Automatic combined sample preparation device and method for iron-55 and nickel-63

Abstract

The invention relates to an automatic combined sample preparation device and method for iron-55 and nickel-63. The device comprises pretreatment equipment, first separation equipment, second separation equipment, liquid transfer and injection equipment and control equipment, the pretreatment equipment is used for concentrating a to-be-treated sample and fixing the volume to obtain a first to-be-treated sample; the liquid transfer and injection equipment is used for conveying a first to-be-treated sample in the pretreatment equipment to the first separation equipment and conveying a liquid reagent to the pretreatment equipment, the first separation equipment and the second separation equipment; the first separation equipment is used for separating the first to-be-treated sample, concentrating the first effluent, adjusting the pH value, and treating the first desorption solution into a first sample; the second separation equipment is used for separating the treated first effluent and treating the second desorption solution into a second sample; the control equipment is electrically connected with the pretreatment equipment, the first separation equipment, the second separation equipment and the liquid transfer and injection equipment respectively. The device can be used for continuous sample preparation of iron and nickel.

Description

Technical Field

[0001] The invention relates to the technical field of radiation environment monitoring, and in particular to an automated combined sample preparation device and method for iron-55 and nickel-63. Background Art

[0002] Iron and nickel are widely used as metal materials in various components of reactors. The corresponding activation products exist in the radioactive solid waste and wastewater produced by the reactor. Iron-55 and nickel-63 are radioactive nuclides with large emissions in the liquid effluents of nuclear power plants and are routine monitoring items for radioactive liquid effluents.

[0003] In the related art, samples of iron-55 and nickel-63 are prepared separately, which involves many separate sample preparation processes, wastes materials, and requires manual sample preparation by highly skilled operators, resulting in high labor costs and low efficiency. The above problems need to be solved urgently. Summary of the invention

[0004] The invention discloses an automated combined sample preparation device and method for iron-55 and nickel-63, aiming to solve the technical problems existing in the prior art.

[0005] The present invention adopts the following technical solutions:

[0006] In a first aspect, the present invention provides an automated combined sample preparation device for iron-55 and nickel-63, comprising: a pretreatment device, a first separation device, a second separation device, a liquid transfer device, and a control device;

[0007] The pretreatment device is used to concentrate the sample to be processed and then fix the volume to obtain a first sample to be processed;

[0008] The liquid transfer device is used to transfer the first sample to be processed in the pretreatment device to the first separation device, and to transfer liquid reagents to the pretreatment device, the first separation device and the second separation device, wherein the liquid reagents at least include a dissolving reagent, a first eluting reagent, a first desorption reagent, a second eluting reagent, a pH adjusting reagent, a second desorption reagent and a volume fixing reagent;

[0009] The first separation device is used to separate the first sample to be processed into a first effluent, a first eluent and a first desorption liquid, and to concentrate the first effluent and then perform a pH adjustment treatment, and the first separation device is also used to process the first desorption liquid into a first sample;

[0010] The second separation device is used to separate the first effluent after treatment to obtain a second effluent, a second eluent and a second analytical solution, and the second separation device is also used to process the second analytical solution into a second sample;

[0011] The control device is electrically connected to the pretreatment device, the first separation device, the second separation device and the liquid transfer device respectively.

[0012] In a second aspect, the present invention also provides an automated combined sample preparation method of iron-55 and nickel-63, comprising the following steps:

[0013] Injecting a sample to be treated into a pretreatment device, adjusting the pH value to less than 2, injecting an iron-55 carrier, a nickel-63 carrier and a counter carrier, stirring evenly and evaporating and concentrating to near dryness, and then injecting a hydrochloric acid solution of a first solubility through the liquid transfer device to obtain a first sample to be treated;

[0014] Passing the first sample to be processed into a first separation device to obtain a first effluent, then injecting a first elution reagent into the first separation device through a liquid transfer device to obtain a first elution liquid; then injecting a first desorption reagent into the first separation device through the liquid transfer device to obtain a first desorption liquid, evaporating the first desorption liquid to near dryness, and then injecting a constant volume reagent into the first desorption liquid through the liquid transfer device to obtain a first sample rich in iron-55;

[0015] The first separation device evaporates the first effluent to near dryness, then adds a dissolving agent to the first effluent through the liquid transfer device, stirs evenly, and adds a pH adjusting agent to pH=9 to obtain the adjusted first effluent;

[0016] The first effluent is passed into a second separation device to obtain a second effluent, and then a second eluent is injected into the second separation device through the liquid transfer device to obtain a second eluent, and then a second desorption reagent is injected into the second separation device to obtain a second desorption liquid; the second desorption liquid is evaporated to near dryness, and then a constant volume reagent is injected to obtain a second sample rich in nickel-63.

[0017] The technical solution adopted by the present invention can achieve the following beneficial effects:

[0018] The present invention mainly provides an automated combined sample preparation device for iron-55 and nickel-63. Through the above device, iron-55 and nickel-63 can be automatically combined for sample preparation, simplifying the sample preparation process, improving the sample preparation efficiency, reducing labor costs and saving raw materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments, which constitute a part of the present invention. The exemplary embodiments of the present invention and their descriptions explain the present invention and do not constitute improper limitations on the present invention. In the drawings:

[0020] Figure 1 This is one of the structural schematic diagrams of an automated combined sample preparation device for iron-55 and nickel-63 of the present invention;

[0021] Figure 2 This is the second structural schematic diagram of an automated combined sample preparation device for iron-55 and nickel-63 of the present invention;

[0022] Figure 3 It is a schematic structural diagram of the liquid transfer device of the present invention.

