CN111896574B - Immersion lanthanum extraction on-site detection system and detection method - Google Patents
Immersion lanthanum extraction on-site detection system and detection method Download PDFInfo
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- 238000001514 detection method Methods 0.000 title claims abstract description 144
- 229910052746 lanthanum Inorganic materials 0.000 title claims abstract description 79
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000000605 extraction Methods 0.000 title claims abstract description 64
- 238000007654 immersion Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 49
- 239000000284 extract Substances 0.000 claims abstract description 42
- 229910052732 germanium Inorganic materials 0.000 claims abstract description 34
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 238000001228 spectrum Methods 0.000 claims abstract description 24
- 230000035945 sensitivity Effects 0.000 claims abstract description 17
- 229920000742 Cotton Polymers 0.000 claims abstract description 10
- 238000009413 insulation Methods 0.000 claims abstract description 10
- 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 17
- 239000000463 material Substances 0.000 claims description 10
- 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
- -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 3
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 10
- 238000013461 design Methods 0.000 abstract description 7
- 238000003723 Smelting Methods 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000003908 quality control method Methods 0.000 abstract description 2
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- 150000002910 rare earth metals Chemical class 0.000 description 10
- 230000005251 gamma ray Effects 0.000 description 6
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- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/227—Measuring photoelectric effect, e.g. photoelectron emission microscopy [PEEM]
- G01N23/2273—Measuring photoelectron spectrum, e.g. electron spectroscopy for chemical analysis [ESCA] or X-ray photoelectron spectroscopy [XPS]
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/2202—Preparing specimens therefor
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses an immersion lanthanum extraction field detection system and a detection method, wherein a detection pipeline is arranged in a cavity, a bulge is arranged at the bottom of the detection pipeline, 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 a shielding ring is arranged at the bottom of the high-purity germanium detector; the detection pipeline is internally provided with a flow sensor, a density sensor and a gamma spectrometer and a PLC (programmable logic controller) controller, and the output ends of the flow sensor, the density sensor and the gamma spectrometer are connected with the PLC controller. During detection, the PLC extracts from the energy spectrumN A 、N b The method comprises the steps of carrying out a first treatment on the surface of the And calculating the detection sensitivity S of lanthanum, the mass DM of lanthanum in the extract liquid and the minimum detectable mass by combining the real-time flow, density and the likeMDM。Compared with the traditional quality control method in the rare earth element lanthanum concentration and smelting process, the method provided by the invention does not need to design a sample injection system alone, and has the characteristics of high distribution degree, good timeliness, low detection limit, high sensitivity and the like.
Description
Technical Field
The invention relates to an online detection system and method in a lanthanum extraction process, in particular to an immersion type lanthanum extraction field detection system and method.
Background
Weathered crust leaching type rare earth ore is taken as one of important rare earth ore deposit types in China, and cascade extraction is mainly adopted for dressing and smelting the rare earth ore of the type in China at present to separate out single rare earth elements. Lanthanum is used as an important rare earth element in weathered crust leaching rare earth ore, and the mass proportion of the lanthanum can reach 29.09 percent. Therefore, mass ratio detection in the separation process is of great importance.
In the current stage, the element distribution characteristic detection of the rare earth ore dressing and smelting process is generally carried out by detecting rare earth ore solids, such as chemical analysis, ICP-MS and ICP-AES methods, and methods for detecting rare earth extract liquid, such as EDXFF, WDXRF and the like. Most of the methods need to rely on large experimental equipment, sampling, sample preparation, detection and other processes often need practice of several hours or even one day, and the detection timeliness is relatively lagged.
For example, in the chemical analysis method in the prior art, an experimenter needs to sample in an extraction tank and send the sample to a related 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 variety of required experimental equipment is more. The detection flow of the detection methods of ICP-AES, ICP-MS and the like is similar to that of chemical analysis, and sample pretreatment is needed. In addition, the detection method has higher equipment cost and more severe detection environment requirements, and laboratory staff needs to be trained by professional technology and generally needs to be finished in a special detection laboratory.
