CN111896574A - Immersion lanthanum extraction field detection system and detection method - Google Patents
Immersion lanthanum extraction field detection system and detection method Download PDFInfo
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- 238000001514 detection method Methods 0.000 title claims abstract description 144
- 238000000605 extraction Methods 0.000 title claims abstract description 93
- 229910052746 lanthanum Inorganic materials 0.000 title claims abstract description 78
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 238000007654 immersion Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 45
- 239000000284 extract Substances 0.000 claims abstract description 29
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 27
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000001228 spectrum Methods 0.000 claims abstract description 26
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- 238000009413 insulation Methods 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims description 56
- 230000000694 effects Effects 0.000 claims description 24
- 238000005259 measurement Methods 0.000 claims description 23
- FZLIPJUXYLNCLC-BJUDXGSMSA-N lanthanum-138 Chemical compound [138La] FZLIPJUXYLNCLC-BJUDXGSMSA-N 0.000 claims description 20
- 238000004458 analytical method Methods 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 13
- 230000007797 corrosion Effects 0.000 claims description 9
- 238000005260 corrosion Methods 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
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- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 238000005057 refrigeration Methods 0.000 claims description 4
- 230000000149 penetrating effect Effects 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims 3
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 18
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- 238000013461 design Methods 0.000 abstract description 5
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Abstract
The invention discloses an immersion lanthanum extraction on-site detection system and a detection method.A detection pipeline is arranged in a cavity, the bottom of the detection pipeline is provided with a bulge, a high-purity germanium detector is arranged in the bulge, the outer wall of the high-purity germanium detector is coated with heat insulation cotton, and the bottom of the high-purity germanium detector is provided with a shielding ring; be equipped with gamma spectrometer and PLC controller outside flow sensor, density sensor, the cavity in the detection pipeline, the output of flow sensor, density sensor and gamma spectrometer connects the PLC controller. During detection, the PLC extracts energy spectrumN A 、N b (ii) a And calculating the detection sensitivity S of lanthanum, the mass DM of lanthanum in the extract liquor and the minimum detectable mass by combining the real-time flow, density and the likeMDM。The invention realizes the on-line control of the extraction quality of the rare earth element lanthanum, does not need to design a sample injection system independently and has high distribution degree compared with the traditional quality control method in the process of selecting and smelting the rare earth element lanthanumGood timeliness, low detection limit, high sensitivity and the like.
Description
Technical Field
The invention relates to an on-line detection system and method in a lanthanum extraction process, in particular to an immersion lanthanum extraction on-site detection system and detection method.
Background
Weathering crust eluviation type rare earth ore is taken as one of important rare earth ore deposit types in China, and at present, a cascade extraction method is mostly adopted for the rare earth ore dressing and smelting in China to separate out single rare earth elements. Lanthanum is used as an important rare earth element in weathering crust elution-deposited rare earth ore, and the mass proportion of the lanthanum can reach 29.09%. Therefore, the quality ratio detection in the separation process has important significance.
At the present stage, the detection of the element distribution characteristics in the process of dressing and smelting the rare earth ore generally comprises the detection of the rare earth ore solid, such as chemical analysis, ICP-MS and ICP-AES methods, and the detection of the rare earth extract, such as EDXFF, WDXRF and the like. The methods mostly need to rely on large-scale experimental equipment, the processes of sampling, sample preparation, detection and the like usually need practice for several hours or even one day, and the detection timeliness is relatively lagged.
For example, in the chemical analysis method in the prior art, a laboratory worker needs to take a sample in an extraction tank and send the sample to a relevant laboratory, and the sample needs to be subjected to pretreatment processes such as precipitation, impurity removal, dilution, extraction, configuration and the like. The detection period is longer, and the types of required experimental equipment are more. The detection processes of detection methods such as ICP-AES, ICP-MS and the like are similar to chemical analysis, and sample pretreatment is required. In addition, the detection method has higher equipment cost and harsher detection environment requirement, and laboratory personnel need to be trained by professional techniques and generally need to be finished in a special detection laboratory.
