Diesel sulfur content measuring device

Abstract

The utility model discloses a diesel oil sulfur content measuring device which is arranged on a diesel oil conveying pipeline or a side line and is used for on-line measurement. The device at least comprises: a sample introduction unit, in which a quartz sample pipe section is arranged in a sample introduction pipeline, and the quartz sample pipe section is a laser irradiation section; the Raman spectrum light splitting unit is used for receiving the laser from the laser device and irradiating the laser with specific wavelength onto the diesel oil sample in the quartz sample tube section through a convex lens and reflective mirror combination to generate Raman scattering light, and the Raman scattering light is further subjected to light splitting treatment through a grating; the array detector is used for receiving the optical signal after the light splitting processing of the grating and converting the optical signal into an electric signal; and the controller is used for receiving the electric signal, obtaining Raman characteristic peak spectrograms aiming at different sulfur types and obtaining sulfur content data in the sample through the Raman characteristic peak spectrograms. The device provided by the utility model not only can carry out on-line rapid measurement, but also can effectively ensure that the laser intensity loss is relatively small and the measurement accuracy is relatively high.

Description

Technical Field

[0001] The utility model relates to the technical field of online monitoring of components of petrochemical products, in particular to a diesel sulfur content measuring device. Background Art

[0002] The sulfur content standard for diesel refers to the weight percentage of sulfur in the fuel, usually expressed in ppm (parts per million). Sulfur is a pollutant that can harm the environment and human health, so it is very important to limit and control the sulfur content in diesel.

[0003] There are generally two methods for detecting sulfur content in diesel, namely chemical analysis and spectral analysis. Chemical analysis includes oxygen combustion, carbon-sulfur analysis and torch ionization. Spectral analysis includes ultraviolet fluorescence and X-ray fluorescence. Before using any detection method, the sample needs to be prepared and pretreated, such as accurately weighing the sample, extracting, mixing, etc. In addition, attention should be paid to the precision and accuracy of the experimental instrument to ensure the reliability and accuracy of the test results. The above methods are only applicable to laboratory testing and cannot be tested online.

[0004] There are also methods for measuring gasoline and diesel components by Raman spectroscopy in the prior art. For example, Chinese patent application CN101403696A discloses a method for measuring gasoline olefin content based on Raman spectroscopy, which includes: determining the olefin content of training samples by fluorescent indicator adsorption method or multidimensional gas chromatography; measuring the Raman spectrum of the training samples; performing smoothing filtering, baseline correction and standard normalization preprocessing on the measured Raman spectrum; using the least squares support vector machine to establish a gasoline olefin content correction model by comparing the preprocessed training sample Raman spectrum with the measured olefin content value; measuring the Raman spectrum of the oil sample to be tested, performing smoothing filtering, baseline correction and standard normalization preprocessing on the Raman spectrum, and calculating the olefin content of the oil sample to be tested according to the correction model. Although this scheme can detect the components of gasoline and diesel online, it mainly detects the olefin content and does not involve the detection of sulfur content; in addition, the light waves of this scheme are transmitted through optical fibers, and the light wave signal intensity loss in the process is large, which will have a certain impact on the accuracy of the measurement.

[0005] Therefore, there is an urgent need for a diesel sulfur content measurement device that can not only measure online but also effectively ensure that the light wave loss is small and the accuracy is high.

[0006] The information disclosed in this background technology section is only intended to increase the understanding of the overall background of the present invention, and should not be regarded as acknowledging or suggesting in any form that the information constitutes the prior art already known to a person skilled in the art. Utility Model Content

[0007] The purpose of the utility model is to provide a diesel sulfur content measuring device, which can not only perform online measurement of sulfur components in diesel by arranging a sampling unit on a diesel delivery pipeline or a side line, but also effectively ensure the intensity of light wave signals, and achieve higher measurement accuracy.

