Integrated detection device for halogen content and sulfur content in hazardous waste sample

Abstract

The utility model relates to the technical field of hazardous waste detection equipment, in particular to an integrated detection device for halogen and sulfur content in hazardous waste samples, which comprises a high-temperature tube furnace, an electrolytic tank and an ion chromatographic analyzer which are connected in sequence, the air inlet end of the high-temperature tube furnace is connected with an air pump, and air is blown into the high-temperature tube furnace through the air pump; the gas outlet end of the electrolytic tank is connected with a main gas pump; waste gas at the gas outlet end of the electrolytic tank is discharged through the main gas pump; a temperature sensing device is installed in the high-temperature tube furnace, a stirring device is installed in the electrolytic tank, and the controller is connected with the temperature sensing device and the stirring device and used for controlling the combustion temperature in the high-temperature tube furnace according to detection data of the temperature sensing device and controlling the stirring speed so that acid gas can be fully absorbed; a liquid outlet of the electrolytic tank is connected with a sample injection pump of the ion chromatographic analyzer through a pipeline; the device is simple to operate, the test recovery rate is improved, and the detection result repeatability is good.

Description

TECHNICAL FIELD

[0001] The utility model relates to dangerous waste detection equipment technical field, concretely is a kind of halogen and sulfur content integrated detection device in dangerous waste sample. BACKGROUND

[0002] Sulfur and halogen elements contained in hazardous waste will be converted into sulfur trioxide and hydrogen halide (including HF, HCL, HBr) and other acid gases during incineration disposal process, which will accelerate the corrosion of equipment and flue wall through which flue gas flows during incineration process, so the total sulfur content and halogen content have been important indicators of industry focus and cost control during hazardous waste disposal process.

[0003] Currently commonly used analysis and detection method refers to the standard "SN / T 4762-2017 Oxygen Bomb Combustion-Ion Chromatography Method" of inspection and quarantine industry or "DL / T 1857-2018 Oxygen Bomb Combustion-Ion Selective Electrode" method of electric power industry, and the specific method is to place the sample in oxygen bomb for oxygen-rich combustion, convert non-metallic elements into gaseous compounds, then use the absorption liquid placed in the bottom of oxygen bomb body in advance to absorb the gas generated after combustion, and finally analyze the absorption liquid by ion chromatography. However, when the oxygen bomb combustion-ion chromatography method is applied to the determination of halogen and sulfur content in dangerous waste sample, the steps are complicated, not only various absorbents need to be added in calorimeter in advance, but also the oxygen bomb needs to be washed and fixed volume multiple times after combustion and then detected by ion chromatography. At the same time, there is a problem that when the acid gas after oxygen bomb combustion is absorbed, the acid gas will overflow, and the loss of acid gas leads to poor repeatability and low recovery rate of detection results.

[0004] Therefore, it is necessary to design a detection device to improve the above problems. UTILITY MODEL CONTENT

[0005] In order to solve the problems of the prior art, the utility model provides a kind of halogen and sulfur content integrated detection device in dangerous waste sample, including high temperature tube furnace, electrolytic cell and ion chromatography analyzer connected in sequence;

[0006] The gas inlet end of the high temperature tube furnace is connected with a gas pump for pumping air into the high temperature tube furnace by the gas pump;The gas outlet end of the electrolytic cell is connected with a main gas pump for discharging waste gas from the gas outlet end of the electrolytic cell by the main gas pump;

[0007] A temperature sensing device is installed in the high temperature tube furnace, and a stirring device is installed in the electrolytic cell, and the controller is connected with the temperature sensing device and the stirring device respectively, for controlling the combustion temperature in the high temperature tube furnace according to the detection data of the temperature sensing device, and controlling the stirring speed to make the acid gas be fully absorbed;

[0008] The liquid outlet of the electrolytic cell is connected to the sample feed pump of the ion chromatograph analyzer through a pipeline, so that the sample in the electrolytic cell can enter the ion chromatograph analyzer for chromatographic analysis;

[0009] Furthermore, the air pump is connected to a high-temperature tube furnace via a drying device;

[0010] The gas outlet of the high-temperature tubular furnace is connected to the main air pump via two drying devices connected in series, and is used to discharge the waste gas after two-stage drying.

[0011] Furthermore, the drying device includes a columnar mounting cylinder filled with silica gel desiccant.

[0012] Furthermore, the gas outlet of the high-temperature tubular furnace is connected to the absorption liquid in the electrolytic cell through a filter to filter the dust after combustion.

