A SCD sulfur chemiluminescence detector
By designing a sulfur chemiluminescence detector (SCD) and utilizing a series-connected redox combustion chamber and a high-temperature oxygen- and hydrogen-rich environment, the problems of poor selectivity and matrix interference in existing equipment were solved, achieving high sensitivity and accurate detection of sulfur compounds.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- SHANGHAI PANNUO SCIENTIFIC INSTRUMENT CO LTD
- Filing Date
- 2025-07-22
- Publication Date
- 2026-05-29
AI Technical Summary
Existing sulfur detection equipment has low selectivity, is easily affected by complex matrices, and is difficult to accurately identify and detect trace sulfur compounds.
A sulfur chemiluminescence detector (SCD) was designed, comprising components such as a sample oxidation-reduction combustion chamber, a ceramic tube, a reaction chamber, and an ozone generator. By connecting the oxidation and reduction combustion chambers in series and combining a high-temperature oxygen-rich and hydrogen-rich environment, the sample is fully oxidized and reduced, and the chemiluminescence reaction is detected using a photomultiplier tube.
It achieves high sensitivity, wide dynamic linear range and excellent resistance to matrix interference, enabling accurate detection of trace sulfur compounds and meeting the requirements of environmental regulations and petrochemical product quality control.
Smart Images
Figure CN224303570U_ABST
Abstract
Description
Technical Field
[0001] This utility model relates to sulfide detection, specifically to an SCD chemiluminescence detector for sulfur. Background Technology
[0002] In the 1980s and 1990s, with a significant increase in global attention to air pollution, sulfur oxides emitted during the combustion of fuels such as gasoline, diesel, and liquefied petroleum gas were identified by the scientific community as one of the key pollutants contributing to acid rain and smog. To effectively curb environmental degradation and protect human health and ecosystems, countries around the world have formulated and implemented increasingly stringent technical specifications and regulatory standards regarding the sulfur content in petroleum and its derivatives.
[0003] Sulfur typically exists in extremely small amounts, even at trace levels, in ambient air and natural water bodies. This characteristic places extremely high demands on detection technologies. However, the traditional sulfur detection equipment commonly used at the time had significant limitations: its selectivity was low, making it difficult to accurately identify target sulfur compounds; it was particularly susceptible to severe interference from a large number of coexisting hydrocarbons in complex matrices, resulting in detection results that could not truly and accurately characterize the actual sulfur content level.
[0004] In the face of increasingly stringent environmental regulations on sulfur content limits and continuously decreasing detection limits, the development and launch of a sulfur chemiluminescence detector (SCD) with ultra-high sensitivity, wide dynamic linear range, and excellent resistance to matrix interference has become an urgent technical requirement to meet the needs of accurate environmental monitoring and petrochemical product quality control, and its importance is becoming increasingly prominent. Utility Model Content
[0005] This invention provides an SCD sulfur chemiluminescence detector, which includes:
[0006] The sample oxidation-reduction combustion chamber is equipped with an oxidation zone combustion chamber and a reduction zone combustion chamber connected in series. Each of the oxidation zone combustion chamber and the reduction zone combustion chamber is equipped with a heating device. The internal temperature of the oxidation zone combustion chamber is higher than that of the reduction zone combustion chamber.
[0007] The first ceramic tube is located in the sample oxidation-reduction combustion chamber and passes through the oxidation zone combustion chamber and the reduction zone combustion chamber in sequence. One end of the first ceramic tube is internally connected to the chromatographic column outlet and the oxygen supply line. The chromatographic column outlet and the oxygen supply line are used to introduce sample gas and combustion-supporting gas into the first ceramic tube, respectively.
[0008] The second ceramic tube has one end located inside the first ceramic tube in the combustion chamber of the reduction zone, and the other end of the second ceramic tube is connected to a hydrogen pipeline. The hydrogen pipeline is used to introduce hydrogen into the first ceramic tube. The outer diameter of the second ceramic tube is smaller than the inner diameter of the first ceramic tube to form a gap channel between the first ceramic tube and the second ceramic tube.
[0009] The reaction chamber is connected at one end to the slit channel at the other end of the first ceramic tube, and at the other end to the vacuum system. The reaction chamber is equipped with a photomultiplier tube and a filter.
