CN107991378B - Method for separating boron from gypsum mineral and/or anhydrite mineral and method for measuring boron isotope - Google Patents
Method for separating boron from gypsum mineral and/or anhydrite mineral and method for measuring boron isotope Download PDFInfo
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Abstract
The invention relates to the technical field of ore element separation and determination, in particular to a method for separating boron from gypsum mineral and/or anhydrite mineral and a method for determining boron isotope. The separation method comprises the following steps: reaction: taking a gypsum mineral and/or anhydrite mineral sample, adding ammonium bicarbonate and de-boric ion water into the gypsum mineral sample for reaction to obtain a first supernatant and a precipitate after the reaction, adding hydrochloric acid into the precipitate for reaction, and obtaining a second supernatant after the precipitate is completely decomposed; separation: b, enriching the first supernatant through a boron-specific resin exchange column, adjusting the pH of the second supernatant to be alkaline, and then enriching the second supernatant through the boron-specific resin exchange column; leaching the boron-enriched special-effect resin exchange column to obtain boron-containing leacheate; and (3) passing the boron-containing leacheate with the boron content of not less than 1 mu g/g through an anion-cation mixed resin exchange column to obtain a neutral boron-containing solution. The method can extract boron from insoluble minerals, and almost no boron isotope fractionation occurs.
Description
Technical Field
The invention relates to the technical field of ore element separation and determination, in particular to a method for separating boron from gypsum mineral and/or anhydrite mineral and a method for determining boron isotope.
Background
The evaporite is a mineral sequence combination of evaporation and precipitation of water bodies such as sea and lake water and the like, comprises carbonate, sulfate and chloride type salt minerals, is an important raw material for human production and life, and is a good carrier for researching environmental change. The scale of the deposition of the evaporite, the economic value and the reflected environmental information are mainly controlled by the source of diagenetic substances and the evolution process thereof, so that the source and the evolution history of the evaporite can be effectively traced and inverted according to the composition characteristics of elements and isotopes in the minerals of the evaporite.
Boron is used as an easily soluble element and is mainly distributed in water bodies such as oceans, lakes and the like and various rocks, and along with evaporation and crystallization of the water bodies, the boron is added into evaporated rock minerals in different forms. Boron has11B and10b is a good tracer of the source of the substance, because the relatively large mass difference of the isotopes results in a wide variation range (-70% o to + 75% o) in different plastids. For example, researchers have studied the presence of boron in the salt of the khaki salt lake and its isotopic distribution characteristics (-0.35% to + 5.84%), with results indicating significant land-phase deposition characteristics; other scientists judge the ore phase deposition by studying the boron isotope composition characteristics (+19.91 ‰ - +31.01 ‰) of the salt of the careless basin and the borate minerals. Therefore, the boron isotope has important application value in the geological significance of the evaporite. But there are deficiencies in that the composition of the boron sulfate isotope in the evaporite sequence has been poorly studied.
Sulfate is an important component of evaporite and is characterized by its production in various geological times, in which gypsum (CaSO) is used4·2H2O) and anhydrite (CaSO)4) The method is mainly used, gypsum is crystallized when one liter of seawater is evaporated, meanwhile, component information of brine mother liquor is contained in the gypsum deposition process, the method is a good carrier for inverting brine evolution, and by researching boron isotope composition and fractionation mechanism of salt minerals, the mineralization rules of different evaporation rock deposits and ancient climate and ancient environment reconstruction can be revealed. Therefore, the research on the composition characteristics, occurrence state and geological application prospect of the boron isotope in the sulfate has important significance.
