CN112933883A - Ship flue gas photoelectrocatalysis seawater desulfurization process and system - Google Patents

Ship flue gas photoelectrocatalysis seawater desulfurization process and system Download PDF

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CN112933883A
CN112933883A CN202110228108.6A CN202110228108A CN112933883A CN 112933883 A CN112933883 A CN 112933883A CN 202110228108 A CN202110228108 A CN 202110228108A CN 112933883 A CN112933883 A CN 112933883A
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seawater
flue gas
washing tower
desulfurization
surface area
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刘昌豹
李春虎
李栋
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Weihai Puyi Marine Environmental Technology Co ltd
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Weihai Puyi Marine Environmental Technology Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1456Removing acid components
    • B01D53/1481Removing sulfur dioxide or sulfur trioxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/007Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by irradiation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/1493Selection of liquid materials for use as absorbents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/14Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
    • B01D53/18Absorbing units; Liquid distributors therefor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/48Sulfur compounds
    • B01D53/50Sulfur oxides
    • B01D53/508Sulfur oxides by treating the gases with solids
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/92Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2252/00Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/10Inorganic absorbents
    • B01D2252/103Water
    • B01D2252/1035Sea water
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2255/00Catalysts
    • B01D2255/80Type of catalytic reaction
    • B01D2255/802Photocatalytic
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/01Engine exhaust gases
    • B01D2258/012Diesel engines and lean burn gasoline engines
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2259/00Type of treatment
    • B01D2259/80Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
    • B01D2259/804UV light

Abstract

A ship flue gas photoelectrocatalysis seawater desulfurization process and system are used for carrying out desulfurization treatment on flue gas discharged by a sulfur-containing ship diesel engine, and comprise the following steps: filling a high specific surface area hydrophilic filler into the washing tower, arranging an excitation light source above the high specific surface area hydrophilic filler, and spraying seawater from the upper part of the washing tower to the inside of the washing tower after the seawater is subjected to electrocatalysis reaction; injecting flue gas into the lower part of a washing tower, wherein the flue gas is in countercurrent contact with seawater, a high-specific-surface-area hydrophilic filler and an excitation light source in the washing tower to perform desulfurization reaction, so as to obtain waste seawater and clean flue gas; the waste seawater is discharged from the bottom of the washing tower, and the clean flue gas is discharged from the top of the washing tower, so that the technical problem of poor desulfurization effect caused by large size of desulfurization equipment and complex desulfurization mode in the traditional desulfurization method is solved, and the method can be widely applied to the fields of ship waste gas treatment and energy conservation and environmental protection.

Description

Ship flue gas photoelectrocatalysis seawater desulfurization process and system
Technical Field
The application relates to the field of ship waste gas treatment and energy conservation and environmental protection, in particular to a ship flue gas photoelectrocatalysis seawater desulfurization process and system.
Background
At present, 85% of goods in the world are transported by sea, about 38 million ships with AIS positions in the world and about 2.6 million ships with over ten thousand tons are transported by sea. 4309 international sailing ships of Chinese nationality, 1345 ships of over ten thousand tons, 6103 ships controlled by the shipowner of China, and 2517 ships of over ten thousand tons. 12.17 million ships are active in one week in China. In ships with more than 1 million loads, dry bulk carriers account for 38.85%, container ships account for 17.09%, and oil tankers account for 13.16%. Among these vessels, the diesel engine vessels using heavy diesel oil as fuel have the largest reserve, the technology of the marine diesel engine is mature, the global fuel supply chain and the ship maintenance chain are the most perfect, the distribution is the widest, the technical personnel and the operation regulation configuration are the best, and the diesel engine vessels can almost reach any port all over the world. It is calculated and counted that shipping vessels consume approximately 3 million tons of fuel oil per year, thereby producing large quantities of flue gas containing sulfur, nitrate and carbon dioxide. According to the article in journal of economic scholars in England, 15 ocean-going large ships with the largest tonnage discharge sulfur and nitrogen oxides beyond the global automobile discharge. Global ocean going vessels must therefore be modified to meet IMO emissions limits. At present, various optional strategies exist for the flue gas