CN112985943B - Based on boats and ships tail gas plume SO 2 Monitored pretreatment device - Google Patents
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- CN112985943B CN112985943B CN202110214713.8A CN202110214713A CN112985943B CN 112985943 B CN112985943 B CN 112985943B CN 202110214713 A CN202110214713 A CN 202110214713A CN 112985943 B CN112985943 B CN 112985943B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
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- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/10—Preparation of ozone
- C01B13/11—Preparation of ozone by electric discharge
- C01B13/115—Preparation of ozone by electric discharge characterised by the electrical circuits producing the electrical discharge
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Abstract
The invention discloses a ship tail gas based smoke plume SO 2 Pretreatment device of monitoring includes: first ship tail gas plume inlet pipeline, NO monitoring sensor before reaction, high-voltage discharge type ozone generator, NO and O 3 The system comprises a reaction chamber, a self-adaptive variable pressure controller, a NO monitoring sensor after reaction and a second ship tail gas plume air inlet pipeline; the invention solves the problem of ship tail gas plume SO 2 SO caused by high-concentration NO in ship tail gas plume of monitoring equipment 2 The problem of inaccurate concentration measurement provides technical support for the supervision that the high-sulfur diesel with the sulfur content of more than 10ppm is illegally used by inland ships based on the sniffing method.
Description
Technical Field
The invention belongs to the technical field of maritime supervision for detecting components of ship tail gas smoke plume and estimating fuel oil quality, and particularly relates to a ship tail gas smoke plume SO-based method 2 The pretreatment device for monitoring eliminates SO caused by high-concentration NO in ship tail gas plume 2 Monitored disturbances.
Background
From 1 month in 2019, GB 17411-2015 modified Bill for bunker fuel oil No. 1 is implemented in China, and the upper limit of the sulfur content of the bunker diesel oil of various models is 10 ppm. Except for using a portable sulfur detector when boarding a ship in the maritime affair law enforcement inspection, ship tail gas plume SO is adopted in advance at home and abroad 2 The monitoring equipment identifies the suspect ship at the bayonet positions of bridges, banks, ship locks and the like so as to improve the efficiency and pertinence of law enforcement inspection.
Ship tail gas plume SO 2 Monitoring deviceThe principle is to synchronously detect the ship tail gas SO 2 And CO 2 The fuel sulfur content was estimated based on the fact that the carbon content in the fuel was about 87%. However, the ship exhaust plume SO 2 The monitoring equipment is mainly suitable for supervision of heavy oil for ships, the upper limit of the sulfur content is 0.5 percent or 0.1 percent, and the monitoring equipment is not suitable for supervision of diesel oil for ships. The main reason is high accuracy SO 2 The analyzer adopts the principle of ultraviolet fluorescence, and NO in the tail gas plume can generate weak fluorescence under the irradiation of ultraviolet rays and can be mistakenly detected as SO 2 . For the supervision of the marine heavy oil, the misdetection can be ignored; however, for marine diesel oil supervision, misdetection results cannot be ignored, and even far exceed real sulfur content results. At present, no ship tail gas plume SO suitable for monitoring the sulfur content of marine diesel oil exists at home and abroad 2 The monitoring equipment and the maritime affair law enforcement check still mainly take the boarding sampling test, and have the defects of low efficiency and lack of pertinence, thereby causing great waste of law enforcement resources.
With the development of science and technology, people think of the smoke plume SO of the ship exhaust 2 A pretreatment device is added in an air inlet pipeline of monitoring equipment, and O is utilized 3 The equal-strength oxidant removes NO in the ship tail gas plume. But how to precisely grasp O 3 The amount of SO produced is critical, too little removal is not clean enough to achieve the effect, and too much removal results in partial SO 2 Is oxidized to SO 3 Formation of sulfuric acid, reduction of SO 2 The monitoring accuracy is also simultaneously accompanied by the side effect of accelerating the corrosion in the equipment.
Therefore, an adaptive control of O is sought 3 Pretreatment device for production quantity to expand ship tail gas plume SO 2 The application range of the monitoring equipment is widened, so that efficient and accurate supervision of the sulfur content of the marine diesel becomes a concern of researchers.