The general evaporite can be dissolved by using the boron-removing ionized water or the dilute hydrochloric acid, and then the subsequent treatment is carried out. However, unlike the above evaporite minerals, gypsum and/or anhydrite minerals are hardly soluble in water and have a solubility of less than 10mg/mL, 8 in hydrochloric acid (1mol/L to 2mol/L) at 25 ℃The solubility in 0 ℃ hydrochloric acid (1-2.28 mol/L) is 31.67mg/mL at the maximum, and the gypsum solubility is reduced as the hydrochloric acid concentration increases. While boron is likely to be BCl in concentrated hydrochloric acid3The higher the evaporation temperature, the more pronounced the evaporation. Before mass spectrometry, the boron solution should generally not be concentrated by evaporation after addition of mannitol to a temperature of more than 70 ℃. Therefore, 100mL to 200mL of hydrochloric acid (1mol/L) is required for completely decomposing 1g to 2g of gypsum and/or anhydrite samples, which increases the subsequent boron ion extraction and separation steps, causes cumulative loss of boron content, and if the samples are not completely decomposed, causes the boron content to be too low to meet the test requirements, or the crystal surfaces of the samples are corroded and crystal lattices are not completely decomposed, thereby seriously affecting the recovery rate of boron, even causing boron isotope fractionation. The dissolution of the sample with nitric acid will seriously interfere with the mass spectrometric determination of the boron isotope, so that11B/10The B ratio is lower. Therefore, the general acidolysis evaporite sample method can not effectively dissolve gypsum and/or anhydrite minerals to separate and extract boron in the gypsum and/or anhydrite minerals, or can cause great influence on the recovery rate of subsequent boron, boron isotope fractionation, boron isotope mass spectrometry and the like, and is not beneficial to analysis and application of boron isotope composition characteristics.
Based on the above analysis, it is necessary to adopt a new method for separating and extracting boron and measuring boron isotope in gypsum mineral and/or anhydrite mineral to solve the above problems.
Disclosure of Invention
In order to overcome the defects of the prior art, the inventor conducts diligent research, and finishes the invention after paying a great deal of creative labor and carrying out deep experimental exploration.
In a first aspect, the present invention provides a method of separating boron from a gypsum mineral and/or anhydrite mineral, comprising the steps of:
reaction: taking a gypsum mineral and/or anhydrite mineral sample, adding ammonium bicarbonate and water with boron ions removed into the gypsum mineral sample for reaction, and obtaining a first supernatant and a precipitate after the reaction; adding hydrochloric acid into the precipitate for reaction, and obtaining a second supernatant after the precipitate is completely decomposed;
separation: enriching boron of the first supernatant through a boron-specific resin exchange column, adjusting the pH of the second supernatant to be alkaline, and then enriching boron of the second supernatant through the boron-specific resin exchange column; leaching the boron-enriched special-effect resin exchange column to obtain boron-containing leacheate; and (3) passing the boron-containing leacheate with the boron content of more than or equal to 1 microgram/gram through an anion-cation mixed resin exchange column to obtain a neutral boron-containing solution.
Wherein Amberlite IRA 743 is adopted as the boron specific resin exchange column; the anion and cation mixed resin Exchange column adopts Ion Exchange II and Dowex50 WX 8.
Further, the reaction steps are: taking 1g of gypsum mineral and/or anhydrite mineral samples, adding 2g of ammonium bicarbonate and 10mL of water with boron ions removed for reaction, and separating the first supernatant from the precipitate after full reaction; and adding 1mol/L hydrochloric acid into the precipitate for reaction, and obtaining the second supernatant after the precipitate is completely decomposed.
Further, in the separation step, 0.8mL of the first supernatant is taken to pass through the boron-specific resin exchange column at a flow rate of 0.5-0.8 mL/min for boron enrichment; adding sub-boiling ammonia water into the second supernatant to adjust the pH value to be alkalescent, and taking 0.8mL of the alkalescent second supernatant to pass through the boron specific resin exchange column at the flow rate of 0.5-0.8 mL/min to enrich boron.
Further, in the separation step, the boron-containing specific resin exchange column enriched with boron is leached by using 0.1mol/L hydrochloric acid at 75 ℃, and the obtained boron-containing leacheate is subjected to boron content test by using ICP-OES.
Further, in the separation step, 0.5mL of the boron-containing leacheate with the boron content of more than or equal to 1 mu g/g is taken to pass through the anion and cation mixed resin exchange column at the flow rate of 0.3mL/min, so as to remove residual hydrochloric acid and other ions and obtain the neutral boron-containing solution.
