CN110501327B - Separation detection method for rhenium in high-copper matrix solid material and liquid material - Google Patents
Separation detection method for rhenium in high-copper matrix solid material and liquid material Download PDFInfo
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- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 title claims abstract description 177
- 229910052702 rhenium Inorganic materials 0.000 title claims abstract description 160
- 239000010949 copper Substances 0.000 title claims abstract description 127
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 115
- 239000011159 matrix material Substances 0.000 title claims abstract description 64
- 238000000926 separation method Methods 0.000 title claims abstract description 31
- 238000001514 detection method Methods 0.000 title claims abstract description 23
- 239000011344 liquid material Substances 0.000 title claims abstract description 7
- 239000011343 solid material Substances 0.000 title claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 95
- 238000000034 method Methods 0.000 claims abstract description 59
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 27
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 24
- 239000007787 solid Substances 0.000 claims abstract description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 22
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 22
- 238000005303 weighing Methods 0.000 claims abstract description 17
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012153 distilled water Substances 0.000 claims abstract description 5
- 239000011521 glass Substances 0.000 claims abstract description 5
- 239000006193 liquid solution Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 62
- 238000001556 precipitation Methods 0.000 claims description 30
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 20
- 229910017604 nitric acid Inorganic materials 0.000 claims description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 10
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 claims description 10
- 239000011550 stock solution Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 abstract description 13
- 230000002378 acidificating effect Effects 0.000 abstract description 9
- 238000003723 Smelting Methods 0.000 abstract description 7
- 238000000605 extraction Methods 0.000 abstract description 5
- 239000002244 precipitate Substances 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 2
- 229910021529 ammonia Inorganic materials 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 58
- 238000005259 measurement Methods 0.000 description 35
- 238000004458 analytical method Methods 0.000 description 23
- 238000011084 recovery Methods 0.000 description 19
- 239000012086 standard solution Substances 0.000 description 18
- 239000002253 acid Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 15
- 229910052785 arsenic Inorganic materials 0.000 description 14
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 14
- 229910052797 bismuth Inorganic materials 0.000 description 14
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 14
- 238000002474 experimental method Methods 0.000 description 12
- 238000002386 leaching Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 239000002893 slag Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 238000011835 investigation Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000003595 spectral effect Effects 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000012490 blank solution Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 238000012421 spiking Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/73—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using plasma burners or torches
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a separation and detection method of rhenium in a high-copper matrix solid material, which comprises a separation method of a high-copper matrix solid sample and a separation method of a high-copper matrix liquid sample, wherein the separation methods comprise the following steps: the method for separating the solid sample with the high copper matrix comprises the following steps: (1) weighing a solid sample with a high copper matrix and placing the solid sample in a beaker; (2) adding hydrochloric acid and ammonium bifluoride into the beaker in sequence; (3) placing the beaker on an electric hot plate for dissolving; (4) Adding hydrogen peroxide into the beaker until the sample is completely dissolved; (5) washing the watch glass and the wall of the beaker by distilled water; (6) Sequentially adding hexamethylenetetramine and a copper reagent, and fully shaking until the precipitate is completely precipitated; also discloses a separation detection method of rhenium in the high-copper matrix liquid material, which comprises the following steps: (1) taking a liquid solution with high copper matrix in a cup; (2) Ammonia was added to the beaker to adjust to just precipitate. The method can effectively realize extraction of rhenium from the copper smelting acidic wastewater.
Description
Technical Field
The invention relates to the technical field of separation and detection methods for rhenium, in particular to a separation and detection method for rhenium in a high-copper base material.
Background
Currently, as the use of rhenium products expands, the demand for rhenium is increasing. Therefore, the recovery of rare metals such as rhenium from secondary resource wastes becomes one of the important tasks of recycling renewable resources in China in the 21 st century, however, the current rhenium separation and detection process cannot be applied to the process for extracting rhenium from copper smelting acidic wastewater.
Disclosure of Invention
Aiming at the technical problems, the invention provides a separation and detection method for rhenium in a high-copper base material, which can effectively realize extraction of rhenium from copper smelting acid wastewater.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a separation detection method for rhenium in a high-copper matrix solid material comprises the following steps:
(1) Weighing 0.2000g of a solid sample with a high copper matrix, and placing the solid sample into a 400mL beaker, wherein the weighing accuracy of the solid sample with the high copper matrix is 0.0002g;
(2) Sequentially adding 10mL of hydrochloric acid and 0.1 to 0.2 g of ammonium bifluoride into a beaker;
(3) Placing the beaker on an electric hot plate with the temperature of less than 200 ℃ for dissolving, adding 15mL of nitric acid, and continuously heating until the volume is reduced to 1-2mL;
(4) Adding 5mL of hydrogen peroxide into the beaker until the sample is completely dissolved;
(5) Washing the watch glass and the wall of the beaker by distilled water, boiling, taking down, cooling, and then transferring into a 200mL volumetric flask for constant volume to obtain a liquid to be measured;
(6) Taking 50.00mL of solution to be detected, putting the solution into a 300mL beaker, adding ammonia water to adjust until precipitation just occurs, sequentially adding 20mL of hexamethylenetetramine and 1g of copper reagent, fully shaking until the precipitation is complete, carrying out dry filtration to a 100mL volumetric flask, and fixing the volume;
(7) Measuring rhenium on the solution obtained in the step (6) on ICP-AES by directly adopting a standard curve method;
a separation detection method for rhenium in a high-copper matrix liquid material comprises the following steps:
(1) Taking 25.00mL of liquid solution with high copper matrix in a 300mL beaker;
(2) Adding ammonia water into a beaker, adjusting until precipitation just occurs, then sequentially adding 20mL of hexamethylenetetramine and 1g of copper reagent, fully shaking until the precipitation is complete, carrying out dry filtration to a 100mL volumetric flask, and fixing the volume;
(3) And (3) directly measuring rhenium on the solution obtained in the step (2) by adopting a standard curve method on ICP-AES.
