Method for gradient elution of gallium and vanadium from amidoxime chelate resin

Abstract

The invention relates to a method for gradient elution of gallium and vanadium from amidoxime chelate resin, which is used for extracting gallium from Bayer process mother liquor and cooperatively recovering vanadium at the same time, and belongs to the technical field of resource recovery. The method mainly comprises the following steps: (1) absorbing gallium and vanadium from Bayer process seed precipitation mother liquor by adopting amidoxime chelate resin; (2) carrying out primary elution on the resin adsorbing gallium and vanadium by adopting a sodium sulfide / sodium hydroxide mixed solution to obtain a Ga-rich eluent; (3) carrying out secondary elution on the gallium-eluted resin by using a hydroxylamine solution to obtain a V-containing eluent; and (4) the resin obtained after gallium and vanadium elution is used for cyclic adsorption of gallium and vanadium in mother liquor, and a new gallium and vanadium co-adsorption-gradient elution-regeneration cycle method is formed. According to the method, gallium and vanadium adsorbed on the amidoxime chelate resin are selectively separated through gradient elution, gallium and vanadium metal resources can be recycled, the phenomenon of resin vanadium poisoning can be relieved, the service life of the resin is prolonged, and remarkable economic benefits are achieved.

Description

Technical Field

[0001] The present invention belongs to the technical field of resource recovery, and particularly relates to a method for stepwise eluting gallium and vanadium from amidoxime chelating resin. Background Art

[0002] Gallium (Ga) and vanadium (V) are important rare metals. Ga is mainly used in the electronics industry, and V is widely used in fields such as iron and steel, metallurgy, aerospace, and national defense industries. In nature, Ga does not form independent ore deposits. 90% of the world's Ga comes from the Bayer liquor. Currently, the main method for extracting Ga from the Bayer liquor is the adsorption method using amidoxime resin. However, during the process of resin adsorption for Ga extraction, a large amount of V is also adsorbed on the resin, and V is difficult to elute, resulting in resin poisoning, reducing the adsorption capacity of the resin for gallium and its performance of recycling and reuse, and shortening the service life of the resin. If V can be recovered synergistically while extracting Ga from the Bayer liquor, it will not only extend the recycling service life of the amidoxime resin, but also significantly improve the economic benefits of alumina production.

[0003] Currently, the elution of gallium on the resin includes acid elution and alkali elution. The article published by Zheng Qi et al. from Guangxi University in 《Metal Mine》 shows that inorganic acids have a significant desorption effect on gallium. HCl, HNO 3 、H 2 SO 4 etc. can elute Ga from the resin, and the desorption rate is higher than 80%. Among them, 1.5 mol / L HCl has the best desorption effect on gallium, and the desorption rate reaches 90%. However, inorganic acids have a poor desorption effect on V, and the desorption rate is less than 5%. When using 1.5 mol / L NaOH, KOH, ammonia water and other alkaline desorbents to desorb gallium respectively, it is found that the desorption rate of gallium is less than 10%, and V is still difficult to desorb. Therefore, the desorption effect of inorganic acids on Ga is higher than that of alkaline solutions, and the desorption effects of V are all very poor. The article published by Zhao Zhuo et al. from Anhui University of Technology in 《ACS Sustainable Chemistry & Engineering》 proposed a two-step desorption process, that is, first using dilute H 2 SO 4 、EDTA and acetone to elute Ga, and then using H 2 SO 4V is eluted with an ammonia solution. In this method, EDTA can effectively desorb Ga, but V still cannot be desorbed from the resin. The invention patent application with the publication number CN101660046B discloses a method for reducing and desorbing vanadium-containing resin, which uses a desorbent composed of reducing agents such as ammonium sulfite, ammonium bisulfite, ammonium pyrosulfite, oxalic acid and sulfuric acid to desorb the vanadium-containing resin to obtain an acidic desorbing solution, but the acidic condition will damage the resin structure. Since the acidic eluent will damage the structure of the amidoxime resin, "Experiment on Gallium Adsorption-Extraction Enrichment from Bayer Cycle Mother Liquor" published by Meng Jiejie et al. in "Mineral Protection and Utilization" in 2020 uses 12 mol / L NaOH to desorb the V adsorbed on the resin, and the desorption rate is 43.68%. The vanadium desorption rate is not high and there is still much room for improvement.

