CN115524363A - Heat value halogen combined analysis system and analysis method - Google Patents
Heat value halogen combined analysis system and analysis method Download PDFInfo
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- CN115524363A CN115524363A CN202211495922.5A CN202211495922A CN115524363A CN 115524363 A CN115524363 A CN 115524363A CN 202211495922 A CN202211495922 A CN 202211495922A CN 115524363 A CN115524363 A CN 115524363A
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- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/38—Diluting, dispersing or mixing samples
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- G01N30/20—Injection using a sampling valve
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- G01N30/02—Column chromatography
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Abstract
The invention discloses a heat value halogen combined analysis system and an analysis method, wherein the analysis system comprises an oxygen bomb combustion device, a gas-liquid switch assembly, a collection device, a chromatographic detection device and a control module which are sequentially connected; the oxygen bomb combustion device is provided with a gas-liquid inlet for introducing oxygen or water, and comprises an oxygen control valve for controlling oxygen to enter the oxygen bomb combustion device and a cleaning control valve for controlling cleaning liquid to enter the oxygen bomb combustion device; the oxygen bomb combustion device is provided with a gas-liquid outlet for discharging combusted gas and cleaning liquid after oxygen bomb combustion, and the gas-liquid switch assembly is arranged at the gas-liquid outlet and used for opening and closing the gas-liquid outlet; the device comprises a first valve body, a second valve body and a first pump body, wherein the first valve body, the second valve body and the first pump body are used for controlling absorption liquid and pure water to enter a collecting device; the chromatographic detection device is used for carrying out halogen content test; the control module is used for controlling each part to work.
Description
Technical Field
The invention mainly relates to the technical field of element analysis equipment, in particular to a heat value halogen combined analysis system and a heat value halogen combined analysis method.
Background
Solid waste refers to solid, semi-solid waste material produced by human beings in production, consumption, life, or other activities. Generally speaking, the garbage is garbage. Mainly comprising solid particles, garbage, slag, sludge, waste products, deteriorated food and the like. In the solid waste industry, fluorine, chlorine and sulfur are the indexes which must be measured at present, and at present, the solid waste is analyzed by halogen and sulfur elements, and the sample pretreatment method mainly adopts an oxygen bomb method.
The analysis standards for measuring the halogen content in the sample by using an oxygen bomb combustion-ion chromatography are available at home and abroad, such as the foreign standard EN 14582-2007 waste characteristics-halogen and sulfur content-oxygen combustion and measuring method in a sealed system; although the national standard GB/T34692-2017 for determining the halogen content of the thermoplastic elastomer, namely the oxygen bomb combustion-ion chromatography, discloses a method for determining halogen by using the oxygen bomb combustion-ion chromatography, all the steps of gas absorption after oxygen bomb combustion, cleaning liquid collection, sample dilution, sample feeding into an ion chromatograph for analysis and the like need manual operation, and due to the fact that the steps are multiple, the manual operation is complex, time-consuming and labor-consuming, the experience requirement on operators is very high, and operation errors and risks of errors are easy to occur when the experience is insufficient, therefore, the problem to be solved by the technical staff needs to be urgently provided with a system capable of automatically completing automatic gas absorption, automatic cleaning liquid collection, automatic dilution, automatic volume determination and automatic ion chromatography.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a full-automatic heat value halogen combined analysis system and method which are simple in structure, can automatically collect gas and cleaning liquid after oxygen bomb combustion, and can automatically dilute, fix volume and analyze.
In order to solve the technical problem, the invention adopts the following technical scheme:
a heat value halogen combined analysis system comprises an oxygen bomb combustion device, a gas-liquid switch assembly, a collecting device, a chromatographic detection device and a control module which are sequentially connected;
the oxygen bomb combustion device is provided with a gas-liquid inlet for introducing oxygen or water into the oxygen bomb combustion device, an oxygen control valve for controlling oxygen to enter the oxygen bomb combustion device and a cleaning control valve for controlling cleaning liquid to enter the oxygen bomb combustion device; the oxygen bomb combustion device is also provided with a gas-liquid outlet for discharging combusted gas and cleaning liquid after oxygen bomb combustion, and the gas-liquid switch assembly is arranged at the gas-liquid outlet and used for opening and closing the gas-liquid outlet;
the device comprises a first valve body, a second valve body and a first pump body, wherein the first valve body, the second valve body and the first pump body are used for controlling absorption liquid and pure water to enter a collecting device;
the chromatographic detection device is used for testing the content of halogen in the collection liquid;
the control module is used for controlling all parts to work.
As a further improvement of the invention: the device is characterized by further comprising a transfer dilution device, wherein the transfer dilution device is connected with the collection device through a second pump body, the transfer dilution device is further connected with the collection device through a fourth valve body and a fifth pump body, and the transfer dilution device is connected with the chromatographic detection device through a third pump body and a third valve body.
As a further improvement of the invention: the water transfer device further comprises a fifth valve body, wherein the fifth valve body is connected with the first pump body and used for controlling pure water to enter the transfer diluting device.
As a further improvement of the invention: still include sample bottle storage component, sample bottle storage component includes sample dish, a plurality of sample bottles, sampling needle and washes the needle subassembly, the sample bottle is arranged on the sample dish, the sampling needle is used for the access to collect the liquid, it is used for wasing the sampling needle to wash the needle subassembly.
