CN109534403B - Method for separating molybdenum in tungstate solution by ion exchange method - Google Patents
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- C01G41/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
Abstract
The invention discloses a method for separating molybdenum in tungstate solution by an ion exchange method. Adding trithiocyanuric acid into a molybdenum-containing tungstate solution to carry out a sulfurization reaction to obtain a thiomolybdate-containing tungstate solution; carrying out ion exchange on a tungstate solution containing thiomolybdate by adopting weak-base anion exchange resin to adsorb the thiomolybdate, so as to obtain a tungstate solution; desorbing the thiomolybdate-loaded weak-base anion exchange resin by using an alkaline desorption solution to obtain a molybdate solution; the method has the advantages of good separation effect on molybdenum in the high-tungsten low-molybdenum solution, small tungsten loss, simple operation, no release of hydrogen sulfide gas in the vulcanization process, no need of adding a hydrogen sulfide gas recovery facility, no need of adopting an oxidant in the desorption process, easy realization of molybdenum recovery, prolonged service life of resin and contribution to realization of industrial application.
Description
Technical Field
The invention relates to a method for removing molybdenum from a tungstate solution, in particular to a method for carrying out vulcanization conversion on a small amount of molybdenum in a tungstate solution containing molybdenum by using a special vulcanizing agent, and then carrying out deep removal and recovery by ion exchange, belonging to the technical field of rare metal metallurgy.
Background
Tungsten and molybdenum belong to the same subgroup in the periodic table of elements, and due to contraction of lanthanide series, tungsten and molybdenum ions and atomic radii are similar, so that the chemical properties of tungsten and molybdenum are similar and the separation is difficult, and therefore the separation of tungsten and molybdenum is always difficult in the tungsten metallurgy process. The existing tungsten-molybdenum separation methods comprise a chemical precipitation method, a solvent extraction method, an ion exchange method and the like. However, with the lower grade of the tungsten-molybdenum concentrate, the performance requirements of people on tungsten-molybdenum metal and alloy thereof are higher and higher, and the requirements on environmental protection are more and more strict, so that the technology of tungsten-molybdenum separation also puts forward a new requirement, which is clearly stated in GB-T10116-3Must not exceed 20X 10-6。
The main method adopted in the industry at present is to sulfide molybdate ions into thiomolybdate ions by utilizing the difference of the affinity of tungsten and molybdenum with sulfur, and then separate the thiomolybdate ions by utilizing a precipitation method, a solvent extraction method, an ion exchange method and the like according to the property difference of the tungstate ions and the thiomolybdate ions. The typical precipitation method comprises the steps of firstly adding a vulcanizing agent under a weak alkaline condition, vulcanizing molybdate to form a thiomolybdate radical according to the difference of thiophilic and oxyphilic properties of tungsten and molybdenum, not vulcanizing tungstate, and then regulating the tungsten and molybdenum to be acidic to decompose thiomolybdate to generate molybdenum trisulfide precipitate, so that tungsten and molybdenum separation is realized. CN 101565778A, 2009) and the like find that the thiomolybdate has strong selectivity on copper, when nascent copper sulfide is used as a precipitating agent, when the mass ratio of copper to molybdenum is 18 or 4, the molybdenum removal rate can reach more than 98 percent, and the effect is very good; research on the generation conditions of thiomolybdate ions in Gomper Van (Gomper Van, Huang Wei Zhuang sodium tungstate solution) [ J ] rare metals and hard alloys, 1987(Z1):44-48.) and the like adopt N263 quaternary ammonium salt extractant to extract thiomolybdate radicals, the separation coefficient of tungsten and molybdenum can reach more than 1000, and the separation effect is very good; chenzhou stream (Chenzhou stream, yellow peony, Zhoujiayi et al. ion exchange method for separating molybdenum from tungstate solution: CN1037882A, 1989.) et al use strong-base anion exchange resin to adsorb thiomolybdate radical, then use sodium chloride to leach, use sodium hypochlorite to desorb, finally the separation effect of tungsten and molybdenum is very good, and the operation is simple.