Further, the separation method further comprises a step of purification before the reaction step, wherein the purification step comprises: preparing heavy liquid by sodium metatungstate monohydrate, stirring, centrifuging, cleaning and drying an impure gypsum mineral and/or anhydrite mineral sample and the heavy liquid, and performing the reaction after determining that the mass percent of gypsum and/or anhydrite in the gypsum mineral and/or anhydrite mineral sample is 98-100%.
Further, in the purification step, the speed of centrifugation is 2000r/min, and the time is 10 min; cleaning the centrifuged gypsum mineral and/or anhydrite mineral sample by using water with boron ions in a water circulation vacuum pump; the drying temperature is 40 ℃; and after drying, carrying out XRD diffraction analysis on the gypsum mineral and/or anhydrite mineral sample.
In a second aspect, the present invention provides a method for measuring a boron isotope, comprising the steps of:
sampling: taking the neutral boron-containing solution separated from the method for separating boron from the gypsum mineral and/or the anhydrite mineral;
and (3) treatment: adding mannitol and cesium carbonate into the neutral boron-containing solution, and concentrating to 0.1mL to obtain a sample of the boron isotope to be detected;
and (3) determination: and measuring the sample of the boron isotope to be detected by mass spectrometry.
Further, in the step of treating, when mannitol and cesium carbonate are added to the neutral boron-containing solution, the ratio of the amount of the substance of boron element to the amount of the substance of cesium element in cesium carbonate in the neutral boron-containing solution is 1:1, and the ratio of the amount of the substance of boron content in the neutral boron-containing solution to mannitol is 1: 1.
Further, the determination steps are that 2 mu L of graphite suspension is coated on the surface of a degassed tantalum band, 1 mu L of prepared sample of the boron isotope to be determined is coated, the sample is steamed to near dryness under the current of 1.2A, then the sample is loaded into a mass spectrometer, and the ion source is vacuumized to 2 × 10-5Pa～3×10-5Pa, the measurement is started. In the present invention, the method for measuring the sample of the boron isotope to be measured by mass spectrometry employs document 1 (heroic et al. automated static double-receiving high-precision thermal ionization mass spectrometry for measuring boron isotope [ J]Mass spectroscopyThe method of any one of 2013,34(2): 75-81); specifically, 308/309 double Faraday cup system is adopted, and mass-to-charge ratio 308 is obtained by static double receiving133Cs2 10B16O2 +) And mass to charge ratio 309: (133Cs2 11B16O2 +) Ion current intensity of I308And I309Calculating to obtain I309And I308Ratio R of309/308Then proceed to17O is corrected to obtain11B and10abundance ratio of two isotopes of B: (11B/10B)Sample (I)，(11B/10B)Sample (I)＝R309/308-0.00078。
For isotopic composition of boron11B represents, calculated according to the following formula:
11B(‰)＝[(11B/10B)sample (I)/(11B/10B)Standard of merit-1]×1000
Wherein the standard substance is NIST SRM951, (A), (B), (C), (11B/10B)Standard of meritMeasured value of (a) is 4.05537 ± 0.00004(2 σ, n ═ 4); wherein, 2 σ: represents the standard deviation between the mean values of boron isotope measurement results of 1 sample per time; n is 4: the boron isotope of the sample was measured 4 times.
The invention has the following beneficial effects:
the invention aims at the indissolvable mineral gypsum and/or anhydrite in the evaporite mineral, and develops a novel method for separating and extracting boron and a method for measuring boron isotopes in order to solve a series of problems that the conventional acidolysis mineral sample is difficult to separate and extract boron and effectively measure the composition characteristic analysis of the boron isotopes. The invention separates and extracts boron in purified gypsum and/or anhydrite by phase transformation decomposition and ion exchange method, namely: the method comprises the steps of sequentially converting and dissolving gypsum and/or anhydrite minerals by using ammonium bicarbonate and dilute hydrochloric acid, enriching boron ions in the generated clear liquid by using boron specific resin (Amberlite IRA 743), and continuously purifying anion and cation mixed resin (Ion Exchange II and Dowex50W x 8) and finally measuring boron isotopes on samples with the boron content of more than 1 mu g/g. The result shows that the separation method of boron can completely decompose gypsum and/or anhydrite minerals, the recovery rates of boron in an experimental sample and a boron standard solution (NIST SRM 951) are both more than 95%, isotope fractionation hardly occurs, the repeated determination of the boron isotope ratio of the experimental sample is good, the test precision is better than 0.05%, and the accurate determination of the boron isotope composition in the insoluble gypsum and/or anhydrite minerals can be well met.