[0013] Furthermore, the air inlet end of the main air pump is connected to the output ends of the two drying devices through a silicone hose, and a flow meter is installed on the silicone hose for the main air pump to control the air extraction speed according to the gas flow rate.

[0014] Furthermore, a pressure sensor and an alarm device are installed on the filter, and the controller is connected to the alarm device and the pressure sensor to detect the pressure difference at both ends of the filter through the pressure sensor to determine whether the filter is clogged. When the filter is clogged, an alarm is issued in time.

[0015] Furthermore, the high-temperature tube furnace is connected to the electrolytic cell via a corrosion-resistant pipe to prevent acidic gas generated after combustion from corroding the flue wall;

[0016] Beneficial effects of the utility model:

[0017] The utility model discloses an integrated detection device for halogen and sulfur content in hazardous waste, which adopts an integrated detection device comprising a high-temperature tube furnace, an electrolytic cell and an ion chromatograph connected in sequence. The high-temperature tube furnace is provided to burn the hazardous waste, so that the halogen and sulfur elements in the hazardous waste sample are fully precipitated and absorbed during the combustion process, thereby improving the test recovery rate. The absorption liquid in the electrolytic cell absorbs the acidic gas elements generated during the combustion process, and the connection to the ion chromatograph also realizes direct detection and reading of elements such as S / F / Cl / Br, thereby saving operation process, being simple to operate and having good repeatability of the detection results. In the entire detection process, the high-temperature tube furnace and the electrolytic cell are integrally connected, thereby realizing complete absorption of the acidic gas. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 This is a schematic diagram of the integrated detection device for halogen and sulfur content in hazardous waste samples provided by the present invention;

[0019] Reference numerals:

[0020] In the figure: 1 - air pump, 2 - high-temperature tube furnace, 3 - electrolytic cell, 4 - drying device, 5 - main air pump, 6 - sample valve, 7 - sample pump, 8 - ion chromatography workstation, 9 - chromatographic column, 10 - detection cell. DETAILED DESCRIPTION

[0021] The technical solutions in the embodiments of the utility model will be apparently and completely described in combination with the drawings in the embodiments of the utility model. Obviously, the described embodiments are only part of the embodiments of the utility model, rather than all the embodiments. Based on the embodiments in the utility model, all the other embodiments obtained by the ordinary skilled in the art without creative labor belong to the protection scope of the utility model.

[0022] Please refer to Figure 1 The utility model provides a kind of integrated detection device of halogen and sulfur content in hazardous waste sample, including high-temperature tube furnace 2, electrolytic cell 3 and ion chromatography analyzer connected in sequence;

[0023] The high-temperature tube furnace 2 is connected with air pump 1 at gas inlet end, for air is blown into high-temperature tube furnace 2 by air pump 1;The electrolytic cell 3 is connected with main air pump 5 at gas outlet end, for waste gas at the gas outlet end of electrolytic cell 3 is discharged by main air pump 5;

[0024] Temperature sensing device is installed in the high-temperature tube furnace 2, stirring device is installed in the electrolytic cell 3, temperature sensing device, stirring device are connected on the controller respectively, for the combustion temperature in high-temperature tube furnace 2 is controlled according to the detection data of temperature sensing device, and by controlling stirring speed, acidic gas (sulfur trioxide, hydrogen chloride, hydrogen bromide) is fully absorbed;

[0025] The liquid outlet of the electrolytic cell is connected with the sample pump of the ion chromatography analyzer by pipeline, so that the sample in the electrolytic cell can enter the ion chromatography analyzer for chromatographic analysis;

[0026] Among them, the ion chromatography analyzer includes ion chromatography workstation 8;

[0027] The ion chromatography workstation 8 is respectively connected with a sample injection pump 7, a sample injection valve 6, a chromatographic column 9 and a detection cell 10, and the liquid inlet end of the sample injection pump 7 is connected with the absorption liquid in the electrolytic cell 3 through the sample injection valve 6, the liquid outlet end of the sample injection pump 7 is connected with the chromatographic column 9, the liquid outlet end of the chromatographic column 9 is connected with the detection cell 10, for controlling the sample injection flow rate and the sample injection flow, so that the sample is separated in the chromatographic column 9, the ions separated through the chromatographic column 9 are detected through the detection cell 10, and the concentration information of the ions is converted into a measurable signal, so as to analyze and detect the ion species and content in the sample; and the output end of the detection cell 10 is connected with the ion chromatography workstation 8, for displaying the detection result on the chromatography workstation.

