Device for detecting organic sulfur in coke oven gas

Abstract

The utility model discloses a coke oven gas organic sulfur detection device which comprises a gas input system, a chromatographic separation column, a gas supply system, a detection system and a trace sulfur analyzer connected with the detection system, the gas supply system is used for supplying hydrogen, nitrogen and oxygen, the gas input system is used for conveying detected gas to the chromatographic separation column, the detection system comprises a flame photometric detector, and the flame photometric detector is connected with the chromatographic separation column. According to the device for detecting the organic sulfur in the coke oven gas, the chromatographic separation column is combined with the flame photometric detector, so that the content of the organic sulfur in the coke oven gas can be quickly and accurately detected.

Description

TECHNICAL FIELD

[0001] The utility model belongs to the industrial gas detection technical field, concretely, the utility model relates to a coke oven gas organic sulfur detection device. BACKGROUND

[0002] Coke oven gas is an important industrial gas, and the content of organic sulfur in coke oven gas has an important influence on the quality of gas, subsequent processing and utilization, and environmental protection. Accurate detection of the content of organic sulfur in coke oven gas is of great significance for ensuring the safe use of gas, optimizing production processes, and reducing environmental pollution.

[0003] The traditional coke oven gas organic sulfur detection has the following problems: the detection equipment is large in size, and it is difficult to realize on-site rapid detection; the separation effect of multi-component sulfide is poor, and the detection precision is limited; the stability of the temperature control system is insufficient, resulting in poor repeatability; the manual sampling mode is easy to introduce human error; the gas path system is complex, resulting in high maintenance cost. It is difficult to meet the requirements of modern industrial production on detection efficiency and accuracy.

[0004] Currently, the laboratory mainly relies on gas chromatography-mass spectrometry (GC-MS) method for coke oven gas organic sulfur detection, but there are problems such as complex equipment maintenance, high operation requirements, and low detection efficiency.

[0005] The above methods are difficult to meet the demand of high efficiency and accurate detection of coke oven gas organic sulfur content in industrial production.

[0006] The Chinese patent with application number 201911134235.9 discloses an oxygen detection system for coke oven gas, which includes an air inlet pipe, an air outlet pipe and a sealed explosion-proof cabinet, a cooler and a purifier are arranged on the explosion-proof cabinet, an oxygen detection device is arranged in the explosion-proof cabinet, an oxygen sensor is arranged in the oxygen detection device, and the air inlet pipe is connected with the air outlet pipe through the cooler, the purifier and the oxygen detection device in sequence.

[0007] It is hoped to provide a coke oven gas organic sulfur detection device, especially how to improve the detection efficiency of coke oven gas organic sulfur content. UTILITY MODEL CONTENT

[0008] The utility model aims at at least solving one of the technical problems existing in the prior art. To this end, the utility model provides a coke oven gas organic sulfur detection device, which aims to improve the detection efficiency of coke oven gas organic sulfur content.

[0009] In order to achieve the above object, the utility model adopts the technical scheme for: coke oven gas organic sulfur detection device, including gas input system, chromatographic separation column, gas supply system, detection system and with detection system connection's trace sulfur analyzer, gas supply system is connected with gas input system and flame photometric detector, gas supply system is set up for supply hydrogen, nitrogen and oxygen, gas input system is set up for with measured gas delivery to chromatographic separation column, detection system includes flame photometric detector, flame photometric detector is connected with chromatographic separation column.

[0010] The detection system further includes a photomultiplier tube electrically connected to the trace sulfur analyzer.

[0011] The chromatographic separation column and the flame photometric detector are electrically connected to a temperature controller.

[0012] The gas input system includes a pre-treater, a gas sampling needle tube, and a six-way valve. The gas sampling needle tube is connected to the six-way valve through a sample inlet hose. The other end of the six-way valve is connected to the chromatographic separation column.

[0013] The gas supply system includes a hydrogen gas cylinder, a nitrogen gas cylinder, and an oxygen gas cylinder. The nitrogen gas cylinder is connected to the six-way valve. The hydrogen gas cylinder and the oxygen gas cylinder are connected to the flame photometric detector.

[0014] The coke oven gas organic sulfur detection device further includes an ignition device configured to ignite a flame in the flame photometric detector.

[0015] The coke oven gas organic sulfur detection device of the utility model adopts a chromatographic separation column combined with a flame photometric detector to achieve rapid and accurate detection of the organic sulfur content in coke oven gas. BRIEF DESCRIPTION OF DRAWINGS

[0016] The present specification includes the following drawings, and the shown contents are respectively:

[0017] Figure 1 It is a structure schematic view of the coke oven gas organic sulfur detection device of the utility model.