[0023] Description of reference numerals:

[0024] 1. Pretreatment equipment; 11. First conveying equipment; 12. First container; 13. First heater; 2. First separation equipment; 21. First separation column; 22. First multi-way valve; 23. Second container; 24. Second heater; 25. Third container; 26. Third heater; 27. Second conveying equipment; 28. Third conveying equipment; 29. ​​First liquid scintillation bottle; 210. First waste liquid bottle; 3. Second separation equipment; 31. Fourth conveying equipment; 32. Second separation column; 33. Second multi-way valve; 34. Fourth container; 35. Fourth heater; 36. Second waste liquid bottle; 37. Fifth Conveying equipment; 38. Second liquid scintillation bottle; 4. Liquid transfer equipment; 41. First multi-interface communicating vessel; 411. First inner mounting plate; 412. First outer mounting plate; 413. First outer channel; 4131. First outgoing material channel; 4132. First outer feeding channel; 414. First inner channel; 42. Connecting pipe; 43. Conveying pump; 44. Second multi-interface communicating vessel; 441. Second inner mounting plate; 442. Second outer mounting plate; 443. Second outer channel; 4431. Second outer feeding channel; 4432. Second outgoing material channel; 444. Second inner channel; 5. Control equipment. DETAILED DESCRIPTION

[0025] In order to make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be clearly and completely described below in conjunction with the specific embodiments of the present invention and the corresponding drawings. In the description of the present invention, it should be noted that the term "or" is usually used in the sense of including "and / or", unless the content clearly indicates otherwise.

[0026] Unless expressly indicated to the contrary, the numerical parameters in this specification and the appended claims may be approximate values ​​and can be changed according to the desired properties obtained by the content of the present invention. Specifically, all numbers used in the specification and claims to express the content of the composition, reaction conditions, etc., should be understood to be modified by the term "about" in all cases. In general, the meaning of the expression is to include a change of ±10% in some embodiments, a change of ±5% in some embodiments, a change of ±1% in some embodiments, and a change of ±0.5% in some embodiments by a specific number.

[0027] Furthermore, the word "comprising" does not exclude the presence of materials or steps not listed in the claims. Ordinal numbers such as "first", "second", "third" and Arabic numerals, letters, etc. used in the specification and claims to modify corresponding elements or steps do not themselves mean the order of the manufacturing method. The use of these ordinals is only used to make the steps clearly distinguishable.

[0028] In addition, unless the steps are specifically described or must occur in sequence, the order of the above steps is not limited to the above list, and can be changed or rearranged according to the required design. And the above embodiments can be mixed and matched with each other or with other embodiments based on design and reliability considerations, that is, the technical features in different embodiments can be freely combined to form more embodiments.

[0029] Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0030] In order to solve the problems existing in the prior art, the embodiments of the present application provide an automated combined sample preparation device and method for iron-55 and nickel-63.

[0031] Example 1

[0032] This embodiment provides an automated combined sample preparation device for iron-55 and nickel-63, such as Figure 1As shown, it comprises: a pretreatment device 1, a first separation device 2, a second separation device 3, a liquid transfer device 4 and a control device 5; the pretreatment device 1 is used to concentrate the sample to be processed and then fix the volume to obtain a first sample to be processed; the liquid transfer device 4 is used to transport the first sample to be processed in the pretreatment device 1 to the first separation device 2, and to transport liquid reagents to the pretreatment device 1, the first separation device 2 and the second separation device 3, and the liquid reagents at least include a dissolving reagent, a first eluting reagent, a first desorption reagent, a volume fixing reagent, a second eluting reagent, a pH adjusting reagent and a second desorption reagent; the first separation device 2 is used to separate the first sample to be processed into a liquid, and then fix the volume of the sample to be processed. The first separation device 2 is used to separate the treated first effluent into a first effluent, a first eluent and a first desorption liquid, and the first effluent is concentrated and then subjected to pH adjustment treatment. The first separation device 2 is also used to treat the first desorption liquid into a first sample (i.e., a liquid sample rich in iron-55); the second separation device 3 is used to separate the treated first effluent to obtain a second effluent, a second eluent and a second analytical liquid, and the second separation device 3 is also used to treat the second analytical liquid into a second sample (i.e., a liquid sample rich in nickel-63); the control device 5 is electrically connected to the pretreatment device 1, the first separation device 2, the second separation device 3 and the liquid transfer device 4, respectively, to control them to work or not.

[0033] The invention discloses an automated combined sample preparation device for iron-55 and nickel-63. Through the device, iron-55 and nickel-63 can be automatically combined for sample preparation, thereby simplifying the sample preparation process, improving the sample preparation efficiency, reducing labor costs and saving raw materials.