Although a great deal of research on tungsten and molybdenum separation has been carried out by many scholars, and some of the scholars also realize industrialization, the problems faced at present are that the grade of tungsten and molybdenum concentrate is gradually reduced, people also put forward more new requirements on metal materials, and mineral raw materials to be processed by many enterprises are more and more complex, for example, in the persimmon and bamboo garden mine which is a comprehensive polymetallic mine in China, m (Mo)/m (WO) in the tungsten concentrate produced by the scholars3) About 2 percent of tungsten middling produced by three channels of Hebei Koelreuteria paniculata, (Mo)/m (WO)3) Up to more than 5%. If conventional vulcanizing agents such as Na are used industrially2S and (NH)4)2S, etc. have the problems of high cost and toxic gas in the production processThe hydrogen sulfide is discharged, the production environment is deteriorated, the environment friendliness is poor, and a hydrogen sulfide gas recovery facility needs to be added; in the process of separating tungsten and molybdenum by adopting an ion exchange method, the sulfo-molybdate acid radical can not be desorbed from resin by using an alkali solution, the sulfo-molybdate acid radical needs to be desorbed by adding oxidants such as hydrogen peroxide, sodium hypochlorite and the like, the heat emitted in the oxidation process and the oxidants can influence the resin, the service life of the resin is shortened, and adverse effects are brought to the subsequent process.
Disclosure of Invention
Aiming at the defects of the method for realizing the separation of a small amount of molybdenum in tungstate solution by thiomolybdate ions in the prior art, the invention aims to provide the method for realizing the selective exchange separation of the Mo-S complex and the tungstate by using trithiocyanuric acid as a novel vulcanizing agent, selectively performing a vulcanization reaction on molybdate ions in the tungstate to generate a Mo-S complex and then using weak-base anion exchange resin.
In order to achieve the technical purpose, the invention provides a method for separating molybdenum in tungstate solution by an ion exchange method, which comprises the following steps:
1) adding trithiocyanuric acid into the molybdenum-containing tungstate solution to carry out a vulcanization reaction to obtain a thiomolybdate-containing tungstate solution;
2) carrying out ion exchange on a tungstate solution containing thiomolybdate by adopting weak-base anion exchange resin to adsorb the thiomolybdate, so as to obtain a tungstate solution;
3) desorbing the thiomolybdate loaded weak-base anion exchange resin by using an alkaline desorption solution to obtain a molybdate solution.
According to the technical scheme, trithiocyanuric acid is used as a selective vulcanizing agent for molybdenum in a molybdenum-containing tungstate solution, and the vulcanizing agent not only can release no hydrogen sulfide gas in the reaction process, almost completely eliminate the generation of hydrogen sulfide, remarkably improve the production environment, but also can selectively vulcanize trace molybdate in a large amount of tungstate solution. On the basis, further research on the technical scheme of the invention discovers that the difference of physical and chemical properties of thiomolybdate and tungstate generated by carrying out vulcanization reaction on cyanuric acid and molybdate is enlarged, particularly the selective adsorption performance of the thiomolybdate and the tungstate by weak base anion exchange resin is completely different, and the selective adsorption capacity of the thiomolybdate by the weak base anion exchange resin is far higher than that of the tungstate, so that adsorption separation of the thiomolybdate and the tungstate can be realized by adopting the weak base anion resin. Meanwhile, researches also find that the thiomolybdate generated by adopting the trithiocyanuric acid and the molybdate is easy to desorb from the anion exchange resin, and the enrichment and recovery of molybdenum are easy to realize. Common thiomolybdate in the tungstate solution can be adsorbed by strong-base anion exchange resin, but an oxidant is required to be added in the desorption process to desorb the thiomolybdate from the strong-base anion exchange resin, the oxidant can reduce the service life of the resin, and the desorption solution is difficult to treat. The thiomolybdate generated by the thiocyanic acid and the molybdate can be adsorbed by weak-base anion exchange resin, and can be directly desorbed by strong alkali solution such as sodium hydroxide solution and the like, so that the use of an oxidant is avoided, the process steps are simplified, and the cost is saved.
