CN109777948B - Technological method for extracting rubidium by flash cycle leaching of silicate - Google Patents
Technological method for extracting rubidium by flash cycle leaching of silicate Download PDFInfo
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Abstract
The invention discloses a process method for extracting rubidium by flash cycle leaching of silicate, which is characterized in that solid ore raw materials are roasted and then subjected to flash cycle leaching-rapid dehydration process, so that the leaching rate of rubidium and the content concentration of rubidium are effectively improved; and in the subsequent extraction process, the extraction efficiency is improved and the loss rate is reduced, so that the technical index of rubidium is obviously improved, and the waste of mineral resources is effectively reduced. The process method has simple treatment flow and low production cost, and is favorable for popularization and application.
Description
Technical Field
The invention relates to the technical field of mineral treatment, in particular to a process method for extracting rubidium by silicate leaching.
Background
Rubidium metal is an extremely active and highly dispersed rare alkali metal, and has wide application in the fields of space technology, electronic industry, bioengineering, material science and the like. To date, no single industrially valuable mineral of rubidium has been found, with rubidium being associated mainly in caesium lepidolite, pollucite, natural carnallite, potash ore seawater and salt lake brine. In recent years, a large amount of rubidium-containing silicate minerals are discovered, and currently, in the prior art, rubidium is mainly extracted from solid silicate, but the technical process is complicated, the loss rate of rubidium is high, and serious waste is caused to mineral resources. Therefore, how to optimize the leaching and extracting technology of rubidium is a technical problem which needs to be urgently solved at present.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a process method for extracting rubidium by flash cycle leaching of silicate, wherein the process method for extracting rubidium by leaching of solid silicate is optimized, the leaching rate of rubidium and the concentration of rubidium in a leaching solution are obviously improved and the loss rate of rubidium is greatly reduced while the treatment process is simplified, so that the quality index of a rubidium product is obviously improved, and the waste of mineral resources is effectively reduced.
The purpose of the invention is realized by the following technical scheme:
the invention provides a process method for extracting rubidium by flash cycle leaching of silicate, which comprises the following steps:
(1) preparation of extract stock solution
(1-1) adding calcium chloride into a silicate ore raw material to perform chloridizing roasting to obtain roasting slag and generate chlorine; the chlorine enters a chlorine absorption tower for treatment;
(1-2) adding water into the roasting slag to carry out flash cycle leaching and dehydration to obtain a leaching solution and leaching slag; wherein the leaching time of each time is less than 5min, the recycling frequency of the leaching solution is more than 8 times, 85-90% of leaching residues are dehydrated by screening, and the rest 10-15% of the leaching residues are dehydrated by filter pressing;
(1-3) adding sodium carbonate into the leachate to perform precipitation reaction, and filtering to obtain filtrate and calcium carbonate precipitate; calcining and decomposing the calcium carbonate precipitate to generate carbon dioxide and calcium oxide; the carbon dioxide is returned to the precipitation reaction of the leachate and sodium carbonate, and the calcium oxide enters the chlorine absorption tower in the step (1-1) to form calcium chloride and is returned to the roasting operation;
(1-4) evaporating and concentrating the filtrate until the concentration ratio is 1/7-1/10 to improve the rubidium concentration to obtain a concentrated solution, salting out potassium chloride, sodium chloride and distilled water;
(1-5) adding sodium hydroxide into the concentrated solution for preparation, wherein the using amount of the sodium hydroxide is 30-40 g/L of the concentrated solution, and obtaining an extraction stock solution;
(2) preparation of rubidium chloride product
(2-1) adding t-BAMBP + dimethylbenzene into the extraction stock solution to be used as an extracting agent for extraction, so as to obtain an organic phase and raffinate; the raffinate enters the leaching operation of the step (1-2);
(2-2) washing the organic phase by using sodium hydroxide with the concentration of 1.5N, and finishing washing when the washing liquid is changed from black to yellow to colorless; the washing liquid enters the leaching operation in the step (1-2);
(2-3) adding hydrochloric acid with the concentration of 4N into the washed organic phase for back extraction to obtain a back extraction solution and a regenerated organic phase; evaporating and concentrating the strip liquor to obtain concentrated reaction liquor, and introducing the regenerated organic phase into the extraction operation in the step (2-1);
(2-4) adding tin tetrachloride pentahydrate into the concentrated reaction solution for precipitation reaction, and filtering to obtain rubidium stannate chloride and a precipitation mother solution;
(2-5) washing the rubidium chlorostannate by using a solution formed by adding hydrochloric acid and tin salt into water as a washing solution; carrying out evaporative crystallization and volatile stannic chloride treatment on the washed washing liquid and the precipitation mother liquor in the step (2-4) in sequence to obtain potassium chloride, sodium chloride and volatile stannic chloride; wherein, the potassium chloride and the sodium chloride enter the roasting operation of the step (1-1), and the volatile tin chloride enters the adsorption operation of the adsorption bottle of the step (2-6);
(2-6) calcining and decomposing the washed rubidium chlorostannate to obtain a rubidium chloride product; the produced tin tetrachloride gas is adsorbed by an adsorption bottle.