[0034] In some preferred embodiments, the pretreatment device 1 includes a first conveying device 11, a first container 12 and a first heater 13; the discharge port of the first conveying device 11 is connected to the feed port of the first container 12, and the first conveying device 11 is electrically connected to the control device 5; the discharge port of the first container 12 is connected to the feed port of the liquid transfer device 4; the first heater 13 is used to heat the first container 12, and is electrically connected to the control device 5; based on the control of the first conveying device 11 and the first heater 13 by the control device 5, the automation of injection is realized, and the method of concentrating the treated sample and then fixing the volume by heating, on the one hand, realizes the subsequent preparation of iron-55 and nickel-63 samples by the first separation device 2 and the second separation device 3, and can reduce the amount of liquid input in the subsequent treatment process; on the second aspect, it can realize accurate control of the sample system (that is, the content of each component) and accurate control of the sample volume.

[0035] Preferably, the control device 5 is also used to detect the near-dry state of the material in the first container 12; there are multiple ways to detect the near-dry state. For example, the model can be trained by network model training so that the model can identify the near-dry state. Monitoring can also be completed by other methods, which are not listed one by one in the embodiments of the present disclosure.

[0036] Preferably, the first conveying device 11 is an injection pump, and there are one or more of them, which are used to convey the sample to be treated, concentrated nitric acid, iron-55 carrier, nickel-63 carrier and anti-carrier; optionally, the sample to be treated, concentrated nitric acid, iron-55 carrier, nickel-63 carrier and anti-carrier can be conveyed by one first conveying device 11 or by multiple first conveying devices 11.

[0037] Specifically, when the treatment starts, the control device 5 controls the first conveying device 11 to feed, and adds the sample to be treated, iron-55 carrier, nickel-63 carrier and anti-carrier into the first container 12 in turn, and then stirs them evenly. The control device 5 controls the first heater 13 to work, heat the first container 12, and evaporate the liquid in the first container 12 to almost dryness. Then, the control device 5 controls the liquid transfer device 4 to inject a fixed volume reagent (hydrochloric acid of a first solubility) into the first container 12 to obtain a first sample to be treated.

[0038] In some preferred embodiments, the first separation device 2 includes a first separation column 21, a first multi-way valve 22, a second container 23, a second heater 24, a third container 25, a third heater 26 and a second conveying device 27; the feed port of the first separation column 21 is connected to the discharge port of the liquid transfer device 4, and the discharge port is connected to the feed port of the first multi-way valve 22; the first multi-way valve 22 includes a plurality of discharge ports, which are respectively connected to the feed ports of the second container 23 and the third container 25; the feed port of the second container 23 is connected to the discharge port of the second conveying device 27, and the discharge port is connected to the feed port of the second separation device 3. The second container 23 is connected, and the feed port of the second container 23 is connected with the discharge port of the liquid transfer device 4; the feed port of the third container 25 is connected with the discharge port of the liquid transfer device 4; the second heater 24 is used to heat the second container 23; the third heater 26 is used to heat the third container 25; the control device 5 electrically connects the first multi-way valve 22, the second heater 24, the third heater 26 and the second conveying device 27; based on the control device 5, the first multi-way valve 22, the second heater 24, the third heater 26 and the second conveying device 27 are controlled to realize automated sample preparation and improve the efficiency of sample preparation.

[0039] Preferably, the second delivery device 27 is a syringe pump for delivering ammonium citrate and ammonia water with a pH value of 9; optionally, the second delivery device 27 is a pump group composed of multiple syringe pumps or a multi-channel syringe pump or a combination of a single-channel syringe pump and a multi-channel syringe pump; or, the second delivery device 27 is integrated in the liquid transfer device 4, that is, the ammonium citrate and ammonia water with a pH value of 9 are delivered by the liquid transfer device 4.

[0040] Preferably, the first separation device 2 further comprises a third conveying device 28 and a first liquid scintillation bottle 29 ; the third conveying device 28 is used to convey the liquid in the third container 25 to the first liquid scintillation bottle 29 ; and the control device 5 is electrically connected to the third conveying device 28 .

[0041] Preferably, the first separation device 2 further includes a first waste liquid bottle 210 ; the feed inlet of the first waste liquid bottle 210 is connected to the discharge outlet of the first multi-way valve 22 .

[0042] Preferably, the first separation column 21 is an anion exchange resin column; for example, a glass piston type ion exchange column with a funnel filled with a strong alkaline anion exchange resin, with a specification of 13x10x200mm.

[0043] Preferably, the first multi-way valve 22 has three outlets, each outlet corresponding to a feed port connected to the second container 23 , the third container 25 and the first waste liquid bottle 210 .