desulfurization of ships: 1. the clean low-sulfur fuel oil is used, but the high price of the clean low-sulfur fuel oil is 1.16 times higher than that of the light diesel oil containing 0.5 percent of sulfur in the sea, because the heavy diesel oil with high calorific value and high viscosity contains a large amount of high-steric-hindrance sulfides such as 2,4 dibenzothiophene and the like, the desulfurization cost is very high, the price difference can be generally kept for 70-300 dollars per ton for a long time, the expensive low-sulfur shipping companies are difficult to accept, and moreover, the low-sulfur diesel oil has certain influence on the working parameters, the calorific value, the pipeline leakage, the lubricity, the health of crew and the like of the diesel engine, and is not beneficial to the maintenance of the marine diesel engine. 2. The installation of scrubbers to remove pollutants from flue gases is currently one of the most promising methods generally accepted. Various harmful pollutants in the flue gas are removed in a unified way by installing a washing tower at a flue gas outlet, wherein the harmful pollutants comprise carbon dioxide, SO2, NOx, VOCs, part of CO2 and the like, the operation cost and investment of the washing tower are inversely proportional to the sulfur content of the fuel oil, the sulfur content of the fuel oil is low, and the investment and operation cost of the corresponding washing tower are also low. Therefore, the price difference between low-sulfur fuel oil and high-sulfur fuel oil is avoided from being reduced, the operation cost is increased possibly due to the selection of the low-sulfur fuel oil, and the synchronous operation cost of the flue gas purification washing tower is also reduced sharply when the low-sulfur fuel oil is selected; 3. by adopting a dual-fuel system, heavy oil with high sulfur content is adopted in the open sea navigation, and light diesel oil with low sulfur content is adopted in 200 seas away from the sea shore, obviously, the method can only be a transition measure, and along with the improvement of a real-time detection means, the smoke pollution emission of the ship in the open sea navigation is also limited; 4. the shore power application technology is characterized in that a diesel generator on a ship is stopped during berthing of the ship, and a land power supply is used for supplying power, so that the exhaust emission is reduced, and obviously, the method is only effective when the ship is berthed; 5. an Exhaust Gas Recirculation (EGR) technology and a common-rail electronic control fuel injection technology can reduce partial NOx emission, but increase fuel consumption and PM content, and are not adopted in a large scale at present; 6. by adopting the LNG power system, the desulfurization can meet the IMO requirement, but the denitration cannot meet the IMO requirement, the ship building cost is high, and the safety requirement is high. The economy and safety of the method are still waiting for time check.
From the above analysis, it can be seen that the installation of a seawater scrubber to remove pollutants from ship flue gas is one of the best generally recognized methods. The reliability of the scrubbing tower and the efficiency of the scrubbing tower for reducing emission are discussed in a workshop of London in 20.2.2020, and the flue gas scrubbing tower has a wide application prospect in treating waste gas practically summarized by more than 200 ship-mounted desulfurization scrubbing towers of three great shippers in Europe.
The seawater desulfurization technology began in the last 70 th century and was rapidly popularized and applied in coastal power plants in europe, america, asia, and the like. As is well known, natural seawater contains a large amount of soluble salts, is generally alkaline, has natural alkalinity of 1.2-2.5 mmol/L, and has natural acid-base buffering capacity and SO absorption capacity2The capacity of the method is a theoretical basis for directly using seawater for flue gas desulfurization.
The core of the seawater desulfurization process is the contact mass transfer of the flue gas and the seawater, and the process is carried out in gas-liquid contact mass transfer equipment. The packed tower is a mass transfer device which takes the packing in the tower as a gas-liquid two-phase contact component and has the advantages of high separation efficiency,Small resistance, large flux, large operation elasticity and the like, and almost has no amplification effect under the condition of good initial distribution of gas and liquid. When the traditional marine flue gas seawater desulfurization washing tower is used, the IMO requirement is met, the liquid-gas ratio is very high and is generally 10L/m3I.e. removing 1m3The sulfur in the flue gas needs to be sprayed with 10 liters of seawater, so that the defects of overlarge volume of a filler washing tower and the diameter of a seawater pipeline, numerous auxiliary equipment and the like are caused. The liquid-gas ratio is high, which causes the power of the sea water pump to be high, the equipment to be heavy and the occupied area to be large. Therefore, the invention provides a high-specific surface area hydrophilic regular catalytic filler and a photoelectric catalytic flue gas seawater desulfurization technology, which is particularly important for greatly reducing the liquid-gas ratio, avoiding aeration and reducing the volume of a washing tower and the diameter of a seawater pipeline.