Disclosure of Invention
In order to solve the technical problem, the invention provides a ship tail gas plume-based SO 2 A monitoring pretreatment device to expand the ship tail gas plume SO 2 The application range of the monitoring equipment is that the sulfur content of the marine diesel oil is accurately reversely pushed by monitoring the smoke plume components of the ship tail gasAnd rapidly identifying the illegal ship with the sulfur content of the marine diesel oil exceeding 10 ppm.
In order to achieve the purpose, the invention provides a ship tail gas plume-based SO 2 The pretreatment device of monitoring includes: first ship tail gas plume inlet pipeline, NO monitoring sensor before reaction, high-voltage discharge type ozone generator, NO and O 3 The system comprises a reaction chamber, a self-adaptive variable pressure controller, a NO monitoring sensor after reaction and a second ship tail gas plume air inlet pipeline;
the first ship tail gas plume inlet pipeline passes through NO and O 3 The reaction chamber is connected with the second ship tail gas plume air inlet pipeline;
the first ship tail gas plume inlet pipeline is sequentially provided with the NO monitoring sensor before reaction and the high-voltage discharge type ozone generator in the horizontal direction; one end of the NO monitoring sensor before reaction is connected with the first ship tail gas plume air inlet pipeline, and the other end of the NO monitoring sensor before reaction is connected with the self-adaptive variable pressure controller; one end of the high-voltage discharge type ozone generator is connected with the first ship tail gas plume air inlet pipeline, and the other end of the high-voltage discharge type ozone generator is connected with the self-adaptive variable-pressure controller;
the reacted NO monitoring sensor is arranged on the second ship tail gas plume inlet pipeline; one end of the NO monitoring sensor after the reaction is connected with the second ship tail gas plume air inlet pipeline, and the other end of the NO monitoring sensor after the reaction is connected with the self-adaptive variable pressure controller.
Preferably, the pre-reaction NO monitoring sensor is made of a solid electrolyte yttria-doped zirconia YSZ ceramic material.
Preferably, the high-voltage discharge type ozone generator and the NO monitoring sensor before reaction are arranged at a distance, and the distance is the response time of the NO monitoring sensor before reaction multiplied by the gas flow rate.
Preferably, the NO is with O 3 The reaction chamber adopts honeycomb inert filler.
Preferably, the NO is with O 3 The porosity times the volume of the reaction chamber equals 5s times the inlet line flow rate.
Preferably, the limit of the residual NO concentration monitored by the post-reaction NO monitoring sensor is in the range of 0.01-0.1 ppm.
Preferably, the adaptive voltage transformation controller comprises a data acquisition instrument and a transformer;
the data acquisition instrument is respectively connected with the NO monitoring sensor before reaction and the NO monitoring sensor after reaction and is used for reading the concentration of NO in the air inlet pipeline before reaction and after reaction in real time;
the transformer is connected with a circuit of the high-voltage discharge type ozone generator and used for adjusting the power supply voltage of the high-voltage discharge type ozone generator in real time.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention reasonably sets the distance between the high-voltage discharge ozone generator and the NO monitoring sensor before reaction, so that the NO gas has right amount of O when reaching the position 3 Generating;
(2) the invention utilizes special NO sensitive electrode material to selectively catalyze NO gas to generate N 2 And O 2 The method is suitable for the rapid change of the NO concentration in the ship tail gas plume, so that the NO concentration in the air inlet pipe can be monitored in real time;
(3) the invention depends on the concentration of NO and O in the air inlet pipeline 3 The residual NO concentration at the outlet of the reaction chamber automatically changes the voltage of the high-voltage discharge type ozone generator to adjust O 3 The generated amount of the tail gas of the ship solves the problem of smoke plume SO of the tail gas of the ship 2 SO caused by high-concentration NO in ship tail gas plume of monitoring equipment 2 The problem of inaccurate concentration measurement provides technical support for the supervision of illegal use of high-sulfur diesel oil with sulfur content exceeding 10ppm by inland ships based on the sniffing method; and NO with a concentration of 0.01-0.1ppm is selected to determine O 3 Can effectively prevent the residual NO existing in the tail gas plume from being misdetected as SO 2 The monitoring result is more accurate.
In conclusion, the application range of the ship tail gas plume SO2 monitoring equipment can be expanded, the sulfur content of the marine diesel oil can be accurately reversely pushed by monitoring the components of the ship tail gas plume, and illegal ships with the sulfur content of the marine diesel oil exceeding 10ppm can be rapidly screened.