[0004] In order to alleviate the phenomenon of resin vanadium poisoning, the patent with the patent number CN102277492B of Xi'an Lannx Technology Co., Ltd. discloses a method for treating the gallium-extracting resin in Bayer process mother liquor. By treating the saturated resin after rinsing and the lean resin after elution with alkali solutions of different concentrations, the vanadium concentration adsorbed on the resin can be reduced by 30% - 50%, and the resin life can be extended to 10 - 20 days. This method can remove the impurity vanadium existing in the process of extracting gallium from the amidoxime resin, but does not consider the recycling of vanadium; the patent with the patent number CN1887724A of Chalco Shandong Co., Ltd. discloses a method for pre-removing vanadium from Bayer process mother liquor, which uses the method of cooling crystallization to reduce the vanadium content in Bayer process mother liquor to reduce the influence of vanadium on the resin. After impurity removal, the Ga content in the mother liquor is 110 - 130 mg / L, and the V content is 140 - 160 mg / L. The V extraction rate can reach 85% - 90%. However, the crude vanadium salt obtained by the cooling crystallization method is a double salt containing various impurities, and the quality of the vanadium salt product is poor and needs to be further purified. Patent CN116397112A discloses a method for extracting V from the crystallized vanadium slag of Bayer process mother liquor. Specifically, it uses NaOH and barium salt to selectively precipitate V, dissolves the vanadium-precipitated slag with acid, leaches it with a leaching agent, filters to obtain a vanadium-enriched solution, adds an ammonium salt to form meta / polyvanadate ammonium, and calcines to obtain a vanadium product. However, barium salt is toxic and poses a great risk to the human body and the environment.

[0005] Regarding the recovery of vanadium during the adsorption of gallium by amidoxime resin, current patent reports mainly focus on vanadium precipitation from the desorbed gallium-enriched solution. The invention patent with the patent number CN102011000A discloses a method for removing vanadium from a gallium-enriched solution of the resin-adsorbed mother liquor of seed precipitation solution. By adding 20 g / L CaO, vanadium in the gallium-enriched solution of the resin-adsorbed mother liquor is removed, reducing the vanadium concentration to below 20 mg / L, which can improve the electrolytic gallium efficiency. The patent CN102021334A of Aluminum Corporation of China discloses a method for precipitating vanadium from the resin eluate. Specifically, water and concentrated acid are used to wash the saturated resin, and BaO is added to the eluate to precipitate vanadium in the form of barium vanadate and separate it from Ga. The above methods mainly aim to remove the entrained vanadium in the gallium eluate and cannot fully elute the vanadium adsorbed on the amidoxime resin. Vanadium still remains on the resin, which is not conducive to the regeneration and recycling of the resin.

[0006] In view of this, the above methods mainly focus on the adsorption and recovery of gallium from the Bayer process mother liquor by resin, while the utilization rate of vanadium is low. The existing process has not solved the problem of resin poisoning caused by the difficult elution of vanadium on the resin. Therefore, there is an urgent need to develop a new method for efficient separation of gallium and vanadium with a short process and low energy consumption. Summary of the Invention

[0007] Aiming at the problems of co-adsorption and difficult elution of vanadium on the resin during the extraction of gallium from the mother liquor of alumina production by the Bayer process, which leads to resin poisoning, the present invention provides a method for stepwise elution of gallium and vanadium from amidoxime chelating resin.