The fluorescence detection methods such as WDXRF and EDXRF are field detection methods which can be used for rare earth dressing and metallurgy in recent years, and compared with the traditional detection method, the method has lower requirements on the pretreatment degree of the sample. But a high-power x-ray tube is still needed as an excitation source to excite the characteristic x-rays of various elements in the extraction liquid so as to realize the purpose of quantitative detection. We take the document CN105136831A as an example, which uses energy dispersive X-ray to analyze the mass ratio of lanthanum in rare earth elements, although the measurement is performed by using the extract. In the method, the sample is irradiated by X-rays to excite the fluorescence of the L-series rays in the rare earth elements, so an excitation source is used, and the method needs to be provided with an active sample feeding device such as a peristaltic pump and an extraction liquid backflow sealing connecting pipeline, so that the system is complex and the cost is high.
In addition, under the technical background that the extraction efficiency is continuously improved, the existing detection method is difficult to match with extraction equipment with higher automation level, so that the production efficiency is low and the product quality is unstable. Therefore, an efficient, stable, simple-structured and distributed continuous detection system is urgently needed to realize the product quality control of the key process nodes.
Disclosure of Invention
The invention aims to provide an immersion lanthanum extraction field detection system and a detection method, which can solve the problems, effectively improve the on-line detection sensitivity of the lanthanum extraction process and reduce the on-line detection limit.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: an immersion lanthanum extraction field detection system comprises a cavity, wherein a detection pipeline horizontally penetrating through two ends of the cavity is arranged in the cavity and is used for allowing lanthanum extraction liquid to flow through;
the bottom of the detection pipeline is provided with a bulge facing the center of the detection pipeline, the bulge is cylindrical, a high-purity germanium detector is arranged in the bulge, the high-purity germanium detector is right opposite to the inside of the detection pipeline, the top of the high-purity germanium detector is attached to the top of the bulge, the outer wall of the detection pipeline is coated with heat insulation cotton, the bottom of the detection pipeline is provided with a shielding ring, and the bottom of the shielding ring is flush with the bottom;
a flow sensor and a density sensor are arranged in the detection pipeline, a gamma spectrometer and a PLC (programmable logic controller) are arranged outside the cavity, and the output ends of the flow sensor, the density sensor and the gamma spectrometer are connected with the PLC;
the flow sensor and the density sensor are respectively used for acquiring flow velocity information v and real-time density information rho of the extraction liquid;
the output end of the high-purity germanium detector is connected with a gamma energy spectrometer and is used for detecting gamma rays in the extraction liquid and obtaining an energy spectrum through analysis of the gamma energy spectrometer;
the PLC is used for setting the measurement time t and extracting the characteristic peak count N of gamma rays with energy of 1.435MeV in lanthanum-138 from the energy spectrumACharacteristic full energy peak interval background count NbAnd combining the flow velocity information v and the real-time density information rho to obtain the detection sensitivity S of lanthanum and the mass DM of lanthanum in the extraction liquid according to the following formula:
S＝η·ALa·γ
in the formula: eta is the detection efficiency of the gamma spectrometer, gamma is the branch ratio of 1.435MeV rays, the value is 65.5 percent, and ALaThe specific activity of natural lanthanum is 826.63Bq/kg, ASThe activity of lanthanum-138 in the extract to be tested.
Preferably, the method comprises the following steps: the detection pipeline is made of stainless steel materials or PVC materials, if the detection pipeline is made of the stainless steel materials, a corrosion-resistant layer is arranged in the detection pipeline, and the corrosion-resistant layer is made of polytetrafluoroethylene and derivatives thereof.
Preferably, the method comprises the following steps: the cross section of the detection pipeline is circular, the inner diameter is 30cm, the outer diameter is 32cm, the size of the bulge is 15cm x12 cm, the wall thickness is 1mm, and the thickness of the heat insulation cotton is 2 cm.
Preferably, the method comprises the following steps: the high-purity germanium detector has a relative detection efficiency of more than or equal to 120%, adopts an electric refrigeration mode and comprises a cold finger and a signal wire, wherein the cold finger and the signal wire are led out from a hole in the middle of a lead shielding ring.
