, containing U: 73.18%, Mo: 0.0519 percent; the purity of ammonium tetramolybdate is 97.99%, and the content of Mo: 57.31%, containing U: 0.0074 percent.

Example 7

The stone coal pickle liquor used in the embodiment contains: v1.56 g/L, U0.0289 g/L, Mo 0.5291g/L and Fe 2.82 g/L. Separating and recycling uranium and molybdenum from the stone coal pickle liquor according to the following steps:

(1) pretreating stone coal pickle liquor: firstly, adjusting the pH value of the solution to 1.3 by using alkali liquor, then introducing air and sulfur dioxide, adding chlorate, ferriferous compound, hypochlorite, hydrosulfite, thiosulfate and sulfide to adjust the redox potential of the solution to 700mV, and finally adding potassium bisulfate to adjust the concentration of the sulfate in the solution to 2 mol/L;

(2) adsorbing uranium and molybdenum: controlling the flow rate of the solution obtained after the pretreatment in the step (1) to be 1.5BV/h, and performing 3-stage series adsorption by using extraction resin with active substances of which the content is 50 wt% and which contains a secondary amine extractant to obtain uranium-rich resin, molybdenum-rich resin and effluent, wherein the uranium concentration in the effluent is less than 0.3ppm, and the molybdenum concentration in the effluent is less than 0.3 ppm;

(3) desorbing uranium and preparing ammonium diuranate: desorbing the uranium-rich and molybdenum-rich resin obtained in the step (2) by using a mixed solution of 15 wt% sulfuric acid and 15 wt% ammonium bisulfate, controlling the flow rate of the solution to be 7.5BV/h, and controlling the final uranium concentration of the desorption to be less than 5ppm to obtain a uranium-rich solution and a molybdenum-rich resin; wherein the concentration of uranium in the desorbed qualified liquid is 36.44g/L, ammonia water is added into the qualified liquid to adjust the pH value of the solution to 8.5, uranium precipitation is carried out at 40 ℃, ammonium diuranate and filtrate are obtained after filtration, and the obtained desorbed barren solution is used as a desorbent for desorbing uranium next time;

(4) desorption of molybdenum and preparation of ammonium tetramolybdate: desorbing the molybdenum-rich resin obtained in the step (3) by using 1 wt% ammonium bicarbonate solution, controlling the desorption flow rate to be 7BV/h, controlling the concentration of molybdenum in the effluent liquid at the desorption end point to be less than 5ppm, and obtaining a molybdenum-rich solution after the desorption is finished; wherein the concentration of molybdenum in the qualified desorption solution is 84.91g/L, sulfuric acid is added into the qualified desorption solution to adjust the pH value of the solution to 2.1, molybdenum is precipitated at 50 ℃, ammonium tetramolybdate and filtrate are obtained after filtration, and the obtained desorption barren solution is used as a desorbent for desorbing molybdenum next time;

Through detection and calculation: the recovery rate of uranium is 96.72 percent, and the recovery rate of molybdenum is 97.83 percent; ammonium diuranate purity 96.55%, U: 73.09%, Mo: 0.0821 percent; the purity of ammonium tetramolybdate is 97.73%, and the content of Mo: 57.08%, containing U: 0.0089%.

Example 8

(1) pretreating stone coal pickle liquor: firstly, adjusting the pH of the solution to 1.7 by using alkali liquor, then adding ammonium persulfate and potassium metabisulfite to adjust the oxidation-reduction potential of the solution to 650mV, and finally adding ammonium sulfate to adjust the sulfate concentration of the solution to 0.4 mol/L;

(2) adsorbing uranium and molybdenum: controlling the flow rate of the solution obtained after the pretreatment in the step (1) to be 8BV/h, and performing 7-stage series adsorption by using extraction resin with active substances of which the content is 35 wt% and which contains tertiary amine extractant to obtain uranium-rich resin, molybdenum-rich resin and effluent, wherein the uranium concentration in the effluent is less than 0.3ppm, and the molybdenum concentration in the effluent is less than 0.4 ppm;