[0008] To achieve the above-mentioned purpose, the utility model provides a diesel sulfur content measuring device, which is arranged on a diesel delivery pipeline or a side line for online measurement; at least comprises: a sampling unit, in which a quartz sample tube section is arranged in the sampling pipeline, and the quartz sample tube section is a laser irradiation section; a Raman spectrum spectroscopic unit, which receives laser light from a laser, and irradiates the laser light with a specific wavelength onto the diesel sample in the quartz sample tube section through a convex lens and a reflector combination to generate Raman scattered light; the Raman scattered light is then spectroscopically processed by a grating; an array detector, which receives the light signal after the grating spectroscopic processing, and converts the light signal into an electrical signal; a controller, which receives the electrical signal and obtains Raman characteristic peak spectra for different sulfur types, and obtains the sulfur content data in the sample through the Raman characteristic peak spectra.

[0009] Furthermore, in the above technical solution, the Raman spectrum splitting unit may include a first convex lens, a first reflector and a second convex lens, and may also include: a narrow-band filter, which is arranged between the first convex lens and the first reflector, allowing light of a specific wavelength of 785nm to pass through and preventing light signals deviating from both sides of this band; a two-way mirror, which is arranged between the first reflector and the second convex lens, for receiving light of a specific wavelength reflected from the first reflector and reflecting it to the second convex lens, and irradiating the light onto the diesel sample after being focused by the second convex lens; the two-way mirror is also used to transmit the generated Raman scattered light and introduce the light into the grating.

[0010] Furthermore, in the above technical solution, a broadband filter may be provided on the optical path at the rear end of the two-way mirror to filter the excitation light and the ambient light.

[0011] Furthermore, in the above technical solution, a second reflector, a grating and a third reflector may be sequentially arranged on the optical path at the rear end of the broadband filter, and the second reflector, the grating and the third reflector are preferably arranged in a triangle; the grating can split the Raman scattered light from the sample into different wavelength light signals including sulfur information, and reflect the reflected split signal into the array detector.

[0012] Furthermore, in the above technical solution, the controller can be connected to the monitoring room via the Internet of Things to transmit the acquired sulfur content data.

[0013] Furthermore, in the above technical solution, the different sulfur types may include sulfur in the form of thiol, thioether, thiophene or thiophene derivatives.

[0014] Furthermore, in the above technical solution, a filter and a cooler may be provided between the sample inlet and the sample outlet of the sample injection unit and at the front end of the quartz sample tube section.

[0015] Furthermore, in the above technical solution, a flow meter may be provided between the quartz sample tube section and the sample outlet.

[0016] Furthermore, in the above technical solution, the ambient light may include sunlight and / or light from an indoor light source.

[0017] Compared with the prior art, the utility model has the following beneficial effects:

[0018] 1) The device of the utility model applies Raman spectroscopy technology to the field of diesel sulfur content measurement, and can realize online measurement of sulfur content;

[0019] 2) The utility model realizes light transmission through the combination of convex lenses, reflectors, etc. Compared with the prior art using optical fiber transmission, it can effectively ensure the intensity of light wave signals and provide guarantee for the accuracy of measurement;

[0020] 3) The utility model can ensure that the samples to be tested entering the quartz sample tube section are in the same condition by setting the filter and cooler on the sampling pipeline, so that the subsequent measurement results are more accurate;

[0021] 4) A second reflector, a grating and a third reflector are sequentially arranged on the optical path at the rear end of the broadband filter of the utility model, and the three are arranged in a triangle. This arrangement can effectively save the space occupied by the device;

[0022] 5) The utility model only takes 3 to 5 seconds from sampling to testing and obtaining results, and can test continuously. Compared with the traditional method of sending on-site sampling to the laboratory for analysis, it not only saves time for each test, but also realizes online real-time testing;

[0023] 6) The utility model embeds the process of spectrum data processing and analysis and calculation of sulfur content in diesel into the controller, which not only simplifies the equipment but also saves measurement time; it can quickly provide data support for diesel product production decision-making of petrochemical enterprises;

[0024] 7) The device of the utility model has fast measurement speed, high accuracy, small size, no need for regular calibration, and is maintenance-free on site, which is of great significance to the quality control of petrochemical production processes.