[0018] Figure 2 It is a structure schematic view of the pre-treater.

[0019] In the figure, the marks are: 1, pre-treater; 2, gas sampling needle tube; 3, six-way valve; 4, chromatographic separation column; 5, flame photometric detector; 6, gas cylinder group; 7, temperature controller; 8, photomultiplier tube; 9, trace sulfur analyzer; 10, ignition device; 11, high-voltage power supply; 12, ceramic filter; 13, membrane filter. DETAILED DESCRIPTION

[0020] The specific embodiments of the present application are further described in detail below with reference to the drawings, and the purpose is to help the technical personnel in the art have a more complete, accurate and in-depth understanding of the concept and technical scheme of the present application, and to help them implement it.

[0021] As Figure 1 shown, the present application provides a coke oven gas organic sulfur detection device, including gas input system, chromatographic separation column 4, gas supply system, detection system, ignition device 10 and with detection system connection trace sulfur analyzer 9, gas supply system and gas input system and flame photometric detector 5 connection, gas supply system is set up for supply hydrogen, nitrogen and oxygen, gas input system is set up for the measured gas is transported to chromatographic separation column 4, the measured gas is coke oven gas.Detection system includes flame photometric detector 5 (FPD), flame photometric detector 5 is connected with chromatographic separation column 4, ignition device 10 is set up for igniting the flame in flame photometric detector 5.

[0022] Specifically, as Figure 1 shown, the gas input system includes preprocessor 1, gas sampling needle tube 2 and six-way valve 3, gas sampling needle tube 2 is connected with six-way valve 3 through sample inlet hose, the other end of six-way valve 3 is connected with chromatographic separation column 4.Gas sampling needle tube 2 is used for extracting coke oven gas sample after preprocessor 1 treatment, for example, using 100ml needle tube, convenient to extract the appropriate sample.Before extraction, the tar and naphthalene impurities in coke oven gas need to be filtered out by preprocessor 1, preprocessor 1 can adopt double-stage filter device (primary ceramic filter element + secondary PTFE membrane, filtration accuracy 0.5 μm), effectively intercepts tar particles.

[0023] As Figure 2 shown, preprocessor 1 includes ceramic filter 12 and membrane filter 13, ceramic filter 12 and membrane filter 13 are arranged in series, the gas outlet of ceramic filter 12 is connected with the gas inlet of membrane filter 13, ceramic filter 12 is used as a rough filtration unit, ceramic filter 12 can adopt honeycomb porous cordierite ceramic material, filtration accuracy 5 μm, supports reverse purge regeneration.Membrane filter 13 is used as a fine filtration unit, which can adopt ePTFE folding filter element, filtration accuracy 0.5 μm.Ceramic filter 12 and membrane filter 13 filter the coke oven gas sample flowing through in turn, realize step-by-step filtration, improve the filtration effect of coke oven gas sample.

[0024] In the embodiment of the utility model, six -way valve 3 is established, the valve core of six -way valve 3 has " sample " and " analysis " two positions. When the valve core of six -way valve 3 is at " sample " position, six -way valve 3 can guide the gas sample in gas sampling needle tube 2 into chromatographic separation column 4, when the valve core of six -way valve 3 is at " analysis " position, gas sample carries out separation detection in chromatographic separation column 4. Six -way valve 3 is connected with gas sampling needle tube 2 and chromatographic separation column 4 through sample inlet hose, and the smooth transmission of gas sample is ensured.

[0025] In the embodiment of the utility model, chromatographic separation column 4 is selected, and chromatographic separation column 4 can effectively separate different sulfides in coke oven gas. Chromatographic separation column 4 is connected with a temperature control system, which is provided with a first temperature adjusting knob for adjusting the column temperature. The temperature of chromatographic separation column 4 is controlled by the temperature control system to ensure that different sulfides are separated under optimal temperature conditions, thereby improving the separation effect.

[0026] In the embodiment of the utility model, flame photometric detector 5 is connected with a temperature control system, which is provided with a second temperature adjusting knob for adjusting the temperature of flame photometric detector 5. Flame photometric detector 5 selects a photomultiplier tube 8 as a photoelectric conversion detection system, and the photomultiplier tube 8 is electrically connected with a micro sulfur analyzer 9. The flame photometric detector 5 has the characteristics of high sensitivity, good selectivity and fast response speed for sulfides.

[0027] As shown in Figure 1 , the temperature control system includes a temperature controller 7, and chromatographic separation column 4 and flame photometric detector 5 are electrically connected with the temperature controller 7 to ensure that the detection process is carried out under suitable temperature conditions.