(3) desorbing uranium and preparing ammonium diuranate: desorbing the uranium-rich and molybdenum-rich resin obtained in the step (2) by using a mixed solution of oxalic acid with the concentration of 1 wt%, sulfuric acid with the concentration of 1 wt% and sodium sulfate with the concentration of 5 wt%, controlling the flow rate of the solution to be 2BV/h, and obtaining a uranium-rich solution and molybdenum-rich resin, wherein the final uranium concentration of the desorption is less than 5 ppm; wherein the concentration of uranium in the desorbed qualified liquid is 28.67g/L, ammonia water is added into the qualified liquid to adjust the pH value of the solution to 6.9, uranium precipitation is carried out at 50 ℃, ammonium diuranate and filtrate are obtained after filtration, and the obtained desorbed barren solution is used as a desorbent for desorbing uranium next time;

(4) desorption of molybdenum and preparation of ammonium tetramolybdate: desorbing the molybdenum-rich resin obtained in the step (3) by using a sodium carbonate solution with the concentration of 20 wt%, controlling the desorption flow rate to be 10BV/h, controlling the concentration of molybdenum in the effluent liquid at the desorption end point to be less than 7ppm, and obtaining a molybdenum-rich solution after the desorption is finished; wherein the concentration of molybdenum in the desorbed qualified liquid is 97.25g/L, ammonium salt is added into the qualified liquid, sulfuric acid is added to adjust the pH of the solution to 1.5, molybdenum is precipitated at 70 ℃, ammonium tetramolybdate and filtrate are obtained after filtration, and the obtained desorbed barren solution is used as a desorbent for desorbing molybdenum next time;

Through detection and calculation: the recovery rate of uranium is 96.18%, and the recovery rate of molybdenum is 97.14%; ammonium diuranate purity was 96.83%, containing U: 73.16%, Mo: 0.0799%; the purity of ammonium tetramolybdate is 97.82%, and the content of Mo: 57.28%, containing U: 0.0084%.

Example 9

The stone coal pickle liquor used in the embodiment contains: v1.53 g/L, U0.0012 g/L, Mo 0.0049g/L and Fe 2.41 g/L. Separating and recycling uranium and molybdenum from the stone coal pickle liquor according to the following steps:

(1) pretreating stone coal pickle liquor: firstly, adjusting the pH of the solution to 1.2 by using alkali liquor, then adding hydrogen peroxide and sodium bisulfite to adjust the oxidation-reduction potential of the solution to 600mV, and finally adding sodium sulfate, ammonium bisulfate and ammonium sulfate to adjust the sulfate concentration of the solution to 0.7 mol/L;

(2) adsorbing uranium and molybdenum: controlling the flow rate of the solution obtained after the pretreatment in the step (1) to be 6BV/h, and performing 5-stage series adsorption by using extraction resin with an active substance of a tertiary amine-containing extractant (the content is 25 wt%) to obtain uranium-rich resin, molybdenum-rich resin and an effluent, wherein the uranium concentration in the effluent is less than 0.2ppm, and the molybdenum concentration in the effluent is less than 0.4 ppm;

(3) desorbing uranium and preparing ammonium diuranate: desorbing the uranium-rich and molybdenum-rich resin obtained in the step (2) by using oxalic acid solution with the concentration of 1 wt%, controlling the flow rate of the solution to be 18BV/h, and obtaining uranium-rich solution and molybdenum-rich resin, wherein the final uranium concentration of the desorption is less than 5 ppm; wherein the concentration of uranium in the desorbed qualified liquid is 17.38g/L, ammonia water is added into the qualified liquid to adjust the pH value of the solution to 8, uranium precipitation is carried out at 70 ℃, ammonium diuranate and filtrate are obtained after filtration, and the obtained desorbed barren solution is used as a desorbent for desorbing uranium next time;