[0025] The above description is only an overview of the technical solution of the utility model. In order to more clearly understand the technical means of the utility model and implement it according to the contents of the specification, and at the same time to make the above and other purposes, technical features and advantages of the utility model easier to understand, one or more preferred embodiments are listed below and described in detail with the accompanying drawings as follows. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The utility model is a connection diagram of a diesel sulfur content measuring device.

[0027] Description of main reference numerals:

[0028] 1-injection unit, 10-quartz sample tube segment, 11-injection port, 12-filter, 13-cooler, 14-flow meter, 15-sample outlet, 2-Raman spectrum spectrometer unit, 20-laser, 21-first convex lens, 22-narrow-band filter, 23-first reflector, 24-two-way mirror, 25-second convex lens, 26-broadband filter, 27-second reflector, 28-grating, 29-third reflector, 3-array detector, 4-controller. DETAILED DESCRIPTION

[0029] The specific implementation modes of the present invention are described in detail below in conjunction with the accompanying drawings, but it should be understood that the protection scope of the present invention is not limited by the specific implementation modes.

[0030] Unless explicitly stated otherwise, throughout the specification and claims, the term “comprise” or variations such as “include” or “comprising”, etc., will be understood to include the stated elements or components but not to exclude other elements or components.

[0031] In this document, for the convenience of description, spatial relative terms such as "below", "below", "down", "above", "above", "upper", etc. may be used to describe the relationship between one element or feature and another element or feature in the accompanying drawings. It should be understood that the spatial relative terms are intended to include different orientations of the object in use or operation in addition to the orientation depicted in the figure. For example, if the object in the figure is turned over, the element described as being "below" or "below" other elements or features will be oriented "above" the element or feature. Therefore, the exemplary term "below" can include both below and above. Objects may also have other orientations (rotated 90 degrees or other orientations) and the spatial relative terms used in this document should be interpreted accordingly.

[0032] In this document, the terms "first", "second", etc. are used to distinguish two different elements or parts, and are not used to limit a specific position or relative relationship. In other words, in some embodiments, the terms "first", "second", etc. can also be interchangeable.

[0033] like Figure 1As shown, the utility model provides a diesel sulfur content measuring device, which is arranged on a diesel delivery pipeline or a side line (not shown in the figure) for online measurement. The device at least includes a sampling unit 1, a Raman spectrum spectrometer unit 2, an array detector 3 and a controller 4. Among them, the sampling unit 1 is provided with a quartz sample tube section 10 in the sampling pipeline, and the quartz sample tube section 10 is a laser irradiation section. The sampling unit 1 can also be provided with a filter 12 and a cooler 13 in the front end pipeline of the quartz sample tube section 10 between the sampling port 11 and the sampling port 15, the filter 12 is used to remove mechanical impurities, and the cooler 13 can reduce the temperature of the sample diesel to a specific temperature (such as 25°C). A flow meter 14 can also be provided between the quartz sample tube section 10 and the sampling port 15. The device of the utility model can be directly installed on the delivery pipeline or side line of the diesel production system. The diesel sample is introduced into the sampling port 11 through the pressure difference sampling method from the opening on the oil pipeline. After filtering and cooling, it enters the quartz sample tube section 10 to complete the Raman spectrum collection and obtain the characteristic Raman spectrum of the diesel sample. The diesel sample after the test is returned to the diesel delivery pipeline through the sample outlet 15.