As a further improvement of the invention: the sample bottle storage assembly further comprises a sixth pump body for controlling the cleaning liquid to enter the needle washing assembly and a seventh pump body for controlling the waste liquid after cleaning to be discharged from the needle washing assembly.
As a further improvement of the invention: the sampling needle is connected with the collecting device through the fourth pump body.
As a further improvement of the invention: and the sampling needle is connected with the transfer dilution device through a fifth pump body and a fourth valve body.
As a further improvement of the invention: and the sampling needle is connected with the chromatographic detection device through the third pump body and the third valve body.
As a further improvement of the invention: the chromatographic detection device comprises a quantitative ring, a six-way valve, a chromatographic column, a suppressor and a detector which are connected in sequence.
As a further improvement of the invention: the chromatography detection device further comprises a plunger pump and a leaching component, wherein the plunger pump is used for sending the leaching solution in the leaching component into the chromatographic column.
As a further improvement of the invention: the gas-liquid switch assembly comprises a gas-discharging water-discharging needle and a gas-liquid channel.
As a further improvement of the invention: a first filter is further arranged at the liquid outlet of the collecting device.
As a further improvement of the invention: and a second filter is arranged at the liquid inlet of the chromatographic detection device.
As a further improvement of the invention: the device also comprises an eighth pump body, wherein the eighth pump body is connected with the waste liquid outlet of the collecting device and is used for discharging redundant collecting liquid.
As a further improvement of the invention: the device also comprises a ninth pump body, and the ninth pump body is connected with the transfer dilution device and is used for discharging redundant collected liquid.
As a further improvement of the invention: and the collecting device is provided with a first constant volume sensor for automatically fixing the volume of the solution in the collecting device.
As a further improvement of the invention: and a second constant volume sensor is arranged on the transfer dilution device and is used for automatically fixing the volume of the solution in the transfer dilution device.
As a further improvement of the invention: an automatic current limiting device is further arranged between the gas-liquid switch assembly and the collecting device.
The invention also provides an analysis method of the heat value halogen combined analysis system, which comprises the following steps:
step S1: placing the weighed sample in a crucible, and placing the crucible in an oxygen bomb combustion device;
step S2: closing the gas-liquid switch assembly, filling oxygen into the oxygen bomb combustion device, igniting a combustion sample and testing the heat value;
and step S3: cleaning an oxygen bomb combustion device, starting a gas-liquid switch assembly, and collecting combusted gas and oxygen bomb cleaning liquid into a collection device;
and step S4: introducing absorption liquid and pure water into the collecting device, cleaning the combusted gas, fixing the volume and diluting the collecting liquid;
step S5: and (4) sending the diluted collecting solution into a chromatographic detection device for halogen content analysis.
As a further improvement of the invention: step S4 specifically includes:
step S41: introducing quantitative absorption liquid into the collecting device, and collecting the combusted gas and the oxygen bomb cleaning liquid into the collecting device;
step S42: introducing quantitative pure water into the collecting device and carrying out constant volume;
step S43: judging whether delay testing is needed, and if the delay testing is needed, storing the sample bottle through the sample bottle storage component; if the suspend test is not required, the process proceeds to step S5.
As a further improvement of the invention: step S5 specifically includes:
step S51: sending the diluted collecting solution into a chromatographic detection device for halogen content analysis; judging whether the analysis result exceeds the range of the marked line, and if so, taking a certain amount of the collected liquid from the collecting device and conveying the collected liquid into the transfer diluting device;
step S52: introducing quantitative pure water into the transfer diluting device for dilution and constant volume;
step S53: and taking a collection liquid after quantitative dilution from the transfer dilution device, and sending the collection liquid to a chromatographic detection device for halogen content analysis.
As a further improvement of the invention: in step S43, when the collected liquid is stored in the sample bottle storage assembly and needs to be analyzed, the method specifically includes:
step S431: controlling the sample disc to rotate to the position of the target sample bottle, and inserting the sampling needle into the sample bottle;
step S432: judging whether the collected liquid needs to be diluted or not, if so, taking a fixed amount of the collected liquid, sending the fixed amount of the collected liquid into a transfer dilution device, introducing fixed amount of pure water, and fixing the volume; if no dilution is required, go to step S433;
step S433: and (4) sending the collected liquid into a chromatographic detection device for halogen content analysis.
Compared with the prior art, the invention has the advantages that:
1. the heat value halogen combined analysis system is provided with the oxygen bomb combustion device, the gas-liquid switch assembly, the collection device, the chromatographic detection device and the control module which are sequentially connected, when a sample needs to be tested, the weighed sample is placed in the crucible and placed in the oxygen bomb combustion device manually, the oxygen bomb combustion device is used for oxygen-filling combustion, the oxygen bomb combustion device is used for cleaning, gas and cleaning liquid are collected, the sample is diluted, the constant volume is determined, the sample is sent into the chromatographic detection device, and the like without manual intervention, the system can automatically complete various operations, the labor intensity is greatly reduced, the risk of human operation errors and errors is reduced, and the reliability of test results is greatly improved.
2. The combined analysis method for the heat value halogen is based on a combined analysis system for the heat value halogen, and can realize automatic combustion of a sample, automatic cleaning of an oxygen bomb combustion device, automatic collection of combusted gas and cleaning liquid, automatic dilution and volume determination, and automatic measurement of the halogen in the sample.