China has a long coastline, nearly 50% of people live near the coastline in China, nearly 70% of GDP in China comes from cities and areas on the coastline, and a plurality of coal-fired power plants for seawater desulfurization are built in coastal areas. Therefore, the invention discloses a high-specific surface area hydrophilic structured packing and a photoelectrocatalysis flue gas seawater desulfurization technology, which not only has important practical significance and strategic significance for the flue gas desulfurization of ships, but also has important practical significance and strategic significance for the seawater desulfurization of coastal coal-fired power plants.
Disclosure of Invention
The application aims to provide a ship flue gas photoelectrocatalysis seawater desulfurization process and system, and aims to solve the technical problem that the traditional desulfurization method is poor in desulfurization effect due to the fact that the size of desulfurization equipment is large and the desulfurization mode is complex.
The first aspect of the embodiment of the application provides a ship flue gas photoelectrocatalysis seawater desulfurization process, which is used for carrying out desulfurization treatment on flue gas exhausted by a sulfur-containing ship diesel engine, and comprises the following steps:
s1, filling a high specific surface area hydrophilic filler into the washing tower, arranging an excitation light source above the high specific surface area hydrophilic filler, and spraying seawater from the upper part of the washing tower to the inside of the washing tower after the seawater is subjected to electrocatalysis reaction;
s2, injecting flue gas into the lower part of the washing tower, wherein the flue gas is in countercurrent contact with the seawater, the hydrophilic filler with the high specific surface area and the excitation light source in the washing tower to perform a desulfurization reaction, so that waste seawater and clean flue gas are obtained;
s3, discharging the waste seawater through the bottom of the washing tower, and discharging the clean flue gas through the top of the washing tower.
In one embodiment, the seawater waste in S2 is also used for cooling the flue gas, and the temperature of the flue gas is adjusted by adjusting the volume of the seawater waste.
In one embodiment, the flue gas temperature in the lower part of the washing tower is 80 ℃, and the flue gas temperature in the washing tower contacted with the high specific surface area hydrophilic packing is 60 ℃.
In one embodiment, the surface of the high specific surface area hydrophilic filler is coated with a photocatalyst composite g-C3N4-TiO2-Al2O3-BiVO4Specific surface area of 2500m2/m3Bulk density of 320-650 kg/m3The void ratio is 70-90%, the F factor is 1.5-3.5, the wave pitch is 10-55 mm, and the tooth form angle is 30-80.
In one embodiment, the electrocatalytic reaction is realized by adopting an electrocatalytic reactor, and the anode of the electrocatalytic reactor contains g-C3N4-TiO2-RuO2The cathode of the/Ti electrocatalytic DSA anode is a titanium plate, hastelloy or hard carbon electrode, and the process conditions of the electrocatalytic reaction are as follows: current density: 500-3000A/m 2, temperature: 15-35 ℃, voltage: 0-90V.
The second aspect of the embodiment of the application provides a boats and ships flue gas electro-catalysis sea water desulfurization system, including the scrubbing tower, the inside of scrubbing tower is equipped with the hydrophilic filler of high specific surface area, the hydrophilic filler top of high specific surface area is equipped with the plasma lamp, the lower part of scrubbing tower is equipped with the flue gas entry, the top of scrubbing tower is equipped with the exhanst gas outlet, the upper portion of scrubbing tower is equipped with sea water spray set, the outside of scrubbing tower is equipped with electro-catalytic reactor, electro-catalytic reactor with sea water spray set connects, the bottom of scrubbing tower is equipped with the sea water export.
In one embodiment, the plasma lamp comprises 5 ultraviolet lamps, and the 5 ultraviolet lamps are started by a magnetic ballast.
In one embodiment, the electro-catalytic reactor is connected with a seawater pump through a seawater pipeline, and the seawater pump is arranged in the sea.