(4) desorption of molybdenum and preparation of ammonium tetramolybdate: desorbing the molybdenum-rich resin obtained in the step (3) by using a potassium carbonate solution with the concentration of 20 wt%, controlling the desorption flow rate to be 12BV/h, controlling the concentration of molybdenum in the effluent liquid at the desorption end point to be less than 4ppm, and obtaining a molybdenum-rich solution after the desorption is finished; wherein the concentration of molybdenum in the desorbed qualified liquid is 53.85g/L, ammonium salt is supplemented to the qualified liquid, sulfuric acid is added to adjust the pH of the solution to 2.6, molybdenum is precipitated at 10 ℃, ammonium tetramolybdate and filtrate are obtained after filtration, and the obtained desorbed barren solution is used as a desorbent for desorbing molybdenum next time;

Through detection and calculation: the recovery rate of uranium is 96.55 percent, and the recovery rate of molybdenum is 97.36 percent; ammonium diuranate purity 96.54%, U: 72.48%, Mo: 0.0372 percent; the purity of ammonium tetramolybdate is 97.99%, and the content of Mo: 57.25%, U: 0.0024%.

Example 10

The stone coal pickle liquor used in the embodiment contains: v1.41 g/L, U0.0016 g/L, Mo 0.0849g/L and Fe 2.51 g/L. Separating and recycling uranium and molybdenum from the stone coal pickle liquor according to the following steps:

(1) pretreating stone coal pickle liquor: firstly, adjusting the pH value of the solution to 1.1 by using alkali liquor, then adding ammonium persulfate and potassium bisulfite to adjust the oxidation-reduction potential of the solution to 400mV, and finally adding sodium sulfate to adjust the sulfate concentration of the solution to 0.6 mol/L;

(2) adsorbing uranium and molybdenum: controlling the flow rate of the solution obtained after the pretreatment in the step (1) to be 15BV/h, and performing 4-stage series adsorption by using extraction resin with active substances of tertiary amine and phosphorus-oxygen neutral extractant (the content is 42 wt%) to obtain uranium-rich resin, molybdenum-rich resin and effluent, wherein the uranium concentration in the effluent is less than 0.4ppm, and the molybdenum concentration in the effluent is less than 0.3 ppm;

(3) desorbing uranium and preparing ammonium diuranate: desorbing the uranium-rich and molybdenum-rich resin obtained in the step (2) by using a sulfuric acid solution with the concentration of 1 wt%, controlling the flow rate of the solution to be 25BV/h, and controlling the desorption end point uranium concentration to be less than 5ppm to obtain a uranium-rich solution and a molybdenum-rich resin; wherein the concentration of uranium in the desorbed qualified liquid is 24.73g/L, ammonia water is added into the qualified liquid to adjust the pH value of the solution to 8.1, uranium precipitation is carried out at 45 ℃, ammonium diuranate and filtrate are obtained after filtration, and the obtained desorbed barren solution is used as a desorbent for desorbing uranium next time;

(4) desorption of molybdenum and preparation of ammonium tetramolybdate: desorbing the molybdenum-rich resin obtained in the step (3) by using a potassium carbonate ammonium solution with the concentration of 1 wt%, controlling the desorption flow rate to be 5BV/h, controlling the concentration of molybdenum in an effluent liquid at the desorption end point to be less than 4ppm, and obtaining a molybdenum-rich solution after the desorption is finished; wherein the concentration of molybdenum in the desorbed qualified liquid is 62.48g/L, ammonium salt is added into the qualified liquid, sulfuric acid is added to adjust the pH of the solution to 3.5, molybdenum is precipitated at 90 ℃, ammonium tetramolybdate and filtrate are obtained after filtration, and the obtained desorbed lean liquid is used as a desorbent for desorbing molybdenum next time;

Through detection and calculation: the recovery rate of uranium is 95.95 percent, and the recovery rate of molybdenum is 96.84 percent; ammonium diuranate purity was 97.25%, containing U: 72.37%, Mo: 0.0466 percent; the purity of ammonium tetramolybdate is 98.27%, and the content of Mo: 56.94%, containing U: 0.0036%.