Drawings
FIG. 1 is a schematic diagram of an analysis system of the present invention.
Fig. 2 is a schematic perspective view of an analysis system according to the present invention.
FIG. 3 is a flow chart of an analysis method of the present invention.
Illustration of the drawings:
1. an oxygen bomb combustion device; 101. a gas-liquid inlet; 102. a gas-liquid outlet; 2. a gas-liquid switch assembly; 201. a gas-discharging water-discharging needle; 202. a gas-liquid channel; 3. a collection device; 4. a chromatographic detection device; 41. a dosing ring; 42. a six-way valve; 43. a chromatographic column; 44. a suppressor; 45. a detector; 46. a plunger pump; 47. leaching the assembly; 5. an oxygen control valve; 6. cleaning the control valve; 7. a first valve body; 8. a second valve body; 9. a first pump body; 10. a transfer dilution device; 11. a second pump body; 12. a third pump body; 13. a third valve body; 14. a fifth valve body; 15. a sample bottle storage assembly; 151. a sample plate; 152. a sample bottle; 153. a sampling needle; 154. a needle washing assembly; 16. a sixth pump body; 17. a seventh pump body; 18. a fourth pump body; 19. a fifth pump body; 20. a fourth valve body; 21. a first filter; 22. a second filter; 23. an eighth pump body; 24. a first capacitance sensor; 25. a second constant volume sensor; 26. a ninth pump body.
Detailed Description
The invention is further described below with reference to the drawings and the specific preferred embodiments, without thereby limiting the scope of protection of the invention.
In the description of the present invention, it is to be understood that the terms "side," "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and are not to be considered limiting of the invention.
The invention will be described in further detail below with reference to the drawings and specific examples.
Example one
As shown in fig. 1 to fig. 2, the present embodiment discloses a calorific value halogen combination analysis system, which includes an oxygen bomb combustion device 1, a gas-liquid switch assembly 2, a collection device 3, a chromatography detection device 4, and a control module, which are connected in sequence;
the oxygen bomb combustion device 1 is provided with a gas-liquid inlet 101 for introducing oxygen or water into the oxygen bomb combustion device 1, and further comprises an oxygen control valve 5 for controlling oxygen to enter the oxygen bomb combustion device 1 and a cleaning control valve 6 for controlling cleaning liquid to enter the oxygen bomb combustion device 1; the oxygen bomb combustion device 1 is also provided with a gas-liquid outlet 102 for discharging combusted gas and cleaning liquid after oxygen bomb combustion, and the gas-liquid switch assembly 2 is arranged at the gas-liquid outlet 102 and used for opening and closing the gas-liquid outlet 102;
the device also comprises a first valve body 7, a second valve body 8 and a first pump body 9 which are used for controlling absorption liquid and pure water to enter the collecting device 3, wherein the collecting device 3 is used for collecting gas after a sample is combusted and cleaning liquid after an oxygen bomb is combusted and carrying out automatic constant volume on the collected liquid;
the chromatographic detection device 4 is used for testing the content of halogen in the collected liquid;
the control module is used for controlling each part to work.
The calorific value halogen of this embodiment allies oneself with uses analytic system, the design has consecutive oxygen bomb burner 1, gas-liquid switch subassembly 2, collection device 3, chromatogram detection device 4 and control module, when needing to test the sample, only need the manual work place the sample of weighing in the crucible and put into oxygen bomb burner 1, oxygen bomb burner 1 oxygenates burning, the oxygen bomb washs, the collection of gas and washing liquid, the sample dilutes and the constant volume and send into operation such as chromatogram detection device 4 and all need not manual intervention, each item operation can be accomplished automatically to the system, greatly reduced intensity of labour, the risk of human operation error and mistake occurrence has been reduced, the reliability of test result has been improved greatly.
In this embodiment, the gas-liquid switch assembly 2 includes a bleed water discharging needle 201 and a gas-liquid passage 202.
The working principle of the oxygen bomb combustion device 1 is as follows:
manually placing the weighed sample into the crucible and the oxygen bomb combustion device 1, closing the oxygen bomb cover and starting the control module; the system is started, the gas-liquid outlet 102 of the oxygen bomb combustion device 1 is closed by the gas-discharging water-discharging needle 201 of the gas-liquid switch component 2, the oxygen control valve 5 is opened to charge oxygen into the oxygen bomb combustion device 1, after the initial period of the test is finished, the ignition wire automatically ignites, the sample is combusted, and after the main period is finished, the heat value test result is automatically obtained; the first valve body 7 is opened, absorption liquid enters the collecting device 3, then the gas discharging water discharging needle 201 of the gas-liquid switch assembly 2 is opened, the combusted gas passes through the gas-liquid channel 202 and enters the collecting device 3 through the automatic flow limiting device, and the absorption liquid washes the combusted gas for the second time, so that the subsequent analysis result of the halogen sulfur is more accurate; after the air release is finished, the cleaning control valve 6 is opened, cleaning water enters the oxygen bomb combustion device 1 to clean the oxygen bomb combustion device, the cleaning liquid flows from the top to the bottom of the oxygen bomb combustion device 1 to completely flush the oxygen bomb combustion device 1, then the cleaning liquid passes through the gas-liquid channel 202 and enters the collection device 3 through the automatic flow limiting device, and the liquid entering the collection device 3 is a sample waiting for halogen analysis.
