Liquid phase ultrasonic quadrupole device for element separation

Abstract

The application relates to a liquid-phase ultrasonic quadrupole device for element separation, which comprises a sample injection unit for raw liquid injection, an ultrasonic unit for element separation, a recovered liquid collection unit for collecting liquid after separation and a power supply (1) for providing electric energy; the ultrasonic unit is connected with the sample injection unit, the power supply and the recovered liquid collection unit respectively. Compared with the prior art, the element separation device directly injects liquid, has simple structure, high separation efficiency, low manufacturing cost and good system stability.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of element separation, in particular to a liquid phase ultrasonic quadrupole device for element separation. BACKGROUND

[0002] In actual analysis work, the samples encountered often contain multiple components, which interfere with each other when measured, not only affecting the accuracy of the analysis results, but even unable to be measured. In order to eliminate interference, the relatively simple method is to control the analysis conditions or use appropriate masking agent. But in many cases, only controlling the analysis conditions or adding masking agent cannot eliminate interference, and the measured elements must be separated from the interfering components before measurement. Common element separation methods mainly include gaseous separation method, precipitation and filtration separation method, extraction separation method, ion exchange separation method, chromatographic separation method, electromagnetic separation method, gas floatation separation method, membrane separation method, etc.

[0003] But these methods have shortcomings, such as the precipitation and filtration separation method is suitable for the separation of constant components but not for the separation of trace components. The extraction separation method has large workload, and the organic extractant is often volatile, flammable and toxic; the ion exchange separation method is complicated and has long cycle. SUMMARY

[0004] The purpose of the present application is to overcome at least one of the defects of the prior art and provide a liquid phase ultrasonic quadrupole device for element separation. The present application uses ion liquid direct injection method, which has the advantages of simple device structure, low manufacturing cost, good system stability, high separation efficiency, low energy consumption and many other advantages.

[0005] The idea of the present application is to use an ultrasonic wave generating device to simulate the electric field structure distribution of the ultrasonic quadrupole, form a quadrupole ultrasonic field, and then place a suitable membrane element in the quadrupole ultrasonic field. The ion liquid is sent into the membrane element through the sample injection system, and the ion liquid is separated from other ions and components under the joint action of the quadrupole ultrasonic field and the membrane element.

[0006] The purpose of the present application can be achieved by the following technical solutions:

[0007] A liquid phase ultrasonic quadrupole device for element separation, the device comprises a sample injection unit for raw liquid injection, an ultrasonic unit for element separation, a recovery liquid collection unit for collecting liquid after separation, and a power supply for providing electric energy; the ultrasonic unit is connected with the sample injection unit, the power supply and the recovery liquid collection unit respectively.

[0008] Further, the ultrasonic unit comprises an ultrasonic quadrupole for separating elements and a membrane element for enriching elements, and the membrane element is located at the middle position of the ultrasonic quadrupole.

[0009] Further, the material of the ultrasonic four-pole is a material with electrostrictive effect or magnetostrictive effect.

[0010] Further, the material of the ultrasonic four-pole is a piezoelectric ceramic sheet with electrostrictive effect.

[0011] Further, the ultrasonic four-pole comprises four poles which are centrally symmetric around the membrane element.

[0012] Further, the device is also provided with a support table in the shape of the Chinese character 'Z', and the ultrasonic unit is fixed on the vertical plate of the support table.

[0013] Further, the liquid outlet of the sample feeding unit is connected with the central position of the ultrasonic unit.

[0014] Further, the recovery liquid collecting unit is provided with three liquid recovery branches, the first liquid recovery branch is connected with the central position of the liquid outlet end of the ultrasonic unit, the second liquid recovery branch is connected with the next edge position of the liquid outlet end of the ultrasonic unit, and the third liquid recovery branch is connected with the most edge position of the liquid outlet end of the ultrasonic unit.

[0015] Further, the material of the membrane element is a ceramic membrane, an organic nanofiltration membrane or other membranes with separation function.

[0016] Further, the sample feeding unit is a peristaltic pump. Specifically, the sample feeding unit can send liquid solution into the membrane element through a pipeline, and can be a peristaltic pump or a liquid feeding unit based on other principles, and the number of feeding pipeline ways is not limited.