In the standard curve method adopted by the ICP-AES, the preparation method of the rhenium standard stock solution comprises the following steps:
(1) Accurately weighing 1.0000g (accurate to 0.0001 g) of metal rhenium powder (more than or equal to 99.99 percent) or 1.4404g of ammonium perrhenate (more than or equal to 99.99 percent) in a beaker;
(2) To a beaker was added 20mL nitric acid (. Rho. =1.42 g/mL) and hydrogen peroxide (30%) was added dropwise to decompose rhenium, added 20mL water to boil and remove the hydrogen peroxide, cooled, transferred to a 1000mL volumetric flask with nitric acid (5 + 95)) and diluted to 1mL solution containing 1 mg rhenium.
In the standard curve method adopted by the ICP-AES, the preparation method of the rhenium standard use solution comprises the following steps:
(1) Accurately dispensing 10.00mL of rhenium standard stock solution into a 100mL volumetric flask;
(2) Diluted with nitric acid (5 + 95) to 1ml solution containing 100 micrograms of rhenium.
The invention has the beneficial effects that: the steps (1) to (6) in the separation detection method of rhenium in the high-copper matrix solid material and the steps (1) and (2) in the separation detection method of rhenium in the high-copper matrix liquid material can completely precipitate copper in the liquid to be detected, eliminate the interference of the copper matrix on rhenium, simultaneously ensure that rhenium elements to be detected are not adsorbed, wrapped and otherwise lost while precipitating and separating the copper matrix, adjust the pH value by ammonia water in the liquid to be detected obtained by the separation method of the liquid to be detected obtained by the steps (1) to (5) in the separation method of the solid sample of the high-copper matrix and the liquid to be detected obtained by the separation method of the liquid sample of the high-copper matrix, add hexamethylenetetramine and copper reagents to precipitate and separate the copper elements in the sample, simultaneously ensure that the rhenium elements to be detected are not adsorbed, wrapped and otherwise lost, then directly determine the rhenium amount on an ICP-rhenium standard curve method, establish a method for effectively determining rhenium in the high-copper matrix material, can accurately and effectively determine the rhenium content in the high-copper matrix material, and the method can realize the analysis result of rhenium elements under the high-copper matrix analysis and the analysis result that the high-copper matrix elements are relatively accurate and the difficult problems.
Drawings
Fig. 1 is a vertical observation height map.
FIG. 2 is a graphical representation of the effect of varying sulfuric acid content on rhenium recovery.
FIG. 3 is a graphical representation of the effect of varying copper content on rhenium recovery.
Fig. 4 is a rhenium standard curve.
Detailed Description
Example 1
The required instruments used by the invention are as follows: ICP 6300 inductively coupled plasma emission spectrometer (ThermoFisher instruments, inc. USA)
The reagents used were: nitric acid (5+95); hydrochloric acid (1+1); nitric acid (. Rho.1.42 g/mL); hydrogen peroxide (30%); hydrochloric acid (5+95); sulfuric acid (1 +1); hydrochloric acid (1 + 10); ammonia water (1 +1); ammonium bifluoride; hexamethylenetetramine (300 g/L); a copper reagent.
Rhenium standard stock solution: accurately weighing 1.0000g (accurate to 0.0001 g) of metal rhenium powder (equal to or more than 99.99 percent) or 1.4404g of ammonium perrhenate (equal to or more than 99.99 percent) in a beaker, adding 20mL of nitric acid (equal to or more than 1.42 g/mL), dripping hydrogen peroxide (30 percent) to decompose rhenium, adding 20mL of water to boil and remove the hydrogen peroxide, and cooling. Transfer to 1000mL volumetric flask with nitric acid (5 + 95)), dilute to the mark and mix well. 1ml of this solution contains 1 mg of rhenium. (or rhenium standards with national standards center);
rhenium standard used solutions: 10.00mL of rhenium standard stock solution is accurately dispensed into a 100mL volumetric flask, diluted to the scale with nitric acid (5 + 95) and mixed evenly. 1ml of this solution contained 100. Mu.g of rhenium.