[0044] Specifically, the working process of the first separation device 2 is as follows: the control device 5 controls the liquid transfer device 4 to transport the first sample to be processed in the pretreatment device 1 to the first separation column 21, and the first multi-way valve 22 opens the discharge port corresponding to the second container 23, so that the first effluent enters the second container 23; the control device 5 controls the liquid transfer device 4 to inject the first elution reagent into the first separation column 21, and the first multi-way valve 22 opens the discharge port corresponding to the first waste liquid bottle 210, so that the first elution liquid flows into the first waste liquid bottle 210 for collection; the control device 5 controls the liquid transfer device 4 to inject the first desorption reagent into the first separation column 21, and the first multi-way valve 22 opens the opening corresponding to the third container 25, so that the first desorption liquid flows into the third container 25; the control device 5 controls the third heater 26 Start heating to evaporate the liquid in the third container 25 until it is nearly dry, stop heating, and then, the control device 5 controls the liquid transfer device 4 to inject a constant volume reagent into the third container 25 to obtain a first sample rich in iron-55; control the third delivery device 28 to deliver to the first liquid scintillation bottle 29; the control device 5 controls the second heater 24 to operate to evaporate the first effluent in the second container 23 until it is nearly dry, and then, the liquid transfer device 4 injects a dissolving reagent into the second container 23, and after stirring evenly, the control device 5 controls the second delivery device 27 to inject a pH adjusting reagent into the second container 23 to obtain a treated first effluent; thereby, the iron-55 sample to be analyzed is prepared and stored in the first liquid scintillation bottle 29 without the need for on-duty supervision, and only needs to be taken to a liquid scintillation counter for direct measurement.

[0045] In some preferred embodiments, the second separation device 3 includes a fourth conveying device 31, a second separation column 32, a second multi-way valve 33, a fourth container 34, a fourth heater 35 and a second waste liquid bottle 36; the feed port of the fourth conveying device 31 is connected to the first separation device 2, and the discharge port is connected to the feed port of the second separation column 32; the discharge port of the second separation column 32 is connected to the feed port of the second multi-way valve 33; the second multi-way valve 33 has multiple discharge ports, which are respectively connected to the feed ports of the fourth container 34 and the second waste liquid bottle 36; the feed port of the fourth container 34 is connected to the discharge port of the liquid transfer device 4; the fourth heater 35 is used to heat the fourth container 34; the control device 5 electrically connects the fourth conveying device 31, the second multi-way valve 33 and the fourth heater 35; based on the control of the fourth conveying device 31, the second multi-way valve 33 and the fourth heater 35 by the control device 5, the automation of the separation and sample preparation process is realized, and the efficiency of sample preparation is improved.

[0046] Preferably, the second separation column 32 is a nickel-specific resin column, such as an ion exchange column filled with nickel-specific resin, with a size of 9x7x50mm.

[0047] Preferably, the second separation device 3 further comprises a fifth conveying device 37 and a second liquid scintillation bottle 38 ; the fifth conveying device 37 is used to convey the liquid in the fourth container 34 to the second liquid scintillation bottle 38 ; and the control device 5 is electrically connected to the fifth conveying device 37 .

[0048] Specifically, the working process of the second separation device 3 is as follows; the control device 5 controls the fourth conveying device 31 to convey the first effluent liquid obtained by the first separation device 2 to the second separation column 32, and the second effluent liquid is separated by the second separation column 32. At the same time, the second multi-way valve 33 is switched to the discharge port and connected to the second waste liquid bottle 36, and the second effluent liquid is conveyed to the second waste liquid bottle 36. Then, the control device 5 controls the liquid transfer device 4 to inject the second elution reagent into the second separation column 32, and the obtained second elution liquid is conveyed to the second waste liquid bottle 36; then, the second multi-way valve 33 is switched to the discharge port and connected to the fourth container 34, and then, the control device 5 controls the liquid transfer device 4 to inject the second desorption reagent into the second separation column 32, and the obtained second desorption liquid is conveyed to the fourth container 34. The control device 5 controls the fourth heater 35 to heat the fourth container 34 until the second desorption liquid is almost dry. Then, the liquid transfer device 4 injects a constant volume reagent into the fourth container 34 to obtain a second sample of nickel-63.

[0049] In some preferred embodiments, the first heater 13, the second heater 24 and the third heater 26 are all electric heating jackets, preferably electric heating jackets with magnetic stirring function; the first container 12, the second container 23, the third container 25 and the fourth container 34 are reagent bottles adapted thereto.

[0050] In some preferred embodiments, Figure 2 and 3 As shown, the liquid transfer device 4 includes a first multi-port connecting vessel 41, a connecting pipe 42, a delivery pump 43, and a second multi-port connecting vessel 44; the first multi-port connecting vessel 41 has a plurality of first feed ports and a first discharge port; the first discharge port can be selectively connected to one of the first feed ports; each first feed port is used to connect different external liquid reagents; the second multi-port connecting vessel 44 has a second feed port and a plurality of second discharge ports; the second feed port can be selectively connected to one of the second discharge ports; each second discharge port is used to It is connected with the pretreatment equipment 1, the first separation equipment 2 and the second separation equipment 3; one end of the connecting pipe 42 is connected to the first discharge port, and the other end is connected to the second feed port; the delivery pump 43 is arranged on the connecting pipe 42, and is used to deliver the material from the first multi-interface connecting vessel 41 to the second multi-interface connecting vessel 44; based on the first multi-interface connecting vessel 41 to form multiple feed ports for inputting different liquid reagents, the second multi-interface connecting vessel 44 to form multiple discharge ports for delivering the liquid reagents to different containers, the structure is simple, and multi-material delivery and multi-container output can be realized.

[0051] Preferably, the connecting tube 42 is a rubber tube; the delivery pump 43 is a peristaltic pump, and is driven by a stepper motor or a servo motor.