[0017] Further, the power supply is an alternating frequency power supply, the output voltage amplitude and frequency of the power supply are adjustable, and the frequency can be adjusted to the vicinity of the resonant frequency of the piezoelectric ceramic sheet in the ultrasonic four-pole.

[0018] Further, the device further comprises a support assembly for fixing the ultrasonic unit.

[0019] Further, the support assembly comprises a support table, a fixing rod and a support piece, the support piece is fixed on the support table, the piezoelectric ceramic sheet is fixed on the support piece through the fixing rod, and the piezoelectric ceramic sheet is in the shape of four poles, the number of piezoelectric ceramic sheets on each pole is not limited and is determined according to the axial length of the entire separation device and the height of a single piezoelectric ceramic sheet. The piezoelectric ceramic sheet can deform and generate ultrasonic waves under the alternating current provided by the power supply. When the output voltage amplitude and frequency of the power supply change, the intensity of the ultrasonic waves will also change.

[0020] Further, the piezoelectric ceramic sheets are symmetrically distributed on the support piece.

[0021] Compared with the prior art, the present application has the following advantages:

[0022] (1) The application provides an element separation device with liquid direct sampling, wherein the sampling unit has simple structure and high sampling speed.

[0023] (2) The application provides an element separation device with liquid direct sampling, wherein the device separates elements by using ultrasonic waves generated by an ultrasonic quadrupole.

[0024] (3) The application provides an element separation device with liquid direct sampling, which has simple structure, high separation efficiency, low manufacturing cost and good system stability. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 It is a schematic diagram of a liquid-phase ultrasonic quadrupole device for element separation.

[0026] Figure 2 It is a structural design diagram of a liquid-phase ultrasonic quadrupole device for element separation.

[0027] Figure 3 It is a field work diagram of a liquid-phase ultrasonic quadrupole device for element separation.

[0028] In the figure, the reference signs are as follows: 1-power supply; 2-sampling unit; 3-ultrasonic quadrupole; 4-membrane element; 5-supporting member; 6-fixing rod; 7-supporting table; 8-raw liquid beaker; 9-second recovery liquid beaker; 10-first recovery liquid beaker; 11-third recovery liquid beaker. DETAILED DESCRIPTION

[0029] The application will be described in detail below in combination with the drawings and specific embodiments. The embodiments are implemented on the premise of the technical scheme of the application, and detailed implementation modes and specific operation processes are given, but the protection scope of the application is not limited to the following embodiments.

[0030] Embodiment 1

[0031] The application provides a liquid-phase ultrasonic quadrupole device for element separation, which comprises a sampling unit for raw liquid sampling, an ultrasonic unit for element separation, a recovery liquid collecting unit for collecting liquid after separation, and a power supply 1 for providing electric energy; the ultrasonic unit is connected with the sampling unit, the power supply and the recovery liquid collecting unit respectively.

[0032] The ultrasonic unit comprises an ultrasonic quadrupole 3 for separating elements and a membrane element 4 for enriching elements, the membrane element 4 being located at the center position of the ultrasonic quadrupole 3. The material of the ultrasonic quadrupole 3 is a material having an electrostrictive effect or a magnetostrictive effect. The material of the ultrasonic quadrupole 3 is a piezoelectric ceramic sheet having an electrostrictive effect. The material of the membrane element 4 is a ceramic membrane or an organic nanofiltration membrane. The ultrasonic quadrupole 3 comprises four pole rods arranged in central symmetry around the membrane element 4. The sample inlet unit 2 is a peristaltic pump. The power supply 1 is an alternating frequency power supply. The device further comprises a support assembly for fixing the ultrasonic unit. The liquid outlet of the sample inlet unit is connected to the center position of the ultrasonic unit. The liquid recovery unit is provided with three liquid recovery branches, the first liquid recovery branch is connected to the central position of the liquid outlet end of the ultrasonic unit, the second liquid recovery branch is connected to the next edge position of the liquid outlet end of the ultrasonic unit, and the third liquid recovery branch is connected to the most edge position of the liquid outlet end of the ultrasonic unit. The support assembly comprises a Z-shaped support table 7, a fixing rod 6 and a support piece 5, the support piece 5 is fixed on the support table 7, and the piezoelectric ceramic sheet is fixed on the support piece 5 through the fixing rod 6. The piezoelectric ceramic sheets are symmetrically distributed on the support piece 5.