Preferably, the molybdenum in the molybdenum-containing tungstate solution exists in the form of molybdate ions, the concentration of the molybdenum is 0.5-5 g/L, the tungsten exists in the form of tungstate ions, and the concentration of the tungsten is WO3The amount is 80-200 g/L. The method is particularly suitable for separating molybdenum in the high-tungsten low-molybdenum solution, and cyanuric acid can be used for selectively sulfurizing molybdate in the high-tungsten low-molybdenum solution.
In the preferable scheme, the molar weight of the trithiocyanuric acid is 4-20 times of that of molybdenum in the molybdenum-containing tungstate solution.
In a preferred embodiment, the vulcanization reaction conditions are as follows: the temperature is 40-70 ℃, and the reaction time is 4-12 hours. Under the preferable conditions, the thioation rate of the molybdate reaches more than 99.5 percent.
In a preferable scheme, the pH value of the sulfuration reaction is controlled to be between 9 and 11 at the end point of the reaction. Preferably, the pH value of the reaction end point is controlled to be between 9.25 and 9.5. The pH value is controlled within a proper range so as to improve the adsorption efficiency of the subsequent weak-base anion exchange resin on molybdenum sulfide ions.
In a preferred embodiment, the preferred weakly basic anion exchange resin is a D363 resin and/or an HBDM-1 resin, more preferably an HBDM-1 resin. While general strongly basic anion exchange resins such as W294 and the like can adsorb molybdenum-sulfur complexes in tungstate solutions, oxidants need to be added in the desorption process, the heat release amount in the desorption process is large due to oxidation reaction, the service life of the resins is seriously affected, and the industrial production is not suitable.
In a preferable scheme, an ascending method is adopted in the ion exchange adsorption process, the length-diameter ratio of an ion exchange column is 10: 1-40: 1, the ratio of the volume of resin to the volume of the exchange column is 1: 1.5-1: 3, and the contact time of a feed liquid is 1-3 h.
Preferably, the desorption process adopts a downstream method, the length-diameter ratio of the ion exchange column is 10: 1-40: 1, the ratio of the volume of the resin to the volume of the exchange column is 1: 1.5-1: 3, and the contact time of the alkaline desorption liquid is 1-3 h.
In a more preferable scheme, the alkaline desorption solution is NaOH solution with the concentration ranging from 1mol/L to 3 mol/L.
Preferably, the molybdate comprises an alkali metal molybdate and/or an ammonium molybdate.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
compared with the vulcanizing agent in the prior art, the technical scheme of the invention has obvious advantages by taking the trithiocyanuric acid as the vulcanizing agent, mainly shows that the trithiocyanuric acid is solid under the normal condition, is very safe and convenient for transportation, storage and metering, is safe and nontoxic, does not release harmful gas, and does not need a hydrogen sulfide gas recovery facility; and has good effect on the selective thioation reaction of molybdate in the tungstate solution containing molybdenum.
According to the technical scheme, the thiomolybdate and the tungstate obtained after the thiocyanic acid and the molybdate are subjected to a vulcanization reaction have large differences in physical and chemical properties, and the selective adsorption performance of the thiomolybdate on the weak-base anion exchange resin is far higher than that of the tungstate, so that adsorption separation of the thiomolybdate and the tungstate can be realized by using the weak-base anion resin.
According to the technical scheme, the trimeric thiocyanic acid is used as a vulcanizing agent, the Mo-S complex generated by the trimeric thiocyanic acid and molybdate radicals can be easily desorbed by adopting macroporous weakly alkaline anion resin after adsorption, only an alkaline solution is needed, an oxidant is not needed to be added into a desorption solution, the desorption process is easy, the desorption and separation effects are good, and a high-purity molybdate solution can be obtained.
Drawings
FIG. 1 is a graph showing the elution of molybdenum-sulfur complex from tungstate solution.