In this embodiment, the automatic flow limiting device is a valve body with adjustable gas or liquid flow rate, such as a ball valve with adjustable flow rate.
In this embodiment, the device further comprises a transfer dilution device 10, the transfer dilution device 10 is connected to the collection device 3 through a second pump body 11, and the transfer dilution device 10 is further connected to the collection device 3 through a fourth valve body 20 and a fifth pump body 19; the transfer dilution device 10 is connected with the chromatographic detection device 4 through a third pump body 12 and a third valve body 13; the device also comprises a fifth valve body 14, wherein the fifth valve body 14 is connected with the first pump body 9 and is used for controlling pure water to enter the transfer dilution device 10; by arranging the transfer dilution device 10, when the test result of the to-be-tested collection liquid exceeds the range of the marked line, the to-be-tested collection liquid can be diluted by the transfer dilution device 10 and then tested, so that the test range of the chromatographic detection device 4 is met.
In this embodiment, the chromatography detection apparatus 4 includes a quantitative ring 41, a six-way valve 42, a chromatography column 43, a suppressor 44, a detector 45, a plunger pump 46, and a washing component 47, which are connected in sequence, where the plunger pump 46 is used to send the washing liquid in the washing component 47 into the chromatography column 43.
In this embodiment, the device further comprises an eighth pump 23, and the eighth pump 23 is connected to the waste liquid outlet of the collecting device 3 for discharging the excessive collected liquid.
In this embodiment, a ninth pump 26 is further included, and the ninth pump 26 is connected to the transfer dilution device 10 for discharging the excess collected liquid.
In this embodiment, the collecting device 3 is provided with a first constant volume sensor 24 for automatically constant volume the solution in the collecting device 3; the transfer dilution device 10 is provided with a second constant volume sensor 25 for automatically constant volume the solution in the transfer dilution device 10.
When the collected liquid in the collecting device 3 is directly tested, the collected liquid is taken through the second pump body 11 and enters the transfer dilution device 10, the third valve body 13 is switched to be communicated with the transfer dilution device 10, the collected liquid in the transfer dilution device 10 is pumped into the quantitative ring 41 of the six-way valve 42 in the chromatographic detection device 4 through the third pump body 12, the ion chromatography quantitative sample injection test is realized, finally, the redundant collected liquid in the collecting device 3 is drained through the eighth pump body 23, and the redundant collected liquid in the transfer dilution device 10 is drained through the ninth pump body 26.
When the collected liquid in the collecting device 3 needs to be diluted and then is tested, the fourth valve body 20 is switched to be connected with the collecting device 3, a quantitative collected liquid is taken from the collecting device 3 through the fifth pump body 19 and enters the transfer diluting device 10, the first valve body 7 is closed, the second valve body 8 is opened, the fifth valve body 14 is switched to be communicated with the transfer diluting device 10, pure water is injected into the transfer diluting device 10 through the first pump body 9, the constant volume is automatically determined through the second constant volume sensor 25 to achieve proportional dilution, the third valve body 13 is switched to be communicated with the transfer diluting device 10, the diluted collected liquid in the transfer diluting device 10 is pumped into the quantitative ring 41 of the six-way valve 42 through the third pump body 12 to achieve quantitative analysis of ion chromatography, finally, redundant collected liquid in the collecting device 3 is exhausted through the eighth pump body 23, and redundant collected liquid in the transfer diluting device 10 is exhausted through the ninth pump body 26.
In this embodiment, the sample bottle storage assembly 15 is further included, the sample bottle storage assembly 15 includes a sample tray 151, a plurality of sample bottles 152, a sampling needle 153, and a needle washing assembly 154, the sample bottles 152 are disposed on the sample tray 151, the sampling needle 153 is used for accessing collected liquid, and the needle washing assembly 154 is used for cleaning the sampling needle 153; the vial storage assembly 15 further includes a sixth pump body 16 for controlling the flow of cleaning fluid into the wash pin assembly 154 and a seventh pump body 17 for controlling the flow of cleaned waste fluid out of the wash pin assembly 154.
In this embodiment, the sampling needle 153 is connected to the collecting device 3 through the fourth pump body 18, and the sampling needle 153 is connected to the transfer dilution device 10 through the fifth pump body 19 and the fourth valve body 20; the sampling needle 153 is connected to the chromatographic detection device 4 through the third pump body 12 and the third valve body 13.
Because the test efficiency of oxygen bomb combustion apparatus 1 is higher (the conventionality is 10 min), and the test efficiency of chromatogram detection device 4 is relatively slower (the conventionality is 30 min), consequently, will ensure that both efficiency match, it has the automatic continuous storage collecting liquid of appearance bottle storage component 15 to design in this embodiment to guarantee that oxygen bomb combustion apparatus 1 can continuous operation, and chromatogram detection device 4 can automatic analysis stores the collecting liquid well, thereby improves entire system's efficiency and user experience.
In this embodiment, a first filter 21 is further disposed at the liquid outlet of the collecting device 3. Large particles in the cleaning liquid collected after the oxygen bomb is combusted are filtered by the first filter 21, and large particle impurities are prevented from entering the transfer dilution device 10.