[0033] As shown in Figure 1 , Figure 2 and Figure 3 , the power supply 1 of the liquid-phase ultrasonic quadrupole device is composed of a double-channel signal generator (1, RIGOL DG822) and a power amplifier (2, ATA4014), the sample inlet unit 2 is an intelligent flow peristaltic pump (1, BT101L), the ultrasonic quadrupole 3 is composed of 12 piezoelectric ceramic sheets with a resonant frequency of 1MHz, the membrane element 4 is composed of a ceramic membrane with a pore size of 8nm, an inner diameter of 19mm, an outer diameter of 25mm and a length of 326mm, and a nanofiltration membrane with a model number of JWNF1-2540F31, and other equipment includes an impedance analyzer, an oscilloscope, an ICP-MS, a volumetric flask, a beaker, a glass rod, a pipette, a rubber dropper, etc. The above-mentioned parts are assembled into a complete liquid-phase ultrasonic quadrupole isotope separation device according to the structure diagram shown in Figure 1 , Figure 2 .

[0034] The specific implementation process of the embodiment is as follows:

[0035] (1) Prepare 1000mL of 0.1mol / L nitric acid, add 500mL of 0.1mol / L nitric acid to a 1000mL volumetric flask, add 1mL of a mixed standard solution of 25 kinds of elements such as barium, bismuth, vanadium, calcium, cadmium, chromium, cobalt, potassium, calcium, phosphorus, aluminum, magnesium, manganese, sodium, nickel, boron, beryllium, lead, arsenic, strontium, antimony, iron, copper, selenium, zinc, etc. with a concentration of 100mg / L, and add 0.1mol / L nitric acid to make up to 1000mL, the obtained target ion concentration is 0.1mg / L.

[0036] (2) The liquid phase ultrasonic four-stage rod isotope separation device has four ultrasonic wave emitting devices (No. 1, No. 2, No. 3 and No. 4) in four dimensions, each of which is composed of three piezoelectric ceramic sheets with a resonance frequency of 1 MHz. The six piezoelectric ceramic sheets in the upper and lower dimensions are connected in series to the positive and negative test terminals of an impedance analyzer, and the impedance-frequency characteristic curve of the six piezoelectric ceramic sheets in series is obtained. The corresponding resonance frequency fs1 and minimum impedance R1 are measured. The six piezoelectric ceramic sheets in the left and right dimensions are connected in series to the positive and negative test terminals of the impedance analyzer, and the impedance-frequency characteristic curve of the six piezoelectric ceramic sheets in series is obtained. The corresponding resonance frequency fs2 and minimum impedance R2 are measured. The channel 1 of the signal generator outputs an alternating current signal 1 with a peak-to-peak value (Vpp) of U, a frequency of fs1 and an initial phase of 0; the channel 2 outputs an alternating current signal 2 with a peak-to-peak value (Vpp) of U, a frequency of fs2 and an initial phase of π. The output end of the channel 1 is connected to the input end of the ATA4014-1, and the output end of the channel 2 is connected to the input end of the ATA4014-2. The amplification multiples of the ATA4014-1 and the ATA4014-2 are adjusted so that the ATA4014-1 outputs an alternating current signal 3 with a peak-to-peak value (Vpp) of k1U, a frequency of fs1 and an initial phase of 0; and the ATA4014-2 outputs an alternating current signal 4 with a peak-to-peak value (Vpp) of k2U (k1≠k2), a frequency of fs2 and an initial phase of π. The alternating current signals output by the ATA4014-1 and the ATA4014-2 are monitored using a digital oscilloscope. The positive and negative terminals of the six piezoelectric ceramic sheets in series corresponding to the ultrasonic wave emitting devices in the No. 1 and No. 3 dimensions are connected to the positive and negative terminals of the output end of the ATA4014-1; the positive and negative terminals of the six piezoelectric ceramic sheets in series corresponding to the ultrasonic wave emitting devices in the No. 2 and No. 4 dimensions are connected to the positive and negative terminals of the output end of the ATA4014-2. The flow meters of 1#, 2# and 3# are adjusted to close the 1#, 2# and 3# liquid outlet pipes, respectively. The 1# liquid outlet pipe is connected to the central position of the liquid outlet end of the separation device, the 2# liquid outlet pipe is connected to the next edge position of the liquid outlet end of the separation device, and the 3# liquid outlet pipe is connected to the most edge position of the liquid outlet end of the separation device. 300 mL of the sample solution prepared in advance is placed in the 0# beaker, and 10 mL of the sample solution is placed in the 0# sampling tube. The peristaltic pump is turned on, and the flow rate of the peristaltic pump is set to 8 mL / min. The sample solution with a concentration of 0.1 mg / L in the 0# beaker is introduced into the ceramic membrane central tube (8 nm-19*25*326) through the peristaltic pump. After the sample solution fills the separation device, the flow meters of the three liquid outlet pipes are opened, and the flow rates of the flow meters are controlled so that the sum of the flow rates of the three liquid outlet pipe flow meters is equal to the inlet flow rate of the peristaltic pump, and V1#<V2#<V3#. The solutions flowing out of the three liquid outlet pipes enter the 1# beaker.Press the signal output button of ATA4014-1 and ATA4014-2, and after the system is stable for 10 minutes, insert 1#, 2# and 3# liquid outlet pipes into 1#, 2# and 3# sampling tubes to collect the separated solutions flowing out from different positions of the separation device, respectively. After 10 mL of solutions are collected in the three sampling tubes, respectively, turn off the three flow meters, turn off the peristaltic pump, and turn off the signal generator, power amplifier and oscilloscope. Analyze the components and concentrations of the solutions in 0#, 1#, 2# and 3# sampling tubes by ICP-MS, and record the experimental data.