1. Sample pretreatment
1. Dissolution and matrix separation of solid samples
(1) Weighing 0.2000g of the solid sample with the high copper matrix, and placing the solid sample with the high copper matrix in a 400mL beaker, wherein the weighing precision of the solid sample with the high copper matrix is 0.0002g;
(2) Sequentially adding 10mL of hydrochloric acid and 0.1 g of ammonium bifluoride into a beaker;
(3) Placing the beaker on an electric hot plate with the temperature of 190 ℃ for dissolution, adding 15mL of nitric acid, and continuing heating until the volume is reduced to 1mL;
(4) Adding 5mL of hydrogen peroxide into the beaker until the sample is completely dissolved;
(5) Washing the watch glass and the wall of the beaker by distilled water, boiling, taking down, cooling, and then transferring into a 200mL volumetric flask for constant volume to obtain a liquid to be measured;
(6) Taking 50.00mL of solution to be detected, putting the solution into a 300mL beaker, adding ammonia water to adjust the solution until precipitation just occurs, sequentially adding 20mL of hexamethylenetetramine and 1g of copper reagent, fully shaking the solution until the precipitation is complete, carrying out dry filtration to a 100mL volumetric flask, and carrying out constant volume.
2. Liquid sample matrix separation
(1) Taking 25.00mL of liquid solution with high copper matrix in a 300mL beaker;
(2) Adding ammonia water into a beaker, adjusting the temperature until precipitation just occurs, then sequentially adding 20mL of hexamethylenetetramine and 1g of copper reagent, fully shaking the mixture until the precipitation is complete, performing dry filtration to the mixture in a 100mL volumetric flask, and performing constant volume.
And (4) dividing the sample to be measured according to the content of the sample, and fixing the volume into a 100mL volumetric flask to be measured as shown in the following table.
Table 1: liquid sample aliquot volume
2. Preparation of working curve
The rhenium standard use solution (1.1.14) is respectively transferred into a volumetric flask with 0.00mL, 0.50mL, 1.00mL, 2.00mL, 5.00mL and 10.00mL constant volume to 100mL to be measured, and the sample concentration is shown in the table 2-2.
Table 2: rhenium Standard solution concentration Table (mg/L)
3. Selection of optimum analysis conditions for the apparatus
1. Selection of analytical lines
The analysis spectral line of the rhenium element is the most sensitive line at 221.426nm, no other spectral line interference exists near the most sensitive line through experimental investigation, and the 221.426nm is reasonably determined as the analysis spectral line in consideration of low rhenium content in a measured sample.
2. Selection of vertical viewing height
The other conditions are fixed and the vertical observation heights are changed to 10mm, 11mm, 12mm, 13mm and 14mm, and the prepared standard solution and the sample to be measured are used for measuring the rhenium intensity value, and the measurement results are shown in the following table 5 and the graph 1:
table 3: selection of vertical viewing height
As can be seen from fig. 1: the Re intensity value is the largest at the vertical observation height of 11mm, where the sensitivity is the highest, so that 11mm is selected as the vertical observation height.
3. Selection of other conditions of the apparatus
With regard to the selection of conditions such as RF generator, assist gas flow rate, pump speed, and the like, RF generator power 1150W, assist gas flow rate 1.0 (L/min), and pump speed 50 (r/min) were selected as the most suitable parameters, with reference to the instrument and equipment specifications.
4. Substrate interference and cancellation
In the process of extracting rhenium from copper smelting waste acid, enrichment raw materials are recovered by mainly adopting sulfuric acid leaching, so that a sample medium is a sulfuric acid system, the sulfate content of a solid sample is between 8 and 15 percent, and the sulfuric acid content of a liquid sample is between 30 and 80g/L, and therefore the interference condition of the sulfuric acid system on rhenium element needs to be investigated. In addition, the interference condition of other components to rhenium in the experiment process of the acidic wastewater extraction process needs to be considered. The contents of rhenium-rich slag, acid water and main elements of a leaching solution sample in a process experiment for extracting rhenium from the acidic wastewater are shown in the table.
TABLE 4: x-fluorescence spectrum scanning results of three rhenium-rich slag samples
TABLE 5: approximate matrix composition results for acid water samples
TABLE 6: leachate sample approximate matrix composition results
The data in the table above shows that: the main samples of rhenium-rich slag, acid water and leaching liquid of a project for extracting rhenium from acid wastewater have high sulfur, copper, arsenic and bismuth contents, so that the interference condition of sulfuric acid, arsenic, copper, bismuth and other media and matrix elements on rhenium needs to be investigated.
1. Investigation and elimination of sulfuric acid interference
Into 10 100mL volumetric flasks were respectively charged 5.00mL of a rhenium standard use solution at a rhenium element concentration of 5.00mg/L, and various amounts of H were added as shown in Table 7 below 2 SO 4 Solution, investigation of H in solution 2 SO 4 The influence of the change on the element to be measured is shown in Table 7 and FIG. 2.