In this embodiment, be equipped with second filter 22 in chromatography detection device 4's inlet port department, second filter 22 adopts the filter that the precision is higher than 0.22um, can further prevent that tiny impurity from getting into chromatography detection device 4, improves chromatography detection device 4's life.
Example two
As shown in fig. 3, the present embodiment further provides an analysis method of a calorific value halogen combined analysis system, including the steps of:
s1, placing the weighed sample in a crucible, and placing the crucible in an oxygen bomb combustion device 1;
step S2: closing the gas-liquid switch assembly 2, filling oxygen into the oxygen bomb combustion device 1, igniting a combustion sample and testing a heat value;
and step S3: cleaning an oxygen bomb combustion device 1, starting a gas-liquid switch assembly 2, and collecting combusted gas and oxygen bomb cleaning liquid into a collection device 3;
and step S4: introducing absorption liquid and pure water into the collecting device 3, cleaning the combusted gas, fixing the volume and diluting the collecting liquid;
step S5: and sending the diluted collection liquid to a chromatographic detection device 4 for halogen content analysis.
In this embodiment, step S4 specifically includes:
step S41: introducing quantitative absorption liquid into the collecting device 3, and collecting the combusted gas and the oxygen bomb cleaning liquid into the collecting device 3;
step S42: introducing quantitative pure water into the collecting device 3 and carrying out constant volume;
step S43: judging whether a delay test is needed, and if the delay test is needed, storing the sample bottle through the sample bottle storage component 15; if the suspend test is not required, the process proceeds to step S5.
In this embodiment, step S5 specifically includes:
step S51: sending the diluted collecting solution into a chromatographic detection device 4 for halogen content analysis; judging whether the analysis result exceeds the range of the marked line, if so, taking a certain amount of the collected liquid from the collecting device 3 and sending the collected liquid into the transfer diluting device 10;
step S52: introducing quantitative pure water into the transfer dilution device 10 for dilution and constant volume;
step S53: the quantitatively diluted collection liquid is taken from the transfer dilution device 10 and sent to the chromatographic detection device 4 for halogen content analysis.
The detailed working flow of the direct test after the cleaning liquid of the oxygen bomb combustion device 1 is collected is as follows:
manually placing the weighed sample into the crucible and the oxygen bomb combustion device 1, tightly closing the oxygen bomb cover, and starting the control module; the system starts to work, a gas discharging and water discharging needle 201 of a gas-liquid switch component 2 closes a gas-liquid outlet 102 of an oxygen bomb combustion device 1, an oxygen control valve 5 is opened to charge oxygen into the oxygen bomb combustion device 1, an ignition wire automatically ignites after the initial period of the test, a sample is combusted, and after the main period of the test, a heat value test result is automatically obtained; the first valve body 7 is opened, absorption liquid enters the collecting device 3, then the gas discharging water discharging needle 201 of the gas-liquid switch assembly 2 is opened, the combusted gas passes through the gas-liquid channel 202 and enters the collecting device 3 through the automatic flow limiting device, and the absorption liquid washes the combusted gas for the second time, so that the subsequent analysis result of the halogen sulfur is more accurate; after the air release is finished, the cleaning control valve 6 is opened, cleaning water enters the oxygen bomb combustion device 1 to clean the oxygen bomb combustion device, the cleaning liquid flows from the top to the bottom of the oxygen bomb combustion device 1 to completely flush the oxygen bomb combustion device 1, then the cleaning liquid passes through the gas-liquid channel 202 and enters the collection device 3 through the automatic flow limiting device, and the liquid entering the collection device 3 is the sample waiting for halogen analysis.
When the collected liquid in the collecting device 3 is directly tested, the collected liquid is taken through the second pump body 11 and enters the transfer dilution device 10, the third valve body 13 is switched to be communicated with the transfer dilution device 10, the collected liquid in the transfer dilution device 10 is pumped into the quantitative ring 41 of the six-way valve 42 in the chromatographic detection device 4 through the third pump body 12, the ion chromatography quantitative sampling test is realized, finally, the redundant collected liquid in the collecting device 3 is exhausted through the eighth pump body 23, and the redundant collected liquid in the transfer dilution device 10 is exhausted through the ninth pump body 26.
When the collected liquid in the collecting device 3 needs to be diluted and then is tested, the fourth valve body 20 is switched to be connected with the collecting device 3, a quantitative collected liquid is taken from the collecting device 3 through the fifth pump body 19 and enters the transfer diluting device 10, the first valve body 7 is closed, the second valve body 8 is opened, the fifth valve body 14 is switched to be communicated with the transfer diluting device 10, pure water is injected into the transfer diluting device 10 through the first pump body 9, the constant volume is automatically determined through the second constant volume sensor 25 to achieve proportional dilution, the third valve body 13 is switched to be communicated with the transfer diluting device 10, the diluted collected liquid in the transfer diluting device 10 is pumped into the quantitative ring 41 of the six-way valve 42 through the third pump body 12 to achieve ion chromatography quantitative sample injection analysis, finally, the collected liquid in the collecting device 3 is exhausted through the eighth pump body 23, and the collected liquid in the transfer diluting device 10 is exhausted through the ninth pump body 26.