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In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
FIG. 1 is a schematic view of the apparatus of the present invention;
in the figure: 1-first ship tail gas plume inlet pipeline, 2-NO monitoring sensor before reaction, 3-high voltage discharge type ozone generator, 4-NO and O 3 The device comprises a reaction chamber, a 5-adaptive variable pressure controller, a 6-NO monitoring sensor after reaction and a 7-second ship tail gas plume air inlet pipeline.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below.
Example 1
Referring to FIG. 1, the invention provides a ship tail gas plume-based SO 2 The pretreatment device of monitoring includes: a first ship tail gas plume air inlet pipeline 1, a NO monitoring sensor 2 before reaction, a high-voltage discharge type ozone generator 3, NO and O 3 The system comprises a reaction chamber 4, a self-adaptive variable pressure controller 5, a NO monitoring sensor 6 after reaction and a second ship tail gas plume air inlet pipeline 7;
the first ship tail gas plume inlet pipeline 1 passes through NO and O 3 Reaction chamber 4 and second ship tail gas plume inlet airThe pipeline 7 is connected;
the first ship tail gas plume inlet pipeline 1 is sequentially provided with a NO monitoring sensor 2 before reaction and a high-voltage discharge type ozone generator 3 along the horizontal direction; one end of a NO monitoring sensor 2 before reaction is connected with a first ship tail gas plume air inlet pipeline 1, and the other end of the NO monitoring sensor is connected with an adaptive variable pressure controller 5; one end of a high-voltage discharge type ozone generator 3 is connected with a first ship tail gas plume air inlet pipeline 1, and the other end of the high-voltage discharge type ozone generator is connected with a self-adaptive variable-voltage controller 5;
a reacted NO monitoring sensor 6 is arranged on the second ship tail gas plume inlet pipeline 7; one end of the NO monitoring sensor 6 after reaction is connected with a second ship tail gas plume air inlet pipeline 7, and the other end of the NO monitoring sensor is connected with the adaptive variable pressure controller 5;
(1) first ship tail gas plume air inlet pipeline 1:
the first ship tail gas plume inlet pipeline 1 is used for collecting ship tail gas plume without high-concentration NO eliminated;
(2) pre-reaction NO monitoring sensor 2:
the NO monitoring sensor 2 before reaction is used for monitoring the ship tail gas plume SO 2 And monitoring the NO concentration in a first ship tail gas plume air inlet pipeline 1 of the equipment. Because the NO concentration in the ship tail gas plume is always in a rapid change state, and the air inlet pipeline is a long and thin hose, an electrochemical NO sensor-solid electrolyte yttria-doped zirconia (YSZ) ceramic material with small volume and short response time is selected, and NO gas is selectively catalyzed by utilizing a special NO sensitive electrode material to generate N 2 And O 2 O from the series 2 Sensor measuring O 2 The concentration represents the NO concentration x.
NO monitoring sensor 2 before reaction from ship tail gas plume SO 2 The air suction amount in the air inlet pipeline of the monitoring device is not more than 1/10.
(3) High-voltage discharge type ozone generator 3:
the high-voltage discharge type ozone generator 3 is used for generating the ozone capable of oxidizing NO into NO 2 O of (A) to (B) 3 A gas. According to the principle, the high-voltage discharge type ozone generator 3 has a working voltage range, and almost no O is generated below the lower limit 3 No effect, above the upper limit would result in O 2 And N 2 Reaction to form NO x The side products and effects are undesirable. In consideration of the difference between products, each high-voltage discharge type ozone generator 3 is calibrated to provide a basis for parameter setting of the subsequent adaptive variable-voltage controller 5.
V＝eC+V 0
Wherein V is less than V 1 ；V 0 To produce O 3 Lower limit voltage of, V 1 To not generate NO x Upper limit voltage of by-product, C is O of high-voltage discharge type ozone generator 3 Amount of generation (in ppm), e is voltage and O 3 The relation coefficient between the generated quantity C, V is the voltage needed by the ozone generator to generate the ozone with the concentration C. During the use process, e can be changed under the influence of various aspects such as air humidity, instrument aging and the like.