[0008] To achieve the above object, the technical solution of the present invention is as follows:

[0009] A method for stepwise elution of gallium and vanadium from amidoxime chelating resin, comprising the following steps:

[0010] Step 1, adsorbing gallium and vanadium: Using amidoxime chelating resin to adsorb gallium and vanadium from the Bayer process seed precipitation mother liquor. After adsorption saturation, solid-liquid separation is carried out to obtain amidoxime chelating resin loaded with gallium and vanadium.

[0011] Step 2, eluting gallium: Washing the amidoxime chelating resin loaded with gallium and vanadium with deionized water, and then adding eluent 1 to desorb the gallium on the resin. After desorption is completed, solid-liquid separation is carried out to obtain a gallium-rich eluate.

[0012] Step 3, eluting vanadium: Adding eluent 2 to the resin after eluting gallium to desorb the vanadium on the resin. After desorption is completed, solid-liquid separation is carried out to obtain a vanadium-rich eluate.

[0013] Step 4, regeneration and recycling: Washing the resin after eluting gallium and vanadium with deionized water to obtain the regenerated resin, and repeating steps 1 to 3 for recycling.

[0014] Further, the amidoxime chelating resin in Step 1 is one or more of LSC-600 chelating resin, Duolite ES-346 chelating resin, LSC700 chelating resin, and DHG 586 chelating resin, and the adsorption temperature is 10-40°C.

[0015] Further, the eluent 1 in Step 2 is a mixed solution of NaOH and Na 2 S.

[0016] Furthermore, in the mixed solution of NaOH and Na 2 S, the concentration of NaOH is 2-12 mol / L, and the concentration of Na 2 S is 0.2-2 mol / L. The volume ratio of NaOH to Na 2 S is 1:1-1:5.

[0017] Further, the solid-liquid ratio of the amidoxime chelating resin loaded with gallium and vanadium to the eluent 1 in Step 2 is 1:10-1:100.

[0018] Further, the desorption temperature in Step 2 is 10-40°C, and the time is 2-12 h.

[0019] Further, the eluent 2 in Step 3 is a hydroxylamine solution.

[0020] Furthermore, the concentration of the hydroxylamine solution is 6-12 mol / L.

[0021] Further, the solid-liquid ratio of the resin after eluting gallium to the eluent 2 in Step 3 is 1:10-1:100.

[0022] Further, the desorption temperature in Step 3 is 10-40°C, and the time is 2-12 h.

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0024] Based on the differences in the interactions between gallium, vanadium, and amidoxime chelating resin in the Bayer process mother liquor, the present invention uses a mixed solution of sodium sulfide + sodium hydroxide and a hydroxylamine solution for the stepwise elution of gallium and vanadium, achieving the selective separation of gallium and vanadium and the efficient elution of vanadium, which is beneficial to the regeneration and recycling of the resin and extends the service life of the resin. Compared with the acid elution process, the gallium and vanadium eluting resin shows good chemical stability under alkaline conditions. The method of the present invention can achieve the co-recovery of vanadium during the process of extracting gallium from the Bayer process mother liquor, improving the resource utilization rate, protecting rare metal resources, and promoting the high-quality development of the aluminum industry. Description of the Drawings

[0025] Figure 1This is a flow chart of a method for stepwise eluting gallium and vanadium from amidoxime chelating resin of the present invention. Detailed implementation manners

[0026] To facilitate the understanding of the present invention, the present invention will be described more comprehensively below. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, these embodiments are provided to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0027] Example 1

[0028] 10 g of LSC-600 chelating resin was used to adsorb gallium and vanadium from 1 L of Bayer process mother liquor. The adsorption temperature was 25 °C, the contact time between the resin and the mother liquor was 12 h. After adsorption saturation, solid-liquid separation was carried out to obtain amidoxime chelating resin loaded with gallium and vanadium. The saturated adsorption capacities of gallium and vanadium on the resin were 20.9 mg / g and 17.2 mg / g respectively;