In this embodiment, in step S43, when the collected liquid is stored in the vial storage module 15 and needs to be analyzed, the steps include:
step S431: controlling the sample disk 151 to rotate to the position of the target sample vial 152 such that the sampling needle 153 is inserted into the sample vial 152;
step S432: judging whether the collected liquid needs to be diluted or not, if so, taking a fixed amount of the collected liquid, sending the fixed amount of the collected liquid into a transfer dilution device 10, introducing fixed amount of pure water, and fixing the volume; if no dilution is required, go to step S433;
step S433: the collected liquid is sent to a chromatographic detection device 4 for halogen content analysis.
The detailed steps of analyzing the collected liquid stored in the sample bottle storage assembly 15 are as follows:
controlling the sample tray 151 to rotate to the position of the target sample bottle 152, so that the sampling needle 153 is inserted into the sample bottle 152, judging whether the collected liquid needs to be diluted, if the collected liquid needs to be diluted, switching the fourth valve body 20 to be communicated with the sampling needle 153, taking quantitative collected liquid through the fifth pump body 19 and sending the quantitative collected liquid into the transfer dilution device 10, closing the first valve body 7, opening the second valve body 8, switching the fifth valve body 14 to be communicated with the transfer dilution device 10, injecting pure water into the transfer dilution device 10 through the first pump body 9, automatically fixing the volume through the second constant volume sensor 25 to achieve proportional dilution, switching the third valve body 13 to be communicated with the transfer dilution device 10, pumping the diluted collected liquid in the transfer dilution device 10 into the quantitative ring 41 of the flow valve 42 through the third pump body 12 to realize ion chromatography quantitative sample injection analysis, finally discharging the collected liquid in the collection device 3 through the eighth pump body 23 to the greatest extent, and discharging the collected liquid in the transfer dilution device 10 through the ninth pump body 26.
If the collected liquid does not need to be diluted, the third valve 13 is switched to be communicated with the sampling needle 153, the collected liquid in the sample bottle 152 is pumped into the quantitative ring 41 of the six-way valve 42 in the chromatographic detection device 4 through the third pump body 12, so as to realize the ion chromatography quantitative sample injection test, and finally, the collected liquid in the washing needle assembly 154 is drained through the seventh pump body 17.
The combined analysis method for the heat value halogen in the embodiment is based on the combined analysis system for the heat value halogen in the first embodiment, automatic combustion of a sample, automatic cleaning of the oxygen bomb combustion device 1, automatic collection of combusted gas and cleaning liquid, automatic dilution and constant volume and automatic measurement of the halogen in the sample can be realized, the sample is placed into the oxygen bomb combustion device 1 only through manual weighing in the whole process, all subsequent operations are unmanned, labor intensity is greatly reduced, the risk of manual operation errors and errors is reduced, and the reliability of a test result is ensured.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-mentioned embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and adaptations to those skilled in the art without departing from the principles of the present invention may be apparent to those skilled in the relevant art and are intended to be within the scope of the present invention.
Claims (22)
1. A heat value halogen combined analysis system is characterized by comprising an oxygen bomb combustion device (1), a gas-liquid switch assembly (2), a collecting device (3), a chromatographic detection device (4) and a control module which are sequentially connected;
the oxygen bomb combustion device (1) is provided with a gas-liquid inlet (101) for introducing oxygen or water into the oxygen bomb combustion device (1), and further comprises an oxygen control valve (5) for controlling oxygen to enter the oxygen bomb combustion device (1) and a cleaning control valve (6) for controlling cleaning liquid to enter the oxygen bomb combustion device (1); the oxygen bomb combustion device (1) is further provided with a gas-liquid outlet (102) for discharging combusted gas and cleaning liquid after oxygen bomb combustion, and the gas-liquid switch assembly (2) is arranged at the gas-liquid outlet (102) and used for opening and closing the gas-liquid outlet (102);
the device is characterized by also comprising a first valve body (7), a second valve body (8) and a first pump body (9) which are used for controlling absorption liquid and pure water to enter the collecting device (3), wherein the collecting device (3) is used for collecting gas generated after the sample is combusted and cleaning liquid generated after the oxygen bomb is combusted and automatically fixing the volume of the collecting liquid;
the chromatographic detection device (4) is used for testing the content of halogen in the collection liquid;
the control module is used for controlling all parts to work.
2. The calorific value halogen combined analysis system according to claim 1, further comprising a transfer dilution device (10), wherein the transfer dilution device (10) is connected with the collection device (3) through a second pump body (11), the transfer dilution device (10) is further connected with the collection device (3) through a fourth valve body (20) and a fifth pump body (19), and the transfer dilution device (10) is connected with the chromatographic detection device (4) through a third pump body (12) and a third valve body (13).
3. A combined calorific value halogen analysis system according to claim 2 further comprising a fifth valve body (14), the fifth valve body (14) being connected to the first pump body (9) for controlling the ingress of pure water into the transfer dilution unit (10).
4. The combined calorific value halogen analysis system according to claim 3, further comprising a sample bottle storage assembly (15), wherein the sample bottle storage assembly (15) comprises a sample tray (151), a plurality of sample bottles (152), a sampling needle (153) and a needle washing assembly (154), wherein the sample bottles (152) are arranged on the sample tray (151), the sampling needle (153) is used for accessing a collected liquid, and the needle washing assembly (154) is used for washing the sampling needle (153).