In one embodiment, the seawater outlet is connected to the electro-catalytic reactor through a three-way valve.
In one embodiment, the outer plate surface of the washing tower is made of carbon steel, and the inner plate surface of the washing tower is made of titanium.
The invention provides a ship flue gas photoelectrocatalysis seawater desulfurization process and a system thereof, which adopts a specific surface area as high as 2500m2/m3The hydrophilic regular catalytic filler has the characteristics of fast mass transfer, good wettability, catalytic oxidation activity, small pressure drop, large flux, seawater corrosion resistance, long service life, small operation liquid and gas and the like; the surface of the high-specific-surface-area hydrophilic catalytic structured packing is coated with g-C3N4-TiO2-Al2O3-BiVO4Under the action of ion lamp, the photocatalyst compound can produce great amount of oxidizing matter, such as superoxide radical, hydroxyl radical, hydrogen peroxide, etc. on the surface to make SO in fume2Fast oxidation to SO3And stable sulfate radicals are formed in the desulfurized seawater in the washing tower, so that the high desulfurization efficiency of the flue gas of the marine diesel engine with high sulfur content is achieved, hydrogen peroxide, hydroxyl radicals, hypochlorite and other strong oxidizing materials are generated on the surface of an electrode by combining electrocatalysis reaction before fresh seawater enters the washing tower, the desulfurized acidic seawater does not contain unstable sulfite radicals but is completely stable sulfate radicals, and the waste desulfurized acidic seawater can reach the standard and be discharged back to the ocean without aeration treatment. Meanwhile, partial water flow can be led out from the acidic seawater, the electrocatalytic reaction electrode plates arranged outside are regularly washed, and the activity of the electrocatalytic reaction electrode plates is recovered after the electrocatalytic reaction caused by seawater sediments is reducedAnd (3) removing the solvent.
Drawings
Fig. 1 is a schematic flow chart of a marine flue gas electrocatalytic seawater desulfurization process provided in an embodiment of the present application;
fig. 2 is a schematic structural diagram of a marine flue gas electro-catalytic seawater desulfurization system according to an embodiment of the present application.
The symbols in the drawings illustrate that:
1. a washing tower; 2. a high specific surface area hydrophilic filler; 3. a flue gas inlet; 4. a flue gas outlet; 5. a seawater spraying device; 6. a seawater outlet; 7. a seawater pipeline; 8. a sea water pump; 9. an ocean; 10. an electrocatalytic reactor; 11. a plasma lamp.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application clearer, the present application is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application.
The traditional seawater desulfurization process usually adopts random packing polypropylene, metal or ceramic structured packing. Generally, these structured packings have a maximum specific surface area of not more than 700m2/m3Surface hydrophilic modification and catalyst loading are also not contemplated. According to the mass transfer theory, Q ═ kda(C0-Ct) I.e. in the concentration difference (C)0-Ct) Under certain conditions, the mass transfer rate and the mass transfer coefficient kdProportional to the specific surface area of the filler. That is, the higher the specific surface area of the filler, the faster the mass transfer rate. And, a mass transfer coefficient kdThe Re number is related to the Re number of the fluid, namely the thickness of a Plant boundary layer, and is closely related to the hydrophilicity of the surface of the filler, when the filler has strong hydrophilicity, the surface liquid holdup is large, the mass transfer is fast, and the high Re number can not cause the occurrence of flooding, so that the operation is deteriorated. Meanwhile, the traditional filler has no catalytic function, SO that SO in the flue gas is caused2The gas-liquid mass transfer rate of the sprayed seawater on the surface of the filler only depends on the mass transfer rate and Henry's theorem.
Example 1
Referring to fig. 1, a schematic flow chart of a marine flue gas electro-catalysis seawater desulfurization process according to an embodiment of the present application is shown, for convenience of description, only the relevant portions of the present embodiment are shown, and the detailed description is as follows:
in one embodiment, the first aspect of the present application provides a marine flue gas electrocatalytic seawater desulfurization process for desulfurizing flue gas discharged from a sulfur-containing marine diesel engine, including the following steps:
s1, filling the high specific surface area hydrophilic filler into the washing tower, arranging an excitation light source above the high specific surface area hydrophilic filler, and spraying seawater from the upper part of the washing tower to the inside of the washing tower after the seawater is subjected to electrocatalysis reaction.