Further, in the step (1-1) of the invention, the chloridizing roasting temperature is 860-980 ℃. And (3) adding water into the roasting slag and the water in the weight ratio of 1: 8-12 in the step (1-2) to carry out flash cycle leaching and dehydration, wherein the leaching time is 3-5 min each time, and the cycle use frequency of the leaching solution is 8-15 times. The leaching rate is more than 85 percent after the treatment of the step (1-2). The concentration of t-BAMBP in the extracting agent in the step (2-1) is 1.0 mol/L; the extraction is performed with a ratio of 1-3. And (4) evaporating and concentrating the strip liquor in the step (2-3) until the acidity is 6-8N. The concentrations of hydrochloric acid and tin salt in the washing solution in the step (2-5) are respectively 4N and 0.1N; the dosage of the washing solution is 8-15 mL/g.Rb/time, and the washing times are 2-5 times. The calcining decomposition temperature of the rubidium chlorostannate washed in the step (2-6) is 650-720 ℃.
The invention has the following beneficial effects:
(1) the invention optimizes the technical process for extracting rubidium from solid silicate, adopts flash cycle leaching-rapid dehydration treatment, ensures that the roasting slag has coarse granularity after flash leaching, can realize rapid filtration and dehydration, and has little loss of rubidium in the leaching slag. Therefore, the process is simple, the treatment time is greatly shortened (more than 3 hours is needed for leaching and dewatering in the prior art), high rubidium leaching rate (leaching rate is more than 85%) is guaranteed through multiple times of circulating leaching, the concentration of rubidium in the leaching solution is effectively improved, the cost is saved for subsequent extraction work, the subsequent extraction efficiency, the treatment of byproducts and the quality index of rubidium products are guaranteed.
(2) In the preparation stage of the extraction stock solution, calcium carbonate as a byproduct is calcined to decompose calcium oxide and flue gas CO2. The calcium oxide as an adsorbent enters a chlorine adsorption tower to adsorb chlorine, and the formed calcium chloride is used as a chlorinating agent for the roasting operation; the latter flue gas CO2The obtained product enters the precipitation reaction of leachate and sodium carbonate for solution purification, thereby realizing double linkage of environmental protection and comprehensive utilization.
(3) In the preparation stage of the rubidium chloride product, the organic phase is washed by 1.5N sodium hydroxide solution, so that non-ferrous metal ions in the organic phase can be completely removed by washing, and the washing loss rate of the rubidium is less than 10% (in the prior art, the washing loss rate of the rubidium is more than 35% by washing with distilled water). In addition, the rubidium chlorostannate is washed for removing coprecipitated potassium chlorostannate and sodium chlorostannate, but the washing loss rate of the rubidium is high (the washing loss rate is more than 30%) by using distilled water in the prior art, but the potassium chlorostannate and the sodium chlorostannate can be completely washed and removed by using a 4N hydrochloric acid 0.1N tin salt solution as a washing liquid, and the washing loss rate of the rubidium chlorostannate can be controlled to be 0.15%. The subsequent washing treatment process of the invention also provides further guarantee for improving the recovery rate of rubidium.
(4) According to the invention, through optimizing the rubidium leaching and extracting technology, the technical index of rubidium is obviously improved, so that the waste of mineral resources is effectively reduced. And the treatment process is simple, the production cost is low, and the method is favorable for popularization and application.
Drawings
The invention will now be described in further detail with reference to the following examples and the accompanying drawings:
FIG. 1 is a flow chart of a process for preparing an extraction stock solution in a process for extracting rubidium by flash cycle leaching of silicate according to an embodiment of the invention;
FIG. 2 is a flow chart of a process for preparing a rubidium chloride product in the process for extracting rubidium by flash cycle leaching of silicate according to the embodiment of the invention.
Detailed Description
In the embodiment of the invention, mica and a mixture of mica and feldspar are respectively used as ore raw materials, and Rb of the ore raw materials is Rb2O3The content is 0.08-1.2% (see table 1).