Table 7: h 2 SO 4 Concentration change to Re elementEffect of the measurement of elements
As can be seen from table 7 and fig. 2: when the concentration of the sulfuric acid in the sample is less than 30g/L, the measurement on the content of rhenium is not interfered, but when the concentration of the sulfuric acid in the sample is more than 30g/L, the measurement result on the content of the Re element is obviously lower. And then analyzing the sulfuric acid content in a plurality of batches of samples, and finding that the sulfuric acid content in the solid sample is less than 30g/L, the sulfuric acid content in the liquid sample is usually between 30 and 80g/L, when the rhenium is measured by the liquid sample, a certain volume of enrichment precipitation matrix needs to be taken for measurement, and the sulfuric acid content in the measured solution is less than 30g/L, so that the rhenium element is not interfered.
2. Interference of copper element
In the process test of extracting rhenium from the acidic wastewater, the tested samples contain different amounts of copper element, and whether rhenium to be tested has interference or not due to the change of the content of the copper element is to be further verified through the test.
5.00mL of rhenium standard use solution was added to each of 7 100mL volumetric flasks at a rhenium element concentration of 5.00mg/L. The effect of varying the Cu concentration in the solution on Re was examined by adding different amounts of Cu concentration as shown in Table 8 below.
Table 8: effect of Cu concentration variation on Re measurements
As can be seen from table 8 and fig. 3: the high and low copper content in the measurement of rhenium affects the measurement of the rhenium content, and the recovery rate of rhenium is reduced to below 30 percent along with the increase of the copper content, so that the existence of the copper element generates serious negative interference on the rhenium and must be eliminated.
And eliminating interference of Cu element. In order to eliminate the interference of copper element, the aim of eliminating the interference is achieved by reducing the sample weighing amount and the dividing volume, the method can reduce the content of a matrix, but the measuring signal of the element rhenium to be measured is reduced, when the content of the element to be measured is lower, the sample weighing amount is reduced, the measuring signal of the rhenium element after the dividing times is increased is close to the detection limit of an instrument, and thus the element rhenium to be measured cannot be effectively detected. This method is therefore not desirable for eliminating copper interference. Several complexing methods have been used to eliminate the interference of copper element, but the effect is not ideal, so that the precipitation separation method is used to eliminate the interference of copper matrix to rhenium.
Transferring 2.00mL of rhenium standard use solution in 5 100mL beakers respectively, adding Cu solutions with different amounts according to the following table 10, then adding ammonia water respectively to adjust the solution until precipitation just occurs, adding 20mL of hexamethylenetetramine, adding 1g of copper reagent, stirring until the precipitation is complete, filtering the solution to a 100mL volumetric flask, measuring the constant volume, and inspecting the condition of rhenium content measurement after the precipitation is separated from the copper matrix.
Table 9: re measurement after separation of Cu substrate
As seen from table 9 above: the interference of copper element on the determination of Re can be eliminated by adopting a method of precipitating and separating a copper matrix by hexamethylenetetramine and a copper reagent.
Tests show that the recovery rate of rhenium can reach more than 97.7% after the copper matrix is separated by precipitation, and then the copper content of the solution after precipitation is measured, and the copper content in the solution after separation is less than 0.0001g/L, so that the copper matrix is judged to be completely separated. Therefore, the method can eliminate the problem of negative interference of copper element in the sample on rhenium determination, thereby achieving the purpose of eliminating the situation that the rhenium analysis result is lower due to the existence of copper.
3. Interference of arsenic, bismuth and lead contents
The content of arsenic, bismuth and lead in a sample of a process experiment for extracting rhenium from acid wastewater is also high, and the three elements need to be verified by experiments if the determination of rhenium elements is interfered.
5.00mL of rhenium standard use solution was added to 7 100mL volumetric flasks, respectively, at which the concentration of rhenium element was 5.00mg/L, and different amounts of arsenic, bismuth and lead were added according to the following tables 10 to 12, and the interference of the change in the concentration of these three elements in the solution with Re was examined.
Table 10: effect of arsenic concentration variation on Re measurements
Table 11: effect of bismuth concentration variation on Re measurement
Table 12: effect of lead concentration variation on Re measurement
As seen from tables 10-12: the change of arsenic, bismuth and lead contents does not interfere with the measurement of rhenium.
5. Linear range of method
Two sets of standard rhenium use solutions, 0.00mL, 0.50mL, 1.00mL, 2.00mL, 5.00mL and 10.00mL, were removed and placed in 100mL volumetric flasks, and one set was made to volume with pure water to the mark (standard solution I). And adding a small amount of ammonia water, 20mL of hexamethylenetetramine and 1g of copper reagent into the other group, fixing the volume to a scale (standard solution II) by using pure water, and drawing a standard curve by using the two groups of standard solutions with the Re concentrations of 0.00 mu g/mL, 0.50 mu g/mL, 1.00 mu g/mL, 2.00 mu g/mL, 5.00 mu g/mL and 10.00 mu g/mL in sequence, wherein the standard curve is shown in figure 4.