Specifically, the washing tower is internally provided with a loaded hydrophilic photocatalyst g-C3N4-TiO2-Al2O3-BiVO4The high specific surface area hydrophilic regular packing has a specific surface area of 2500m2/m30.4m of hydrophilic regular packing3The bulk density of the hydrophilic packing with high specific surface area is 320-650 kg/m3The void ratio is 70-90%, the F factor is 1.5-3.5, the wave pitch is 10-55 mm, and the tooth form angle is 30-80; a plasma lamp is arranged above the hydrophilic filler with the high specific surface area, the plasma lamp comprises 5 ultraviolet lamp tubes, the power of the ultraviolet lamp tubes is 300W, the 5 ultraviolet lamp tubes are started through a magnetic ballast, and an excitation light source is emitted through the ultraviolet lamp tubes; pumping fresh seawater into the photocatalytic reactor via seawater pump, arranging photocatalytic reaction plate with g-C anode in the reactor3N4-TiO2-RuO2The cathode of the electro-catalytic DSA anode of/Ti is a titanium plate, hastelloy or hard carbon electrode, and the process conditions of the electro-catalytic reaction are as follows: current density: 500-3000A/m 2, temperature: 15-35 ℃, voltage: 0-90V; in the embodiment, the marine diesel engine adopts a 4R32E model diesel engine manufactured by TIN blue, the power is 1620kW, the stroke number is 4, the fuel type is HFO, the sulfur content is 3.5%, and the total flue gas amount is 3876m3/h,SO2The concentration is 2420mg/m3
And S2, injecting the flue gas into the lower part of the washing tower, and carrying out countercurrent contact on the flue gas, the seawater and the hydrophilic filler with high specific surface area in the washing tower to carry out desulfurization reaction so as to obtain the waste seawater and the clean flue gas.
Specifically, flue gas discharged by the diesel engine is injected into the washing tower through the lower part of the washing tower, the flue gas is in countercurrent contact with seawater, hydrophilic filler with high specific surface area and an excitation light source in the washing tower to carry out desulfurization reaction, and photocatalyst g-C on the surface of the filler3N4-TiO2-Al2O3-BiVO4After being excited by the plasma ultraviolet lamp tube with the magnet, a large amount of oxidizing substances such as superoxide radicals, hydroxyl radicals, hydrogen peroxide and the like are generated on the surface of the photocatalyst, SO that SO in the flue gas2Fast oxidation to SO3Obtaining waste seawater and clean flue gas; the waste seawater is also used for cooling the flue gas, and the temperature of the flue gas is adjusted by adjusting the volume of the waste seawater, in this embodiment, the temperature of the flue gas at the lower part of the washing tower is 80 ℃, and the temperature of the flue gas in the washing tower, which is in contact with the hydrophilic filler with the high specific surface area, is 60 ℃.
And S3, discharging the waste seawater through the bottom of the washing tower, and discharging the clean flue gas through the top of the washing tower.
Specifically, the desulfurized acidic wastewater seawater does not contain unstable sulfite, but all contains stable sulfate radicals, the desulfurized acidic wastewater seawater can be discharged back to the ocean after reaching the standard without aeration treatment, and the desulfurized clean flue gas is discharged from the top of the washing tower.
The temperature of the seawater entering the tower is 15-30 ℃, and the spraying amount of the seawater is 7m respectively3/h、9m3/h、11m3/h、13m3H and 15m3H, respectively corresponding to liquid-gas ratios of 1.8L/Nm3, 2.3L/Nm3, 2.8L/Nm3, 3.4L/Nm3 and 3.8L/Nm3, and testing the photoelectric catalysis of the removal of SO from the flue gas of the marine diesel engine with seawater2The reaction results of (A) are shown in Table 1.