[0029] The above-mentioned amidoxime chelating resin loaded with gallium and vanadium was washed with deionized water, and Ga on the resin was desorbed with a 6 mol / L NaOH + 1 mol / L Na 2 S mixed solution. The volume ratio of NaOH to Na 2 S was 1:1. The desorption temperature was 25 °C, the solid-liquid ratio for desorption was 1:100, and the desorption time was 12 h. After desorption, solid-liquid separation was carried out to obtain a Ga-rich eluate. The desorption rate of Ga was 90.5%, and V was basically not desorbed;

[0030] 8 mol / L hydroxylamine solution was added to the resin after eluting Ga. The solid-liquid ratio for desorption was 1:100, the desorption temperature was 25 °C, and the desorption time was 8 h. After desorption, solid-liquid separation was carried out to obtain a V-rich eluate. The desorption rate of V was 99.1%;

[0031] The resin after eluting gallium and vanadium was washed with deionized water to obtain the regenerated resin, and then the regenerated resin was used for a new round of cyclic adsorption. The saturated adsorption capacities of the resin for gallium and vanadium were 20.7 mg / g and 16.5 mg / g respectively.

[0032] Example 2

[0033] 10 g of Duolite ES-346 chelating resin was used to adsorb gallium and vanadium from 1 L of Bayer process mother liquor. The adsorption temperature was 10 °C, the contact time between the resin and the mother liquor was 12 h. After adsorption saturation, solid-liquid separation was carried out to obtain amidoxime chelating resin loaded with gallium and vanadium. The saturated adsorption capacities of gallium and vanadium on the resin were 21.7 mg / g and 19.1 mg / g respectively;

[0034] Wash the above-mentioned amidoxime chelating resin loaded with gallium and vanadium with deionized water, and use 6 mol / L NaOH + 1 mol / L Na 2 S mixed solution to desorb Ga on the resin. The volume ratio of NaOH to Na 2 S is 1:3, the desorption temperature is 25 °C, the solid-liquid ratio of desorption is 1:100, the desorption time is 12 h. After desorption, perform solid-liquid separation to obtain a Ga-rich eluate. The desorption rate of Ga is 89.72%, and V is basically not desorbed;

[0035] Add 6 mol / L hydroxylamine solution to the resin after eluting Ga. The solid-liquid ratio of desorption is 1:100, the desorption temperature is 25 °C, the desorption time is 10 h. After desorption, perform solid-liquid separation to obtain a V-rich eluate. The desorption rate of V is 93.6%;

[0036] Wash the resin after eluting gallium and vanadium with deionized water to obtain the regenerated resin, and then use the regenerated resin for a new round of cyclic adsorption. The saturated adsorption capacities of the resin for gallium and vanadium are 20.1 mg / g and 18.7 mg / g respectively.

[0037] Example 3

[0038] Use 10 g of LSC700 chelating resin to adsorb gallium and vanadium from 1 L of Bayer process mother liquor. The adsorption temperature is 30 °C, the contact time between the resin and the mother liquor is 12 h. After adsorption saturation, perform solid-liquid separation to obtain the amidoxime chelating resin loaded with gallium and vanadium. The saturated adsorption capacities of gallium and vanadium on the resin are 19.6 mg / g and 16.7 mg / g respectively;

[0039] Wash the above-mentioned amidoxime chelating resin loaded with gallium and vanadium with deionized water, and use 6 mol / L NaOH + 1.5 mol / L Na 2 S mixed solution to desorb Ga on the resin. The volume ratio of NaOH to Na 2 S is 1:1, the desorption temperature is 25 °C, the solid-liquid ratio of desorption is 1:100, the desorption time is 12 h. After desorption, perform solid-liquid separation to obtain a Ga-rich eluate. The desorption rate of Ga is 90.0%, and V is basically not desorbed;

[0040] Add 12 mol / L hydroxylamine solution to the resin after eluting Ga. The solid-liquid ratio of desorption is 1:100, the desorption temperature is 25 °C, the desorption time is 8 h. After desorption, perform solid-liquid separation to obtain a V-rich eluate. The desorption rate of V is 99.8%;

[0041] Wash the resin after eluting gallium and vanadium with deionized water to obtain the regenerated resin, and then use the regenerated resin for a new round of cyclic adsorption. The saturated adsorption capacities of the resin for gallium and vanadium are 18.4 mg / g and 16.6 mg / g respectively.