A detection method of an immersion lanthanum extraction on-site detection system comprises the following steps:
(1) establishing an immersion lanthanum extraction field detection system, and connecting a detection pipeline in series on a pipeline through which the extract liquid to be detected flows;
(2) starting a system, collecting flow velocity information v and real-time density information rho of the extraction liquid by a flow sensor and a density sensor, detecting gamma rays in the extraction liquid by a high-purity germanium detector, sending the gamma rays into a gamma energy spectrometer for analysis to obtain a measurement energy spectrum, and outputting the measurement energy spectrum;
(3) the PLC extracts the 1.435MeV characteristic peak count N of the lanthanum-138 from the superposition energy spectrumAThe background count N of the characteristic full energy peak intervalb(ii) a Calculating the detection sensitivity S of lanthanum and the mass DM of lanthanum in the extraction liquid according to the following formula;
S＝η·ALa·γ
in the formula: eta is the detection efficiency of the gamma spectrometer, gamma is the branch ratio of 1.435MeV rays, the value is 65.5 percent, and ALaThe specific activity of natural lanthanum is 826.63Bq/kg, ASThe activity of lanthanum-138 in the extract to be tested.
Preferably, the method comprises the following steps: further comprising the step (4) of calculating the minimum detectable mass MDM of lanthanum according to the following formula;
the method is used for measuring the gamma ray characteristic peak of radioactive isotope lanthanum-138 with energy of 1.435MeV in the extraction liquid and calculating the mass ratio of lanthanum in the rare earth elements by measuring the gamma ray characteristic peak. By the method, the detection sensitivity S of lanthanum is higher, and the minimum detectable mass MDM is lower.
The detection pipeline is structurally made of stainless steel materials or PVC materials, if the detection pipeline is made of the stainless steel materials, a corrosion-resistant layer is arranged in the detection pipeline, and the corrosion-resistant layer is made of polytetrafluoroethylene and derivatives thereof. Because the extract has a certain corrosiveness, if stainless steel material is used, a corrosion-resistant layer is needed.
The detector is a high-purity germanium detector, and realizes the measurement of 1.435MeV characteristic gamma rays of the lanthanum-138 nuclide in the extract liquid flowing in the pipeline. The bottom of the detection pipeline is provided with a bulge, the detector is positioned in the bulge, namely the detector is immersed in the extraction liquid, the detection solid angle of the detector is increased, and the effective counting N of the gamma ray characteristic peak with the energy of 1.435MeV can be increasedA. Meanwhile, the detector is immersed in the extraction liquid, and self-shielding of the radioactive background of the surrounding environment can be realized, namely, the background count is reduced and the N is reducedb。
The outer wall of the high-purity germanium detector is coated with heat insulation cotton, and the purpose is as follows: the performance of the detector is influenced by the working temperature, and besides the built-in refrigeration part, the heat insulation cotton in the design can ensure that the temperature in the bulge is relatively constant, so that the influence of the temperature change of the extraction liquid in the pipeline on the performance of the detector is reduced.
The bottom is provided with a shielding ring for shielding U series, Th series and40the interference of gamma rays generated by the decay of K natural radioactive nuclide and the interference of gamma rays generated by other possible natural and artificial radioactive nuclides further realizes the further reduction of the background count NbThe purpose of (1). According to the formula
It is known that N is increasedADecrease NbThe peak back ratio xi of the characteristic peak can be effectively improved.
In the invention, the formula S is equal to eta.ALa·γ、
To calculate the detection sensitivity S of lanthanum, since N is increasedACan improve the detection sensitivity eta of the gamma spectrometer because of ALaIs the specific activity of natural lanthanum, is constant, and gamma is 1.435The branch ratio of the MeV rays, which is also constant, is 65.5%%. Therefore, it can be seen from the formula that the lanthanum detection sensitivity S can be improved.
The invention utilizes the formula
To calculate the minimum detectable mass MDM of lanthanum due to the reduction of NbThe invention can effectively reduce the minimum detectable mass MDM of lanthanum.