As can be seen from fig. 4 above: the rhenium curve fitting coefficients of the two groups of standard solutions are both above 0.9999, the linearity is good, and the analysis requirements can be met. And the standard solution I and the standard solution II have good inosculation, so that the addition of hexamethylenetetramine and a copper reagent does not influence the measured value of the standard solution, and a working curve is prepared according to the working curve.
6. Method detection limit
Under the optimal working conditions of the selected instrument, 5mL of sulfuric acid, 20mL of hexamethylenetetramine and 1g of copper reagent are added, the mixture is placed in a 100mL volumetric flask, the volume is fixed to a scale by water, the scale is used as a blank solution for continuous measurement for 13 times, the detection limit is 3 times of the standard deviation of the measurement result divided by the slope of the curve, and the measurement results are shown in the following table 13.
Table 13: method for detecting limit data
As can be seen from table 13: the rhenium detection limit measured by the method is 0.00036mg/L, and the analysis requirement of the sample can be met.
7. Precision test
In order to examine the coincidence degree of the measured data of the method, under the selected optimal working conditions, 11 times of analyses were carried out on the 1# rhenium-rich slag prepared by manual simulation and several random Re contents, and the results of measuring rhenium are shown in the table 14.
Table 14: experiment of sample precision
As can be seen from the precision experimental data table 14: the method is used for measuring the rhenium content in samples such as raw materials, rhenium-rich slag, leaching liquid, dust collecting liquid and the like, and the RSD is measured to be between 1.92% and 4.11%, so that the analysis requirement can be met.
8. Recovery rate of added standard
In order to examine the accuracy of the method, four actual samples were randomly selected to perform the standard recovery rate experiment, and the data of the standard recovery rate are shown in table 15.
Table 15: sample spiking recovery data
As can be seen from table 15: the standard addition recovery rate of the sample is between 91.2% and 108.4%, which shows that the method has better accuracy and can be suitable for the measurement and analysis requirements of rhenium content in rhenium recovery process related materials in a copper smelting system.
9. Compared with artificially simulated synthetic samples
In order to further verify the accuracy of the established analytical method for determining the rhenium content in ten materials such as raw materials, rhenium-rich residues, leaching residues, acid water, leaching liquid and the like by ICP-AES, other methods are needed for comparing the rhenium content, but no other method can determine the rhenium content in the sample at present, so that 3 rhenium-rich residues and 3 acid water solutions are artificially synthesized and determined by the method, and the results and the data of the determined samples are shown in Table 16.
Table 16: comparison table for artificial simulated synthetic sample and determination result
Example 2
The required instruments used by the invention are as follows: ICP 6300 inductively coupled plasma emission spectrometer (ThermoFisher instruments, inc. USA)
The reagents used were: nitric acid (5+95); hydrochloric acid (1+1); nitric acid (. Rho.1.42 g/mL); hydrogen peroxide (30%); hydrochloric acid (5 + 95); sulfuric acid (1 +1); hydrochloric acid (1+10); ammonia water (1 +1); ammonium bifluoride; hexamethylenetetramine (300 g/L); a copper reagent.
Rhenium standard stock solution: accurately weighing 1.0000g (accurate to 0.0001 g) of metal rhenium powder (more than or equal to 99.99%) or 1.4404g of ammonium perrhenate (more than or equal to 99.99%) in a beaker, adding 20mL of nitric acid (rho =1.42 g/mL), dripping hydrogen peroxide (30%) to decompose rhenium, adding 20mL of water to boil and remove the hydrogen peroxide, and cooling. Transfer to 1000mL volumetric flask with nitric acid (5 + 95)), dilute to the mark and mix well. 1ml of this solution contained 1 mg of rhenium. (or rhenium standards with national standards center);
rhenium standard used solutions: 10.00mL of rhenium standard stock solution is accurately dispensed into a 100mL volumetric flask, diluted to the mark with nitric acid (5 + 95) and mixed evenly. 1ml of this solution contains 100. Mu.g of rhenium.
1. Sample pretreatment
1. Dissolution and matrix separation of solid samples
(1) Weighing 0.2000g of a solid sample with a high copper matrix, and placing the solid sample into a 400mL beaker, wherein the weighing accuracy of the solid sample with the high copper matrix is 0.0002g;
(2) Sequentially adding 10mL of hydrochloric acid and 0.2 g of ammonium bifluoride into a beaker;
(3) Placing the beaker on an electric hot plate at the temperature of 180 ℃ for dissolution, adding 15mL of nitric acid, and continuing heating until the volume is reduced to 2mL;
(4) Adding 5mL of hydrogen peroxide into the beaker until the sample is completely dissolved;
(5) Washing the watch glass and the wall of the beaker by distilled water, boiling, taking down, cooling, and then transferring into a 200mL volumetric flask for constant volume to obtain a liquid to be measured;
(6) Taking 50.00mL of solution to be detected, putting the solution in a 300mL beaker, adding ammonia water to adjust until precipitation just occurs, sequentially adding 20mL of hexamethylenetetramine and 1g of copper reagent, fully shaking until the precipitation is complete, carrying out dry filtration to a 100mL volumetric flask, and carrying out constant volume.