As shown in fig. 1 and fig. 2, a process method for extracting rubidium by flash cycle leaching of silicate according to an embodiment of the present invention includes the following steps:
(1) preparation of extract stock solution
(1-1) adding calcium chloride into a silicate ore raw material to perform chloridizing roasting at the temperature of 900 ℃, wherein the dosage of the calcium chloride is 70 wt% of the silicate ore raw material, the roasting time is 90min, so as to obtain roasting slag and generate chlorine; wherein, chlorine enters a chlorine absorption tower for treatment;
(1-2) adding water into the roasted residues according to the weight ratio of the roasted residues to the water of 1: 10 to carry out flash cycle leaching and dehydration to obtain a leaching solution and leaching residues; wherein, the leaching time of each time is 4min, the recycling frequency of the leaching solution is 10 times, 87 percent of leaching residues are dehydrated by screening, and the rest 13 percent of leaching residues are dehydrated by filter pressing; the leaching rate of each example is shown in table 1.
(1-3) adding sodium carbonate into the leachate to perform precipitation reaction, and filtering to obtain filtrate and calcium carbonate precipitate; calcining the calcium carbonate precipitate to decompose the calcium carbonate precipitate to generate carbon dioxide and calcium oxide, wherein the carbon dioxide is returned to the precipitation reaction of the leachate and sodium carbonate for solution purification, and the calcium oxide enters the chlorine absorption tower in the step (1-1) to be used as an adsorbent to adsorb chlorine so as to form calcium chloride and is returned to the calcining operation;
(1-4) evaporating and concentrating the filtrate until the concentration ratio is 1/8 to increase the rubidium concentration to obtain a concentrated solution, salting out potassium chloride, sodium chloride and distilled water;
(1-5) adding sodium hydroxide into the concentrated solution for preparation, wherein the dosage of the sodium hydroxide is 35g/L of the concentrated solution, and obtaining an extraction stock solution;
(2) preparation of rubidium chloride product
(2-1) adding t-BAMBP + xylene into the extraction stock solution to serve as an extracting agent (the concentration of the t-BAMBP in the extracting agent is 1.0mol/L) for extraction, and comparing with O/A (2), so as to obtain an organic phase and raffinate; the raffinate enters the leaching operation of the step (1-2);
(2-2) washing the organic phase by using sodium hydroxide with the concentration of 1.5N, and finishing washing when the washing liquid is changed from black to yellow to colorless; the washing liquid enters the leaching operation in the step (1-2);
(2-3) adding hydrochloric acid with the concentration of 4N into the washed organic phase according to the ratio of O/A to 10 for back extraction to obtain a back extraction solution and a regenerated organic phase; evaporating and concentrating the strip liquor until the acidity is 6-8N to obtain concentrated reaction liquor, and introducing a regenerated organic phase into the extraction operation in the step (2-1);
(2-4) adding tin tetrachloride pentahydrate into the concentrated reaction solution for precipitation reaction, and filtering to obtain rubidium stannate chloride and a precipitation mother solution;
(2-5) washing the rubidium chlorostannate by using a solution formed by adding hydrochloric acid and tin salt into water as a washing solution (the concentrations of the hydrochloric acid and the tin salt in the washing solution are respectively 4N and 0.1N), wherein the dosage of the washing solution is 10 mL/g.Rb/time, and the washing times are 3 times; carrying out evaporative crystallization and volatile stannic chloride treatment on the washed washing liquid and the precipitation mother liquor in the step (2-4) in sequence to obtain potassium chloride, sodium chloride and volatile stannic chloride; wherein, potassium chloride and sodium chloride enter the roasting operation of the step (1-1), and volatile tin chloride enters the adsorption operation of the adsorption bottle of the step (2-6);
(2-6) calcining and decomposing the washed rubidium chlorostannate at 680 ℃ to obtain a rubidium chloride product; the produced tin tetrachloride gas is adsorbed by an adsorption bottle.
Table 1 ore feed, Rb for each example of the invention2O3Technical indexes of content and leaching rate
| Examples | Ore feedstock | Rb2O3Content% | The leaching rate is% |
| Example one | Mica 15% + feldspar 85% | 0.082 | 86 |
| Example two | Mica of 100% | 0.51 | 93 |
| EXAMPLE III | Mica 80% + feldspar 20% | 1.20 | 95 |
The RbCl content of the rubidium chloride product prepared by the embodiment of the invention reaches more than 99.5% (see table 2), and the quality of the rubidium chloride product meets the quality standard (Q/TJTE 17-2004) of rubidium chloride industrial products. The leached slag meets the quality requirement of concrete consolidation waterproofing agent. The salted-out sodium chloride and potassium chloride meet the quality requirements of respective products after flotation separation.