[0010] An ozone generator is connected at one end to an oxygen supply pipeline and at the other end to a reaction chamber. The ozone generator is used to produce ozone and deliver it to the reaction chamber.
[0011] Furthermore, the oxygen supply pipeline is connected to the first ceramic tube and the ozone generator via a tee, and a pressure regulating valve is installed between the tee and the ozone generator.
[0012] Furthermore, it also includes a tailpipe, which is internally connected to one end of the first ceramic tube.
[0013] Furthermore, it also includes a preheating device, which is a heating base installed in the sample oxidation-reduction combustion chamber near the oxidation zone combustion chamber. The tail blow pipeline, the chromatographic column outlet and the oxygen supply pipeline all pass through the heating base and are connected to the inside of the first ceramic tube.
[0014] Furthermore, the oxygen supply line, hydrogen supply line, and tailpipe line are all equipped with electronic flow control valves.
[0015] Furthermore, the vacuum system includes a vacuum pump and an ozone destructor.
[0016] Furthermore, temperature sensors are installed in both the oxidation zone combustion chamber and the reduction zone combustion chamber.
[0017] Furthermore, it also includes a circuit control system, with temperature sensors, electronic flow control valves, vacuum systems, ozone generators, and pressure regulating valves all connected to the circuit control system.
[0018] After separation and preheating in the detector, the sample continues upwards to undergo an oxidation reaction in a high-temperature, oxygen-rich environment, generating oxygen-containing sulfides. Then, in a high-temperature, hydrogen-rich environment, it is reduced to SO. Finally, the sample reduced to SO is drawn into the reaction chamber and undergoes a chemiluminescent reaction with ozone. The light signal is detected and amplified by a photomultiplier tube, thereby quantitatively analyzing the sulfur content.
[0019] From the perspective of detector principles, the combustion chamber acts as a redox chamber, and oxidation requires a high-temperature, oxygen-rich environment. This application improves upon this by maintaining the high-temperature zone of the oxidation combustion chamber at 920-950°C using a heating device, and adding an additional heating device to provide a reduction environment for the sample. This ensures the high-temperature state of the oxidation zone. Furthermore, this application increases the sample reaction distance to guarantee complete oxidation, thereby greatly improving the stability of the results. Attached Figure Description
[0020] To more clearly illustrate the technical solutions in the embodiments of this utility model, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this utility model. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0021] Figure 1 This is a structural diagram of the sample redox combustion chamber of the sulfur chemiluminescence detector structure of this utility model;
[0022] Figure 2 This is a flowchart of the analysis process for the sulfur chemiluminescence detector of this invention. Detailed Implementation
[0023] In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention. However, it will be apparent to those skilled in the art that the present invention can be practiced without one or more of these details. In other instances, certain technical features well-known in the art have not been described in order to avoid confusion with the present invention.
[0024] To fully understand this utility model, detailed steps and structures will be presented in the following description to illustrate the technical solution of this utility model. Preferred embodiments of this utility model are described in detail below; however, in addition to these detailed descriptions, this utility model may have other embodiments.
[0025] Reference Figure 1-2 As shown, this utility model provides an SCD sulfur chemiluminescence detector, which includes:
[0026] The sample oxidation-reduction combustion chamber 1 is provided with an oxidation zone combustion chamber 11 and a reduction zone combustion chamber 12 connected in series. The oxidation zone combustion chamber 11 and the reduction zone combustion chamber 12 are respectively provided with heating devices to provide heating temperature for oxidation-reduction. The internal temperature of the oxidation zone combustion chamber 11 is higher than the internal temperature of the reduction zone combustion chamber 12.
[0027] The first ceramic tube 2 is located in the sample oxidation-reduction combustion chamber 1 and passes through the oxidation zone combustion chamber 11 and the reduction zone combustion chamber 12 in sequence. One end of the first ceramic tube 2 is internally connected to the chromatographic column outlet 3 and the oxygen supply line 4. The chromatographic column outlet 3 and the oxygen supply line 4 are used to introduce sulfur-containing sample gas and combustion-supporting gas (composed of oxygen and air) into the first ceramic tube 2, respectively.
[0028] The second ceramic tube 5 has one end located inside the first ceramic tube 2 in the combustion chamber 12 of the reduction zone, and the other end of the second ceramic tube 5 is connected to a hydrogen pipeline 6, which is used to introduce hydrogen into the first ceramic tube 2. The outer diameter of the second ceramic tube 5 is smaller than the inner diameter of the first ceramic tube 2 to form a gap channel between the first ceramic tube 2 and the second ceramic tube 5.