2. Liquid sample matrix separation
(1) Taking 25.00mL of liquid solution with high copper matrix in a 300mL beaker;
(2) Adding ammonia water into a beaker, adjusting until precipitation just occurs, then sequentially adding 20mL of hexamethylenetetramine and 1g of copper reagent, fully shaking until the precipitation is complete, carrying out dry filtration to a 100mL volumetric flask, and fixing the volume.
And (4) dividing the sample to be measured according to the content of the sample, and metering the volume of the sample to be measured into a 100mL volumetric flask to be measured as shown in the following table.
Table 17: liquid sample aliquot volume
2. Preparation of working curve
The rhenium standard use solution (1.1.14) is respectively transferred into a volumetric flask with 0.00mL, 0.50mL, 1.00mL, 2.00mL, 5.00mL and 10.00mL constant volume to 100mL for measurement, and the sample concentration is shown in the table.
Table 18: rhenium Standard solution concentration Table (mg/L)
3. Selection of optimum analysis conditions for the apparatus
1. Selection of analytical lines
The analysis spectral line of the rhenium element is the most sensitive line at 221.426nm, no other spectral line interference exists near the most sensitive line through experimental investigation, and the 221.426nm is reasonably determined as the analysis spectral line in consideration of low rhenium content in a measured sample.
2. Selection of vertical viewing height
Fixing other conditions, changing the vertical observation heights to 10mm, 11mm, 12mm, 13mm and 14mm, and measuring the intensity value of rhenium by using the prepared standard solution and the sample to be measured, wherein the measurement results are shown in the following table and in figure 1:
table 19: selection of vertical viewing height
As can be seen from fig. 1: the Re intensity value is maximum at a vertical observation height of 11mm, where the sensitivity is highest, so that 11mm is selected for the vertical observation height.
3. Selection of other conditions of the apparatus
With respect to the selection of conditions such as RF generator, assist gas flow, pump speed, and the like, the RF generator power 1150W, assist gas flow 1.0 (L/min), and pump speed 50 (r/min) are selected as the most suitable parameters, with reference to the instrument and equipment specifications.
4. Matrix interference and cancellation
In the process of extracting rhenium from copper smelting waste acid, enrichment raw materials are recovered by mainly adopting sulfuric acid leaching, so that a sample medium is a sulfuric acid system, the sulfate content of a solid sample is between 8 and 15 percent, and the sulfuric acid content of a liquid sample is between 30 and 80g/L, and therefore the interference condition of the sulfuric acid system on rhenium element needs to be investigated. In addition, the interference condition of other components to rhenium in the experiment process of the acidic wastewater extraction process needs to be considered. The contents of rhenium-rich slag, acid water and main elements of a leaching solution sample in a process experiment for extracting rhenium from the acidic wastewater are shown in the table.
TABLE 20: x-fluorescence spectrum scanning results of three rhenium-rich slag samples
TABLE 21: approximate matrix composition results for acid water samples
Table 22: leachate sample approximate matrix composition results
The data in the table above shows that: the main samples of rhenium-rich slag, acid water and leaching solution of the project for extracting rhenium from the acid wastewater have high sulfur, copper, arsenic and bismuth contents, so that the interference condition of mediums and matrix elements such as sulfuric acid, arsenic, copper, bismuth and the like on rhenium needs to be examined.
1. Investigation and elimination of sulfuric acid interference
5.00mL of rhenium standard use solution, at a rhenium element concentration of 5.00mg/L, were added to 10 100mL volumetric flasks, respectively, in different amounts H, as shown in Table 7 below 2 SO 4 Solution, investigation of H in solution 2 SO 4 The influence of the change (2) on the element to be measured is shown in Table 7 and FIG. 2.
Table 23: h 2 SO 4 Effect of concentration Change on Re element determination
As seen from table 23 and fig. 2: when the concentration of the sulfuric acid in the sample is less than 30g/L, the measurement on the content of rhenium is not interfered, but when the concentration of the sulfuric acid in the sample is more than 30g/L, the measurement result on the content of the Re element is obviously lower. And then analyzing the sulfuric acid content in a plurality of batches of samples, and finding that the sulfuric acid content in the solid sample is less than 30g/L, the sulfuric acid content in the liquid sample is usually between 30 and 80g/L, when the rhenium is measured by the liquid sample, a certain volume of enrichment precipitation matrix needs to be taken for measurement, and the sulfuric acid content in the measured solution is less than 30g/L, so that the rhenium element is not interfered.
2. Interference of copper element
In the process test of extracting rhenium from the acidic wastewater, the tested samples contain different amounts of copper element, and whether rhenium to be tested has interference or not due to the change of the content of the copper element is to be further verified through the test.