5. The combined calorific value halogen analysis system according to claim 4, wherein the sample bottle storage assembly (15) further comprises a sixth pump body (16) for controlling the entry of cleaning liquid into the wash needle assembly (154) and a seventh pump body (17) for controlling the discharge of cleaned waste liquid from the wash needle assembly (154).
6. A calorific value halogen combination analysis system according to claim 5, wherein the sampling needle (153) is connected to the collection means (3) through a fourth pump body (18).
7. The combined calorific value halogen analysis system according to claim 6, wherein the sampling needle (153) is connected to the transfer dilution device (10) through a fifth pump body (19) and a fourth valve body (20).
8. The combined calorific value halogen analysis system of claim 7, wherein the sampling needle (153) is connected to the chromatographic detection device (4) through a third pump body (12) and a third valve body (13).
9. A calorific value halogen combination analysis system according to any one of claims 1 to 8, wherein the chromatographic detection means (4) comprises a quantification ring (41), a six-way valve (42), a chromatographic column (43), a suppressor (44) and a detector (45) connected in series.
10. A calorific value halogen combined analysis system according to claim 9, wherein the chromatographic detection apparatus (4) further comprises a plunger pump (46) and a rinsing assembly (47), the plunger pump (46) being adapted to feed the rinsing liquid in the rinsing assembly (47) into the chromatographic column (43).
11. A calorific value halogen usage analysis system according to any one of claims 1 to 8, wherein said gas-liquid switch assembly (2) comprises a bleeder needle (201) and a gas-liquid passage (202).
12. A calorific value halogen combination analysis system according to any one of claims 1 to 8, wherein a first filter (21) is further provided at the outlet of the collection means (3).
13. A calorific value halogen combined analysis system according to claim 9, wherein a second filter (22) is provided at the inlet of the chromatographic detection means (4).
14. A calorific value halogen combination analysis system according to any one of claims 1 to 8, further comprising an eighth pump body (23), said eighth pump body (23) being connected to the waste liquid outlet of the collection means (3) for draining excess collection liquid.
15. A calorific value halogen combination analysis system according to any one of claims 2 to 8, further comprising a ninth pump body (26), said ninth pump body (26) being connected to a transfer dilution means (10) for discharging excess collected liquid.
16. A calorific value halogen combination analysis system according to any one of claims 1 to 8, wherein the collection means (3) is provided with a first volumetric sensor (24) for automatically metering the volume of the solution in the collection means (3).
17. A calorific value halogen combined analysis system according to any one of claims 2 to 8, wherein the transfer dilution device (10) is provided with a second constant volume sensor (25) for automatically constant volume the solution in the transfer dilution device (10).
18. A calorific value halogen combined analysis system according to any one of claims 1 to 8, wherein an automatic current limiting device is further provided between the gas-liquid switch assembly (2) and the collecting device (3).
19. An analysis method based on the heat value halogen combined analysis system of any one of claims 1 to 18, characterized by comprising the steps of:
step S1: placing the weighed sample in a crucible, and placing the crucible in an oxygen bomb combustion device (1);
step S2: closing the gas-liquid switch assembly (2), filling oxygen into the oxygen bomb combustion device (1), igniting and combusting a sample, and testing a heat value;
and step S3: cleaning an oxygen bomb combustion device (1), starting a gas-liquid switch assembly (2), and collecting combusted gas and oxygen bomb cleaning liquid into a collection device (3);
and step S4: introducing absorption liquid and pure water into the collecting device (3), cleaning the combusted gas, fixing the volume and diluting the collecting liquid;
step S5: and (5) sending the diluted collection liquid to a chromatographic detection device (4) for halogen content analysis.
20. The analytical method of a combined heat value halogen analytical system according to claim 19, wherein step S4 specifically includes:
step S41: introducing quantitative absorption liquid into the collecting device (3), and collecting the combusted gas and the oxygen bomb cleaning liquid into the collecting device (3);
step S42: introducing quantitative pure water into the collecting device (3) and performing constant volume;
step S43: whether the test needs to be delayed is judged, and if the test needs to be delayed, the test is stored through a sample bottle storage assembly (15); if the suspend test is not required, the process proceeds to step S5.
21. The analytical method of a combined heat value halogen analytical system according to claim 19, wherein step S5 specifically includes:
step S51: sending the diluted collecting solution into a chromatographic detection device (4) for halogen content analysis; judging whether the analysis result exceeds the range of the marked line, and if so, taking a certain amount of collection liquid from the collection device (3) and sending the collection liquid to the transfer dilution device (10);
step S52: introducing quantitative pure water into the transfer dilution device (10) for dilution and constant volume;
step S53: and taking a quantitative diluted collection liquid from the transfer dilution device (10) and sending the collection liquid to a chromatographic detection device (4) for halogen content analysis.
22. The analytical method for a combined thermal value halogen analysis system according to claim 20, wherein in step S43, when the collected solution is stored in the sample bottle storage assembly (15) and then needs to be analyzed, the specific steps include:
step S431: controlling the sample plate (151) to rotate to the position of the target sample bottle (152), and inserting the sampling needle (153) into the sample bottle (152);
step S432: judging whether the collected liquid needs to be diluted or not, if so, taking a fixed amount of the collected liquid, sending the fixed amount of the collected liquid into a transfer dilution device (10), introducing fixed amount of pure water, and fixing the volume; if no dilution is required, go to step S433;
step S433: and (4) sending the collected liquid into a chromatographic detection device (4) for halogen content analysis.