Drawings
FIG. 1 is an XRD diffractogram before the flotation purification of anhydrite minerals in the analysis of the influence of the purification step in the method for separating boron from gypsum minerals and/or anhydrite minerals according to the invention;
FIG. 2 is an XRD diffractogram after the anhydrite mineral is purified by flotation in the analysis of the influence of the purification step in the method for separating boron from the gypsum mineral and/or the anhydrite mineral according to the present invention;
FIG. 3 is an XRD diffraction pattern of a gypsum mineral (after purification and before reaction with ammonium bicarbonate) in a method for separating boron from the gypsum mineral according to an embodiment of the present invention;
FIG. 4 is an XRD diffraction pattern of a gypsum mineral (after reaction with ammonium bicarbonate) in the method for separating boron from the gypsum mineral according to the embodiment of the present invention.
Detailed Description
Examples
The embodiment provides a method for separating boron from a gypsum mineral, which comprises the following steps:
and (3) purification: is prepared by sodium metatungstate monohydrate with the specific gravity of 2.31g/cm3The heavy liquid of (1) fully stirring an impure gypsum mineral sample and the heavy liquid in a polyethylene centrifugal tube, then centrifuging for 10min in a centrifuge with the speed of 2000r/min, quickly cleaning the centrifuged gypsum mineral sample by using boron-ion water, drying in an oven at 40 ℃, and then carrying out XRD diffraction analysis until the mass percentage of gypsum in the gypsum mineral sample is98％～100％；
Reaction: putting 1g of the purified gypsum mineral sample into a first polyethylene centrifuge tube, adding 2g of ammonium bicarbonate and 10mL of water without boron ions into the first polyethylene centrifuge tube for reaction to obtain a first supernatant and a precipitate after the reaction, and putting the first supernatant into a second polyethylene centrifuge tube for separation from the precipitate; adding 1mol/L hydrochloric acid into the precipitate for reaction, obtaining a second supernatant after the precipitate is completely decomposed, and placing the second supernatant into a third polyethylene centrifuge tube; wherein the first supernatant is weakly alkaline ammonium sulfate supernatant, and the second supernatant is weakly acidic calcium chloride supernatant;
separation: taking 0.8mL of first supernatant fluid to carry out boron enrichment through a boron specific resin exchange column at a flow rate of 0.5 mL/min-0.8 mL/min; adding sub-boiling ammonia water into the weakly acidic second supernatant to adjust the pH value to be 7.35-7.45 weak alkaline, and then taking 0.8mL of the weak alkaline second supernatant to perform boron enrichment through a boron specific resin exchange column at the flow rate of 0.5-0.8 mL/min; then, leaching the boron-enriched special-effect resin exchange column by using 0.1mol/L hydrochloric acid at 75 ℃ to obtain boron-containing leacheate; and (3) diluting the boron-containing leacheate, testing the boron content of the boron-containing leacheate through ICP-OES, and removing residual hydrochloric acid and other ions by enabling the boron-containing leacheate with the boron content of more than or equal to 1 mu g/g to pass through an anion-cation mixed resin exchange column to obtain a neutral boron-containing solution.
Wherein, the boron specific resin exchange column adopts Amberlite IRA 743; the anion and cation mixed resin Exchange column adopts Ion Exchange II and Dowex50 WX 8.