[0052] In some preferred embodiments, the first multi-port connector 41 includes a first inner mounting disk 411 and a first outer mounting disk 412; the first outer mounting disk 412 is arranged around the outer periphery of the first inner mounting disk 411 and has a plurality of first outer channels 413, that is, the first outer mounting disk 412 is a circular ring structure, and the first inner mounting disk 411 is on the inner side of the circular ring; the first inner mounting disk 411 has a first inner channel 414; one of the plurality of first outer channels 413 is a first outgoing material channel 4131, and the rest are first outgoing material feed channels 4132; one end of each first outgoing material feed channel 4132 is arranged close to the outer periphery of the first outer mounting disk 412, forming There are multiple first feed ports, and the other end is used to connect with one end of the first inner channel 414; the other end of the first inner channel 414 is connected with one end of the first outer feed channel 4131; the other end of the first outer feed channel 4131 forms a first discharge port; the first outer mounting disk 412 and the first inner mounting disk 411 can rotate with each other, so that one end of the first inner channel 414 can be connected with one end of each first outer feed channel 4132 one by one, and the other end of the first inner channel 414 remains connected with the first outer feed channel 4131; based on this, a structure in which one discharge port corresponds to multiple feed ports is formed, and the structure is simple and convenient to switch.

[0053] Preferably, the first inner mounting disk 411 and the first outer mounting disk 412 are relatively rotated by a servo motor, for example, the servo motor drives the first inner mounting disk 411 to rotate.

[0054] Preferably, the first inner channel 414 is a hose, one end of which is connected to the first outer feed channel 4131 and has a fixed relative position, and the other end of which can change direction as the first inner mounting disk 411 rotates to connect with different first outer feed channels 4132 .

[0055] Preferably, the ends of the first outer feed channel 4132 that are connected to the first inner channel 414 are elastically abutted and sealed;

[0056] Preferably, the first external feed channel 4132 and the first external feed channel 4131 are both rigid tubes.

[0057] or,

[0058] The second multi-port communication device 44 includes a second inner mounting disk 441 and a second outer mounting disk 442; the second outer mounting disk 442 is arranged around the outer periphery of the second inner mounting disk 441 and has a plurality of second outer channels 443; the second inner mounting disks 441 can rotate relative to each other and have second inner channels 444; one of the plurality of second outer channels 443 is a second outer feed channel 4431, and the rest are second outer feed channels 4432; one end of each second outer feed channel 4432 is arranged close to the outer periphery of the second outer mounting disk 442, forming a plurality of second outer channels 4431 and a second outer feed channel 4432; The second discharge port, the other end of which is used to dock and communicate with one end of the second inner channel 444; the other end of the second inner channel 444 is connected to one end of the second outer material channel 4432; the other end of the second outer material feed channel 4431 forms a second feed port; the second outer mounting plate 442 and the second inner mounting plate 441 can rotate with each other, so that one end of the second inner channel 444 can dock and communicate with one end of each second outer material channel 4432 one by one, and the other end of the second inner channel 444 remains docked and communicated with one end of the second outer material feed channel 4431. Based on this, a structure is formed in which one feed port corresponds to multiple discharge ports, and the structure is simple and easy to switch.

[0059] Preferably, the second inner mounting disk 441 and the second outer mounting disk 442 are relatively rotated by a servo motor, for example, the servo motor drives the second inner mounting disk 441 to rotate.

[0060] Preferably, the second inner channel 444 is a hose, one end of which is connected to the second outer feed channel 4131 and has a fixed relative position, and the other end of which can change direction as the second inner mounting plate 441 rotates to connect with different second outer feed channels 4132 .

[0061] Preferably, the ends of the second outgoing material channel 4132 that are connected to the second inner channel 444 are elastically abutted and sealed;

[0062] Preferably, the second external feed channel 4431 and the second external feed channel 4432 are both rigid tubes.

[0063] In some preferred embodiments, the control unit 16 can also be controlled by mechanical devices such as a robotic arm. After a round of automated sample preparation is completed, it is detected that the iron-55 sample to be analyzed in the first liquid scintillation bottle 29 meets the measurement conditions and can be measured. Then, the first liquid scintillation bottle 29 is transferred to a liquid scintillation counter for measurement by the robotic arm, and is taken out after the measurement is completed, and the results are obtained, and a log is generated and recorded.

[0064] In some preferred embodiments, in the combined sample preparation device, various problems that may arise in the mechanical design, such as the acid resistance of components, the degree of resin treatment, and the prevention of cross contamination, can be solved by using polytetrafluoroethylene pipes, sample collection bottles, etc. to achieve the purpose of automated pre-treatment-sample preparation-analysis-recording in the embodiments of the present disclosure. The sample preparation and analysis efficiency can be improved, the steps of manual operation can be reduced, the labor cost can be reduced, and raw materials can be saved.

[0065] The device of the present invention can realize a fully automated pre-treatment-sample preparation-analysis-recording process, accurately control the liquid volume through positive pressure loading, and avoid cross contamination through independent valves. The control device 5 controls the on and off of the injection pump to realize the quantitative addition of reagents and the control of the flow rate through the column. All operations are controlled and realized on the LCD screen of the control device 5.