The MDM of the invention, namely the minimum value of the detection quality which can be realized by the detection system under certain confidence condition, is calculated by the following method,
in the formula, LDThe method is a detection limit of a gamma energy spectrometer for effective counting of a lanthanum-138 characteristic peak area, m is the mass of extraction liquid in a pipeline, and the formula is m ═ rho.v.t, and the method can be obtained by calculation of density, flow velocity and measurement time t. While
The detection limit of the counting rate of the gamma spectrometer is under the condition of 95% of unilateral confidence probability, so the formula can be rewritten as follows:
it can be seen that when the state of the extract is stable, MDM and the background count N of the characteristic full energy peak intervalbProportional and inversely proportional to the measurement time t. The device can reduce N through effective structural designbThe detection efficiency eta is improved, and then the MDM is effectively reduced.
In this formula, the background counts in the characteristic peak region
Measuring by a gamma spectrometer; and gamma, ALaEta is constant, rho and v can be sensed by flow and densityLearning by the device; t is the measurement time, set by the detection system. It can be seen that when the state of the extract is stable, MDM is proportional to the background count and inversely proportional to the measurement time.
The integrated measuring pipeline is connected with the extraction centrifuge pipeline, and the measuring instrument is connected in series in the process flow of the multistage extraction centrifuge without additional equipment such as a peristaltic pump and the like. Compared with the on-line analysis methods based on spectrophotometry, x-fluorescence on-line analysis and the like at the present stage, the extraction liquid sample return pipeline does not need to be designed independently.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a novel detection device and a novel detection method, which utilize the device to directly detect extraction liquid and extract the characteristic peak count N of gamma rays with energy of 1.435MeV in lanthanum-138 from the superposition energy spectrum of the extraction liquidACharacteristic full energy peak interval background count NbAnd combining the flow velocity information v and the real-time density information rho, the detection sensitivity S of lanthanum, the mass DM of lanthanum in the extraction liquid and the minimum detectable mass MDM can be obtained. The invention overcomes the defect that the detection analysis must be carried out by solid sampling or the extraction liquid must depend on an active excitation source to excite and measure the activity of the natural radionuclide in the extraction liquid in the prior art. A method for extracting the characteristic peak count N of gamma ray from the energy spectrum of extraction liquid is disclosedACharacteristic full energy peak interval background count NbTo perform DM measurements. The method extracts the characteristic peak count N of gamma ray with energy of 1.435MeV in lanthanum-138 from the superposition energy spectrum of extraction liquidACharacteristic full energy peak interval background count NbAnd combining the flow velocity information v and the real-time density information rho, the detection sensitivity S of lanthanum, the mass DM of lanthanum in the extraction liquid and the minimum detectable mass MDM can be obtained.
(2) The invention has simple structure and convenient installation, can detect the quality of single-stage extraction and can realize the detection of multi-stage series quality flow. During installation, the extraction liquid reflux pipeline can be effectively simplified by directly adopting a series connection mode to be installed between extraction tanks or on an extraction liquid circulating pipeline without additional equipment such as a peristaltic pump and the like, and the system design is simpler and has lower cost.
(3) Compared with the existing spectrophotometric online analysis method, x-fluorescence online analysis method and the like, the method does not need an active excitation source, directly measures the activity of the natural radionuclide in the extract, belongs to a passive detection method, has a detection result less influenced by the factors of the instrument, can effectively avoid the influence of the equipment on the detection result, and can effectively improve the N content based on the structure of the inventionALowering NbThus, the sensitivity S for lanthanum detection is higher and the minimum detectable mass MDM is lower.
Drawings
FIG. 1 is a schematic structural view of the present invention;
FIG. 2 is a cross-sectional view A-A of the test tube of FIG. 1;
FIG. 3 is a cross-sectional view B-B of the test tube of FIG. 1
FIG. 4 is a schematic diagram of a sampling process of a conventional on-line detection system for a multi-stage extraction tank;
FIG. 5 is a schematic diagram of a sampling process according to the present invention;
FIG. 6 is a full spectrum of the measurement process of the present invention;
FIG. 7 is a processed real-time measured background energy spectrum of FIG. 6 after expansion of the arrow region.