The WDXRF, EDXRF and other fluorescent detection methods are field detection methods which are used for rare earth dressing and smelting and are in recent years, and compared with the traditional detection methods, the method has lower requirements on the pretreatment degree of the sample. High-power x-ray tubes are still required as excitation sources to excite characteristic x-rays of various elements in the extract to achieve the purpose of quantitative detection. Taking comparative document CN105136831a as an example, the method of this patent uses energy dispersive X-ray to analyze the mass fraction of lanthanum in rare earth elements, although the method uses an extraction solution for measurement. In the method, the sample is irradiated by X-rays to excite the L-ray fluorescence in the rare earth elements, so an excitation source is required to be used, and an active sample feeding device such as a peristaltic pump and an extraction liquid reflux sealing connecting pipeline are required to be arranged, so that the system is complex and the cost is high.
In addition, under the technical background that extraction efficiency is continuously improved, the existing detection method is difficult to match with extraction equipment with higher automation level, so that production efficiency is low, and product quality is unstable. Therefore, there is an urgent need for an efficient, stable, simple structure, distributed continuous detection system that achieves product quality control for critical process nodes.
Disclosure of Invention
The invention aims to provide an immersed lanthanum extraction field detection system and an immersed lanthanum extraction field detection method, which can effectively improve the sensitivity of online detection in the lanthanum extraction process and reduce the limit of online detection.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the 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 the detection pipeline is used for flowing through lanthanum extraction liquid;
the bottom of the detection pipeline is provided with a bulge which faces 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 high-purity germanium detector is coated with heat insulation cotton, the bottom of the high-purity germanium detector is provided with a shielding ring, and the bottom of the shielding ring is level with the bottom of the bulge;
the flow sensor, the density sensor and the gamma energy spectrometer are arranged in the detection pipeline, and the gamma energy spectrometer and the PLC are arranged outside the cavity, and the output ends of the flow sensor, the density sensor and the gamma energy spectrometer are connected with the PLC;
the flow sensor and the density sensor are respectively used for collecting flow velocity information v and real-time density information rho of the extracting solution;
the output end of the high-purity germanium detector is connected with a gamma spectrometer and is used for detecting gamma rays in the extracting solution and analyzing the gamma rays by the gamma spectrometer to obtain energy spectrum;
the PLC is used for setting the measurement time t and extracting the characteristic peak count N of the gamma rays with the energy of 1.435MeV in lanthanum-138 from the energy spectrum A Background count N of characteristic full-energy peak interval b Combining flow velocity information v and real-time densityInformation ρ, and obtain detection sensitivity S of lanthanum, mass DM of lanthanum in the extract according to the following formula:
S＝η·A La ·γ
wherein: eta is the detection efficiency of a gamma spectrometer, gamma is the branching ratio of 1.435MeV rays, the value is 65.5 percent, A La The specific activity of natural lanthanum is 826.63Bq/kg, A S Is the activity of lanthanum-138 in the extract to be measured.
As preferable: the detection pipeline is made of stainless steel material or PVC material, and if the detection pipeline is made of stainless steel material, a corrosion-resistant layer is arranged in the detection pipeline, and the corrosion-resistant layer is made of polytetrafluoroethylene and derivatives thereof.
As preferable: 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 2cm.
As preferable: the relative detection efficiency of the high-purity germanium detector is more than or equal to 120%, and an electric refrigeration mode is adopted, wherein the high-purity germanium detector comprises a cold finger and a signal wire, and the cold finger and the signal wire are led out from a hole in the middle of a lead shielding ring.
The detection method of the immersion lanthanum extraction field detection system comprises the following steps:
(1) Establishing an immersed lanthanum extraction field detection system, and connecting a detection pipeline in series on a pipeline through which an extraction liquid to be detected flows;
(2) Starting the system, collecting flow velocity information v and real-time density information rho of the extracting solution by a flow sensor and a density sensor, detecting gamma rays in the extracting solution by a high-purity germanium detector, and 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 controller extracts lanthanum-138 from the superposition energy spectrum1.435MeV characteristic Peak count N A Background count N of the characteristic full-energy peak interval b The method comprises the steps of carrying out a first treatment on the surface of the Calculating the detection sensitivity S of lanthanum and the mass DM of lanthanum in the extract according to the following formula;
S＝η·A La ·γ
wherein: eta is the detection efficiency of a gamma spectrometer, gamma is the branching ratio of 1.435MeV rays, the value is 65.5 percent, A La The specific activity of natural lanthanum is 826.63Bq/kg, A S Is the activity of lanthanum-138 in the extract to be measured.