[0042] Example 4

[0043] 10 g of DHG 586 chelating resin was used to adsorb gallium and vanadium from 1 L of Bayer process seed mother liquor. The adsorption temperature was 15 °C, the contact time between the resin and the mother liquor was 12 h. After adsorption saturation, solid-liquid separation was carried out to obtain amidoxime chelating resin loaded with gallium and vanadium. The saturated adsorption capacities of gallium and vanadium on the resin were 21.1 mg / g and 19.2 mg / g, respectively;

[0044] The above-mentioned amidoxime chelating resin loaded with gallium and vanadium was washed with deionized water, and Ga on the resin was desorbed with a 6 mol / L NaOH + 2 mol / L Na 2 S mixed solution. The volume ratio of NaOH to Na 2 S was 1:1, the desorption temperature was 25 °C, the solid-liquid ratio for desorption was 1:100, and the desorption time was 12 h. After desorption was completed, solid-liquid separation was carried out to obtain a Ga-rich eluate. The desorption rate of Ga was 90.7%, and V was basically not desorbed;

[0045] 10 mol / L hydroxylamine solution was added to the resin after eluting Ga. The solid-liquid ratio for desorption was 1:100, the desorption temperature was 25 °C, and the desorption time was 6 h. After desorption was completed, solid-liquid separation was carried out to obtain a V-rich eluate. The desorption rate of V was 94.6%;

[0046] The resin after eluting gallium and vanadium was washed with deionized water to obtain the regenerated resin, and then the regenerated resin was used for a new round of cyclic adsorption. The saturated adsorption capacities of the resin for gallium and vanadium were 19.4 mg / g and 16.7 mg / g, respectively.

[0047] Example 5

[0048] 10 g of LSC-600 chelating resin was used to adsorb gallium and vanadium from 1 L of Bayer process seed mother liquor. The adsorption temperature was 35 °C, the contact time between the resin and the mother liquor was 12 h. After adsorption saturation, solid-liquid separation was carried out to obtain amidoxime chelating resin loaded with gallium and vanadium. The saturated adsorption capacities of gallium and vanadium on the resin were 19.0 mg / g and 18.5 mg / g, respectively;

[0049] The above-mentioned amidoxime chelating resin loaded with gallium and vanadium was washed with deionized water, and Ga on the resin was desorbed with a 6 mol / L NaOH + 1 mol / L Na 2 S mixed solution. The volume ratio of NaOH to Na 2 S was 1:5, the desorption temperature was 25 °C, the solid-liquid ratio for desorption was 1:100, and the desorption time was 12 h. After desorption was completed, solid-liquid separation was carried out to obtain a Ga-rich eluate. The desorption rate of Ga was 89.6%, and V was basically not desorbed;

[0050] Add 8 mol / L hydroxylamine solution to the resin after eluting Ga. The solid-liquid ratio for desorption is 1:100, the desorption temperature is 25 °C, the desorption time is 6 h. After desorption, perform solid-liquid separation to obtain a V-rich eluate. The desorption rate of V is 98.4%;

[0051] Wash the resin after eluting gallium and vanadium with deionized water to obtain the regenerated resin, and then use the regenerated resin for a new round of cyclic adsorption. The saturated adsorption capacities of the resin for gallium and vanadium are 17.3 mg / g and 18.2 mg / g respectively.