TABLE 1 high specific surface area hydrophilic regular catalytic packing photoelectrocatalysis for removing SO from seawater2Removal rate of
Figure BDA0002957631360000071
Therefore, when the liquid-gas ratio is 3.4L/Nm3, the electro-catalysis seawater desulfurization rate of the high-specific-surface-area hydrophilic regular catalytic packing can reach 99%, 66% of spraying water amount is saved compared with the traditional packing liquid-gas ratio of 10L/Nm3, and the power, the equipment weight and the floor area of the seawater pump are effectively reduced.
Example 2
The rest is the same as example 1, except that: the fixed seawater spraying amount is 11m3The corresponding liquid-gas ratio is 3.4L/Nm3, the fixed current density is 1000A/m2 for protecting and prolonging the service life of the electro-catalytic reaction plate, and the pressure drop of the bed layer of the washing tower and the SO removal of the flue gas of the photoelectrocatalysis seawater marine diesel engine are tested by changing the operating temperature of the seawater washing tower2The reaction results of (A) are shown in Table 2.
TABLE 2 scrubbing tower pressure drop and photoelectrocatalytic SO removal from seawater2Removal rate of
Experimental number Temperature (. degree.C.) Scrubber pressure drop (Pa) SO2Removal Rate (%)
1 30 200 99
2 40 200 99
3 50 210 99
4 60 220 99
5 70 198 99
Therefore, within the temperature range of 30-70 ℃, the electro-catalysis seawater desulfurization rate of the high-specific-surface-area hydrophilic regular catalytic packing can reach 99% at different temperatures, and the desulfurization effect is obvious. Meanwhile, the pressure drop of the bed layer of the washing tower is low and is only about 200Pa, and the flue gas discharged from the ship flue gas chimney cannot be influenced.
Example 3
The rest is the same as the example 2, except that: after 90 days of continuous operation, the desulfurization effect and the washing of the electrocatalytic reaction plate were tested. After the operation for 90 days, the electro-catalytic reaction plate has slight scaling and the desulfurization activity is reduced, the desulfurized acidic waste seawater is introduced into the electro-catalytic reactor through a three-way valve, the acidic seawater is flushed for 30 minutes at the linear speed of 1.2m/s, and the removal of SO from the flue gas of the ship diesel engine of the photoelectrocatalysis seawater is tested2The relationship between the reaction result and the lifetime of (1) is shown in Table 3.
TABLE 3 photoelectrocatalysis of flue gas from marine diesel engine with seawater to remove SO2Reaction result and lifetime relationship of
Experimental number Run time (sky) Acid seawater cleaning time (minute) SO2Removal Rate (%)
1 90 0 98
2 90 30 99
3 120 0 98
4 120 30 99
5 150 30 99
Therefore, after the electro-catalytic seawater scrubber operates for a period of time (90 days), the desulfurization rate is slightly reduced due to the fact that seawater contains a large amount of calcium and magnesium ions and microorganisms, scale is easy to deposit and the like, but the desulfurization rate is recovered as before after the power supply is turned off and the desulfurized acidic seawater (pH is less than or equal to 2.5) is cleaned for 30 minutes.
Referring to fig. 2, a schematic structural diagram of a marine flue gas electro-catalytic seawater desulfurization system according to an embodiment of the present application, for convenience of description, only the relevant parts of the present embodiment are shown, and the details are as follows:
the second aspect of the embodiment of the application provides a boats and ships flue gas electro-catalysis sea water desulfurization system, including scrubbing tower 1, the inside of scrubbing tower 1 is equipped with the hydrophilic filler 2 of high specific surface area, the hydrophilic filler 2's of high specific surface area top is equipped with plasma lamp 11, the lower part of scrubbing tower 1 is equipped with flue gas entry 3, the top of scrubbing tower is equipped with exhanst gas outlet 4, the upper portion of scrubbing tower is equipped with sea water spray set 5, the outside of scrubbing tower 1 is equipped with electro-catalytic reactor 10, electro-catalytic reactor 10 is connected with sea water spray set 5, the bottom of scrubbing tower 1 is equipped with sea water outlet 6.
Specifically, the washing tower 1 is a rectangular tower or a circular tower, which can be determined according to the ship east requirement and the ship installation space, in this embodiment, the washing tower 1 is a rectangular tower, the length × width × height is 800 × 400 × 6000, the washing tower 1 is made of "explosion welding titanium composite material", the outer plate surface of the washing tower 1 is made of carbon steel, the manufacturing cost of the washing tower can be effectively reduced, the inner plate surface of the washing tower 1 is made of titanium, the seawater corrosion can be effectively prevented, and both the inner plate surface and the outer plate surface of the washing tower 1 can be made of titanium.