[0066] Example 2

[0067] This embodiment provides an automated combined sample preparation method of iron-55 and nickel-63, comprising the following steps:

[0068] S1. Inject the sample to be treated into the pretreatment device 1, and then adjust the pH value to less than 2, preferably, by concentrated nitric acid; then inject the iron-55 carrier, the nickel-63 carrier and the counter-carrier Co, Zn, Cs carrier, stir evenly and evaporate and concentrate to near dryness, and then inject the constant volume reagent into the liquid transfer device 4 to obtain the first sample to be treated;

[0069] Specifically, the amount of sample to be processed injected is 20ml-1L;

[0070] Preferably, considering that the resin has a limited carrying capacity in the subsequent treatment process, the weight of each carrier also has corresponding requirements, 5 mg each of the iron-55 carrier and the nickel-63 carrier, and 1 mg each of the counter-carrier Co, Zn, and Cs carriers.

[0071] Preferably, the constant volume reagent is 7 mol / L hydrochloric acid, and the injection volume is 15 mL;

[0072] Further preferably, the fixed volume reagent can be injected using a first preset flow rate, and the first preset flow rate can be 0.5 mL / min, 0.4 mL / min, etc.

[0073] Specifically, when the treatment starts, the control device 5 controls the first conveying device 11 to feed, and adds the sample to be treated, iron-55 carrier, nickel-63 carrier and anti-carrier into the first container 12 in turn, and then stirs them evenly. The control device 5 controls the first heater 13 to work, heat the first container 12, evaporate the liquid in the first container 12 to nearly dry, and then the control device 5 controls the liquid transfer device 4 to inject a hydrochloric acid solution of the first solubility into the first container 12 to obtain a first sample to be treated.

[0074] S2. The first sample to be processed is passed into the first separation device 2 to obtain a first effluent liquid, and then the liquid transfer device 4 injects a first elution reagent into the first separation device 2 to obtain a first elution liquid; then, the liquid transfer device 4 injects a first desorption reagent into the first separation device 2 to obtain a first desorption liquid, evaporates the first desorption liquid to nearly dryness, and then injects a constant volume reagent into the first desorption liquid through the liquid transfer device 4 to obtain an iron-rich sample;

[0075] Preferably, the first elution reagent is 30 mL 4 mol / L hydrochloric acid.

[0076] Preferably, the first desorption reagent is 40 mL 0.1 mol / L hydrochloric acid.

[0077] Preferably, the constant volume reagent is 0.1 mol / L hydrochloric acid, and the specific injection amount can be determined according to actual conditions.

[0078] Preferably, the first desorption reagent can be carried out at a second preset flow rate, and the second preset flow rate can also be set according to actual needs and controlled by the control device 5, preferably 0.5mL / min, which is beneficial to improve the adsorption and desorption effects and improve the overall recovery rate.

[0079] S3. The first separation device 2 evaporates the first effluent to near dryness, then adds a dissolving agent to the first effluent through the liquid transfer device 4, stirs evenly, and adds a pH adjusting agent to pH = 9; to obtain a treated first effluent;

[0080] Preferably, the dissolving agent is 1 mol / L hydrochloric acid, and the specific injection amount can be determined according to actual conditions.

[0081] Preferably, the pH adjusting agent comprises 1 mol / L amine citrate (C6H 17 N3O7) and ammonia (NH4OH).

[0082] Specifically, the working process of the first separation device 2 is as follows: the control device 5 controls the liquid transfer device 4 to transport the first to-be-processed sample in the pretreatment device 1 to the first separation column 21, and the first multi-way valve 22 opens the discharge port corresponding to the second container 23, so that the first effluent enters the second container 23; the control device 5 controls the liquid transfer device 4 to inject the first elution reagent into the first separation column 21, and the first multi-way valve 22 opens the discharge port corresponding to the first waste liquid bottle 210, so that the first elution liquid flows into the first waste liquid bottle 210 for collection; the control device 5 controls the liquid transfer device 4 to inject the first desorption reagent into the first separation column 21, and the first multi-way valve 22 opens the opening corresponding to the third container 25, so that The first desorption liquid flows into the third container 25; the control device 5 controls the third heater 26 to start heating, evaporates the liquid in the third container 25 to nearly dryness, stops heating, and then controls the liquid transfer device 4 to inject a constant volume reagent into the third container 25 to obtain a liquid sample of iron-55; controls the third conveying device 28 to convey to the first liquid scintillation bottle 29; the control device 5 controls the second heater 24 to work, evaporates the first effluent liquid in the second container 23 to nearly dryness, and then, the liquid transfer device 4 injects a dissolving reagent into the second container 23, and after stirring evenly, the control device 5 controls the second conveying device 27 to inject a pH adjusting reagent into the second container 23 to obtain a treated first effluent liquid.

[0083] S4. Pass the first effluent liquid into the second separation device 3 to obtain the second effluent liquid, then inject the second elution reagent into the second separation device 3 through the liquid transfer device 4 to obtain the second elution liquid, and then inject the second desorption reagent into the second separation device 3 to obtain the second desorption liquid; evaporate the second desorption liquid to nearly dryness, and then inject the constant volume reagent to obtain a nickel-rich sample.

[0084] Preferably, the second washing reagent is ammonium citrate at pH=9.

[0085] Preferably, the second desorption reagent is 3 mol / L nitric acid, and the added amount may be 30 mL.