The embodiment also provides a method for measuring a boron isotope, which comprises the following steps:
sampling: taking a neutral boron-containing solution, wherein the neutral boron-containing solution is obtained by the method for separating boron from the gypsum mineral;
and (3) treatment: adding mannitol and cesium carbonate into a neutral boron-containing solution, wherein the quantity ratio of mannitol to substances of boron content in the neutral boron-containing solution is 1:1, the quantity ratio of boron elements in the neutral boron-containing solution to substances of cesium element in the cesium carbonate is 1:1, and evaporating and concentrating the mixture in an oven to 0.1mL to obtain a sample of a boron isotope to be detected;
measuring the sample of the boron isotope to be measured by mass spectrometry, specifically coating 2 mu L of graphite suspension on the surface of a degassed tantalum band, coating 1 mu L of the prepared sample of the boron isotope to be measured, steaming to near dryness under the current of 1.2A, then loading into a mass spectrometer, vacuumizing an ion source to 2 × 10-5Pa～3×10-5Pa, the measurement is started.
In this example, a method for measuring a sample of a boron isotope to be measured by mass spectrometry employs reference 1 (heroic et al]The method described in Mass Spectrometry, 2013,34(2): 75-81); it adopts 308/309 double Faraday cup system, static double receiving to obtain mass-to-charge ratio 308: (133Cs2 10B16O2 +) And mass to charge ratio 309: (133Cs2 11B16O2 +) Ion current intensity of I308And I309Calculating to obtain I309And I308Ratio R of309/308Then proceed to17O is corrected to obtain11B and10abundance ratio of two isotopes of B: (11B/10B)Sample (I)，(11B/10B)Sample (I)＝R309/308-0.00078。
For isotopic composition of boron11B represents, calculated according to the following formula:
11B(‰)＝[(11B/10B)sample (I)/(11B/10B)Standard of merit-1]×1000
Wherein the standard substance is NIST SRM951, (A), (B), (C), (11B/10B)Standard of meritMeasured value of (a) is 4.05537 ± 0.00004(2 σ, n ═ 4); wherein, 2 σ: represents the standard deviation between the mean values of boron isotope measurement results of 1 sample per time; n is 4: the boron isotope of the sample was measured 4 times.
In this embodiment, after the phase transformation and decomposition of the gypsum mineral sample in the reaction step, other ions are simultaneously present in the generated boron-containing solution, and the boron content is directly measured, so that the ICP-OES atomizer is blocked or the measurement signal of boron is shifted due to the excessively high salinity and the interference effect of the matrix of other ions, and the boron content in the solution is lower than the detection limit of ICP-OES and cannot be measured when the boron solution is diluted (as shown in table 1 below, the detection limit and the lower quantitative limit of boron element of ICP-OES are shown). Therefore, in the separation method of boron in this embodiment, trace boron ions are preferentially enriched by the boron specific resin exchange column in the separation step, and then the ICP-OES is performed to measure the boron content. Although the determination of the low boron content can also be performed by isotope dilution thermal ionization mass spectrometry, in the subsequent determination method of the boron isotope in the embodiment, the boron isotope is determined by using mass spectrometry, and mannitol and cesium carbonate are added according to the boron content in the boron isotope sample to be determined before the mass spectrometry, so that the evaporation and ionization conditions for the determination of the boron isotope are ensured, and the volatilization and isotope fractionation of boron are inhibited. Therefore, the boron separation method and the boron isotope determination method developed for gypsum minerals in the embodiment solve the problem of accurate determination of the boron content in low-boron gypsum minerals and/or anhydrite minerals, and can meet the requirement of boron isotope determination.