Example 11

(1) pretreating stone coal pickle liquor: firstly, adjusting the pH of a solution to-0.5 by using alkali liquor, then introducing oxygen and ozone, simultaneously adding perchlorate, nitrite, nitrate, manganese-containing compounds with the valence of more than two, hydrosulfide and sulfur powder to adjust the oxidation-reduction potential of the solution to 580mV, and finally adding sodium sulfate and sodium bisulfate to adjust the sulfate concentration of the solution to 0.9 mol/L;

(2) adsorbing uranium and molybdenum: controlling the flow rate of the solution obtained after the pretreatment in the step (1) to be 2BV/h, and performing 6-stage series adsorption by using extraction resin of which the active substance is a neutral extractant (the content is 33 wt%) containing primary amine, secondary amine and phosphorus-oxygen to obtain uranium-and molybdenum-rich resin and effluent, wherein the uranium concentration in the effluent is less than 0.4ppm, and the molybdenum concentration in the effluent is less than 0.4 ppm;

(3) desorbing uranium and preparing ammonium diuranate: desorbing the uranium-rich and molybdenum-rich resin obtained in the step (2) by using a mixed solution of 5 wt% sulfuric acid, 20 wt% potassium sulfate and 20 wt% potassium bisulfate, controlling the flow rate of the solution to be 25BV/h, and controlling the uranium concentration at the desorption end point to be less than 5ppm to obtain a uranium-rich solution and a molybdenum-rich resin; wherein the concentration of uranium in the desorbed qualified liquid is 28.36g/L, ammonia water is added into the qualified liquid to adjust the pH value of the solution to 7.1, uranium precipitation is carried out at room temperature, ammonium diuranate and filtrate are obtained after filtration, and the obtained desorbed barren solution is used as a desorbent for desorbing uranium next time;

(4) desorption of molybdenum and preparation of ammonium tetramolybdate: desorbing the molybdenum-rich resin obtained in the step (3) by using a mixed solution of 5 wt% of ammonia water and 10 wt% of ammonium carbonate, controlling the desorption flow rate to be 18BV/h, and finishing the desorption until the concentration of molybdenum in the effluent liquid at the desorption end is less than 4ppm to obtain a molybdenum-rich solution; wherein the concentration of molybdenum in the qualified desorption solution is 73.43g/L, sulfuric acid is added into the qualified desorption solution to adjust the pH value of the solution to be 1.8, molybdenum is precipitated at room temperature, ammonium tetramolybdate and filtrate are obtained after filtration, and the obtained lean desorption solution is used as a desorbent for desorbing molybdenum next time;

Through detection and calculation: the recovery rate of uranium is 96.27 percent, and the recovery rate of molybdenum is 97.84 percent; ammonium diuranate purity 96.95%, U: 72.83%, Mo: 0.0294%; the purity of ammonium tetramolybdate is 97.82%, and the content of Mo: 57.02%, containing U: 0.0025%.

Example 12

(1) pretreating stone coal pickle liquor: firstly, adjusting the pH of the solution to 0.9 by using alkali liquor, then adding hydrogen peroxide and sodium sulfite to adjust the oxidation-reduction potential of the solution to 700mV, and finally adding sodium bisulfate and ammonium bisulfate to adjust the sulfate concentration of the solution to 0.3 mol/L;

(2) adsorbing uranium and molybdenum: controlling the flow rate of the solution obtained after the pretreatment in the step (1) to be 12.5BV/h, and performing 5-stage series adsorption by using extraction resin with active substances of primary amine and quaternary ammonium salt-containing extractant (the content is 45 wt%) to obtain uranium-rich resin, molybdenum-rich resin and effluent, wherein the uranium concentration in the effluent is less than 0.2ppm, and the molybdenum concentration in the effluent is less than 0.5 ppm;