5.00mL of the rhenium standard use solution was added to 7 100mL volumetric flasks, respectively, at which the concentration of rhenium element was 5.00mg/L. The following table was followed to add different amounts of Cu concentration and examine the effect of changes in Cu concentration in the solution on Re.
Table 24: effect of Cu concentration variation on Re measurements
As can be seen from table 24 and fig. 3: the high and low copper content in the measurement of rhenium affects the measurement of the rhenium content, and the recovery rate of rhenium is reduced to below 30 percent along with the increase of the copper content, so that the existence of the copper element generates serious negative interference on the rhenium and must be eliminated.
And eliminating Cu element interference. In order to eliminate the interference of copper element, the aim of eliminating the interference is achieved by reducing the sample weighing amount and the dividing volume, the method can reduce the content of a matrix, but the measuring signal of the element rhenium to be measured is reduced, when the content of the element to be measured is lower, the sample weighing amount is reduced, the measuring signal of the rhenium element after the dividing times is increased is close to the detection limit of an instrument, and thus the element rhenium to be measured cannot be effectively detected. This method is therefore not desirable for eliminating copper interference. Several complexing methods have been used to eliminate the interference of copper element, but the effect is not ideal, so that the precipitation separation method is used to eliminate the interference of copper matrix to rhenium.
Transferring 2.00mL of rhenium standard use solution into 5 100mL beakers respectively, adding Cu solutions with different amounts according to the following table 10, then adding ammonia water respectively to adjust the solution until precipitation just appears, adding 20mL of hexamethylenetetramine, adding 1g of copper reagent, stirring until the precipitation is complete, filtering into a 100mL volumetric flask, performing constant volume determination, and inspecting the condition of rhenium content determination after separating a copper matrix from the precipitation.
Table 25: re measurement after separation of Cu substrate
From table 25 above, it appears that: the interference of copper element on the determination of Re can be eliminated by adopting a method of precipitating and separating a copper matrix by hexamethylenetetramine and a copper reagent.
Tests show that the recovery rate of rhenium can reach more than 97.7 percent after the copper matrix is separated by precipitation, and then the copper content of the solution after precipitation is measured, and the copper content in the solution after separation is all less than 0.0001g/L, thereby judging that the copper matrix is completely separated. Therefore, the method can eliminate the problem of negative interference of copper element in the sample on rhenium determination, thereby achieving the purpose of eliminating the situation that the rhenium analysis result is lower due to the existence of copper.
3. Interference of arsenic, bismuth and lead contents
The content of arsenic, bismuth and lead in a sample of a rhenium extraction process experiment from acidic wastewater is also high, and the three elements need to be verified by experiments if interference is generated on the determination of rhenium elements.
5.00mL of rhenium standard use solution was added to 7 100mL volumetric flasks, respectively, at which the rhenium element concentration was 5.00mg/L, and different amounts of arsenic, bismuth and lead were added according to the following tables 26-28, and the interference of the solutions with Re due to the changes in the concentrations of these three elements was examined.
Table 26: effect of arsenic concentration variation on Re measurements
Table 27: effect of bismuth concentration variation on Re measurement
Table 28: effect of lead concentration variation on Re measurement
As seen from tables 26-28: the change of arsenic, bismuth and lead contents does not interfere with the measurement of rhenium.
5. Linear range of method
Two sets of standard rhenium use solutions, 0.00mL, 0.50mL, 1.00mL, 2.00mL, 5.00mL and 10.00mL, were removed and placed in 100mL volumetric flasks, and one set was made to volume with pure water to the mark (standard solution I). And adding a small amount of ammonia water, 20mL of hexamethylenetetramine and 1g of copper reagent into the other group, fixing the volume to a scale (standard solution II) by using pure water, and drawing a standard curve by using the two groups of standard solutions with the Re concentrations of 0.00 mu g/mL, 0.50 mu g/mL, 1.00 mu g/mL, 2.00 mu g/mL, 5.00 mu g/mL and 10.00 mu g/mL in sequence, wherein the standard curve is shown in figure 4.
As can be seen from fig. 4 above: the rhenium curve fitting coefficients of the two groups of standard solutions are both above 0.9999, the linearity is good, and the analysis requirements can be met. And the standard solution I and the standard solution II have good inosculation, so that the addition of hexamethylenetetramine and a copper reagent does not influence the measured value of the standard solution, and a working curve is prepared according to the working curve.
6. Method detection limit
Under the optimal working conditions of the selected instrument, 5mL of sulfuric acid, 20mL of hexamethylenetetramine and 1g of copper reagent are added, the mixture is placed in a 100mL volumetric flask, the volume is fixed to a scale by water, the scale is used as a blank solution for continuous measurement for 13 times, the detection limit is 3 times of the standard deviation of the measurement result divided by the slope of the curve, and the measurement results are shown in the following table 29.