TABLE 1 detection limit and lower limit of quantitation of boron element in ICP-OES
Analysis of influence of purification step in process for separating boron from gypsum mineral and/or anhydrite mineral
The purification steps in the boron separation method in the embodiment are adopted to respectively carry out flotation purification on the anhydrite mineral and the gypsum mineral, and the specific gravity of the purified anhydrite mineral is 2.98g/cm3The specific gravity of the purified gypsum mineral is 2.31g/cm3The sodium metatungstate monohydrate heavy liquid. As shown in fig. 1 and fig. 2, which are XRD diffractograms before and after the purification of anhydrite, respectively, XRD diffractometry shows that no new minerals related to heavy liquid are found before and after the purification of the sample, and the separation efficiency of the heavy liquid to the (anhydrite) reaches more than 99%. The process is simple and efficient physical separation process, and does not cause loss of boron content and isotope thereof in the (anhydrite)And (4) fractional distillation. The following table 2 shows the compositions of the anhydrite minerals and the gypsum minerals after the purification step in percentage by mass:
TABLE 2 anhydrite minerals and gypsum minerals in terms of the percentage by mass of the mineral composition after the purification step
Effect of different acid-base dissolution experiments on extracting boron from gypsum mineral
In the method for separating boron from gypsum mineral of this example, before and after the reaction with ammonium bicarbonate, XRD diffraction analysis was performed on gypsum and a nascent mineral, respectively. Referring to fig. 3 and 4, fig. 3 is an XRD diffractogram of gypsum mineral before reacting with ammonium bicarbonate, wherein the mass percentage of gypsum is more than 99%; figure 4 is an XRD diffractogram of gypsum mineral after reaction with ammonium bicarbonate, where 92% of the gypsum mineral has been converted to calcium carbonate mineral and a small amount of gypsum coexisting will complete the conversion as the reaction proceeds. Dilute hydrochloric acid (1mol/L) was added to the nascent calcium carbonate mineral and as the reaction proceeded, the carbonate mineral gradually dissolved completely.
By adopting the reaction steps in the boron separation method in the above embodiment, sodium bicarbonate, potassium carbonate, sodium carbonate and hydrochloric acid are respectively used to replace ammonium bicarbonate in the embodiment to perform a parallel phase transformation experiment on the gypsum mineral. The ICP-OES measurement of the boron content of the converted phase after the boron specific resin is enriched shows that the conversion efficiency of ammonium bicarbonate to boron in gypsum minerals is 0.5122mg/L (shown in the following table 3), which indicates that the decomposition of the gypsum minerals and/or anhydrite minerals and the extraction of boron can be maximally realized by the step.
TABLE 3 effect of different alkali dissolution parallel experiments on extraction of boron from gypsum mineral
Boron recovery experiment and full-process boron isotope fractionation
In the experiment, different boron-containing samples are adopted for carrying out boron recovery experiments, wherein the numbers 1 and 2 are common gypsum, the number 3 is a boric acid reagent, the numbers 4, 5 and 6 are analytically pure gypsum, and the number 7 is a boron standard solution (prepared by NIST SRM 951). The recovery experiment was carried out by the whole flow from the purification step to the boron content measurement step of ICP-OES in the above examples, with 1 and 2 each added with 2mL of a boric acid reagent solution (10. mu.g/mL), 4, 5 and 6 each added with 1mL of a boron standard solution (30. mu.g/mL) and a boric acid reagent and a boron standard solution. The boron content of 1 common gypsum is 9.785 mug after the original gypsum is subjected to the whole process, the boron content of the added boric acid reagent is 29.984 mug after the whole process, and the ratio of the difference of the two to the boron content is the recovery rate, and reaches 100.9 percent. Similarly, the recovery rates of the rest samples are 102.2%, 96.76%, 109.75%, 102.08%, 111.42% and 110.75% (see table 4), and seven groups of experiments show that the full process from the purification step to the step of testing the boron content of ICP-OES has higher recovery efficiency of boron in the gypsum sample, can meet the requirement of boron isotope determination in the sample on the boron content, and simultaneously is the fundamental guarantee that the boron isotope in the full process is not fractionated.