[0052] Example 6

[0053] Use 10 g of Duolite ES-346 chelating resin to adsorb gallium and vanadium from 1 L of Bayer process seed mother liquor. The adsorption temperature is 25 °C, the contact time between the resin and the mother liquor is 12 h. After adsorption saturation, perform solid-liquid separation to obtain the amidoxime chelating resin loaded with gallium and vanadium. The saturated adsorption capacities of gallium and vanadium on the resin are 19.6 mg / g and 17.8 mg / g respectively;

[0054] Wash the above-mentioned amidoxime chelating resin loaded with gallium and vanadium with deionized water, and use an 8 mol / L NaOH + 1 mol / L Na 2 S mixed solution to desorb Ga on the resin. The volume ratio of NaOH and Na 2 S is 1:1, the desorption temperature is 25 °C, the solid-liquid ratio for desorption is 1:100, the desorption time is 12 h. After desorption, perform solid-liquid separation to obtain a Ga-rich eluate. The desorption rate of Ga is 89.2%, and V is basically not desorbed;

[0055] Add 10 mol / L hydroxylamine solution to the resin after eluting Ga. The solid-liquid ratio for desorption is 1:100, the desorption temperature is 25 °C, the desorption time is 8 h. After desorption, perform solid-liquid separation to obtain a V-rich eluate. The desorption rate of V is 94.1%;

[0056] Wash the resin after eluting gallium and vanadium with deionized water to obtain the regenerated resin, and then use the regenerated resin for a new round of cyclic adsorption. The saturated adsorption capacities of the resin for gallium and vanadium are 18.6 mg / g and 16.1 mg / g respectively.

[0057] Example 7

[0058] Use 10 g of LSC700 chelating resin to adsorb gallium and vanadium from 1 L of Bayer process seed mother liquor. The adsorption temperature is 20 °C, the contact time between the resin and the mother liquor is 12 h. After adsorption saturation, perform solid-liquid separation to obtain the amidoxime chelating resin loaded with gallium and vanadium. The saturated adsorption capacities of gallium and vanadium on the resin are 20.4 mg / g and 16.0 mg / g respectively;

[0059] Wash the above-mentioned amidoxime chelating resin loaded with gallium and vanadium with deionized water, and use a 6 mol / L NaOH + 1 mol / L Na 2 S mixed solution to desorb Ga on the resin. The volume ratio of NaOH to Na 2 S is 1:2, the desorption temperature is 25 °C, the solid-liquid ratio for desorption is 1:100, the desorption time is 12 h. After desorption, perform solid-liquid separation to obtain a Ga-rich eluate. The desorption rate of Ga is 89.7%, and V is basically not desorbed;

[0060] Add a 12 mol / L hydroxylamine solution to the resin after eluting Ga. The solid-liquid ratio for desorption is 1:100, the desorption temperature is 25 °C, the desorption time is 6 h. After desorption, perform solid-liquid separation to obtain a V-rich eluate. The desorption rate of V is 96.7%;

[0061] Wash the resin after eluting gallium and vanadium with deionized water to obtain the regenerated resin, and then use the regenerated resin for a new round of cyclic adsorption. The saturated adsorption capacities of the resin for gallium and vanadium are 20.4 mg / g and 15.7 mg / g respectively.

[0062] Example 8

[0063] Use 10 g of DHG 586 chelating resin to adsorb gallium and vanadium from 1 L of Bayer process mother liquor. The adsorption temperature is 40 °C, the contact time between the resin and the mother liquor is 12 h. After adsorption saturation, perform solid-liquid separation to obtain the amidoxime chelating resin loaded with gallium and vanadium. The saturated adsorption capacities of gallium and vanadium on the resin are 17.6 mg / g and 16.8 mg / g respectively;

[0064] Wash the above-mentioned amidoxime chelating resin loaded with gallium and vanadium with deionized water, and use a 6 mol / L NaOH + 1 mol / L Na 2 S mixed solution to desorb Ga on the resin. The volume ratio of NaOH to Na 2 S is 1:4, the desorption temperature is 25 °C, the solid-liquid ratio for desorption is 1:100, the desorption time is 12 h. After desorption, perform solid-liquid separation to obtain a Ga-rich eluate. The desorption rate of Ga is 90.8%, and V is basically not desorbed;