[0028] As shown in Figure 1 , the gas supply system includes hydrogen gas cylinders, nitrogen gas cylinders and oxygen gas cylinders and corresponding gas valves for providing carrier gas and combustion-supporting gas required for detection. The nitrogen gas cylinder is connected with six -way valve 3, and the hydrogen gas cylinder and the oxygen gas cylinder are connected with flame photometric detector 5.

[0029] As shown in Figure 1 , the ignition device 10 is arranged to ignite the flame in the flame photometric detector 5 to ensure the smooth progress of the detection process. The ignition device 10 can be an electronic igniter. The photomultiplier tube 8 is connected with a high-voltage power supply 11, which provides high voltage (700-1000 volts) for the photomultiplier tube (PMT) 8 to generate a secondary electron amplification signal through a multiplier electrode.

[0030] The trace sulfur analyzer 9 is used for analyzing and processing the detection result, the trace sulfur analyzer 9 is connected with the photomultiplier 8 of the detection system, can receive the signal detected by the detection system, and processes the signal. The trace sulfur analyzer 9 automatically generates a data analysis report of the content of organic sulfur, and the content of organic sulfur in the report is μg / L (equivalent to mg / m 3 ).

[0031] The coke oven gas organic sulfur detection device provided by the utility model has the following advantages:

[0032] Open the hydrogen, nitrogen and oxygen gas valves to provide necessary gas for the detection process;

[0033] Turn on the detection instrument, adjust the temperature of the chromatographic separation column 4 and the flame photometric detector 5 to the set value, generally set the temperature of the chromatographic separation column 4 to 110℃ and the temperature of the flame photometric detector 5 to 130℃.

[0034] When the temperature of the chromatographic separation column 4 and the flame photometric detector 5 reaches the set value, ignite the flame in the detector with an electronic igniter;

[0035] Turn on the high-voltage power supply 11: press the "high-voltage power supply 11" switch after determining that the flame is ignited;

[0036] Draw the measured gas into the gas sampling needle tube 2, block the outlet of the gas sampling needle tube 2 with a blind hole needle, rotate the six-way valve 3 from the "analysis" position to the "sample injection" position, insert the front hole of the gas sampling needle tube 2 into the sample injection hose, and slowly push in 20-30ml of gas, then rotate the six-way valve 3 from the sample injection position to the "analysis" position to complete the sample injection;

[0037] After the trace sulfur analyzer 9 receives the data, it automatically analyzes the detection result and obtains a data report of the content of organic sulfur, with the unit of μg / L, which is equivalent to mg / m 3 .

[0038] The coke oven gas organic sulfur detection device has the following advantages:

[0039] 1. Improve the detection accuracy: by selecting appropriate chromatographic separation column 4 and flame photometric detector 5 (FPD) and accurately controlling the column temperature and detector temperature, the organic sulfur in the coke oven gas can be effectively separated and detected, and the accuracy of the detection result is improved.

[0040] 2. Fast detection speed: the chromatographic separation column 4 combined with the flame photometric detector 5 has fast detection speed, high sensitivity and small sample consumption, and can quickly and accurately detect the content of organic sulfur in the coke oven gas.

[0041] 3. Easy to operate: The detection process is highly automated, easy to operate, reduces human error, and improves the reliability of the detection results. The six-way valve 3 controls the sample injection, which is simple and easy to operate. At the same time, the micro-sulfur analyzer 9 automatically generates an analysis report, reducing the workload and error of manual calculation.

[0042] 4. Good stability: The systems work together, the overall stability of the equipment is high, and it can meet the needs of long-term and continuous detection in industrial production.

[0043] 5. Suitable for modern industrial production, environmental monitoring and scientific research, etc., with wide application prospects.

[0044] 6. Technical effect: Detection speed is improved: single detection time ≤15min (traditional method needs 30min); detection limit is as low as: 0.1μg / L (calculated by thiophene); repeatability error (precision) reaches ±2% (RSD), which is better than the industry standard (±5%); operation is simplified: one-key detection process is started.