[0028] The gas pump 1 is connected with the high-temperature tube furnace 2 through the drying device 4.

[0029] The gas outlet end of the high-temperature tube furnace 2 is connected with the main gas pump 5 through two drying devices 4 in series; for discharging the exhaust gas after two-stage drying.

[0030] The drying device 4 comprises a column-shaped mounting cylinder, and the column-shaped mounting cylinder is filled with silica gel drying agent.

[0031] The gas outlet end of the high-temperature tube furnace 2 is connected with the absorption liquid in the electrolytic cell 3 through a filter, for filtering the dust after complete combustion.

[0032] The gas inlet end of the main gas pump 5 is connected with the output ends of the two drying devices 4 through a silica gel hose, and a flow meter is mounted on the silica gel hose, for controlling the air suction speed of the main gas pump 5 according to the gas flow.

[0033] The filter is mounted with a pressure sensor and an alarm device, and a controller is connected with the alarm device and the pressure sensor, for judging whether the filter is blocked or not by detecting the pressure difference between the two ends of the filter through the pressure sensor, and timely sending an alarm when the filter is blocked.

[0034] The high-temperature tube furnace 2 is connected with the electrolytic cell 3 through a corrosion-resistant pipeline, wherein the corrosion-resistant pipeline is a stainless steel pipeline, for preventing the acid gas generated after combustion from corroding the flue wall.

[0035] It is worth noting that the present scheme does not need pretreatment, and the hazardous waste sample is directly placed in the sulfur determination instrument porcelain boat for combustion.

[0036] The acid gas generated by combustion is absorbed by the absorption liquid in the electrolytic cell. The ion chromatography directly detects the element content in the absorption liquid; realizes complete absorption of the gas, saves the operation process, improves the test recovery rate, and has good repeatability of the detection result.

[0037] The detection process of the halogen and sulfur content in the hazardous waste sample in the present application is as follows:

[0038] First, sample preparation and combustion process:

[0039] 1. Accurately weigh 0.5-1 g of hazardous waste sample in a porcelain boat, and then place it in the center of the high temperature tube furnace 2 of the sulfur determination instrument, where the temperature is kept constant at 1150℃, and the air during combustion is purified in advance through a silica gel tube, and the air is pumped in through the air pump 1. The sample is completely burned at high temperature, and the acidic gas (such as SO2, SO3, HCl, HBr, HF) produced is absorbed into the absorption liquid of the electrolytic cell.

[0040] 2. At this time, the sample is stably combusted in the high temperature tube furnace 2, and the gas produced will be absorbed into the absorption liquid of the electrolytic cell 3 at the back end by the main air pump 5. The electrolytic cell 3 has a stirrer, which is beneficial to the complete absorption of the gas and can completely absorb the acidic gas in the exhaust gas.

[0041] Second, gas absorption:

[0042] 3. The main component of the absorption liquid in the electrolytic cell 3 is (NH4)2CO3 solution with a concentration of 10 g / L, and 300 mL of (NH4)2CO3 absorption liquid needs to be added to the electrolytic cell 3. The electrolytic cell has a stirring device to ensure complete gas absorption.

[0043] 4. The remaining gas is discharged after passing through two-stage drying device 4 (silica gel desiccant).

[0044] 5. This process can automatically control the combustion temperature and gas flow and detect data through the computer, and the final result is directly displayed on the computer operation interface.

[0045] Third, ion chromatography detection:

[0046] 6. Connect the electrolytic cell 3 with the ion chromatography sample valve 6 with a silica gel hose. At this time, the sample pump 7 starts to sample the absorption liquid of the electrolytic cell 3 into the chromatographic column 9 through the silica gel hose, and the content of halogen and sulfur elements in the sample is detected by ion chromatography;