TABLE 4 recovery experiment after the Gypsum sample full run
Repeated determination of boron isotope composition in gypsum mineral and anhydrite mineral
The experiment respectively carries out the repeatability determination of boron isotope to the gypsum mineral and anhydrite mineral samples in different areas. By adopting the method for separating boron from the gypsum mineral and the method for measuring the boron isotope in the embodiment, the impure gypsum mineral samples in the embodiment are respectively replaced by the Yunnan Lajing gypsum mineral sample, the Hexi gypsum mineral sample and the Laos anhydrite mineral sample for measuring the boron isotope, and the result shows that: the Yunan Lajing gypsum sample, Hexi gypsum sample and Laos anhydrite sample are subjected to the steps from the purification step to the determination of boron isotope by mass spectrometry in the above examplesAfter the whole process is repeated for the measurement,11the distribution range of B value is +39.14 ‰ 43.09 ‰, +36.91 ℃ - +41.95 ‰, +35.39 ℃ - +37.85 ‰ (see Table 5), respectively11The B value is similar to the average value, the repeatability is good, and the boron isotope determination precision is better than 0.05 percent (the external precision is between 0.02 per thousand and 0.18 per thousand); well-drawing gypsum sample11The B value is in negative correlation with the boron content of the sample, and the remaining two groups are in positive correlation, which shows that the recovery rate of the boron content in the gypsum mineral sample and the anhydrite mineral sample has no obvious influence on the boron isotope ratio, but the higher the recovery rate is, the more advantageous the accurate determination of the boron isotope value is. Of individual gypsum samples (Lajing, Hexi)11The repeated measurement results of the B value have certain difference, but the B value still has important significance for tracing the source, and the results of the samples are obtained11B value and marine evaporite11The distribution range of the B value is more consistent with +18.2 ‰ -31.7 ‰, which indicates that it is most likely to be a marine phase evaporation cause, and this is in connection with Lajing and Hexi Gypsum Fibrosum34S value and borate of sylvite mining area where Laos anhydrite is located11The B value is consistent, and the boron isotope composition of the (hard) gypsum mineral can well trace the source of the evaporite deposit.
TABLE 5 Gypsum mineral samples and anhydrite mineral samples11Repeated measurement of B value
It should be understood that the above examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. It should also be understood that after reading the technical content of the present invention, those skilled in the art can make appropriate changes to the conditions and steps in the technical solution of the invention to realize the final technical solution without departing from the principle of the present invention, and all the equivalent forms are also within the protection scope defined by the appended claims of the present application.
Claims (10)
1. A method for separating boron from gypsum minerals and/or anhydrite minerals, characterized by comprising the following steps:
reaction: taking a gypsum mineral and/or anhydrite mineral sample, adding ammonium bicarbonate and water with boron ions removed into the gypsum mineral sample for reaction, and obtaining a first supernatant and a precipitate after the reaction; adding hydrochloric acid into the precipitate for reaction, and obtaining a second supernatant after the precipitate is completely decomposed;
separation: enriching boron of the first supernatant through a boron-specific resin exchange column, adjusting the pH of the second supernatant to be alkaline, and then enriching boron of the second supernatant through the boron-specific resin exchange column; leaching the boron-enriched special-effect resin exchange column to obtain boron-containing leacheate; and (3) passing the boron-containing leacheate with the boron content of not less than 1 mu g/g through an anion-cation mixed resin exchange column to obtain a neutral boron-containing solution.
2. The separation method according to claim 1, characterized in that: the reaction steps are as follows: taking 1g of gypsum mineral and/or anhydrite mineral samples, adding 2g of ammonium bicarbonate and 10mL of water with boron ions removed for reaction, and separating the first supernatant from the precipitate after full reaction; and adding 1mol/L hydrochloric acid into the precipitate for reaction, and obtaining the second supernatant after the precipitate is completely decomposed.
3. The separation method according to claim 1, characterized in that: in the separation step, 0.8mL of the first supernatant is taken to pass through the boron specific resin exchange column at a flow rate of 0.5-0.8 mL/min for enriching boron; adding sub-boiling ammonia water into the second supernatant to adjust the pH value to be alkalescent, and taking 0.8mL of the alkalescent second supernatant to pass through the boron specific resin exchange column at the flow rate of 0.5-0.8 mL/min to enrich boron.
4. The separation method according to claim 1, characterized in that: in the separation step, the boron-enriched special-effect resin exchange column is leached by using 0.1mol/L hydrochloric acid at 75 ℃, and the boron content of the obtained boron-containing leacheate is tested by using ICP-OES.
5. The separation method according to claim 1, characterized in that: in the separation step, 0.5mL of the boron-containing leacheate with the boron content of more than or equal to 1 mu g/g is taken to pass through the anion and cation mixed resin exchange column at the flow rate of 0.3mL/min, and residual hydrochloric acid and other ions are removed to obtain the neutral boron-containing solution.