[0045] Example 1

[0046] The conventional detection process using the coke oven gas organic sulfur detection device in this embodiment is as follows:

[0047] (1) System initialization

[0048] After starting, the air tightness detection is automatically performed (nitrogen is pressurized to 0.3MPa, and the pressure drop is <0.01MPa / min, which is considered qualified);

[0049] Temperature control module self-check: the chromatographic separation column 4 is heated to 110℃ (heating rate 5℃ / min), and the temperature fluctuation is <±0.3℃;

[0050] (2) Sample analysis

[0051] Sample injection stage: six-way valve 3 switches to "sample injection" position, and 25ml of filtered gas sample is injected into the quantitative ring;

[0052] Separation stage: the carrier gas provided by the nitrogen cylinder (carrier gas is N2, carrier gas flow rate is 30ml / min) drives the gas sample through the chromatographic separation column 4, and the sulfides are separated according to the boiling point order;

[0053] Detection stage: sulfides are excited to characteristic spectrum in the hydrogen-rich flame (H2 flow rate is 60ml / min, oxygen flow rate is 20ml / min) of the flame photometric detector 5;

[0054] (3) Data processing

[0055] The signal of photomultiplier tube 8 is converted by 24-bit ADC, and the sampling rate is 100Hz;

[0056] After receiving the data, the micro sulfur analyzer 9 automatically calculates the peak area by the built-in software of the computer, and outputs the total sulfur content (μg / L and mg / m 3 Dual unit display).

[0057] Example Two

[0058] The process of detecting the thiophene content in the coke oven gas by using the coke oven gas organic sulfur detection device in this embodiment is as follows:

[0059] After the device is turned on, the system automatically performs the air tightness detection (pressure sensor monitoring);

[0060] The analysis parameters are set through the touch screen: the temperature of the chromatographic separation column 4 is set to 110℃, the temperature of the flame photometric detector 5 is set to 130℃, and the carrier gas flow rate is set to 30ml / min;

[0061] The gas input system absorbs 100ml of sample gas to complete the filtration and impurity removal;

[0062] The six-way valve 3 switches to send 20ml of sample into the chromatographic separation column 4;

[0063] The signal of the photomultiplier tube 8 is converted into a chromatogram after 32-bit ADC conversion;

[0064] The micro sulfur analyzer 9 automatically calculates the peak area and outputs the total sulfur content (mg / m 3 ).

[0065] Example Three

[0066] The coke oven gas organic sulfur detection device is applied in the coking plant for 30 consecutive days to detect the coke oven gas samples.

[0067] Data comparison: the detection results are compared with the laboratory gas chromatograph GC-MS, and the correlation coefficient R 2 =0.9987 (n=150), which indicates that the device has good repeatability and accuracy.

[0068] Detection efficiency: the single sample detection time is 12.3±0.8min (the traditional method needs 28.5min).

[0069] Fault record: no hydrogen leakage or ignition failure event occurs during the period.

[0070] The utility model is described exemplarily above combined with the drawings. Apparently, the specific implementation of the utility model is not limited by the above-mentioned mode. As long as various non-essential improvements are made by adopting the method concept and technical scheme of the utility model; or the above-mentioned concept and technical scheme of the utility model are directly applied to other occasions without improvement, all of which are within the protection scope of the utility model.

Claims

1. A device for detecting organic sulfur in coke oven gas, characterized in that: The gas input system, the chromatographic separation column, the gas supply system, the detection system and the micro sulfur analyzer connected with the detection system, the gas supply system is connected with the gas input system and the flame photometric detector, the gas supply system is arranged for supplying hydrogen, nitrogen and oxygen, the gas input system is arranged for transporting the measured gas to the chromatographic separation column, the detection system comprises a flame photometric detector, and the flame photometric detector is connected with the chromatographic separation column.

2. The coke oven gas organic sulfur detection device according to claim 1, characterized in that: The detection system further comprises a photomultiplier tube, and the photomultiplier tube is electrically connected with the micro sulfur analyzer.

3. The coke oven gas organic sulfur detection device according to claim 1, characterized in that: The chromatographic separation column and the flame photometric detector are electrically connected with a temperature controller.

4. The coke oven gas organic sulfur detection device according to any one of claims 1 to 3, characterized in that: The gas input system comprises a pre-treater, a gas sampling needle tube and a six-way valve, the gas sampling needle tube is connected with the six-way valve through a sample inlet hose, and the other end of the six-way valve is connected with the chromatographic separation column.

5. The coke oven gas organic sulfur detection device according to claim 4, characterized in that: The gas supply system comprises a hydrogen gas cylinder, a nitrogen gas cylinder and an oxygen gas cylinder, the nitrogen gas cylinder is connected with the six-way valve, and the hydrogen gas cylinder and the oxygen gas cylinder are connected with the flame photometric detector.

6. The coke oven gas organic sulfur detection device according to any one of claims 1 to 3, characterized in that: Further comprising an ignition device arranged for igniting the flame in the flame photometric detector. Further comprising an ignition device arranged for igniting the flame in the flame photometric detector.

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