FIG. 2 is a desorption curve for desorption of molybdenum-sulfur complexes using sodium hydroxide.
FIGS. 3 and 4 are graphs showing the elution of the adsorbed molybdenum-sulfur complex at different times in example 6.
FIG. 5 is a desorption curve of HBDM-1 resin for dynamic separation of tungsten and molybdenum.
FIGS. 6 and 7 are graphs showing the elution of the adsorbed molybdenum-sulfur complex at different times in example 8.
FIG. 8 is a desorption curve of dynamic separation of tungsten and molybdenum from D363 resin.
FIG. 9 is a schematic process flow diagram of the principle of the present invention for ion exchange separation of small amounts of molybdenum from tungstate solutions.
Detailed Description
The following examples are intended to illustrate the invention but not to further limit it.
Example 1
The feed liquid is a prepared molybdenum-containing ammonium tungstate solution, which is pre-vulcanized by a vulcanizing agent under the vulcanizing conditions that: preparation of 5L of WO-containing3100g/L, Mo1g/L of simulated feed liquid, and 148g of trithiocyanuric acid as a vulcanizing agent. The vulcanization temperature is 70 ℃, and the pH value of the feed liquid is adjusted to 9.5 after the material liquid is subjected to the thionization. The thionation rate is 99.5 percent by adopting an extraction method. Taking 20ml feed liquid and 5ml HBDM-1 resin in a beaker each time, adsorbing for 1 hr at normal temperatureIn the process, the adsorption result shows that the adsorption rate of tungsten and molybdenum is greatly changed along with the pH, when the pH is 9.25-9.5, the adsorption rate of molybdenum reaches the maximum and reaches 78.79%, and the adsorption rate of tungsten is increased along with the reduction of the pH. Calculation shows that the separation coefficient of tungsten and molybdenum can reach 3.28 when the pH is within the range of 9.25-9.5, namely the tungsten and molybdenum separation effect is the best.
Example 2
The feed liquid is the ammonium tungstate solution containing molybdenum after the thioation prepared in the example 1, 20ml of the feed liquid is taken each time, 5ml of HBDM-1 resin is put in a beaker for adsorption for 1 hour, and the adsorption temperature is controlled to be between the normal temperature (25 ℃) and 60 ℃. The experimental result shows that the adsorption rate of tungsten and molybdenum continuously rises along with the rise of temperature, the separation coefficient is continuously increased by calculation, the adsorption rates of tungsten and molybdenum are respectively 27.19% and 60.63% at normal temperature, and the separation requirement of tungsten and molybdenum is met at normal temperature by considering the actual economic factors and the experimental result.
Example 3
The feed liquid is the ammonium tungstate solution containing molybdenum after the thioation prepared in example 1, 20ml of the feed liquid and 5ml of HBDM-1 resin are taken each time, and the adsorption time is 5 min-2 h at normal temperature, and the results show that the adsorption rate of tungsten and molybdenum is continuously increased along with the extension of the adsorption time, and the separation coefficient is continuously increased by calculation, which indicates that the longer the adsorption time is, the better the separation effect of tungsten and molybdenum is. The adsorption rate of tungsten and molybdenum after 2 hours is implicitly stable and reaches an equilibrium state.
Example 4
The feed liquid is the vulcanized ammonium tungstate solution containing molybdenum prepared in example 1, the adsorption capacity of the resin is measured by adsorbing fresh feed liquid for multiple times, 5ml of HBDM-1 resin and 20ml of D363 resin are respectively measured and added into the two resins, the resin is filtered out after adsorbing for 1 hour at normal temperature, and fresh feed liquid is added, and the experimental result shows that part of tungsten is desorbed from the resin after the HBDM-1 resin is removed from the resin for the third time; the molybdenum adsorbed by the resin gradually reaches the equilibrium at about 0.3g/L from the fifth time; while the equilibrium of adsorption of molybdenum from the D363 resin after the third time is reached, it is clear that the exchange capacity of the D363 resin is not as good as that of the HBDM-1 resin.