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004092722A2 (en) * | 2003-04-17 | 2004-10-28 | Anton Paar Gmbh | Method and device for the combustion of samples in an oxygenated atmosphere |
| CN105973666A (en) * | 2016-05-04 | 2016-09-28 | 新奥科技发展有限公司 | Chlorine and sulfur extraction and determination method and apparatus thereof |
| CN108572232A (en) * | 2017-03-16 | 2018-09-25 | 中国科学院青岛生物能源与过程研究所 | The burning measurement device and assay method of chlorinity in a kind of solid fuel |
| CN108802149A (en) * | 2018-06-19 | 2018-11-13 | 湖南师范大学 | A kind of Oxygen Bomb Combustion quickly measures the detection method of PAHs in coal content |
| CN109030703A (en) * | 2018-06-08 | 2018-12-18 | 江苏省产品质量监督检验研究院 | A kind of method of content of halogen in Oxygen Bomb Combustion-sulfate by ion chromatography cable nonmetallic materials |
| CN109425506A (en) * | 2017-08-24 | 2019-03-05 | 湖南三德科技股份有限公司 | A kind of sample liquid sampling analysis method, apparatus and elemental analyser |
| CN208860819U (en) * | 2019-03-01 | 2019-05-14 | 奥星衡迅生命科技（上海）有限公司 | Liquid chromatograph |
| CN113189139A (en) * | 2021-04-21 | 2021-07-30 | 武汉深维鼎测科技有限公司 | Oxygen bomb device based on wall temperature monitoring |
| CN113424058A (en) * | 2019-02-19 | 2021-09-21 | 株式会社岛津制作所 | Liquid chromatograph |
| CN215727928U (en) * | 2021-07-07 | 2022-02-01 | 安图实验仪器(郑州)有限公司 | Automatic clinical analyzer |
| CN114062522A (en) * | 2020-07-30 | 2022-02-18 | 湖南三德盈泰环保科技有限公司 | Sample pretreatment automation device and method |
| CN114062523A (en) * | 2020-07-30 | 2022-02-18 | 湖南三德盈泰环保科技有限公司 | Waterway system for high-temperature combustion ion chromatography system |
| CN114062521A (en) * | 2020-07-30 | 2022-02-18 | 湖南三德盈泰环保科技有限公司 | High temperature combustion ion chromatography system |
| CN115343387A (en) * | 2022-08-04 | 2022-11-15 | 浙江大学 | Method for detecting content of non-metal elements in organic hazardous waste |
-
2022
- 2022-11-28 CN CN202211495922.5A patent/CN115524363B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004092722A2 (en) * | 2003-04-17 | 2004-10-28 | Anton Paar Gmbh | Method and device for the combustion of samples in an oxygenated atmosphere |
| CN105973666A (en) * | 2016-05-04 | 2016-09-28 | 新奥科技发展有限公司 | Chlorine and sulfur extraction and determination method and apparatus thereof |
| CN108572232A (en) * | 2017-03-16 | 2018-09-25 | 中国科学院青岛生物能源与过程研究所 | The burning measurement device and assay method of chlorinity in a kind of solid fuel |
| CN109425506A (en) * | 2017-08-24 | 2019-03-05 | 湖南三德科技股份有限公司 | A kind of sample liquid sampling analysis method, apparatus and elemental analyser |
| CN109030703A (en) * | 2018-06-08 | 2018-12-18 | 江苏省产品质量监督检验研究院 | A kind of method of content of halogen in Oxygen Bomb Combustion-sulfate by ion chromatography cable nonmetallic materials |
| CN108802149A (en) * | 2018-06-19 | 2018-11-13 | 湖南师范大学 | A kind of Oxygen Bomb Combustion quickly measures the detection method of PAHs in coal content |
| CN113424058A (en) * | 2019-02-19 | 2021-09-21 | 株式会社岛津制作所 | Liquid chromatograph |
| CN208860819U (en) * | 2019-03-01 | 2019-05-14 | 奥星衡迅生命科技（上海）有限公司 | Liquid chromatograph |
| CN114062522A (en) * | 2020-07-30 | 2022-02-18 | 湖南三德盈泰环保科技有限公司 | Sample pretreatment automation device and method |
| CN114062523A (en) * | 2020-07-30 | 2022-02-18 | 湖南三德盈泰环保科技有限公司 | Waterway system for high-temperature combustion ion chromatography system |
| CN114062521A (en) * | 2020-07-30 | 2022-02-18 | 湖南三德盈泰环保科技有限公司 | High temperature combustion ion chromatography system |
| CN113189139A (en) * | 2021-04-21 | 2021-07-30 | 武汉深维鼎测科技有限公司 | Oxygen bomb device based on wall temperature monitoring |
| CN215727928U (en) * | 2021-07-07 | 2022-02-01 | 安图实验仪器(郑州)有限公司 | Automatic clinical analyzer |
| CN115343387A (en) * | 2022-08-04 | 2022-11-15 | 浙江大学 | Method for detecting content of non-metal elements in organic hazardous waste |
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|---|---|
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