[0029] The reaction chamber 7 is connected at one end to the slit channel at the other end of the first ceramic tube 2, and at the other end to the vacuum system 8. The reaction chamber 7 is equipped with a chemiluminescence zone, which includes a photomultiplier tube and a filter. The final step of the sample reaction is carried out in this position.
[0030] Ozone generator 9 is connected at one end to oxygen supply pipeline 4 and at the other end to reaction chamber 7. Ozone generator 9 is used to generate ozone and deliver it to reaction chamber 7.
[0031] In an optional embodiment, the oxygen supply line 4 is connected to the first ceramic tube 2 and the ozone generator 9 via a tee 41, and a pressure regulating valve 42 is provided between the tee 41 and the ozone generator 9.
[0032] In an optional embodiment, the present invention further includes a tailpipe 10, which is internally connected to one end of the first ceramic tube 2 for conveying nitrogen gas.
[0033] In an optional embodiment, a preheating device 13 is also included. The preheating device 13 is a heating base installed in the sample redox combustion chamber 1 near the oxidation zone combustion chamber 11, which preheats the gas entering the combustion chamber and connects the capillary column to the sample redox combustion chamber 1.
[0034] In an optional embodiment, the oxygen supply line 4, the hydrogen supply line 6, and the tailpipe line 10 are all equipped with electronic flow control valves.
[0035] In an optional embodiment, the vacuum system 8 includes a vacuum pump and an ozone destruction trap. The vacuum pump is used to evacuate the detector system to a negative pressure state, and the ozone destruction trap is used to decompose ozone into oxygen.
[0036] In an optional embodiment, temperature sensors are provided in both the oxidation zone combustion chamber 11 and the reduction zone combustion chamber 12 to determine the heating temperature of the oxidation zone combustion chamber 11 and the reduction zone combustion chamber 12, respectively.
[0037] In an optional embodiment, the system further includes a circuit control system, a signal acquisition system, and a vacuum detection system. The temperature sensor, electronic flow control valve, vacuum system 8, ozone generator 9, and pressure regulating valve are all connected to the circuit control system. The signal acquisition system is used to record detector signal values. The vacuum detection system is used to read the vacuum level of the piping system. The circuit control system, signal acquisition system, and vacuum detection system are existing technologies and will not be described in detail here.
[0038] The implementation steps of this utility model are as follows:
[0039] 1) The sample flows through the chromatographic column to the heating base, and then enters the large ceramic tube (i.e., the first ceramic tube 2) through the nozzle.
[0040] 2) The existing preheating zone (i.e., oxidation zone combustion chamber 11) remains unchanged, but a lower heating device is added. The lower heating device of oxidation zone combustion chamber 11 can reach a maximum temperature of 1200℃. The lower heating device is responsible for oxidation and is set at 920-950℃. Oxygen or air flows from the heating base into the lower heating device. In this way, the lower device meets both the conditions of high temperature and oxygen enrichment, which can ensure the complete oxidation of the sample. When sulfur-containing compounds pass through the bottom, they are first oxidized into sulfur-containing oxides at high temperature.
[0041] 3) The upper heating device of the combustion chamber 12 in the reduction zone is set at 700-800℃, and excess hydrogen gas is introduced above the upper heating device, flowing out from below through the small ceramic tube (i.e., the second ceramic tube 5). At this time, the upper heating device meets the conditions of high temperature and hydrogen richness, which can ensure the complete reduction of the sample. When the oxidized sulfur oxides are carried to the upper part by the pump, they are reduced to SO in the hydrogen-rich high-temperature environment. Then, they reach the reaction chamber 7 through the transmission line and undergo a chemiluminescent reaction with excess ozone. The spectrum is captured by the multiplier, thus obtaining the response.
[0042] This invention is designed to adapt to a newly added heating device for the reduction zone combustion chamber. The length of the first ceramic tube needs to be increased accordingly to allow it to pass through both the oxidation zone and the reduction zone combustion chamber simultaneously. The advantages of this design are as follows:
[0043] 1) Ensuring oxidation conditions. The increased pipeline length leads to a larger reaction volume. Traditional structures have short combustion chambers, with only one chamber, approximately half the length of current structures. This application connects two heating devices in series into a continuous channel via a first ceramic tube, allowing for smoother gas flow, higher sample transfer efficiency, and ensuring the continuity of the oxidation-reduction reaction.