As preferable: the method further comprises 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 with the radioisotope lanthanum-138 energy of 1.435MeV in the extracting solution, and calculating the mass ratio of lanthanum in the rare earth element through the gamma ray characteristic peak measurement. And by the method, the detection sensitivity S to lanthanum is higher, and the minimum detectable mass MDM is lower.
In the structure, the detection pipeline is made of stainless steel material or PVC material, and if the detection pipeline is made of stainless steel material, 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, and if a stainless steel material is used, a corrosion-resistant layer is required.
The detector is a high-purity germanium detector, and is used for measuring 1.435MeV characteristic gamma rays of lanthanum-138 nuclide in the extraction liquid flowing in the pipeline. The bottom of the detection pipeline is provided with a bulgeThe detector is arranged in the bulge, which is equivalent to being immersed in the extraction liquid, increases the detection solid angle of the detector, and can increase the effective count N of the gamma ray characteristic peak with the energy of 1.435MeV A . Meanwhile, the detector is immersed in the extracting solution, so that the self-shielding of the radioactive background of the surrounding environment can be realized, namely, the background count is reduced and the N is reduced b 。
The outer wall of the high-purity germanium detector is coated with heat insulation cotton, and the purposes are as follows: the performance of the detector is affected by the working temperature, besides the built-in refrigeration part, the heat insulation cotton can enable the temperature in the bulge to be relatively constant in the design, and the influence of the temperature change of the extraction liquid in the pipeline on the performance of the detector is reduced.
A shielding ring is arranged at the bottom for shielding U-system, th-system and natural environment 40 Gamma ray interference of K's natural radionuclide decaying, and possibly other natural and artificial radionuclides, thereby further reducing background count N b Is a target of (a). According to the formulaIt can be seen that N is increased A Reduce N b The peak-to-back ratio xi of the characteristic peak can be effectively improved.
In the present invention, we pass the formula s=η·a La ·γ、To calculate the detection sensitivity S of lanthanum, since N is improved A Can improve the detection sensitivity eta of the gamma spectrometer and is also because A La The specific activity of natural lanthanum was constant, the branching ratio of gamma was 1.435MeV rays, and the value was 65.5%. Therefore, from the formula, the detection sensitivity S of lanthanum can be improved.
The invention uses the formulaTo calculate the minimum detectable mass MDM of lanthanum, due to the reduction of N b The invention can effectively reduce the minimum detectable quality of lanthanumMDM。
The MDM of the present invention, i.e., the minimum value of the detection mass that can be achieved by the detection system under certain confidence conditions, is calculated by,
wherein L is D The method is characterized in that the method is a detection limit of the gamma spectrometer for effectively counting lanthanum-138 characteristic peak areas, m is the mass of an extraction liquid in a pipeline, and a formula is m=ρ.v.t, and the method can be obtained through calculation of density, flow rate and measurement time t. WhileUnder the condition of 95% single-side confidence probability, the detection limit of the counting rate of the gamma spectrometer is adopted, so the formula can be rewritten as follows:
it can be seen that when the state of the extract is stable, the MDM and the characteristic total energy peak interval background count N b Proportional to and inversely proportional to the measurement time t. The device can reduce N through effective structural design b The detection efficiency eta is improved, and the MDM is further effectively reduced.
In the formula, background count in characteristic peak areaMeasured by a gamma spectrometer; and gamma, A La η is constant, and ρ and v can be known by a flow and density sensor; t is the measurement time, set by the detection system. It can be seen that when the state of the extract is stable, the MDM is proportional to the background count and inversely proportional to the measurement time.