(3) desorbing uranium and preparing ammonium diuranate: desorbing the uranium-rich and molybdenum-rich resin obtained in the step (2) by using a mixed solution of 1 wt% sulfuric acid and 20 wt% sodium sulfate, controlling the flow rate of the solution to be 3.5BV/h, and controlling the final uranium concentration to be less than 6ppm at the desorption end point to obtain a uranium-rich solution and a molybdenum-rich resin; wherein the concentration of uranium in the desorbed qualified liquid is 23.84g/L, ammonia water is added into the qualified liquid to adjust the pH value of the solution to 8.8, uranium precipitation is carried out at 75 ℃, ammonium diuranate and filtrate are obtained after filtration, and the obtained desorbed barren solution is used as a desorbent for desorbing uranium next time;

(4) desorption of molybdenum and preparation of ammonium tetramolybdate: desorbing the molybdenum-rich resin obtained in the step (3) by using a sodium bicarbonate solution with the concentration of 20 wt%, controlling the desorption flow rate to be 6.8BV/h, controlling the concentration of molybdenum in the effluent liquid at the desorption end point to be less than 8ppm, and obtaining a molybdenum-rich solution after the desorption is finished; wherein the concentration of molybdenum in the qualified desorption solution is 85.93g/L, ammonium salt is supplemented to the qualified desorption solution, sulfuric acid is added to adjust the pH of the solution to 3.7, molybdenum is precipitated at room temperature, ammonium tetramolybdate and filtrate are obtained after filtration, and the obtained lean desorption solution is used as a desorbent for desorbing molybdenum next time;

Through detection and calculation: the recovery rate of uranium is 97.73 percent, and the recovery rate of molybdenum is 98.24 percent; ammonium diuranate purity was 97.95%, containing U: 73.11%, Mo: 0.0159 percent; the purity of ammonium tetramolybdate is 98.52%, and the content of Mo: 57.17%, containing U: 0.0017 percent.

Example 13

(1) pretreating stone coal pickle liquor: firstly, adjusting the pH of the solution to 0.5 by using alkali liquor, then adding potassium persulfate and sodium metabisulfite to adjust the oxidation-reduction potential of the solution to 680mV, and finally adding ammonium sulfate and ammonium bisulfate to adjust the sulfate concentration of the solution to 0.8 mol/L;

(2) adsorbing uranium and molybdenum: controlling the flow rate of the solution obtained after the pretreatment in the step (1) to be 2BV/h, and performing 7-stage series adsorption by using extraction resin of which the active substance is a neutral extractant (the content is 27 wt%) containing secondary amine, carbon and oxygen and sulfur to obtain uranium-and molybdenum-rich resin and effluent, wherein the uranium concentration in the effluent is less than 0.4ppm, and the molybdenum concentration in the effluent is less than 0.5 ppm;

(3) desorbing uranium and preparing ammonium diuranate: desorbing the uranium-rich and molybdenum-rich resin obtained in the step (2) by using a mixed solution of 5 wt% sulfuric acid and 20 wt% potassium oxalate, controlling the flow rate of the solution to be 7.5BV/h, and controlling the final uranium concentration of the desorption to be less than 6ppm to obtain a uranium-rich solution and molybdenum-rich resin; wherein the concentration of uranium in the desorbed qualified liquid is 32.73g/L, ammonia water is added into the qualified liquid to adjust the pH value of the solution to 8.6, uranium precipitation is carried out at 50 ℃, ammonium diuranate and filtrate are obtained after filtration, and the obtained desorbed barren solution is used as a desorbent for desorbing uranium next time;