[0034] Further Figure 1As shown, the Raman spectrum spectrometer unit 2 receives the laser from the laser 20, and irradiates the laser with a specific wavelength onto the diesel sample in the quartz sample tube section 10 through a convex lens and a reflector, generating Raman scattered light; the Raman scattered light can then be spectroscopically processed by a grating 28. Specifically, the Raman spectrum spectrometer unit 2 starts from the laser 20, and sequentially arranges the first convex lens 21, the narrow-band shading sheet 22, the first reflector 23, the two-way mirror 24, the second convex lens 25, the broadband shading sheet 26, the second reflector 27, the grating 28 and the third reflector 29 and other components along the light path. Among them, the narrow-band filter 22 is arranged between the first convex lens 21 and the first reflector 23, allowing the light of a specific wavelength of 785nm to pass through (that is, the Raman excitation light), and filtering out the light of other wavelengths. The filtered light is reflected by the first reflector 23 to the two-way mirror 24. The two-way mirror 24 can selectively reflect or transmit. It is arranged between the first reflector 23 and the second convex lens 25, and is used to receive the Raman excitation light of the aforementioned specific wavelength reflected from the first reflector 23 and reflect it to the second convex lens 25. The Raman excitation light is focused by the second convex lens 25 and irradiated onto the diesel sample in the quartz sample tube section 10 to form scattering. When the Raman scattered light returns to the two-way mirror 24, the two-way mirror is in the transmission use mode, that is, the two-way mirror 24 is also used to transmit the generated Raman scattered light and introduce the light into the grating 28 at the rear end of the optical path. A broadband filter 26 is arranged on the optical path at the rear end of the transmission two-way mirror 24, which is used to filter the excitation light and ambient light. The ambient light includes but is not limited to sunlight, light from indoor light sources, etc., to ensure that only the sample signal light enters the grating later. Furthermore, a second reflector 27, a grating 28 and a third reflector 29 are sequentially arranged on the optical path at the rear end of the broadband filter 26, and the three are preferably arranged in a triangle, so that the space occupied by the device can be saved. The grating 28 is used to split the Raman scattered light from the sample according to different wavelength light signals including sulfur information, and reflect the reflected split light signal to the array detector 3. The first reflector 23 and the second reflector 27 of the utility model can be plane mirrors, and the third reflector 29 can be a concave mirror.

[0035] Further Figure 1 As shown, the array detector 3 receives the optical signal after the grating 28 spectroscopic processing and converts the optical signal into an electrical signal. The controller 4 is used to receive the electrical signal from the array detector 3 and obtain the Raman characteristic peak spectra for different sulfur types, and obtain the sulfur content data in the sample through calculation and processing of the Raman characteristic peak spectra. Different sulfur types may include sulfur in the form of thiol, thioether, thiophene or thiophene derivatives. The controller 4 can further be connected to the monitoring room through the Internet of Things to transmit the acquired sulfur content data.

[0036] The above-mentioned device of the utility model is an online diesel sulfur content measuring device based on Raman spectroscopy technology. The device can be directly installed in the delivery pipeline or side line of the diesel production device. The measurement process is as follows: the diesel sample is opened from the oil pipeline, and the diesel sample is introduced into the sampling port 11 by the pressure difference sampling method. After filtering and cooling, it enters the quartz sample tube section 10 to complete the Raman spectrum collection, and obtains the characteristic Raman spectrum of the diesel sample. The sulfur in the diesel mainly exists in the form of mercaptan, sulfide, thiophene and thiophene derivatives. The spectrum data processing method can be used to perform spectrum processing on the Raman characteristic peaks of different sulfur types to obtain the corresponding peak area. The corresponding diesel sulfur content is calculated by the analysis model of the correlation between the peak area and the sulfur content built into the controller 4 (which can be obtained through experiments and data fitting), and it is directly displayed on the controller 4. The measurement results can also be transmitted to the quality control room in real time through the Internet of Things. The diesel is pollution-free during the test process, and the diesel sample after the test can be returned to the diesel delivery pipeline through the sample outlet 15.