[0037] In the implementation process, the specific parameters are as follows:

[0038] Piezoelectric ceramic sheet parameters

[0039] The resonant frequency of No. I and No. III piezoelectric ceramic sheets is 1.03327 MHz;

[0040] The resonant frequency of No. II and No. IV piezoelectric ceramic sheets is 1.03774 MHz;

[0041] The signal generator output is Vpp=1V;

[0042] The amplifier ATA4014-1 output is 2V (Vpp) with a frequency of 1.03327 MHz;

[0043] The amplifier ATA4014-1 output is 4V (Vpp) with a frequency of 1.03774 MHz;

[0044] After 20 minutes of separation, the separated solutions are collected:

[0045] 1-1 colorimetric tube: liquid flowing out from 1# liquid outlet pipe;

[0046] 1-2 colorimetric tube: liquid flowing out from 2# liquid outlet pipe;

[0047] 1-3 colorimetric tube: liquid flowing out from 3# liquid outlet pipe;

[0048] 1-4 colorimetric tube: original solution.

[0049] Through ICP-MS analysis, the concentrations of sodium ions and calcium ions in the original solution are 12 μg / L and 7 μg / L, respectively.

[0050] The concentration of sodium ions in 1-1 colorimetric tube is 3 μg / L, and the concentration of calcium ions is 6 μg / L; the concentration of sodium ions in 1-2 colorimetric tube is 5 μg / L, and the concentration of calcium ions is 0.6 μg / L; the concentration of sodium ions in 1-3 colorimetric tube is 4 μg / L, and the concentration of calcium ions is 0.4 μg / L.

[0051] Example 2

[0052] Example 2 has substantially the same operating conditions as Example 1, except that the specific operating parameters are as follows:

[0053] The amplifier ATA4014-1 outputs 2V (Vpp) at a frequency of 1.03327MHz;

[0054] The amplifier ATA4014-1 outputs 8V (Vpp) at a frequency of 1.03774MHz;

[0055] After 20 minutes of separation, the separated solution is collected:

[0056] 2-1 cuvette: 1# outlet pipe effluent;

[0057] 2-2 cuvette: 2# outlet pipe effluent;

[0058] 2-3 cuvette: 3# outlet pipe effluent;

[0059] 1-4 cuvette: original solution.

[0060] ICP-MS analysis shows that the concentrations of sodium ions and calcium ions in the original solution are 12μg / L and 7μg / L, respectively.

[0061] The concentration of sodium ions in the 2-1 cuvette is 2.5μg / L, and the concentration of calcium ions is 5.8μg / L; the concentration of sodium ions in the 2-2 cuvette is 4μg / L, and the concentration of calcium ions is 0.45μg / L; the concentration of sodium ions in the 2-3 cuvette is 5.5μg / L, and the concentration of calcium ions is 0.75μg / L.