(4) desorption of molybdenum and preparation of ammonium tetramolybdate: desorbing the molybdenum-rich resin obtained in the step (3) by using a mixed solution of 1 wt% ammonia water and 20 wt% potassium bicarbonate, controlling the desorption flow rate to be 10BV/h, and finishing the desorption until the concentration of molybdenum in an effluent liquid at the desorption end is less than 7ppm to obtain a molybdenum-rich solution; wherein the concentration of molybdenum in the qualified desorption solution is 69.28g/L, sulfuric acid is added into the qualified desorption solution to adjust the pH value of the solution to 2.2, molybdenum is precipitated at 35 ℃, ammonium tetramolybdate and filtrate are obtained after filtration, and the obtained lean desorption solution is used as a desorbent for desorbing molybdenum next time;

Through detection and calculation: the recovery rate of uranium is 97.35 percent, and the recovery rate of molybdenum is 98.09 percent; ammonium diuranate purity 96.27%, U: 72.62%, Mo: 0.0258%; the purity of ammonium tetramolybdate is 98.01%, and the content of Mo: 57.64%, containing U: 0.0019 percent.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims

1. A method for separating and recovering uranium and molybdenum from stone coal pickle liquor is characterized by comprising the following steps:

(2) adsorbing the solution obtained in the step (1) by using extraction resin, wherein the extraction resin consists of an active substance and a polymer coated on the surface of the active substance, the content of the active substance in the extraction resin is 20-60 wt%, the active substance is a neutral and/or amine extractant, the extraction resin is converted into sulfate radical type extraction resin by using sulfuric acid before adsorption, so that uranium-and molybdenum-rich resin and an effluent are obtained, the penetration points of uranium and molybdenum in the effluent are both 0.5ppm, and adsorption is stopped when either of the uranium and the molybdenum reaches the penetration point;

(3) desorbing the uranium-rich and molybdenum-rich resin obtained in the step (2) in sequence to obtain a uranium-rich solution and a molybdenum-rich solution; wherein the uranium desorption operation is as follows: desorbing the uranium-rich and molybdenum-rich resin obtained in the step (2) by using a uranium desorbent to obtain a uranium-rich solution and molybdenum-rich resin, wherein the uranium desorbent is oxalic acid and/or oxalate; the operation of desorbing the molybdenum comprises the following steps: and desorbing the molybdenum-rich resin obtained after uranium desorption by using ammonia water and/or a carbonate solution to obtain a molybdenum-rich solution.

2. The method according to claim 1, wherein the pH of the stone coal pickle liquor is adjusted to 1-2 in the step (1).

3. The method according to claim 1, wherein the concentration of the sulfate salt is adjusted to 0.3 to 1mol/L in the step (1).

4. The method according to claim 1, wherein the redox potential in step (1) is adjusted to 500 to 750 mV.

5. The method of claim 1, wherein the oxidation-reduction potential is adjusted by adding an oxidizing agent and a reducing agent in step (1).

6. The method of claim 5, wherein the oxidizing agent is any one of chlorate, hypochlorite, perchlorate, nitrate, nitrite, a manganese-containing compound greater than divalent, peroxide, ferride, persulfate, oxygen, ozone, or air, or a combination of at least two thereof.

7. The method of claim 6, wherein the oxidizing agent is a peroxide and/or a persulfate.

8. The method of claim 7, wherein the oxidant is any one of hydrogen peroxide, ammonium persulfate, sodium persulfate, or potassium persulfate, or a combination of at least two thereof.

9. The method of claim 5, wherein the reducing agent is any one of or a combination of at least two of sulfite, bisulfite, metabisulfite, thiosulfate, sulfide, hydrosulfide, sulfur dioxide, or sulfur powder.

10. The method of claim 1, wherein the active substance of step (2) is an amine-based extractant.

11. The method of claim 1, wherein the neutral extractant is any one of carbon-oxygen, phosphorus-oxygen or sulfur-containing neutral extractants or a combination of at least two of the same.

12. The method of claim 11, wherein the neutral extractant is a phosphorus-oxygen neutral extractant.

13. The method of claim 1, wherein the amine extractant is any one of a primary, secondary, tertiary amine, or quaternary ammonium salt extractant, or a combination of at least two thereof.