In the figure: 1. a cavity; 2. detecting a pipeline; 3. a high purity germanium detector; 4. heat insulation cotton; 5. a flow sensor; 6. a density sensor; 7. a shield ring; 8. a status indicator light; 9. a power and data interface; 10. and (4) protruding.
Detailed Description
The invention will be further explained with reference to the drawings.
Example 1: referring to fig. 1 to 3, an immersion lanthanum extraction field detection system comprises a cavity 1, wherein a detection pipeline 2 horizontally penetrates through two ends of the cavity 1, and the detection pipeline 2 is used for flowing a lanthanum extraction liquid;
the bottom of the detection pipeline 2 is provided with a protrusion 10 towards the center of the detection pipeline, the protrusion 10 is cylindrical, a high-purity germanium detector 3 is arranged in the protrusion 10, the high-purity germanium detector 3 is right opposite to the inside of the detection pipeline 2, the top of the high-purity germanium detector is attached to the top of the protrusion 10, the outer wall of the detection pipeline is coated with heat insulation cotton 4, the bottom of the detection pipeline is provided with a shielding ring 7, and the bottom of the shielding ring 7 is flush with the bottom of the;
a flow sensor 5 and a density sensor 6 are arranged in the detection pipeline 2, a gamma spectrometer and a PLC (programmable logic controller) are arranged outside the cavity 1, and the output ends of the flow sensor 5, the density sensor 6 and the gamma spectrometer are connected with the PLC;
the flow sensor 5 and the density sensor 6 are respectively used for collecting flow velocity information v and real-time density information rho of the extraction liquid;
the output end of the high-purity germanium detector 3 is connected with a gamma energy spectrometer and is used for detecting gamma rays in the extraction liquid and obtaining an energy spectrum through analysis of the gamma energy spectrometer;
the PLC is used for setting the measurement time t and extracting the characteristic peak count N of gamma rays with energy of 1.435MeV in lanthanum-138 from the energy spectrumACharacteristic full energy peak interval background count NbAnd combining the flow velocity information v and the real-time density information rho to obtain the detection sensitivity S of lanthanum and the mass DM of lanthanum in the extraction liquid according to the following formula:
S＝η·ALa·γ
in the formula: eta is the detection efficiency of the gamma spectrometer, gamma is the branch ratio of 1.435MeV rays, the value is 65.5 percent, and ALaThe specific activity of natural lanthanum is 826.63Bq/kg, ASThe activity of lanthanum-138 in the extract to be tested.
The detection pipeline 2 is made of stainless steel materials or PVC materials, if the detection pipeline is made of the stainless steel materials, a corrosion-resistant layer is arranged in the detection pipeline 2, and the corrosion-resistant layer is made of polytetrafluoroethylene and derivatives thereof.
The cross section of the detection pipeline 2 is circular, the inner diameter is 30cm, the outer diameter is 32cm, the size of the bulge 10 is 15cm x12 cm, the wall thickness is 1mm, and the thickness of the heat insulation cotton 4 is 2 cm.
The high-purity germanium detector 3 has a relative detection efficiency of not less than 120%, and adopts an electric refrigeration mode, and comprises a cold finger and a signal wire, wherein the cold finger and the signal wire are led out from a hole in the middle of the lead shielding ring 7. In this embodiment, the high-purity germanium detector 3 is a kaberra GX12021 type detector, and if other types of detectors are adopted, the same effect can be achieved, and the invention is within the protection scope of the present application.
A detection method of an immersion lanthanum extraction on-site detection system comprises the following steps:
(1) establishing an immersion lanthanum extraction field detection system, and connecting the detection pipeline 2 in series on a pipeline through which the extract liquid to be detected flows;
(2) starting the system, collecting flow velocity information v and real-time density information rho of the extraction liquid by a flow sensor 5 and a density sensor 6, detecting gamma rays in the extraction liquid by a high-purity germanium detector 3, sending the gamma rays into a gamma energy spectrometer for analysis to obtain a measurement energy spectrum, and outputting the measurement energy spectrum;
(3) the PLC extracts the 1.435MeV characteristic peak count N of the lanthanum-138 from the superposition energy spectrumAThe background count N of the characteristic full energy peak intervalb(ii) a Calculating the detection sensitivity S of lanthanum and the mass DM of lanthanum in the extraction liquid according to the following formula;
S＝η·ALa·γ
in the formula: eta is the detection efficiency of the gamma spectrometer, gamma is the branch ratio of 1.435MeV rays, the value is 65.5 percent, and ALaThe specific activity of natural lanthanum is 826.63Bq/kg, ASThe activity of lanthanum-138 in the extract to be tested.