[0086] Preferably, the constant volume reagent is 0.1 mol / L hydrochloric acid, and the specific injection amount can be determined according to actual conditions.

[0087] Specifically, the working process of the second separation device 3 is as follows; the control device 5 controls the fourth conveying device 31 to convey the first effluent liquid obtained by the first separation device 2 to the second separation column 32, and the second effluent liquid is separated by the second separation column 32. At the same time, the second multi-way valve 33 is switched to the discharge port and connected to the second waste liquid bottle 36, and the second effluent liquid is conveyed to the second waste liquid bottle 36. Then, the control device 5 controls the liquid transfer device 4 to inject the second elution reagent into the second separation column 32, and the obtained second elution liquid is conveyed to the second waste liquid bottle 36; then, the second multi-way valve 33 is switched to the discharge port and connected to the fourth container 34, and then, the control device 5 controls the liquid transfer device 4 to inject the second desorption reagent into the second separation column 32, and the obtained second desorption liquid is conveyed to the fourth container 34. The control device 5 controls the fourth heater 35 to heat the fourth container 34 until the second desorption liquid is almost dry. Then, the liquid transfer device 4 injects a constant volume reagent into the fourth container 34 to obtain a liquid sample of nickel-63.

[0088] The automated combined sample preparation method of iron-55 and nickel-63 of the present invention is based on sample preparation using the sample preparation device in Example 1, and can realize automated pre-treatment, sample preparation and analysis of iron-55 and nickel-63 throughout the entire process, thereby reducing manual operation processes, reducing labor costs, and improving processing efficiency. In addition, combined processing can save raw materials and improve processing efficiency.

[0089] Experimental example

[0090] 50mL of wastewater sample was separated, purified and prepared by the device, and the obtained sample was measured by low-level liquid scintillation spectrometer, and the measurement results of iron-55 and nickel-63 were 0.25Bq / L and 1.27Bq / L. The sample preparation method and device can be well used for sample measurement.

[0091] The embodiments of the present invention are described above in conjunction with the accompanying drawings, but the present invention is not limited to the above-mentioned specific implementation modes, which are merely illustrative rather than restrictive. Under the guidance of the present invention, ordinary technicians in this field can also make many forms without departing from the scope of protection of the present invention and the claims, all of which are within the protection of the present invention.

Claims

1. An automated combined sample preparation device for iron-55 and nickel-63, characterized in that: include: Pretreatment equipment, first separation equipment, second separation equipment, liquid transfer equipment and control equipment; The pretreatment device is used to concentrate the sample to be processed and then fix the volume to obtain a first sample to be processed; The liquid transfer device is used to transfer the first sample to be processed in the pretreatment device to the first separation device, and to transfer liquid reagents to the pretreatment device, the first separation device and the second separation device, wherein the liquid reagents at least include a dissolving reagent, a first eluting reagent, a first desorption reagent, a second eluting reagent, a pH adjusting reagent, a second desorption reagent and a volume fixing reagent; The first separation device is used to separate the first sample to be processed into a first effluent, a first eluent and a first desorption liquid, and to concentrate the first effluent and then perform a pH adjustment treatment, and the first separation device is also used to process the first desorption liquid into a first sample; The second separation device is used to separate the first effluent after treatment to obtain a second effluent, a second eluent and a second analytical solution, and the second separation device is also used to process the second analytical solution into a second sample; The control device is electrically connected to the pretreatment device, the first separation device, the second separation device and the liquid transfer device respectively.

2. The automated combined sample preparation device for iron-55 and nickel-63 according to claim 1, characterized in that: The pretreatment device includes a first conveying device, a first container and a first heater; The discharge port of the first conveying device is connected to the feed port of the first container, and the first conveying device is electrically connected to the control device; The discharge port of the first container is connected to the feed port of the liquid transfer device, and the feed port is connected to the discharge port of the liquid transfer device; The first heater is used to heat the first container and is electrically connected to the control device.

3. The automated combined sample preparation device for iron-55 and nickel-63 according to claim 1, characterized in that: The first separation device comprises a first separation column, a first multi-way valve, a second container, a second heater, a third container, a third heater, and a second conveying device; The feed port of the first separation column is connected to the discharge port of the liquid transfer device, and the discharge port is connected to the feed port of the first multi-way valve; The first multi-way valve comprises a plurality of outlets, which are respectively connected to the inlets of the second container and the third container; The feed port of the second container is communicated with the discharge port of the second conveying device, the discharge port is communicated with the feed port of the second separation device, and the feed port of the second container is communicated with the discharge port of the liquid transfer device; The feed port of the third container is connected to the discharge port of the liquid transfer device; The second heater is used to heat the second container; The third heater is used to heat the third container; The control device electrically connects the first multi-way valve, the second heater, the third heater, and the second delivery device.

4. The automated combined sample preparation device for iron-55 and nickel-63 according to claim 3, characterized in that: The first separation device also includes a third delivery device and a first liquid scintillation bottle; The third conveying device is used to convey the liquid in the third container to the first liquid scintillation bottle; The control device is electrically connected to the third conveying device.

5. The automated combined sample preparation device for iron-55 and nickel-63 according to claim 3, characterized in that: The first separation device also includes a first waste liquid bottle; The feed inlet of the first waste liquid bottle is connected to the discharge outlet of the first multi-way valve.