[0047] 7. The ion chromatography has been pre-prepared SO3 2- , SO4 2-and F, Cl, Br ion curve calibration in ion chromatography, at this time the detection pool is working, complete detection. The results are directly output in the ion chromatography workstation 8; the chromatograph includes the ion chromatography workstation 8, the ion chromatography workstation 8 is connected with the sample pump 7, the sample valve 6, the chromatographic column 9 and the detection pool 10 respectively, and the ion chromatography analyzer includes the chromatographic column 9, the detection pool 10 and the ion chromatography workstation 8. The chromatograph controls the flow rate and direction of the absorption liquid, so that the ions to be measured in the absorption liquid can be separated in the chromatographic column 9, and converted into an electrical signal through the detection pool 10, wherein the function of the detection pool 10 in the ion chromatography analyzer is to detect the ions separated by the chromatographic column, and convert the concentration and other information of the ions into measurable signals (such as current, absorbance, etc.), so as to realize the analysis and determination of the ion types and contents in the sample; finally, the ion chromatography workstation 8 is used for data processing and analysis by ion chromatography; the chromatography workstation 8 is the core of data processing, responsible for receiving and processing signals from the detection pool 10, and processing and analyzing the signals by ion chromatography technology, wherein the chromatographic column 9 is responsible for separating the components in the mixture, and the detection pool 10 converts the separated components into measurable signals; the chromatograph is a comprehensive analysis instrument integrating these components, and the ion chromatography is a technology specially used for ion analysis;

[0048] 8, the detection conditions of ion chromatography are:

[0049] The eluent is 20mmol / L NaOH solution, the flow rate is 1.0ml / min, the column temperature is 30℃, the suppression current is 57mA, the sample volume is 25μl, and the system pressure is 1500-1600psi. In ion chromatography, the selection of eluent is crucial to the separation effect. According to the search results, the type, concentration and flow rate of the eluent will affect the retention and separation degree of ions. The flow rate and column temperature are also important factors affecting the separation effect of ion chromatography. Increasing the flow rate can shorten the retention time, but may sacrifice the separation degree and column pressure;

[0050] 9, preparation of standard solutions of chloride ions, fluoride ions and bromide ions:

[0051] Cl - The series of standard solution concentrations are: 1mg / L, 2mg / L, 4mg / L, 10mg / L, 20mg / L, 40mg / L;

[0052] F - The series of standard solution concentrations are: 1mg / L, 2mg / L, 4mg / L, 10mg / L, 20mg / L, 40mg / L;

[0053] Br -The series of standard solution concentrations are: 1 mg / L, 2 mg / L, 4 mg / L, 10 mg / L, 20 mg / L, 40 mg / L;

[0054] SO4 2- The series of standard solution concentrations are: 1 mg / L, 2 mg / L, 4 mg / L, 10 mg / L, 20 mg / L, 40 mg / L;

[0055] SO3 2- The series of standard solution concentrations are: 1 mg / L, 2 mg / L, 4 mg / L, 10 mg / L, 20 mg / L, 40 mg / L;

[0056] According to the ion chromatography detection conditions described above, the peak area of the target element is detected, and the standard working curve of the relationship between the peak area of the target element and the concentration is established by the calibration curve method. The blank solution is taken as the zero point to add the standard working curve, and the total chlorine, total fluorine and total bromine, and total sulfur content in the sample to be measured are calculated according to the standard working curve.

[0057] It is worth noting that 1. The detection device utilizes the high-temperature tube furnace in the sulfur determination instrument to perform hazardous waste sample combustion, and utilizes the absorption liquid in the electrolytic cell to absorb the acidic gas elements generated in the combustion process. The electrolytic cell and the high-temperature tube furnace are integrally connected through a corrosion-resistant pipeline to prevent the overflow of acidic gas, thereby achieving the complete absorption of acidic gas.

[0058] 2. The present application realizes direct detection reading of S / F / CL / Br elements by connecting an ion chromatograph.

[0059] 3. The present application optimizes hazardous waste combustion, which is conducive to the complete analysis and absorption of halogen and sulfur elements in the combustion process, is easy to implement in actual operation, and effectively improves the test recovery rate; wherein the total chlorine content recovery rate is 92.5%-98.0%, the total sulfur content recovery rate is 95.5%-99.0%, the total fluorine content recovery rate is 93.5%-97.0%, and the bromine recovery rate is 92.5%-98.0%.

[0060] 4. The recovery rates of the acidic gas elements obtained after hazardous waste combustion by the method provided in the present application are: fluorine > 82%, chlorine > 87%, bromine > 86%, and sulfur > 86%.

[0061] 5. The present application only needs to operate once for sample injection, avoiding the need for multiple washing-constant volume-filtration-ion chromatography injection operations in the oxygen bomb combustion-ion chromatography operation process.