(4) Calculating the minimum detectable mass MDM of lanthanum according to the following formula;
during measurement, in order to ensure the accuracy of data, measurement is generally started after the extraction liquid flow is detected to be stable. The outer wall of the cavity 1 can be provided with a status indicator light 8 and a power supply and data interface 9, and the status indicator light 8 can be used for indicating whether equipment such as various sensors work normally or whether the flow rate and the density are stable or not. Can be set according to the needs. The power supply and data interface 9 is used for supplying power to each internal power consumption unit.
For example: the detection pipeline 2 is connected with the extraction centrifuge in series, and the extraction liquid passes through the detection pipeline 2 in the extraction process; the flow sensor 5 monitors the flow in the detection pipeline 2 in real time; after the flow of the extraction liquid is stable, the state indicator lamp 8 flickers; the high-purity germanium detector 3 in the cavity 1 starts to automatically detect the extraction liquid flowing in the pipeline, the gamma ray energy spectrum is measured and sent to the PLC, the built-in data processing system calculates the mass component of the rare earth element lanthanum, the detection result can be stored locally or uploaded to a main control room through a power supply and data interface 9, and the measurement process is controlled by computer software.
As can be seen from fig. 4, in the immersion lanthanum extraction field detection system and method according to the present invention, the integrated detection pipeline 2 is connected in series in the process flow of the multistage extraction centrifuge, and no additional equipment such as a "peristaltic pump" is required. Compared with the on-line analysis methods based on a spectrophotometry on-line analysis method, an x fluorescence on-line analysis method and the like at the present stage, the extraction liquid reflux pipeline does not need to be separately designed. The sampling system of the invention has simpler design and lower cost.
Example 2: referring to fig. 1 to 5, an embodiment 2 applying the apparatus and method of the present invention is shown on the basis of the embodiment 1.
(1) First, we need to establish a plurality of distributed lanthanum extraction online detection systems based on gamma spectroscopy as described in example 1. Next, the mounting is performed according to FIG. 4. In FIG. 4, let S1 be the raw liquid pool, E1-En be n extraction pools, i.e. n-stage extraction pools, and the immersed lanthanum extraction field detection systems of the present invention are also n, respectively labeled as Q1-Qn. As can be seen from the figure, the method provided by the invention directly measures the activity of the natural radionuclide in the extract without an active excitation source, belongs to a passive detection method, and has a detection result less influenced by the factors of the instrument.
In fig. 4, the flow direction of the liquid is: the stock solution with rare earth metal lanthanum is firstly placed in a stock solution tank S1, and is sequentially connected with a plurality of stages of extraction tanks through pipelines, and the immersed lanthanum extraction on-site detection system is installed on the pipelines, particularly, is connected on the pipelines in series through the detection pipelines 2. Then Q1-Qn, respectively, can analyze and detect the extraction liquid of the rare earth metal lanthanum from E1-En.
We use Q1-Qn as the detection node and we probe at Q2, which is located between the extraction cells E2, E3. We connected it in series on the pipe between E2, E3. The flow velocity v of the extract to be detected at the node is 5.235L/min, the density rho is 1.2kg/L, and the activity of the internal natural radionuclide is known, as shown in Table 1:
TABLE 1 Natural radionuclide U line, Th line in the pipeline,40specific Activity of K (Bq/mL)
| U is | Th system | 40K |
| 3.75 | 0.44 | 0.15 |
These natural radionuclides constitute the radioactive background of the extraction liquid in the pipeline.