14. The method of claim 13, wherein the amine extractant is any one of a primary, secondary, tertiary amine extractant, or a combination of at least two thereof.

15. The method of claim 1, wherein the polymer of step (2) is a styrene-divinylbenzene copolymer resin.

16. The method according to claim 1, wherein the flow rate of the solution in the adsorption process in the step (2) is 0.5 to 30 BV/h.

17. The method according to claim 16, wherein the flow rate of the solution in the adsorption process in the step (2) is 1 to 20 BV/h.

18. The method according to claim 16, wherein the flow rate of the solution in the adsorption process in the step (2) is 5-10 BV/h.

19. The method according to claim 1, wherein the adsorption in the step (2) is multistage series adsorption, and the number of adsorption stages is 2-8.

20. The method of claim 19, wherein the adsorption stage number in the step (2) is 3 to 5.

21. The process according to claim 1, wherein the effluent obtained in step (2) is used for the recovery of vanadium.

22. The method according to claim 1, wherein the concentration of oxalic acid in the uranium desorbent in step (3) is 1 to 20 wt%.

23. The method of claim 1, wherein the concentration of oxalate in the uranium desorbent in step (3) is from 1 to 15 wt%.

24. The method of claim 1, wherein the oxalate salt is any one of sodium oxalate, potassium oxalate, or ammonium oxalate, or a combination of at least two thereof.

25. The method of claim 24, wherein the oxalate salt is ammonium oxalate.

26. The method of claim 1, wherein the flow rate of the solution during uranium desorption is 0.5-30 BV/h.

27. The method of claim 26, wherein the solution flow rate during uranium desorption is 1-20 BV/h.

28. The method of claim 26, wherein the flow rate of the solution during uranium desorption is 2-10 BV/h.

29. The method according to claim 1, wherein the concentration of uranium in the effluent at the end point of desorption in the uranium desorption process is 2-10 ppm.

30. The method of claim 29, wherein the concentration of uranium in the effluent at the end of desorption during said desorption of uranium is from 2 to 5 ppm.

31. The method of claim 1, wherein the effluent with the uranium concentration being more than or equal to 1g/L in the uranium desorption process is qualified desorption liquid, and the effluent with the uranium concentration being less than 1g/L is desorption barren liquid.

32. The method of claim 31, wherein the qualified desorbed liquid is subjected to uranium precipitation and the lean desorbed liquid is used as a desorbent for the next desorption of uranium.

33. The method according to claim 1, characterized in that ammonia water is added into the obtained uranium-rich solution to adjust the pH value for uranium precipitation, and ammonium diuranate and filtrate are obtained after solid-liquid separation.

34. The method of claim 33, wherein the pH is adjusted to 6 to 9 by adding ammonia.

35. The method of claim 34, wherein the pH is adjusted to 7 to 8 by adding ammonia.

36. The method of claim 33, wherein the temperature of the uranium precipitation process is 10-90 ℃.

37. The method of claim 36, wherein the temperature of the uranium precipitation process is from 25 ℃ to 70 ℃.

38. The process of claim 33, wherein the filtrate is returned to the stone coal pickle liquor of step (1).

39. The method of claim 1, wherein the concentration of the aqueous ammonia in the step (3) is 1 to 20 wt%.

40. The method of claim 1, wherein the carbonate solution of step (3) has a concentration of 1 to 20 wt%.

41. The method of claim 1, wherein the carbonate in step (3) is any one of sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate or ammonium bicarbonate or a combination of at least two thereof.

42. The method of claim 41, wherein the carbonate salt is ammonium carbonate and/or ammonium bicarbonate.

43. The method according to claim 1, wherein the flow rate of the solution during the desorption of molybdenum is 0.5 to 30 BV/h.

44. The method of claim 43, wherein the flow rate of the solution during the desorption of molybdenum is 1 to 20 BV/h.

45. The method of claim 43, wherein the flow rate of the solution during the desorption of molybdenum is 2-10 BV/h.

46. The method of claim 43, wherein the concentration of molybdenum in the effluent at the end of desorption during the desorption of molybdenum is 2-10 ppm.