Example 5
NaOH is used for desorption, and the concentration of NaOH is controlled to be 0mol/L, 0.5mol/L, 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L and 3 mol/L. Firstly, 35ml of HBDM-1 resin and 140ml of feed liquid are measured, the resin is filtered after being adsorbed for 1 hour at normal temperature, the resin is divided into 7 groups after being cleaned by pure water, alkali with corresponding concentration is added, and each group is desorbed for 1 hour at normal temperature. The concentration of the feed liquid is as follows: 100g/L of tungsten trioxide and 1g/L of molybdenum. The concentration of the post-hybridization solution is as follows: 51.86g/L tungsten trioxide, 0.4184g/L molybdenum, the results are shown in Table 1.
TABLE 1 relationship between desorption solution concentration and desorption effluent tungsten-molybdenum content
As can be seen from Table 1, as the desorption effect of molybdenum becomes better and better with the increase of the NaOH concentration, the point with the best desorption effect of molybdenum is selected, and the desorption solution concentration is selected to be 2mol/L by comprehensively considering economic factors and actual conditions.
Example 6
The pre-cross liquid was the thiolated molybdenum-containing tungstate solution prepared in example 1, the column was packed with 30ml of HBDM-1 resin, the column was phi 15mm × 450mm, the experiment was performed in such a manner that the pre-cross liquid flowed in from the lower end of the column and the post-cross liquid flowed out from the upper end, the flow rate of the feed liquid was controlled at 15ml/h, the post-cross liquid was collected using an automatic collector, and the concentration of tungsten trioxide and molybdenum in the post-cross liquid was measured every hour. The outflow curves are shown in fig. 3 and 4, and fig. 3 is WO in post-crossing fluid3Concentration, Mo concentration and WO in pre-cross fluid3The relation curve of the ratio of the concentration to the Mo concentration and the time, and FIG. 4 is the WO in the post-crosslinking liquid3Concentration, Mo concentration and time.
FIGS. 3 and 4 show that at a feed pH of 9.13, the molybdenum concentration in the post-crosslinking solution exceeded 2ppm at hour 46, i.e., the molybdenum reached the breakthrough point at 690ml of effluent, at which time the resin had adsorbed all of the molybdenum in the feed solution 23 times the volume of the resin. After 32 hours, the adsorption of tungsten reached equilibrium and the resin no longer adsorbed tungsten, and after 144 hours the adsorption of molybdenum by the resin also reached equilibrium.
Example 7
The saturated HBDM-1 resin in example 6 was desorbed, 2mol/L NaOH solution was selected as the desorption solution, pure water was first fed from the upper end of the column and discharged from the lower end of the column to wash the HBDM-1 resin until the wash solution was colorless, the former diluted solution was fed from the upper end of the column and discharged from the lower end of the column, the discharge rate of the desorption effluent was controlled at 15ml/h, the concentration of tungsten trioxide and molybdenum in the effluent was measured per hour, and the desorption curve was plotted as shown in FIG. 5.
As can be seen from the graph, the tungsten concentration decreased all the way from the start of desorption, molybdenum peaked in 4 hours, the maximum concentration of molybdenum in the effluent was 32.075g/L, the average concentration was 6.05g/L, and the resin was considered to be complete after 13 hours. Thus indicating that the HBDM-1 resin can well separate tungsten and molybdenum.
Example 8
The pre-crosslinking solution is the thiolated molybdenum-containing tungstate solution prepared in example 1, 30ml of D363 resin is filled into an exchange column, phi 15mm is multiplied by 450mm, an up-flow method is adopted for experiment, the outflow speed of post-crosslinking solution is controlled to be 15ml/h, the post-crosslinking solution is collected by an automatic collector, and the concentration of tungsten trioxide and molybdenum in the post-crosslinking solution is measured every hour. The outflow curves are shown in FIGS. 6 and 7, and FIG. 6 shows WO in the post-crossing fluid3Concentration, Mo concentration and WO in pre-cross fluid3The relation curve of the ratio of the concentration to the Mo concentration and the time, and FIG. 7 is the WO in the post-crosslinking liquid3Concentration, Mo concentration and time.