The plasma lamp 10 comprises 5 ultraviolet lamp tubes, the power of the ultraviolet lamp tubes is 300W, the 5 ultraviolet lamp tubes are started through a magnetic ballast, an excitation light source is emitted through the ultraviolet lamp tubes, a seawater spraying device 5 is connected with an electro-catalytic reactor 10, the electro-catalytic reactor 10 is connected with a seawater pump 8 through a seawater pipeline 7, the seawater pump 8 is arranged in the ocean 9, the seawater pump 8 pumps the seawater in the ocean 9 into the electro-catalytic reactor 10 through the seawater pipeline 7, the seawater is sprayed into the washing tower 1 through the seawater spraying device 5, the flue gas discharged by a sulfur-containing ship diesel engine enters the lower part of the washing tower 1 through a flue gas inlet 3, the flue gas is in countercurrent contact with the seawater and the hydrophilic filler 2 with high specific surface area in the washing tower 1 for desulfurization reaction, the acidic waste seawater after desulfurization is discharged into the ocean 9 through a seawater outlet 6, the seawater outlet 6 is also connected with the electro-catalytic reactor 10 through a three-way valve, part of the waste seawater drained by the three-way valve regularly cleans an electro-catalytic reaction plate in the electro-catalytic reactor 10, and the cleaned waste seawater is discharged into the sea; the waste seawater is also used for cooling the flue gas, the temperature of the flue gas is adjusted by adjusting the volume of the waste seawater, and the desulfurized clean flue gas is discharged through a flue gas outlet 4 at the top of the washing tower 1.
In conclusion, the invention provides a process and a system for marine flue gas electro-catalysis seawater desulfurization, which adopts the specific surface area as high as 2500m2/m3The hydrophilic regular catalytic filler has the characteristics of fast mass transfer, good wettability, catalytic oxidation activity, small pressure drop, large flux, seawater corrosion resistance, long service life, small operation liquid and gas and the like; the surface of the high-specific-surface-area hydrophilic catalytic structured packing is coated with g-C3N4-TiO2-Al2O3-BiVO4Under the action of ion lamp, the photocatalyst compound can produce great amount of oxidizing matter, such as superoxide radical, hydroxyl radical, hydrogen peroxide, etc. on the surface to make SO in fume2Fast oxidation to SO3And stable sulfate radicals are formed in the desulfurized seawater in the washing tower, so that the high desulfurization efficiency of the flue gas of the marine diesel engine with high sulfur content is achieved, hydrogen peroxide, hydroxyl radicals, hypochlorite and other strong oxidizing materials are generated on the surface of an electrode by combining electrocatalysis reaction before fresh seawater enters the washing tower, the desulfurized acidic seawater does not contain unstable sulfite radicals but is completely stable sulfate radicals, and the waste desulfurized acidic seawater can reach the standard and be discharged back to the ocean without aeration treatment. Meanwhile, partial water flow can be led out from the acidic seawater, the electrocatalytic reaction electrode plate arranged outside is regularly washed, and the activity of the electrocatalytic reaction electrode plate is recovered after the electrocatalytic reaction caused by seawater sediments is reduced.
Various embodiments are described herein for various devices, circuits, apparatuses, systems, and/or methods. Numerous specific details are set forth in order to provide a thorough understanding of the overall structure, function, manufacture, and use of the embodiments as described in the specification and illustrated in the accompanying drawings. However, it will be understood by those skilled in the art that the embodiments may be practiced without such specific details. In other instances, well-known operations, components and elements have been described in detail so as not to obscure the embodiments in the description. It will be appreciated by those of ordinary skill in the art that the embodiments herein and shown are non-limiting examples, and thus, it can be appreciated that the specific structural and functional details disclosed herein may be representative and do not necessarily limit the scope of the embodiments.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present application, and not for limiting the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; such modifications and substitutions do not substantially depart from the spirit and scope of the embodiments of the present application and are intended to be included within the scope of the present application.