TABLE 2 main chemical composition (%)
| Item | RbCl | Al | Fe | K | Na |
| Content (wt.) | 99.64 | 0.00082 | 0.0002 | 0.0477 | 0.0091 |
| Item | Li | Cs | Mg | Ca | Pb |
| Content (wt.) | 0.0081 | 0.1801 | 0.00070 | 0.00470 | 0.00036 |
Claims (5)
1. A process method for extracting rubidium by flash cycle leaching of silicate is characterized by comprising the following steps:
(1) preparation of extract stock solution
(1-1) adding calcium chloride into a silicate ore raw material, and performing chloridizing roasting at the temperature of 860-980 ℃ to obtain roasting slag and generate chlorine; the chlorine enters a chlorine absorption tower for treatment;
(1-2) adding water into the roasted slag according to the weight ratio of the roasted slag to the water of 1: 8-12 to perform flash cycle leaching and dehydration to obtain a leaching solution and leached slag; wherein the leaching time of each time is 3-5 min, the recycling time of the leaching solution is 8-15 times, 85-90% of leaching residues are dehydrated by screening, the rest 10-15% of the leaching residues are dehydrated by filter pressing, and the leaching rate is more than 85%;
(1-3) adding sodium carbonate into the leachate to perform precipitation reaction, and filtering to obtain filtrate and calcium carbonate precipitate; calcining and decomposing the calcium carbonate precipitate to generate carbon dioxide and calcium oxide; the carbon dioxide is returned to the precipitation reaction of the leachate and sodium carbonate, and the calcium oxide enters the chlorine absorption tower in the step (1-1) to form calcium chloride and is returned to the roasting operation;
(1-4) evaporating and concentrating the filtrate until the concentration ratio is 1/7-1/10 to improve the rubidium concentration to obtain a concentrated solution, salting out potassium chloride, sodium chloride and distilled water;
(1-5) adding sodium hydroxide into the concentrated solution for preparation, wherein the using amount of the sodium hydroxide is 30-40 g/L of the concentrated solution, and obtaining an extraction stock solution;
(2) preparation of rubidium chloride product
(2-1) adding t-BAMBP + dimethylbenzene into the extraction stock solution to be used as an extracting agent for extraction, so as to obtain an organic phase and raffinate; the raffinate enters the leaching operation of the step (1-2);
(2-2) washing the organic phase by using sodium hydroxide with the concentration of 1.5N, and finishing washing when the washing liquid is changed from black to yellow to colorless; the washing liquid enters the leaching operation in the step (1-2);
(2-3) adding hydrochloric acid with the concentration of 4N into the washed organic phase for back extraction to obtain a back extraction solution and a regenerated organic phase; evaporating and concentrating the strip liquor to obtain concentrated reaction liquor, and introducing the regenerated organic phase into the extraction operation in the step (2-1);
(2-4) adding tin tetrachloride pentahydrate into the concentrated reaction solution for precipitation reaction, and filtering to obtain rubidium stannate chloride and a precipitation mother solution;
(2-5) washing the rubidium chlorostannate by using a solution formed by adding hydrochloric acid and tin salt into water as a washing solution; carrying out evaporative crystallization and volatile stannic chloride treatment on the washed washing liquid and the precipitation mother liquor in the step (2-4) in sequence to obtain potassium chloride, sodium chloride and volatile stannic chloride; wherein, the potassium chloride and the sodium chloride enter the roasting operation of the step (1-1), and the volatile tin chloride enters the adsorption operation of the adsorption bottle of the step (2-6);
(2-6) calcining and decomposing the washed rubidium chlorostannate to obtain a rubidium chloride product; the produced tin tetrachloride gas is adsorbed by an adsorption bottle.
2. The process method for extracting rubidium by silicate flash cycle leaching according to claim 1, is characterized in that: the concentration of t-BAMBP in the extracting agent in the step (2-1) is 1.0 mol/L; the extraction is performed with a ratio of 1-3.
3. The process method for extracting rubidium by silicate flash cycle leaching according to claim 1, is characterized in that: and (4) evaporating and concentrating the strip liquor in the step (2-3) until the acidity is 6-8N.
4. The process method for extracting rubidium by silicate flash cycle leaching according to claim 1, is characterized in that: the concentrations of hydrochloric acid and tin salt in the washing solution in the step (2-5) are respectively 4N and 0.1N; the dosage of the washing solution is 8-15 mL/g.Rb/time, and the washing times are 2-5 times.
5. The process method for extracting rubidium by silicate flash cycle leaching according to claim 1, is characterized in that: the calcining decomposition temperature of the rubidium chlorostannate washed in the step (2-6) is 650-720 ℃.
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