As can be seen from the figure, when the pH of the feed liquid is 9.25, the concentration of molybdenum in the liquid after the cross-linking reaches the point of leakage at the 8 th hour, the resin adsorbs all molybdenum in the feed liquid with the volume 4 times that of the resin during the leakage, the tungsten adsorbed by the resin reaches the equilibrium after the 26 th hour, and the molybdenum adsorbed by the resin reaches the equilibrium after the 78 th hour
Example 9
Desorbing the saturated D363 resin in the example 8, selecting 2mol/L NaOH solution as desorption solution, firstly using pure water to flow in from the upper end of the exchange column, flowing out from the lower end of the exchange column to wash the D363 resin until the washing solution is colorless, then using the former dilute solution to flow in from the upper end of the exchange column, flowing out from the lower end of the exchange column, controlling the outflow speed of desorption effluent to be 15ml/h, using an automatic collector to collect the desorption effluent, and measuring the concentration of tungsten trioxide and molybdenum in the effluent every hour. The desorption curve is plotted as shown in fig. 8.
As can be seen from FIG. 8, the tungsten concentration decreased from the start of desorption until the molybdenum concentration reached a peak at 4 hours, and the maximum concentration of molybdenum in the desorption effluent was 8.4g/L and the average concentration was 1.78 g/L. After 18 hours the resin can already be considered as complete.
Claims (6)
1. A method for separating molybdenum in tungstate solution by an ion exchange method is characterized in that: the method comprises the following steps:
1) adding trithiocyanuric acid into the molybdenum-containing tungstate solution to carry out a vulcanization reaction to obtain a thiomolybdate-containing tungstate solution; controlling the pH value of the reaction end point to be 9.25-9.5 in the vulcanization reaction;
2) carrying out ion exchange on a tungstate solution containing thiomolybdate by adopting weak-base anion exchange resin to adsorb the thiomolybdate, so as to obtain a tungstate solution; the weak base anion exchange resin is D363 resin and/or HBDM-1 resin; the ion exchange adsorption process adopts an ascending method, the length-diameter ratio of an ion exchange column is 10: 1-40: 1, the ratio of the volume of resin to the volume of the exchange column is 1: 1.5-1: 3, and the contact time of a feed liquid is 1-3 h;
3) desorbing the thiomolybdate loaded weak-base anion exchange resin by using an alkaline desorption solution to obtain a molybdate solution.
2. The method for separating molybdenum in tungstate solution by ion exchange method as claimed in claim 1, wherein: molybdenum exists in the molybdenum-containing tungstate solution in the form of molybdate ions, the concentration of the molybdenum is 0.5-5 g/L, tungsten exists in the form of tungstate ions, and the concentration of the tungsten is WO3The amount is 80-200 g/L.
3. The method for separating molybdenum in tungstate solution by ion exchange method as claimed in claim 1, wherein: the molar weight of the trithiocyanuric acid is 4-20 times of that of molybdenum in the molybdenum-containing tungstate solution.
4. The method for separating molybdenum in tungstate solution by ion exchange method as claimed in claim 1, wherein: the conditions of the sulfurization reaction are as follows: the temperature is 40-70 ℃, and the reaction time is 4-12 hours.
5. The method for separating molybdenum in tungstate solution by ion exchange method as claimed in claim 1, wherein: the desorption process adopts a downstream method, the length-diameter ratio of an ion exchange column is 10: 1-40: 1, the ratio of the volume of resin to the volume of the exchange column is 1: 1.5-1: 3, and the contact time of alkaline desorption liquid is 1-3 h.
6. The method for separating molybdenum in tungstate solution by using ion exchange method as claimed in claim 5, wherein: the alkaline desorption solution is NaOH solution with the concentration ranging from 1mol/L to 3 mol/L.
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| CN111057849B (en) * | 2019-12-16 | 2021-09-28 | 北京工业大学 | Method for removing molybdenum in tungstate by ion exchange adsorption |
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