The integrated measuring pipeline is connected with the pipeline of the extraction centrifuge, 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. Compared with the online analysis methods based on spectrophotometry online analysis method, x fluorescence online analysis method and the like at the present stage, the method does not need to separately design an extraction liquid sample reflux pipeline.
Compared with the prior art, the invention has the advantages that:
(1) The invention provides a novel detection device and a method, wherein the device is used for directly detecting an extraction liquid and extracting characteristic peak count N of gamma rays with the energy of 1.435MeV in lanthanum-138 from the superposition energy spectrum of the extraction liquid A Background count N of characteristic full-energy peak interval b And combining the flow velocity information v and the real-time density information rho to obtain the detection sensitivity S of lanthanum, the mass DM of lanthanum in the extract liquid and the minimum detectable mass MDM. The invention overcomes the defects that detection analysis is needed by solid sampling or an active excitation source is needed to be relied on for the extract liquid to excite and measure the activity of the natural radionuclide in the extract liquid in the prior art. Provides a method for extracting characteristic peak count N of gamma rays from energy spectrum of extract A Background count N of characteristic full-energy peak interval b To perform the DM measurement method. The method extracts the characteristic peak count N of gamma rays with the energy of 1.435MeV in lanthanum-138 from the superposition energy spectrum of the extract A Background count N of characteristic full-energy peak interval b And combining the flow velocity information v and the real-time density information rho to obtain the detection sensitivity S of lanthanum, the mass DM of lanthanum in the extract liquid and the minimum detectable mass MDM.
(2) The invention has simple structure and convenient installation, can detect the single-stage extraction quality and can realize the multi-stage serial quality flow detection. During installation, the device is directly installed between extraction tanks or on a pipeline through which the extraction liquid flows in a serial connection mode, and additional equipment such as peristaltic pumps is not needed, so that an extraction liquid return pipeline can be effectively simplified, and the system is simpler in design and lower in cost.
(3) Compared with the existing spectrophotometry online analysis method, x fluorescence online analysis method and the like, the method does not need an active excitation source to directly measure the activity of the natural radionuclide in the extract, belongs to a passive detection method, has less influence on the detection result due to the factors of the instrument, and can effectively avoid the influence of the equipment on the detection resultBased on the structure of the invention, N can be effectively improved A Reduce N b So that the detection sensitivity S for lanthanum is higher and the minimum detectable mass MDM is lower.
Drawings
FIG. 1 is a schematic diagram of the structure of the present invention;
FIG. 2 is a cross-sectional view A-A of the detection conduit of FIG. 1;
FIG. 3 is a B-B cross-sectional view of the test tube of FIG. 1
FIG. 4 is a schematic diagram of a sampling flow of a conventional multi-stage extraction tank online detection system;
FIG. 5 is a schematic diagram of a sampling flow according to the present invention;
FIG. 6 is a full spectrum of the measurement process of the present invention;
FIG. 7 is a graph of the background energy of the processed real-time measurement after the expansion of the arrow area in FIG. 6.
In the figure: 1. a cavity; 2. detecting a pipeline; 3. a high purity germanium detector; 4. thermal insulation cotton; 5. a flow sensor; 6. a density sensor; 7. a shielding ring; 8. status indicator lights; 9. a power supply and data interface; 10. a protrusion.
Detailed Description
The invention will be further described with reference to the accompanying 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 penetrating through two ends of the cavity 1 is arranged in the cavity 1, and the detection pipeline 2 is used for flowing lanthanum extraction liquid;
the bottom of the detection pipeline 2 is provided with a bulge 10 facing the center of the detection pipeline, the bulge 10 is cylindrical, a high-purity germanium detector 3 is arranged in the bulge 10, the high-purity germanium detector 3 is opposite to the inside of the detection pipeline 2, the top of the high-purity germanium detector is attached to the top of the bulge 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 level with the bottom of the bulge 10;
a flow sensor 5, a density sensor 6 and a gamma spectrometer and a PLC (programmable logic controller) are arranged in the detection pipeline 2, 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 ρ of the extraction liquid;
the output end of the high-purity germanium detector 3 is connected with a gamma spectrometer and is used for detecting gamma rays in the extracting solution and analyzing the gamma rays by the gamma spectrometer to obtain an energy spectrum;
the PLC is used for setting the measurement time t and extracting the characteristic peak count N of the gamma rays with the energy of 1.435MeV in lanthanum-138 from the energy spectrum A Background count N of characteristic full-energy peak interval b Combining the flow velocity information v and the real-time density information rho, and obtaining the detection sensitivity S of lanthanum and the mass DM of lanthanum in the extract according to the following formula:
S＝η·A La ·γ
wherein: eta is the detection efficiency of a gamma spectrometer, gamma is the branching ratio of 1.435MeV rays, the value is 65.5 percent, A La The specific activity of natural lanthanum is 826.63Bq/kg, A S Is the activity of lanthanum-138 in the extract to be measured.