6. The automated combined sample preparation device for iron-55 and nickel-63 according to claim 1, characterized in that: The second separation device comprises a fourth conveying device, a second separation column, a second multi-way valve, a fourth container, a fourth heater and a second waste liquid bottle; The feed port of the fourth conveying device is connected to the first separation device, and the discharge port is connected to the feed port of the second separation column; The outlet of the second separation column is connected to the inlet of the second multi-way valve; The second multi-way valve has a plurality of outlets, which are respectively connected to the inlet of the fourth container and the second waste liquid bottle; The feed port of the fourth container is connected to the discharge port of the liquid transfer device; The fourth heater is used to heat the fourth container; The control device electrically connects the fourth delivery device, the second multi-way valve, and the fourth heater.

7. The automated combined sample preparation device for iron-55 and nickel-63 according to claim 6, characterized in that: The second separation device also includes a fifth conveying device and a second liquid scintillation bottle; The fifth conveying device is used to convey the liquid in the fourth container to the second liquid scintillation bottle; and the control device is electrically connected to the fifth conveying device.

8. The automated combined sample preparation device for iron-55 and nickel-63 according to claim 1, characterized in that: The liquid transfer device comprises a first multi-port communicating vessel, a communicating pipe, a delivery pump, and a second multi-port communicating vessel; The first multi-port connector has a plurality of first feed ports and a first discharge port; the first discharge port can be selectively connected to one of the first feed ports; Each of the first feed ports is used to communicate with different external liquid reagents; The second multi-port communication device has a second feed port and a plurality of second discharge ports; the second feed port can be selectively connected to one of the second discharge ports; Each of the second discharge ports is used to communicate with the pretreatment equipment, the first separation equipment and the second separation equipment; One end of the connecting pipe is connected to the first discharge port, and the other end is connected to the second feed port; The delivery pump is arranged on the connecting pipe, and is used for delivering materials from the first multi-port connecting vessel to the second multi-port connecting vessel.

9. The automated combined sample preparation device of iron-55 and nickel-63 according to claim 8, characterized in that: The first multi-port connector includes a first inner mounting plate and a first outer mounting plate; The first outer mounting plate is disposed around the outer periphery of the first inner mounting plate and has a plurality of first outer channels; The first inner mounting disk has a first inner channel; One of the plurality of first external channels is a first external material channel, and the rest are first external material feed channels; One end of each first external feed channel is arranged close to the outer periphery of the first external mounting plate to form a plurality of first feed ports, and the other end is used for docking and communicating with one end of the first internal channel; The other end of the first inner channel is connected to one end of the first outgoing material channel; The other end of the first outgoing material channel forms the first outgoing material outlet; The first outer mounting disk and the first inner mounting disk can rotate relative to each other, so that one end of the first inner channel can be docked and connected with one end of each of the first outer feed channels one by one, and the other end of the first inner channel remains docked and connected with the first outer feed channel; or, The second multi-port connector includes a second inner mounting plate and a second outer mounting plate; The second outer mounting plate is disposed around the outer periphery of the second inner mounting plate and has a plurality of second outer channels; The second inner mounting plate has a second inner channel; One of the plurality of second external channels is a second external feed channel, and the rest are second external feed channels; One end of each second external material channel is arranged close to the outer periphery of the second outer mounting plate to form a plurality of second material outlets, and the other end is used for docking and communicating with one end of the second internal channel; The other end of the second inner channel is connected to one end of the second outgoing material channel; The other end of the second external feed channel forms the second feed port; The second outer mounting disk and the second inner mounting disk can rotate relative to each other so that one end of the second inner channel can be docked and connected with one end of each second outer feeding channel one by one, and the other end of the second inner channel remains docked and connected with one end of the second outer feeding channel.

10. An automated combined sample preparation method for iron-55 and nickel-63, characterized in that: The steps include: Injecting a sample to be treated into a pretreatment device, adjusting the pH value to less than 2, injecting an iron-55 carrier, a nickel-63 carrier and a counter carrier, stirring evenly and evaporating and concentrating to near dryness, and then injecting a hydrochloric acid solution of a first solubility through the liquid transfer device to obtain a first sample to be treated; Passing the first sample to be processed into a first separation device to obtain a first effluent, then injecting a first elution reagent into the first separation device through a liquid transfer device to obtain a first elution liquid; then injecting a first desorption reagent into the first separation device through the liquid transfer device to obtain a first desorption liquid, evaporating the first desorption liquid to near dryness, and then injecting a constant volume reagent into the first desorption liquid through the liquid transfer device to obtain a first sample rich in iron-55; The first separation device evaporates the first effluent to near dryness, then adds a dissolving agent to the first effluent through the liquid transfer device, stirs evenly, and adds a pH adjusting agent to pH=9 to obtain the adjusted first effluent; The first effluent is passed into a second separation device to obtain a second effluent, and then a second eluent is injected into the second separation device through the liquid transfer device to obtain a second eluent, and then a second desorption reagent is injected into the second separation device to obtain a second desorption liquid; the second desorption liquid is evaporated to near dryness, and then a constant volume reagent is injected to obtain a second sample rich in nickel-63.

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