[0044] 2) Extending the oxidation zone. Increasing the length of the first ceramic tube prolongs the sample's residence time in the oxidation combustion chamber. Combined with the high-temperature, oxygen-rich environment, this ensures complete oxidation of sulfur-containing compounds. For example, for difficult-to-oxidize sulfide compounds, a longer oxidation time prevents them from entering the reduction zone due to incomplete reaction, thus reducing detection errors.
[0045] In addition, the extended first ceramic tube adopts a one-piece molding design without seams, which can reduce the adsorption and residue of gas in the pipeline, further improving the sensitivity and repeatability of detection, and is especially suitable for the detection of trace sulfur.
[0046] The preferred embodiments of this utility model have been described above. It should be understood that this utility model is not limited to the specific embodiments described above. Devices and structures not described in detail herein should be understood as being implemented in a conventional manner within the art. Any person skilled in the art can make many possible variations and modifications to the technical solutions of this utility model using the disclosed methods and techniques, or modify them into equivalent embodiments with equivalent changes, without departing from the scope of the technical solution of this utility model. This does not affect the essential content of this utility model. Therefore, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of this utility model, without departing from the content of the technical solution of this utility model, still fall within the protection scope of the technical solution of this utility model.
Claims
1. An SCD sulfur chemiluminescence detector, characterized in that, The SCD sulfur chemiluminescence detector includes: The sample oxidation-reduction combustion chamber is equipped with an oxidation zone combustion chamber and a reduction zone combustion chamber connected in series. Each of the oxidation zone combustion chamber and the reduction zone combustion chamber is equipped with a heating device. The internal temperature of the oxidation zone combustion chamber is higher than that of the reduction zone combustion chamber. The first ceramic tube is located in the sample oxidation-reduction combustion chamber and passes through the oxidation zone combustion chamber and the reduction zone combustion chamber in sequence. One end of the first ceramic tube is internally connected to the chromatographic column outlet and the oxygen supply line. The second ceramic tube has one end located inside the first ceramic tube in the combustion chamber of the reduction zone, and the other end is connected to a hydrogen pipeline. The outer diameter of the second ceramic tube is smaller than the inner diameter of the first ceramic tube to form a gap channel between the first ceramic tube and the second ceramic tube. The reaction chamber is connected at one end to the slit channel and at the other end to the vacuum system. The reaction chamber is equipped with a photomultiplier tube and a filter. An ozone generator is connected at one end to an oxygen supply pipeline and at the other end to a reaction chamber. The ozone generator is used to produce ozone and deliver it to the reaction chamber.
2. The SCD sulfur chemiluminescence detector as described in claim 1, characterized in that, The oxygen supply line is connected to the first ceramic tube and the ozone generator via a tee, and a pressure regulating valve is installed between the tee and the ozone generator.
3. The SCD sulfur chemiluminescence detector as described in claim 2, characterized in that, It also includes a tailpipe, which is internally connected to one end of the first ceramic tube.
4. The SCD sulfur chemiluminescence detector as described in claim 2, characterized in that, It also includes a preheating device, which is a heating base installed in the sample oxidation-reduction combustion chamber near the oxidation zone combustion chamber. The tail blow line, the chromatographic column outlet and the oxygen supply line all pass through the heating base and are connected to the inside of the first ceramic tube.
5. The SCD sulfur chemiluminescence detector as described in claim 3, characterized in that, The oxygen supply line, hydrogen line, and tailpipe line are all equipped with electronic flow control valves.
6. The SCD sulfur chemiluminescence detector as described in claim 1, characterized in that, The vacuum system includes a vacuum pump and an ozone destructor.
7. The SCD sulfur chemiluminescence detector as described in claim 5, characterized in that, Temperature sensors are installed in both the oxidation zone combustion chamber and the reduction zone combustion chamber.
8. The SCD sulfur chemiluminescence detector as described in claim 7, characterized in that, It also includes a circuit control system, with temperature sensors, electronic flow control valves, vacuum systems, ozone generators, and pressure regulating valves all connected to the circuit control system.