The high-voltage discharge type ozone generator 3 is arranged on a pipeline at a certain distance behind the NO monitoring sensor 2 before reaction, the distance is equal to the response time of the NO monitoring sensor 2 before reaction multiplied by the gas flow rate, and the proper amount of O is ensured to be prepared when NO gas reaches the position 3 And (4) generating. Due to O 3 Is an extremely unstable gas, and too short or too long a distance will result in a large compromise in the effect of adaptively controlling the high-voltage discharge type ozone generator 3.
(4) NO and O 3 Reaction chamber 4:
NO and O 3 The reaction chamber 4 is NO and O 3 The reaction provides a site in the air intake line for sufficient mixing and reaction time. To ensure NO and O 3 Fully mixing NO and O 3 The reaction chamber 4 is filled with honeycomb inert filler. According to the research, NO and O 3 When the mixture is sufficiently mixed, NO can be completely reacted within 5 seconds. Thus, NO and O 3 The porosity times the volume of the reaction chamber 4 equals 5s times the inlet line flow rate.
Due to O 3 Unstable and will be continuously decomposed into O at normal temperature 2 (ii) a Thus, NO and O 3 The reaction chamber 4 is closely adjacent to the high-voltage discharge type ozone generator 3, and O is ensured 3 Reaction with NO in preference to O 3 And (4) decomposing the self.
(5) Post-reaction NO monitoring sensor 6:
NO monitoring sensor 6 used for monitoring NO and O after reaction 3 The residual NO concentration at the outlet of the reaction chamber 4 adopts the principle and hardware consistent with the NO monitoring sensor 2 before reaction. The concentration is set at three levels, which are respectively lower than 0.01ppm, between 0.01 and 0.1ppm and higher than 0.1 ppm.
If the concentration is less than 0.01ppm, it is judged that O is present 3 Too much, need to reduce O 3 The amount of production; if it is higher than 0.1ppm, it is judged that O is present 3 Insufficient, need to increase O 3 A production amount; between 0.01 and 0.1ppm, judging that O is 3 Is suitable. According to scientific research, NO at a concentration of 0.1ppm can be mistakenly measured as SO of about 1ppb 2 Considering the ship tail gas plume SO 2 Ultraviolet fluorescence method SO adopted by monitoring equipment 2 The detection limit of the analyzer is about 1ppb, and the existence of NO with the concentration of 0.01-0.1ppm can not be kept to SO 2 The monitoring results gave significant deviations.
NO monitoring sensor 6 after reaction between NO and O 3 The second ship tail gas plume after the reaction chamber 4 is pumped into the air inlet pipeline 7, and the air pumping quantity cannot exceed 1/10.
(6) The adaptive variable voltage controller 5:
the self-adaptive variable voltage controller 5 is used for controlling the concentration of NO and O in the air inlet pipeline 1 according to the smoke plume of the first ship tail gas 3 The residual NO concentration y at the outlet of the reaction chamber 4 automatically changes the voltage of the high-voltage discharge type ozone generator 3 to adjust O 3 The amount of production of (c). The adaptive voltage transformation controller 5 consists of two parts, namely a data acquisition instrument and a transformer. The former is connected with a NO monitoring sensor 2 before reaction and a NO monitoring sensor 6 after reaction, and the concentration of NO in the pipeline before reaction and the concentration of NO in the pipeline after reaction are read in real time; the latter is connected with the circuit of the high-voltage discharge type ozone generator 3 to adjust the power supply voltage of the high-voltage discharge type ozone generator 5 in real time.
If x is less than 0.05ppm, controlling the voltage V of the high-voltage discharge type ozone generator 3 to be less than V 0 Alarming to prompt that the tail gas concentration is too low and no ship passes or suggests ship tail gas plume SO 2 The air inlet of the monitoring device is properly close to the chimney port of the ship;
if x is not less than 0.05ppm, the voltage V of the high-voltage discharge ozone generator 3 is controlled to be e (x-0.05ppm) + V 0 The variation of V depends on the variation of x;
if x is more than or equal to 0.05ppm and y is more than 0.01ppm and less than 0.1ppm, judging that e is proper and keeping unchanged;
if x is more than or equal to 0.05ppm and y is less than or equal to 0.01ppm, judging that e is too large, and correcting the value of e to be (x-0.05ppm)/(x-0.01ppm) e;
if x is 0.05ppm or more and y is 0.1ppm or more, it is judged that e is too small, and corrected to (x-0.05ppm)/(x-0.1ppm) e.