[0065] Add a 6 mol / L hydroxylamine solution to the resin after eluting Ga. The solid-liquid ratio for desorption is 1:100, the desorption temperature is 25 °C, the desorption time is 12 h. After desorption, perform solid-liquid separation to obtain a V-rich eluate. The desorption rate of V is 95.4%;

[0066] Wash the resin after eluting gallium and vanadium with deionized water to obtain the regenerated resin, and then use the regenerated resin for a new round of cyclic adsorption. The saturated adsorption capacities of the resin for gallium and vanadium are 16.2 mg / g and 14.8 mg / g respectively.

[0067] The above are only embodiments for better explaining the present invention, and are not intended to limit it. Any modification or equivalent replacement that does not depart from the spirit and scope of the present invention shall fall within the scope covered by the present invention.

Claims

1. A method for stepwise elution of gallium and vanadium from amidoxime chelating resin, characterized in that: The following steps are involved: Step 1, adsorption of gallium and vanadium: using amidoxime chelating resin to adsorb gallium and vanadium from the seed liquor of the Bayer process, and performing solid-liquid separation after adsorption saturation to obtain amidoxime chelating resin loaded with gallium and vanadium; Step 2, eluting gallium: washing the gallium-vanadium-loaded amidoxime chelating resin with deionized water, then adding eluent 1 to desorb the gallium on the resin, and performing solid-liquid separation after the desorption is completed to obtain a gallium-rich eluent; Step 3, eluting vanadium: adding the eluent 2 to the resin after eluting gallium, desorbing the vanadium on the resin, and performing solid-liquid separation after the desorption is completed to obtain a vanadium-rich eluent; Step 4, regeneration cycle: wash the resin after eluting gallium and vanadium with deionized water to obtain a regenerated resin, and repeat steps 1 to 3 for recycling.

2. A method for stepwise elution of gallium and vanadium from amidoxime chelating resin according to claim 1, characterized in that: In the step 1, the amidoxime chelate resin is one or more of LSC-600 chelate resin, Duolite ES-346 chelate resin, LSC700 chelate resin and DHG 586 chelate resin, and the adsorption temperature is 10-40°C.

3. The method for stepwise elution of gallium and vanadium from amidoxime chelating resin according to claim 1, characterized in that: In step 2, the eluent 1 is a mixed solution of NaOH and Na2S.

4. A method for stepwise elution of gallium and vanadium from amidoxime chelating resin according to claim 3, characterized in that: In the mixed solution of NaOH and Na2S, the concentration of NaOH is 2-12 mol / L, the concentration of Na2S is 0.2-2 mol / L, and the volume ratio of NaOH to Na2S is 1:1-1:

5.

5. The method for stepwise elution of gallium and vanadium from amidoxime chelating resin according to claim 1, characterized in that: In the step 2, the solid-liquid ratio of the gallium-vanadium-loaded amidoxime chelating resin and the eluent 1 is 1:10 to 1:

100.

6. A method for stepwise elution of gallium and vanadium from amidoxime chelating resin according to claim 1, characterized in that: The desorption temperature in step 2 is 10-40° C. and the desorption time is 2-12 hours.

7. A method for stepwise elution of gallium and vanadium from amidoxime chelating resin according to claim 1, characterized in that: In the step 3, the eluent 2 is a hydroxylamine solution.

8. A method for stepwise elution of gallium and vanadium from amidoxime chelating resin according to claim 7, characterized in that: The concentration of the hydroxylamine solution is 6-12 mol / L.

9. The method for stepwise elution of gallium and vanadium from amidoxime chelating resin according to claim 1, characterized in that: In the step 3, the solid-liquid ratio of the resin after gallium is eluted to the eluent 2 is 1:10 to 1:

100.

10. The method for stepwise elution of gallium and vanadium from amidoxime chelating resin according to claim 1, characterized in that: The desorption temperature in step 3 is 10-40° C. and the desorption time is 2-12 hours.

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