6. The separation method according to any one of claims 1 to 5, characterized in that: the separation method further comprises a step of purification before the reaction step, wherein the purification step comprises the following steps: preparing heavy liquid by sodium metatungstate monohydrate, stirring, centrifuging, cleaning and drying an impure gypsum mineral and/or anhydrite mineral sample and the heavy liquid, and performing the reaction after determining that the mass percent of gypsum and/or anhydrite in the gypsum mineral and/or anhydrite mineral sample is 98-100%.
7. The separation method according to claim 6, characterized in that: in the purification step, the centrifugation speed is 2000r/min and the time is 10 min; cleaning the centrifuged gypsum mineral and/or anhydrite mineral sample by using water with boron ions in a water circulation vacuum pump; the drying temperature is 40 ℃; and after drying, carrying out XRD diffraction analysis on the gypsum mineral and/or anhydrite mineral sample.
8. A method for measuring a boron isotope, comprising the steps of:
sampling: taking the neutral boron-containing solution separated in the separation method according to any one of claims 1 to 7;
and (3) treatment: adding mannitol and cesium carbonate into the neutral boron-containing solution, and concentrating to 0.1mL to obtain a sample of the boron isotope to be detected;
and (3) determination: and measuring the sample of the boron isotope to be detected by mass spectrometry.
9. The method for measuring according to claim 8, wherein: in the step of treating, when mannitol and cesium carbonate are added to the neutral boron-containing solution, the ratio of the amount of the substance of boron element to the amount of the substance of cesium element in cesium carbonate in the neutral boron-containing solution is 1:1, and the ratio of the amount of the substance of boron content in the neutral boron-containing solution to the amount of the mannitol is 1: 1.
10. The method of claim 8, wherein the sample to be tested is coated with 2. mu.L of graphite suspension on the surface of the degassed tantalum strip, then coated with 1. mu.L of the prepared sample, evaporated to near dryness under a current of 1.2A, and then loaded into a mass spectrometer, and the ion source is evacuated to 2 × 10-5Pa～3×10-5Pa, the measurement is started.
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| CN108956252B (en) * | 2018-08-01 | 2019-05-14 | 中国地质科学院矿产资源研究所 | Boron isotope analysis method for carbonate rock in old stratum |
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| CN113310970A (en) * | 2021-04-30 | 2021-08-27 | 临沂大学 | Method for simulating isotope fractionation in boron adsorption process of clay minerals and application of method |
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| CN116067740B (en) * | 2023-03-13 | 2023-07-25 | 中国科学院南京地质古生物研究所 | A boron isotope determination method for silicate based on hydrolysis Na2O2 alkali fusion method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101274217A (en) * | 2007-12-26 | 2008-10-01 | 中国核动力研究设计院 | Technique for separating boron isotope with boron specific resin ion-exchange chromatography |
| CN106167267A (en) * | 2015-05-21 | 2016-11-30 | 中国石油化工集团公司 | A kind of method of boron in separation and Extraction boron-containing solution |
-
2017
- 2017-11-17 CN CN201711146655.XA patent/CN107991378B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101274217A (en) * | 2007-12-26 | 2008-10-01 | 中国核动力研究设计院 | Technique for separating boron isotope with boron specific resin ion-exchange chromatography |
| CN106167267A (en) * | 2015-05-21 | 2016-11-30 | 中国石油化工集团公司 | A kind of method of boron in separation and Extraction boron-containing solution |
Non-Patent Citations (3)
| Title |
|---|
| 《岩石中硼的提取分离及同位素组成的测定》;王刚等;《岩矿测试》;20000930;第19卷(第3期);第169-172页 * |
| 《碳铵法制硼酸》;冉启培;《无机盐工业》;19791231;第20-23页 * |
| 《重液材料多钨酸钠在青海湖沉积物重力分离中的应用》;李善营等;《矿物岩石地球化学通报》;20080131;第27卷(第1期);第69-71页 * |
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