The detection pipeline 2 is made of stainless steel or PVC, and if the detection pipeline is made of stainless steel, 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 multiplied by 12cm, the wall thickness is 1mm, and the thickness of the heat insulation cotton 4 is 2cm.
The relative detection efficiency of the high-purity germanium detector 3 is more than or equal to 120%, and an electric refrigeration mode is adopted, wherein the high-purity germanium detector comprises a cold finger and a signal wire, and 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 model-kanbang GX12021 detector, and if other types of detectors are adopted, the same effect can be achieved, which falls within the protection scope of the present invention.
The detection method of the immersion lanthanum extraction field detection system comprises the following steps:
(1) Establishing an immersed lanthanum extraction field detection system, and connecting a detection pipeline 2 in series on a pipeline through which an extraction liquid to be detected flows;
(2) The system is started, the flow sensor 5 and the density sensor 6 collect flow velocity information v and real-time density information rho of the extracting solution, the high-purity germanium detector 3 detects gamma rays in the extracting solution, and the gamma rays are sent into the gamma energy spectrometer for analysis to obtain a measurement energy spectrum and output;
(3) The PLC extracts 1.435MeV characteristic peak count N of lanthanum-138 from the superposition energy spectrum A Background count N of the characteristic full-energy peak interval b The method comprises the steps of carrying out a first treatment on the surface of the Calculating the detection sensitivity S of lanthanum and the mass DM of lanthanum in the extract according to the following formula;
S＝η·A La ·γ
wherein: eta is the detection efficiency of a gamma spectrometer, gamma is the branching ratio of 1.435MeV rays, the value is 65.5 percent, A La The specific activity of natural lanthanum is 826.63Bq/kg, A S Is the activity of lanthanum-138 in the extract to be measured.
(4) Calculating a minimum detectable mass MDM of lanthanum according to the following formula;
in order to ensure the accuracy of the data, the measurement is generally started after the stability of the flow of the extraction liquid is detected. The outer wall of the cavity 1 can be provided with a status indicator lamp 8 and a power supply and data interface 9, wherein the status indicator lamp 8 can be used for indicating whether various sensors and other devices work normally or whether the flow rate and the density are stable or not. Can be set according to the needs. The power and data interface 9 is used to power the internal power units.
For example: the detection pipeline 2 is connected with the extraction centrifuge in series, and during the extraction process, the extraction liquid passes through the detection pipeline 2; the flow sensor 5 monitors the flow in the detection pipeline 2 in real time; after the flow of the extract is stable, the status indicator lamp 8 flashes; the high-purity germanium detector 3 in the cavity 1 starts to automatically detect in the extraction liquid flowing in the pipeline, measures the gamma ray energy spectrum, sends the gamma ray energy spectrum to the PLC, calculates the mass component of rare earth element lanthanum therein by a built-in data processing system, and 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, the immersion lanthanum extraction on-site detection system and method according to the present invention connects the integrated detection pipeline 2 in series in the process flow of the multistage extraction centrifuge without additional equipment such as a peristaltic pump. Compared with the online analysis methods based on the spectrophotometry online analysis method, the x fluorescence online analysis method and the like, the method does not need to separately design an extraction liquid reflux pipeline. The sampling system of the invention has simpler design and lower cost.