Claims (10)

1. A ship flue gas photoelectrocatalysis seawater desulfurization process is used for carrying out desulfurization treatment on flue gas discharged by a sulfur-containing ship diesel engine, and is characterized by comprising the following steps:
s1, filling a high specific surface area hydrophilic filler into the washing tower, arranging an excitation light source above the high specific surface area hydrophilic filler, and spraying seawater from the upper part of the washing tower to the inside of the washing tower after the seawater is subjected to electrocatalysis reaction;
s2, injecting flue gas into the lower part of the washing tower, wherein the flue gas is in countercurrent contact with the seawater, the hydrophilic filler with the high specific surface area and the excitation light source in the washing tower to perform a desulfurization reaction, so that waste seawater and clean flue gas are obtained;
s3, discharging the waste seawater through the bottom of the washing tower, and discharging the clean flue gas through the top of the washing tower.
2. The marine flue gas photoelectrocatalysis seawater desulfurization process of claim 1, wherein the effluent seawater in the S2 is also used for cooling the flue gas, and the temperature of the flue gas is adjusted by adjusting the volume of the effluent seawater.
3. The marine flue gas photoelectrocatalytic seawater desulfurization process as set forth in claim 2, wherein the flue gas temperature at the lower portion of the scrubber is 80 ℃, and the flue gas temperature in contact with the high specific surface area hydrophilic filler in the scrubber is 60 ℃.
4. The marine flue gas photoelectrocatalytic seawater desulfurization process as claimed in claim 1, wherein the surface of the high specific surface area hydrophilic filler is coated with a photocatalyst composite g-C3N4-TiO2-Al2O3-BiVO4Specific surface area of 2500m2/m3Bulk density of 320-650 kg/m3The void ratio is 70-90%, the F factor is 1.5-3.5, the wave pitch is 10-55 mm, and the tooth form angle is 30-80.
5. The marine flue gas photoelectrocatalysis seawater desulfurization process according to claim 1, wherein the electrocatalysis reaction is realized by adopting an electrocatalysis reactor, and the anode of the electrocatalysis reactor contains g-C3N4-TiO2-RuO2The cathode of the/Ti electrocatalytic DSA anode is a titanium plate, hastelloy or hard carbon electrode, and the process conditions of the electrocatalytic reaction are as follows: current density: 500-3000A/m 2, temperature: 15-35 ℃, voltage: 0-90V.
6. The utility model provides a boats and ships flue gas photoelectrocatalysis sea water desulfurization system, includes the scrubbing tower, its characterized in that, the inside of scrubbing tower is equipped with the hydrophilic filler of high specific surface area, the hydrophilic filler top of high specific surface area is equipped with the plasma lamp, the lower part of scrubbing tower is equipped with the flue gas entry, the top of scrubbing tower is equipped with the exhanst gas outlet, the upper portion of scrubbing tower is equipped with sea water spray set, the outside of scrubbing tower is equipped with the electro-catalytic reactor, the electro-catalytic reactor with sea water spray set connects, the bottom of scrubbing tower is equipped with the sea water export.
7. The marine flue gas photoelectrocatalysis seawater desulfurization system of claim 6, wherein the plasma lamp comprises 5 ultraviolet lamp tubes, and 5 ultraviolet lamp tubes are started by a magnetic ballast.
8. The marine flue gas photoelectrocatalysis seawater desulfurization system of claim 6, wherein the electrocatalysis reactor is connected with a seawater pump through a seawater pipeline, and the seawater pump is arranged in the sea.
9. The marine flue gas photoelectrocatalysis seawater desulfurization system of claim 6, wherein the seawater outlet is connected with the electrocatalysis reactor through a three-way valve.
10. The marine flue gas photoelectrocatalysis seawater desulfurization system of claim 6, wherein the outer plate surface of the scrubbing tower is made of carbon steel, and the inner plate surface of the scrubbing tower is made of titanium.
CN202110228108.6A 2021-03-02 2021-03-02 Ship flue gas photoelectrocatalysis seawater desulfurization process and system Pending CN112933883A (en)

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Application publication date: 20210611