If x is not less than 0.05ppm, y is not less than 0.1ppm, and V after e correction is not less than V 1 Judging that the NO concentration exceeds the capability range of the high-voltage discharge type ozone generator, alarming to prompt that the tail gas concentration is too high, and recommending ship tail gas plume SO 2 The air inlet of the monitoring device is suitably remote from the vessel chimney port.
(7) A second ship tail gas plume air inlet pipeline 7:
and the second ship tail gas plume inlet pipeline 7 is used for collecting the ship tail gas plume after the high-concentration NO is removed.
In conclusion, the invention solves the problem of ship tail gas plume SO 2 SO caused by high-concentration NO in ship tail gas plume of monitoring equipment 2 The problem of inaccurate concentration measurement provides technical support for the supervision that the high-sulfur diesel with the sulfur content of more than 10ppm is illegally used by inland ships based on the sniffing method.
In the description of the present invention, it is to be understood that the terms "longitudinal", "lateral", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on those shown in the drawings, are merely for convenience of description of the present invention, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention.
The above-described embodiments are only intended to illustrate the preferred embodiments of the present invention, and not to limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.
Claims (5)
1. Based on boats and ships tail gas plume SO 2 The pretreatment device of monitoring, its characterized in that includes: a first ship tail gas plume air inlet pipeline (1), a pre-reaction NO monitoring sensor (2), a high-voltage discharge type ozone generator (3), NO and O 3 The device comprises a reaction chamber (4), a self-adaptive variable pressure controller (5), a NO monitoring sensor (6) after reaction and a second ship tail gas plume air inlet pipeline (7);
the first ship tail gas plume air inlet pipeline (1) passes through NO and O 3 The reaction chamber (4) is connected with the second ship tail gas plume air inlet pipeline (7);
the first ship tail gas plume air inlet pipeline (1) is sequentially provided with the NO monitoring sensor (2) before reaction and the high-voltage discharge type ozone generator (3) along the horizontal direction; one end of the NO monitoring sensor (2) before reaction is connected with the first ship tail gas plume air inlet pipeline (1), and the other end of the NO monitoring sensor is connected with the self-adaptive variable pressure controller (5); one end of the high-voltage discharge type ozone generator (3) is connected with the first ship tail gas plume air inlet pipeline (1), and the other end of the high-voltage discharge type ozone generator is connected with the self-adaptive variable-voltage controller (5);
the second ship tail gas plume inlet pipeline (7) is provided with the NO monitoring sensor (6) after reaction; one end of the NO monitoring sensor (6) after the reaction is connected with the second ship tail gas plume air inlet pipeline (7), and the other end of the NO monitoring sensor is connected with the adaptive variable pressure controller (5);
the NO monitoring sensor (2) adopts a solid electrolyte yttria-doped zirconia YSZ ceramic material;
the self-adaptive variable voltage controller (5) comprises a data acquisition instrument and a transformer;
the data acquisition instrument is respectively connected with the pre-reaction NO monitoring sensor (2) and the post-reaction NO monitoring sensor (6) and is used for reading the concentration of NO in the gas inlet pipeline before and after the reaction in real time;
the transformer is connected with a circuit of the high-voltage discharge type ozone generator (3) and used for adjusting the power supply voltage of the high-voltage discharge type ozone generator (3) in real time.
2. The ship tail gas plume SO based on claim 1 2 The pretreatment device for monitoring is characterized in that a distance is reserved between the high-voltage discharge type ozone generator (3) and the position where the NO monitoring sensor (2) before reaction is located, and the distance is the product of the response time of the NO monitoring sensor (2) before reaction and the gas flow rate.
3. The ship tail gas plume-based SO as claimed in claim 1 2 The pretreatment device for monitoring is characterized in that NO and O are 3 The reaction chamber (4) adopts honeycomb inert fillers.
4. The ship tail gas plume SO based on claim 1 2 The pretreatment device for monitoring is characterized in that NO and O are 3 The porosity times the volume of the reaction chamber (4) is equal to 5s times the inlet line flow rate.
5. The ship tail gas plume-based SO as claimed in claim 1 2 The pretreatment device for monitoring is characterized in that the limit range of the residual NO concentration monitored by the NO monitoring sensor (6) after the reaction is 0.01-0.1 ppm.
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