Example 2: with reference to fig. 1 to 5, we present an example 2 of the application of the apparatus and method of the present invention on the basis of example 1.
(1) First, we need to build a plurality of gamma-spectroscopy based distributed lanthanum extraction online detection systems as described in example 1. Next, the mounting is performed according to fig. 4. In FIG. 4, let S1 be the source tank, E1-En be n extraction tanks, i.e., n-stage extraction tanks, and the immersion lanthanum extraction in situ detection system of the present invention be n, respectively labeled Q1-Qn. The figure shows that the method does not need an active excitation source to directly measure the activity of the natural radionuclide in the extract, belongs to a passive detection method, and has less influence on the detection result 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 multi-stage extraction tank through a pipeline, and the immersed lanthanum extraction field detection system is installed on the pipeline, specifically, is connected in series on the pipeline through a detection pipeline 2. Q1-Qn can analyze and detect the extraction liquid of the rare earth lanthanum which flows out from E1-En respectively.
We have Q1-Qn as the detection node, we probe at Q2, which is located between extraction cells E2, E3. We connect it in series on the pipeline between E2, E3. The flow velocity v of the extract to be measured at this node is 5.235L/min, the density ρ is 1.2kg/L, and the activity of the internal natural radionuclide is known, as shown in Table 1:
table 1 the natural radionuclides U-based, th-based, 40 specific activity of K (Bq/mL)
| U system | Th system | 40 K |
| 3.75 | 0.44 | 0.15 |
These natural radionuclides constitute the radioactive background of the extract in the tube.
(2) Starting Q2, and simultaneously monitoring and collecting the flow velocity information v of the extracting solution to 5.235L/min and the real-time density information rho to 1.2kg/L by a flow sensor 5 and a density sensor 6; the high-purity germanium detector 3 and the gamma spectrometer form a detection system,continuous measurement of natural radionuclides in extracts 138 Gamma spectrum of L, the natural radionuclide 138 The gamma spectrum of L includes the natural radionuclide, and 138 la; the full spectrum of the continuous measurement is shown in fig. 6 and 7. As can be seen from the figure, the invention can lead the lanthanum-138 characteristic peak area to have no interference of gamma rays of other nuclides, and in addition, the background value N of the peak area b Has been reduced to 0.7-0.85/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. 6 A 20% by weight; characteristic full energy peak interval background count N b 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=82 g of lanthanum in the extract liquid, and the minimum detectable mass MDM;
S＝η·A La ·γ
eta is the detection efficiency of the gamma spectrometer and is influenced by N A 、A S Constraint, which is a fixed value of 0.7%, corresponding to A of different extractive solutions to be tested S Different. Gamma is the branching ratio of 1.435MeV ray, which is also a constant value of 65.5%, A La Is the specific activity of natural lanthanum and is also a constant value, the value is 826.63Bq/kg, A S Is the activity of lanthanum-138 in the extract to be measured.
We can also calculate the minimum detectable mass MDM of lanthanum according to step (4);
due to N b 13.8/min, 65.5% gamma, 1min measurement time t, 5.235L/mi extract flow vn, the real-time density rho is 1.2kg/L, A La The natural lanthanum has a specific activity of 826.63Bq/kg, and the minimum detectable mass MDM is 2.6 per mill.
Example 3 to illustrate that the invention reduces the minimum detectable quality of lanthanum obtained by the detection system, we have selected 7 samples of the extract using the apparatus and method of the invention, and after passing the system and method of the invention, the system obtains the minimum detectable quality of lanthanum.