(2) Starting Q2, simultaneously monitoring and acquiring extraction liquid flow velocity information v of 5.235L/min and real-time density information rho of 1.2kg/L by the flow sensor 5 and the density sensor 6; the high-purity germanium detector 3 and the gamma spectrometer form a detection system for continuously measuring the natural radionuclide in the extraction liquid138Gamma energy spectrum of L, said natural radionuclide138The gamma spectrum of L includes natural radionuclides, and138la; the full spectrum of the continuous measurement is shown in fig. 6 and 7. As can be seen from the figure, the invention can ensure that the characteristic peak area of lanthanum-138 has no interference of gamma rays of other nuclides, and in addition, the background value N of the peak areabHas been reduced to 0.7 to 0.85/min.
(3) The PLC controller extracts the characteristic peak count N of gamma rays with energy of 1.435MeV in lanthanum-138 from the energy spectrum of FIG. 6AIs 20; background count of characteristic full energy peak interval NbIs 13.8; and calculating the detection sensitivity S of lanthanum according to the following formula, wherein the value is 0.24count per minute/g, the mass DM of lanthanum in the extraction liquid is 82g, and the minimum detectable mass MDM;
S＝η·ALa·γ
eta is the detection efficiency of gamma spectrometer, which is influenced by NA、ASConstraint is a fixed value of 0.7%, and the different extracts to be tested correspond to ASDifferent. Gamma is the branching ratio of 1.435MeV ray, and is also a constant value of 65.5%, ALaIs the specific activity of natural lanthanum and has a fixed value of 826.63Bq/kg, ASThe activity of lanthanum-138 in the extract to be tested.
We can also calculate the minimum detectable mass MDM of lanthanum according to step (4);
due to Nb13.8/min, gamma 65.5%, measuring time t of 1min, flow rate v of the extraction liquid of 5.235L/min, real-time density rho of 1.2kg/L, ALaThe value for the specific activity of natural lanthanum is 826.63Bq/kg, which gives a minimum detectable mass MDM of 2.6 ‰.
Example 3 to illustrate the ability of the present invention to reduce the minimum detectable mass of lanthanum obtained by a detection system, we selected 7 samples of extraction fluid using the apparatus and method of the present invention, and after passing through the system and method of the present invention, the system obtained the minimum detectable mass of lanthanum.
The seven extract samples have different U series, Th series,40Specific activity K conditions, see table 2:
TABLE 2 Natural radionuclides U, Th,40specific Activity of K (Bq/mL)
| Test sequence number | U is | Th system | 40K | MDM‰ |
| 1 | 4.30 | 0.37 | 0.30 | 2.96 |
| 2 | 1.47 | 0.35 | 0.17 | 1.90 |
| 3 | 0.09 | 0.33 | 0.17 | 1.16 |
| 4 | 0.15 | 0.36 | 0.21 | 1.28 |
| 5 | 0.14 | 0.33 | 0.20 | 1.25 |
| 6 | 0.20 | 4.82 | 0.22 | 2.79 |
| 7 | 0.13 | 0.27 | 0.14 | 1.09 |
At present, lanthanum detection methods are laboratory methods, such as ICP-AES, MS, XRF, and the like, and 7 samples described in table 2 are measured by ICP-AES, XRF, chemiluminescence analysis, polarography, voltammetry, and catalytic dynamic fluorescence spectrophotometry, respectively, and compared with the measurement results of the method of the present invention, to obtain the minimum detectable mass, which can be specifically referred to table 3:
table 3 minimum detectable mass of prior art analytical techniques for lanthanum
From Table 3, it can be seen that the detection limit of the present invention is low, which is about 1 order of magnitude lower than that of chemiluminescence analysis and polarography and voltammetry, and XRF method. But the measurement condition is simpler, complex equipment, sample preparation and pretreatment processes are not needed, and online detection can be realized.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. The utility model provides an immersion lanthanum extraction field detection system, includes a cavity, its characterized in that: a detection pipeline horizontally penetrating through two ends of the cavity is arranged in the cavity and is used for allowing lanthanum extraction liquid to flow through;
the bottom of the detection pipeline is provided with a bulge facing the center of the detection pipeline, the bulge is cylindrical, a high-purity germanium detector is arranged in the bulge, the high-purity germanium detector is right opposite to the inside of the detection pipeline, the top of the high-purity germanium detector is attached to the top of the bulge, the outer wall of the detection pipeline is coated with heat insulation cotton, the bottom of the detection pipeline is provided with a shielding ring, and the bottom of the shielding ring is flush with the bottom;