[0062] Example 3

[0063] Example 3 has substantially the same operating conditions as Example 1, except that the specific operating parameters are as follows:

[0064] The amplifier ATA4014-1 outputs 4V (Vpp) at a frequency of 1.03327MHz;

[0065] The amplifier ATA4014-1 outputs 8V (Vpp) at a frequency of 1.03774MHz;

[0066] After 20 minutes of separation, the separated solution is collected:

[0067] 3-1 cuvette: 1# outlet pipe effluent;

[0068] 3-2 cuvette: 2# outlet pipe effluent;

[0069] 3-3 cuvette: 3# outlet pipe effluent;

[0070] 1-4 cuvette: original solution.

[0071] The concentrations of sodium ions and calcium ions in the stock solution were 12 μg / L and 7 μg / L respectively by ICP-MS analysis.

[0072] The concentration of sodium ions in the 3-1 colorimetric tube was 1.5 μg / L, and the concentration of calcium ions was 5.2 μg / L; the concentration of sodium ions in the 3-2 colorimetric tube was 3.8 μg / L, and the concentration of calcium ions was 0.4 μg / L; the concentration of sodium ions in the 3-3 colorimetric tube was 6.7 μg / L, and the concentration of calcium ions was 1.4 μg / L.

[0073] The results of Example 1-3 show that after the separation of different elements by liquid phase ultrasonic quadrupole, the concentrations of sodium ions and calcium ions in the solutions collected from different positions of the 1#, 2# and 3# sampling tubes are different, indicating that the diffusion rates of sodium ions and calcium ions are different under the combined action of ultrasonic waves and membranes, the diffusion rate of sodium ions to the edge is faster, and the diffusion rates of the two kinds of ions increase with the increase of voltage, and the device plays a role in separating sodium ions and calcium ions.

[0074] The above is only a preferred embodiment of the present application, and is not intended to limit the present application in other forms. Any skilled person in the art can modify or change the above disclosed technical content to equivalent embodiments. However, any simple modification, equivalent change and modification of the above embodiments without departing from the technical solution of the present application, according to the technical essence of the present application, still belongs to the protection scope of the technical solution of the present application.

Claims

1. A liquid-phase ultrasonic quadrupole device for elemental separation, characterized by, The device comprises a sample injection unit for sample injection, an ultrasonic unit for element separation, a recovery liquid collection unit for collection of separated liquid, and a power supply (1) for providing electric energy; The ultrasonic unit is connected with the sample injection unit, the power supply and the recovery liquid collection unit respectively; The ultrasonic unit comprises an ultrasonic quadrupole (3) for separating elements and a membrane element (4) for enriching elements, and the membrane element (4) is located at the middle position of the ultrasonic quadrupole (3); The recovery liquid collection unit is provided with three liquid recovery branches, the first liquid recovery branch is connected with the central position of the liquid outlet end of the ultrasonic unit, the second liquid recovery branch is connected with the next edge position of the liquid outlet end of the ultrasonic unit, and the third liquid recovery branch is connected with the most edge position of the liquid outlet end of the ultrasonic unit.

2. The liquid ultrasonic quadrupole device for elemental separation according to claim 1, characterized in that, The material of the ultrasonic quadrupole (3) is a material with electrostrictive effect or magnetostrictive effect.

3. The liquid ultrasonic quadrupole device for elemental separation according to claim 1, wherein, The material of the ultrasonic quadrupole (3) is a piezoelectric ceramic sheet with electrostrictive effect.

4. The liquid ultrasonic quadrupole device for elemental separation according to claim 1, wherein, The ultrasonic quadrupole (3) comprises four pole rods which are centrally symmetric around the membrane element (4).

5. The liquid ultrasonic quadrupole device for elemental separation according to claim 1, wherein, The device is further provided with a support table (7) in the shape of the Chinese character " " (zhi), and the ultrasonic unit is fixed on the vertical plate of the support table (7).

6. The liquid ultrasonic quadrupole device for elemental separation according to claim 1, wherein, The liquid outlet pipe of the sample injection unit is connected with the central position of the ultrasonic unit.

7. The liquid ultrasonic quadrupole device for elemental separation according to claim 1, wherein, The material of the membrane element (4) is a ceramic membrane or an organic nanofiltration membrane.

8. The liquid ultrasonic quadrupole device for elemental separation according to claim 1, wherein, The sample injection unit is a peristaltic pump, and the power supply (1) is an alternating frequency power supply.

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