[0037] The device of the utility model applies Raman spectroscopy technology to the field of diesel sulfur content measurement, and can realize online measurement of sulfur content; light transmission is realized by a combination of convex lenses, reflectors, etc., which can effectively ensure the light wave signal intensity compared with the use of optical fiber transmission in the prior art; the filter and cooler settings on the sampling pipeline can create better conditions for the sample to be irradiated entering the quartz sample tube section, so that subsequent measurement results are more accurate; the utility model only takes 3 to 5 seconds from sampling to testing to complete the result, and can test continuously, compared with the traditional method of sending on-site sampling to the laboratory for analysis, it not only saves the time of each test, but also realizes online real-time testing; it can quickly provide data support for the diesel product production decision of the chemical plant; the utility model embeds the process of spectrum data processing and analysis and calculation of the sulfur content in diesel into the controller, which not only simplifies the equipment but also saves measurement time.

[0038] The foregoing description of specific exemplary embodiments of the utility model is for the purpose of illustration and illustration. These descriptions are not intended to limit the utility model to the precise form disclosed, and it is clear that many changes and variations can be made based on the above teachings. The purpose of selecting and describing the exemplary embodiments is to explain the specific principles of the utility model and its practical application, so that those skilled in the art can realize and utilize various different exemplary embodiments of the utility model and various different options and changes. Any simple modifications, equivalent changes and modifications made to the above exemplary embodiments should fall within the scope of protection of the utility model.

Claims

1. A diesel sulfur content measuring device, characterized in that: Installed in diesel transmission pipeline or side line for online measurement; including: The sampling unit is provided with a quartz sample tube section in the sampling pipeline, and the quartz sample tube section is a laser irradiation section; A Raman spectroscopy unit receives laser light from a laser, and irradiates the laser light with a specific wavelength onto the diesel sample in the quartz sample tube section through a convex lens and a reflector, thereby generating Raman scattered light; the Raman scattered light is then subjected to spectroscopic processing through a grating; An array detector receives the optical signal after grating spectroscopic processing and converts the optical signal into an electrical signal; A controller receives the electrical signal and obtains Raman characteristic peak spectra for different sulfur types, and obtains sulfur content data in the sample through the Raman characteristic peak spectra.

2. The diesel sulfur content measuring device according to claim 1, characterized in that: The Raman spectrum splitting unit includes a first convex lens, a first reflector and a second convex lens, and also includes: A narrow-band filter, which is arranged between the first convex lens and the first reflector, allows light of a specific wavelength of 785 nm to pass through and blocks light signals deviating from both sides of the wavelength band; A two-way mirror is arranged between the first reflector and the second convex lens, and is used to receive the light of the specific wavelength reflected from the first reflector and reflect it to the second convex lens, and then irradiate the diesel sample after being focused by the second convex lens; the two-way mirror is also used to transmit the generated Raman scattered light and introduce the light into the grating.

3. The diesel sulfur content measuring device according to claim 2, characterized in that: A broadband filter is provided on the optical path at the rear end of the two-way mirror for filtering the excitation light and the ambient light.

4. The diesel sulfur content measuring device according to claim 3, characterized in that: A second reflector, the grating and the third reflector are sequentially arranged on the optical path at the rear end of the broadband filter, and the second reflector, the grating and the third reflector are arranged in a triangle; the grating splits the Raman scattered light from the sample into light signals of different wavelengths including sulfur information, and reflects the reflected split signal into the array detector.

5. The diesel sulfur content measuring device according to claim 1, characterized in that: The controller is connected to the monitoring room via the Internet of Things for transmitting the acquired sulfur content data.

6. The diesel sulfur content measuring device according to claim 1, characterized in that: The different sulfur types include sulfur in the form of thiols, thioethers, thiophenes or thiophene derivatives.

7. The diesel sulfur content measuring device according to claim 1, characterized in that: A filter and a cooler are arranged between the sample inlet and the sample outlet of the sample injection unit and at the front end of the quartz sample tube section.

8. The diesel sulfur content measuring device according to claim 1, characterized in that: A flow meter is arranged between the quartz sample tube section and the sample outlet.

9. The diesel sulfur content measuring device according to claim 3, characterized in that: The ambient light includes sunlight and / or light from indoor light sources.

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