Table 29: method for detecting limit data
As can be seen from table 29: the rhenium detection limit measured by the method is 0.00036mg/L, and the analysis requirement of the sample can be met.
7. Precision test
In order to examine the degree of agreement between the measured data of the method, under the selected optimal working conditions, 11 analyses were carried out on the 1# rhenium-rich slag prepared by manual simulation and several random Re contents, and the results of the measured rhenium are shown in Table 30.
Table 30: experiment of sample precision
As can be seen from the precision experimental data table 30: the method is used for measuring the rhenium content in samples such as raw materials, rhenium-rich slag, leaching liquid, dust collecting liquid and the like, and the RSD is measured to be between 1.92% and 4.11%, so that the analysis requirement can be met.
8. Recovery rate of added standard
In order to examine the accuracy of the method, four actual samples are randomly selected to perform the standard recovery rate experiment, and the data of the standard recovery rate are shown in a table 31.
Table 31: sample spiking recovery data
As can be seen from table 31: the standard recovery rate of the sample is between 91.2% and 108.4%, which shows that the method has good accuracy and can be suitable for the measurement and analysis requirements of rhenium content in the rhenium recovery process related materials in the copper smelting system.
9. Compared with artificially simulated synthetic samples
In order to further verify the accuracy of the established analytical method for determining the rhenium content in ten materials such as raw materials, rhenium-rich residues, leaching residues, acid water, leaching liquid and the like by ICP-AES, other methods are needed for comparing the rhenium content, but no other method can determine the rhenium content in the sample at present, so that 3 rhenium-rich residues and 3 acid water solutions are artificially synthesized and determined by the method, and the results and the data of the determined samples are shown in a table 32.
Table 32: comparison table for artificial simulated synthetic sample and determination result
Claims (4)
1. A separation and detection method of rhenium in high-copper matrix solid materials is characterized in that,
the method comprises the following steps:
(1) Weighing 0.2000g of the solid sample with the high copper matrix, and placing the solid sample with the high copper matrix in a 400mL beaker, wherein the weighing precision of the solid sample with the high copper matrix is 0.0002g;
(2) Sequentially adding 10mL of hydrochloric acid and 0.1 to 0.2 g of ammonium bifluoride into a beaker;
(3) Placing the beaker on an electric hot plate with the temperature of less than 200 ℃ for dissolving, adding 15mL of nitric acid, and continuously heating until the volume is reduced to 1-2mL;
(4) Adding 5mL of hydrogen peroxide into the beaker until the sample is completely dissolved;
(5) Washing the watch glass and the wall of the beaker by using distilled water, boiling, taking down, cooling, and then transferring into a 200mL volumetric flask for constant volume to obtain a liquid to be measured;
(6) Taking 50.00mL of solution to be detected, putting the solution into a 300mL beaker, adding ammonia water to adjust until precipitation just occurs, sequentially adding 20mL of hexamethylenetetramine and 1g of copper reagent, fully shaking until the precipitation is complete, carrying out dry filtration to a 100mL volumetric flask, and fixing the volume;
(7) And (4) directly measuring rhenium on the solution obtained in the step (6) by adopting a standard curve method on ICP-AES.
2. A separation detection method for rhenium in a high-copper matrix liquid material is characterized by comprising the following steps:
(1) Taking 25.00mL of liquid solution with high copper matrix in a 300mL beaker;
(2) Adding ammonia water into a beaker, adjusting until precipitation just occurs, then sequentially adding 20mL of hexamethylenetetramine and 1g of copper reagent, fully shaking until the precipitation is complete, carrying out dry filtration to a 100mL volumetric flask, and fixing the volume;
(3) And (3) directly measuring rhenium on the solution obtained in the step (2) by adopting a standard curve method on ICP-AES.
3. The method for separating and detecting rhenium in the high copper matrix solid material according to the claim 1 or the method for separating and detecting rhenium in the high copper matrix liquid material according to the claim 2, characterized in that, in the standard curve method adopted by the ICP-AES, the preparation method of the rhenium standard stock solution comprises the following steps:
(1) Accurately weighing 1.0000g of metal rhenium powder with the concentration of more than or equal to 99.99 percent or 1.4404g of ammonium perrhenate with the concentration of more than or equal to 99.99 percent in a beaker;
(2) 20mL of nitric acid,. Rho.1.42 g/mL, is added to a beaker and 30% hydrogen peroxide is added dropwise to decompose rhenium, 20mL of water is added to boil and remove the hydrogen peroxide, cooled, transferred to a 1000mL volumetric flask with nitric acid (5 + 95) and diluted to 1mL of solution containing 1 mg of rhenium.
4. The separation and detection method for rhenium according to the claim 3, characterized in that, in the standard curve method adopted by the ICP-AES, the preparation method of the rhenium standard using solution comprises the following steps:
(1) Accurately dispensing 10.00mL of rhenium standard stock solution into a 100mL volumetric flask;
(2) Diluted with nitric acid (5 + 95) to 1ml solution containing 100 micrograms rhenium.
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