[0062] 6. The detection device is used for detecting the halogen and sulfur content in the hazardous waste sample, the detection limit of total fluorine content can reach 0.02%, the highest detection limit is 4%, the detection limit of total sulfur content can reach 0.01%, the highest detection limit is 40%, the detection limit of total chlorine content can reach 0.03%, the highest detection limit is 4%, the detection limit of bromine can reach 0.02%, the highest detection limit is 4%, the relative standard deviation RSD value of total chlorine content is 3.28%, the relative standard deviation RSD value (precision) of total fluorine content can reach 3.87% or less, the relative standard deviation RSD value of total sulfur content is 3.21%, the relative standard deviation RSD value of bromine content is 3.28%, the detection results can achieve good repeatability, meet the laboratory detection requirements, and realize accurate measurement of high-sulfur and high-halogen substances.

[0063] It is worth noting that the utility model discloses a hazardous waste halogen and sulfur content integrated detection device, and the integrated detection device is suitable for a wide range of hazardous waste types, adopts a high-temperature tube furnace, an electrolytic cell and an ion chromatography analyzer connected in sequence, and sets up the high-temperature tube furnace to burn the hazardous waste, so that the halogen and sulfur elements in the hazardous waste sample are analyzed and absorbed in the combustion process, and the test recovery rate is improved, the acidic gas elements generated in the combustion process are absorbed by the absorption liquid in the electrolytic cell, the direct detection reading of S / F / CL / Br and other elements is realized through the connected ion chromatography, the operation process is saved, the operation is simple, the detection result repeatability is good, and the high-temperature tube furnace and the electrolytic cell are integrally connected in the whole detection process, so that the acidic gas is completely absorbed.

[0064] The above only describes the preferred embodiments of the utility model, and does not limit the utility model, and any modification, equivalent replacement, improvement, etc. within the spirit and principle of the utility model should be included in the protection scope of the utility model.

Claims

1. An integrated detection device for halogen and sulfur content in hazardous waste samples, characterized in that: It includes a high temperature tube furnace, an electrolytic cell and an ion chromatograph which are connected in sequence; The air inlet end of the high-temperature tubular furnace is connected to an air pump for blowing air into the high-temperature tubular furnace through the air pump; the air outlet end of the electrolytic cell is connected to a main air pump for discharging the exhaust gas from the air outlet end of the electrolytic cell through the main air pump; A temperature sensing device is installed in the high-temperature tube furnace, and a stirring device is installed in the electrolytic cell. The controller is connected to the temperature sensing device and the stirring device, respectively, and is used to control the combustion temperature in the high-temperature tube furnace according to the detection data of the temperature sensing device, and to control the stirring speed so that the acid gas is fully absorbed; The liquid outlet of the electrolytic cell is connected to the sample feed pump of the ion chromatograph analyzer through a pipeline, so that the sample in the electrolytic cell can enter the ion chromatograph analyzer for chromatographic analysis.

2. The integrated detection device for halogen and sulfur content in hazardous waste samples according to claim 1 is characterized in that: The air pump is connected to the high-temperature tube furnace via a drying device; The gas outlet of the high-temperature tubular furnace is connected to the main air pump via two drying devices connected in series, and is used to discharge the waste gas after two-stage drying.

3. The integrated detection device for halogen and sulfur content in hazardous waste samples according to claim 2, characterized in that: The drying device comprises a columnar mounting cylinder filled with silica gel desiccant.

4. The integrated detection device for halogen and sulfur content in hazardous waste samples according to claim 1, characterized in that: The gas outlet end of the high-temperature tubular furnace is connected to the absorption liquid in the electrolytic cell through a filter, so as to filter the dust after combustion.

5. The integrated detection device for halogen and sulfur content in hazardous waste samples according to claim 2, characterized in that: The air inlet end of the main air pump is connected to the output ends of the two drying devices through a silicone hose, and a flow meter is installed on the silicone hose for the main air pump to control the air extraction speed according to the gas flow rate.

6. The integrated detection device for halogen and sulfur content in hazardous waste samples according to claim 4, characterized in that: The filter is equipped with a pressure sensor and an alarm device. The controller is connected to the alarm device and the pressure sensor to detect the pressure difference at both ends of the filter through the pressure sensor to determine whether the filter is clogged. When the filter is clogged, an alarm is issued in time.

7. The integrated detection device for halogen and sulfur content in hazardous waste samples according to claim 1, characterized in that: The high-temperature tube furnace is connected to the electrolytic cell via a corrosion-resistant pipe to prevent acidic gas generated after combustion from corroding the flue wall.

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