a flow sensor and a density sensor are arranged in the detection pipeline, a gamma spectrometer and a PLC (programmable logic controller) are arranged outside the cavity, and the output ends of the flow sensor, the density sensor and the gamma spectrometer are connected with the PLC;
the flow sensor and the density sensor are respectively used for acquiring flow velocity information v and real-time density information rho of the extraction liquid;
the output end of the high-purity germanium detector is connected with a gamma energy spectrometer and is used for detecting gamma rays in the extraction liquid and obtaining an energy spectrum through analysis of the gamma energy spectrometer;
the PLC is used for setting the measurement time t and extracting the characteristic peak count N of gamma rays with energy of 1.435MeV in lanthanum-138 from the energy spectrumACharacteristic full energy peak interval background count NbAnd combining the flow velocity information v and the real-time density information rho to obtain the detection sensitivity S of lanthanum and the mass DM of lanthanum in the extraction liquid according to the following formula:
S＝η·ALa·γ
in the formula: eta is the detection efficiency of the gamma spectrometer, gamma is the branch ratio of 1.435MeV rays, the value is 65.5 percent, and ALaThe specific activity of natural lanthanum is 826.63Bq/kg, ASThe activity of lanthanum-138 in the extract to be tested.
2. The in-situ immersion lanthanum extraction test system of claim 1, wherein: the detection pipeline is made of stainless steel materials or PVC materials, if the detection pipeline is made of the stainless steel materials, a corrosion-resistant layer is arranged in the detection pipeline, and the corrosion-resistant layer is made of polytetrafluoroethylene and derivatives thereof.
3. The in-situ immersion lanthanum extraction test system of claim 1, wherein: the cross section of the detection pipeline is circular, the inner diameter is 30cm, the outer diameter is 32cm, the size of the bulge is 15cm x12 cm, the wall thickness is 1mm, and the thickness of the heat insulation cotton is 2 cm.
4. The in-situ immersion lanthanum extraction test system of claim 1, wherein: the high-purity germanium detector has a relative detection efficiency of more than or equal to 120%, adopts an electric refrigeration mode and comprises a cold finger and a signal wire, wherein the cold finger and the signal wire are led out from a hole in the middle of a lead shielding ring.
5. The method of claim 1, wherein the at least one sensor is a sensor for detecting the immersion lanthanum extraction field test system, and the method comprises the following steps: the method comprises the following steps:
(1) establishing an immersion lanthanum extraction field detection system, and connecting a detection pipeline in series on a pipeline through which the extract liquid to be detected flows;
(2) starting a system, collecting flow velocity information v and real-time density information rho of the extraction liquid by a flow sensor and a density sensor, detecting gamma rays in the extraction liquid by a high-purity germanium detector, sending the gamma rays into a gamma energy spectrometer for analysis to obtain a measurement energy spectrum, and outputting the measurement energy spectrum;
(3) the PLC extracts the 1.435MeV characteristic peak count N of the lanthanum-138 from the superposition energy spectrumAThe background count N of the characteristic full energy peak intervalb(ii) a Calculating the detection sensitivity S of lanthanum and the mass DM of lanthanum in the extraction liquid according to the following formula;
S＝η·ALa·γ
in the formula: eta is the detection efficiency of the gamma spectrometer, gamma is the branch ratio of 1.435MeV rays, the value is 65.5 percent, and ALaThe specific activity of natural lanthanum is 826.63Bq/kg, ASThe activity of lanthanum-138 in the extract to be tested.
6. The method of claim 5, wherein the at least one sensor is a sensor for detecting the immersion lanthanum extraction field test system, and the method comprises the following steps: further comprising the step (4) of calculating the minimum detectable mass MDM of lanthanum according to the following formula;
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