47. The method of claim 46, wherein the concentration of molybdenum in the effluent at the end of desorption during the desorption process is 2-5 ppm.

48. The method as claimed in claim 1, wherein the effluent with the molybdenum concentration being more than or equal to 1g/L in the molybdenum desorption process is qualified desorption liquid, and the effluent with the molybdenum concentration being less than 1g/L is lean desorption liquid.

49. The method of claim 48, wherein the qualified desorption solution is subjected to molybdenum precipitation, and the lean desorption solution is used as a desorbent for next desorption of molybdenum.

50. The method of claim 1, wherein when ammonia is used for desorption, sulfuric acid is directly added to the obtained molybdenum-rich solution to adjust the pH value for molybdenum precipitation, and ammonium tetramolybdate and filtrate are obtained after solid-liquid separation.

51. The process of claim 50, wherein when a carbonate solution is used as the desorbent, NH is added to the resulting molybdenum-rich solution prior to the pH adjustment to precipitate molybdenum₄ ⁺。

52. The method of claim 50, wherein the pH is adjusted to 1 to 4 by the addition of sulfuric acid.

53. The method of claim 52, wherein the pH is adjusted to 2 to 3 by the addition of sulfuric acid.

54. The method of claim 50, wherein the temperature of the molybdenum precipitation process is 10-90 ℃.

55. The method of claim 54, wherein the temperature of the molybdenum precipitation process is from 25 ℃ to 50 ℃.

56. The method of claim 50, wherein the filtrate is returned to the stone coal pickle liquor of step (1).

57. The method of claim 1, wherein the method comprises the steps of:

(2) carrying out 2-8-stage series adsorption on the solution obtained in the step (1) by using extraction resin, converting the extraction resin into sulfate radical type extraction resin by using sulfuric acid before adsorption, wherein the flow speed of the solution in the adsorption process is 0.5-30 BV/h, the penetration points of uranium and molybdenum in the effluent are both 0.5ppm, and the adsorption is stopped when either of the uranium and molybdenum reaches the penetration point, so that uranium-rich resin, molybdenum-rich resin and the effluent are obtained; the extraction resin consists of 20-60 wt% of active substances and a polymer coated on the surface of the extraction resin, wherein the active substances are neutral and/or amine extractants, and the polymer is styrene-divinylbenzene copolymer resin;

(3) desorbing the uranium-rich and molybdenum-rich resin obtained in the step (2) by using at least one of oxalic acid or oxalate as a uranium desorbent, wherein the flow rate of the solution is 0.5-30 BV/h, and the concentration of uranium in an effluent liquid at the end of desorption is 2-10 ppm, so as to obtain a uranium-rich solution and molybdenum-rich resin; adding ammonia water into the obtained uranium-rich solution to adjust the pH value to 6-9, sinking uranium at 10-90 ℃, performing solid-liquid separation to obtain ammonium diuranate and filtrate, and returning the filtrate to the stone coal pickle liquor in the step (1);

(4) desorbing the molybdenum-rich resin obtained after uranium desorption by using ammonia water and/or a carbonate solution, wherein the flow rate of the solution is 0.5-30 BV/h, and the concentration of molybdenum in an effluent liquid at the end of desorption is 2-10 ppm, so as to obtain a molybdenum-rich solution; when ammonia water is used for desorption, sulfuric acid is directly added into the obtained molybdenum-rich solution to adjust the pH value to 1-4, and when carbonate solution is used as a resolving agent, NH is supplemented into the obtained molybdenum-rich solution₄ ⁺And (3) adjusting the pH value to 1-4, precipitating molybdenum at 10-90 ℃, performing solid-liquid separation to obtain ammonium tetramolybdate and filtrate, and returning the filtrate to the stone coal pickle liquor in the step (1).