The seven extract samples have different U-series and Th-series, 40 The K specific activity conditions can be seen in Table 2:
table 2 the natural radionuclides U-based, th-based, 40 specific activity of K (Bq/mL)
| Test sequence number | U system | Th system | 40 K | 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, the lanthanum detection methods are laboratory methods, such as ICP-AES, MS, XRF, and the like, and the 7 samples in Table 2 are respectively measured by ICP-AES, XRF, chemiluminescence analysis, polarography, voltammetry and catalytic kinetic fluorescence photometry and compared with the measurement results of the method to obtain the minimum detectable quality, and the specific reference can be seen in Table 3:
TABLE 3 minimum detectable quality of lanthanum for the prior art analysis
From Table 3, it can be seen that the advantages of the present invention have low detection limits, approximately 1 order of magnitude lower than chemiluminescent analysis and polarography and voltammetry, and XRF methods. But the measurement condition is simpler, complex equipment and sample preparation and pretreatment processes are not needed, and the on-line detection can be realized.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (6)
1. 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 flowing through lanthanum extract;
the bottom of the detection pipeline is provided with a bulge which faces 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 high-purity germanium detector is coated with heat insulation cotton, the bottom of the high-purity germanium detector is provided with a shielding ring, and the bottom of the shielding ring is level with the bottom of the bulge;
the flow sensor, the density sensor and the gamma energy spectrometer are arranged in the detection pipeline, and the gamma energy spectrometer and the PLC are arranged outside the cavity, and the output ends of the flow sensor, the density sensor and the gamma energy spectrometer are connected with the PLC;
the flow sensor and the density sensor are respectively used for collecting flow velocity information v and real-time density information rho of the extracting solution;
the output end of the high-purity germanium detector is connected with a gamma spectrometer and is used for detecting gamma rays in the extracting solution and analyzing the gamma rays by the gamma spectrometer to obtain energy spectrum;
the PLC is used for setting the measurement time t and extracting the characteristic peak count N of the gamma rays with the energy of 1.435MeV in lanthanum-138 from the energy spectrum A Background count N of characteristic full-energy peak interval b Combining the flow velocity information v and the real-time density information rho, and obtaining the detection sensitivity S of lanthanum, the mass DM of lanthanum in the extract and the minimum detectable mass MDM of lanthanum according to the following formula;
S＝η·A La ·γ
wherein: eta is the detection efficiency of a gamma spectrometer, gamma is the branching ratio of 1.435MeV rays, the value is 65.5 percent, A La The specific activity of natural lanthanum is 826.63Bq/kg, A S Is the activity of lanthanum-138 in the extract to be measured.
2. An immersion lanthanum extraction field detection system as claimed in claim 1, wherein: the detection pipeline is made of stainless steel material or PVC material, and if the detection pipeline is made of stainless steel material, a corrosion-resistant layer is arranged in the detection pipeline, and the corrosion-resistant layer is made of polytetrafluoroethylene and derivatives thereof.
3. An immersion lanthanum extraction field detection system as claimed in 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 2cm.
4. An immersion lanthanum extraction field detection system as claimed in claim 1, wherein: the relative detection efficiency of the high-purity germanium detector is more than or equal to 120%, and an electric refrigeration mode is adopted, wherein the high-purity germanium detector comprises a cold finger and a signal wire, and the cold finger and the signal wire are led out from a hole in the middle of a lead shielding ring.
5. The method for detecting the immersion lanthanum extraction field detection system according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
(1) Establishing an immersed lanthanum extraction field detection system, and connecting a detection pipeline in series on a pipeline through which an extraction liquid to be detected flows;
(2) Starting the system, collecting flow velocity information v and real-time density information rho of the extracting solution by a flow sensor and a density sensor, detecting gamma rays in the extracting solution by a high-purity germanium detector, and 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 1.435MeV characteristic peak count N of lanthanum-138 from the superposition energy spectrum A Background count N of the characteristic full-energy peak interval b The method comprises the steps of carrying out a first treatment on the surface of the Calculating the detection sensitivity S of lanthanum and the mass DM of lanthanum in the extract according to the following formula;
S＝η·A La ·γ
wherein: eta is the detection efficiency of a gamma spectrometer, gamma is the branching ratio of 1.435MeV rays, the value is 65.5 percent, A La The specific activity of natural lanthanum is 826.63Bq/kg, A S Is the activity of lanthanum-138 in the extract to be measured.
6. The method for detecting the immersion lanthanum extraction field detection system according to claim 5, wherein the method comprises the following steps: the method further comprises the step (4) of calculating the minimum detectable mass MDM of lanthanum according to the following formula;
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