CN107486016B - Low-temperature desulfurization and denitrification technology applicable to high-sulfur fuel oil for marine low-speed diesel engine - Google Patents
Low-temperature desulfurization and denitrification technology applicable to high-sulfur fuel oil for marine low-speed diesel engine Download PDFInfo
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- CN107486016B CN107486016B CN201710722266.0A CN201710722266A CN107486016B CN 107486016 B CN107486016 B CN 107486016B CN 201710722266 A CN201710722266 A CN 201710722266A CN 107486016 B CN107486016 B CN 107486016B
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
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- B01D53/34—Chemical or biological purification of waste gases
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Abstract
The invention provides a low-temperature desulfurization and denitrification technology suitable for a marine low-speed diesel engine of high-sulfur fuel oil, which comprises a diesel engine host, an SCR system, a SOx oxidizer, an organic Rankine cycle system, a low-temperature sulfuric acid treatment device, a steam power generation set, a condenser, a pump and the like; the rear part of the diesel engine is sequentially connected with an exhaust box, an evaporation mixer, an SCR reactor and a turbocharger, the rear part of the turbocharger is connected with an SOx oxidizer and a waste gas boiler, then waste gas flows through an organic working medium Rankine cycle to heat an organic working medium in a heat exchanger, and low-temperature waste heat in the waste gas is utilized for power generation; finally, a low-temperature sulfuric acid treatment device is connected to treat sulfuric acid generated in the waste gas, and the aim of low-temperature waste gas desulfurization and denitrification is fulfilled; and the organic Rankine cycle system is simultaneously connected with the compressor and used for cooling the gas compressed by the compressor.
Description
Technical Field
The invention relates to the field of low-temperature desulfurization and denitration of a low-speed diesel engine for a high-sulfur fuel oil ship, in particular to a low-temperature desulfurization and denitration technology suitable for the low-speed diesel engine for the high-sulfur fuel oil ship.
Technical Field
At present, ships become main air pollution sources in coastal and coastal areas of China. According to the data of the monitoring center of the national environmental protection department, 58.8 million tons of sulfur dioxide are discharged by ships berthing at ports of China in 2013, which accounts for about 8.4 percent of the total national discharge amount, 27.8 million tons of nitrogen oxide discharge amount of the ships at the ports and accounts for about 11.3 percent of the total national discharge amount. According to the convention of MARPOL 73/78 issued by IMO (International maritime organization), the emission requirement of ships in an emission control area from 1/2016 reaches the Tier III emission standard, and the emission of harmful components in ship exhaust gas is strictly limited, so that the development of ship atmospheric pollution control technology is urgent.
The desulfurization method of the exhaust gas of the marine diesel engine can be divided into two methods, namely using low-sulfur fuel oil and installing an exhaust gas post-washing desulfurization post-treatment device, and the methods are verified in a real ship. The existing waste gas washing and desulfurizing device mainly adopts alkaline working media (seawater, sodium alkali, magnesium alkali and the like) to wash and treat waste gas so as to meet the emission control requirements of relevant SOx specified by IMO (inertial measurement of chemical oxygen demand), but the existing waste gas washing and desulfurizing device has the practical problems of large volume, high energy consumption, large water consumption and the like. In contrast, the adoption of low-sulfur fuel oil is more convenient, can meet the requirement of workers on the sulfur content of the ship fuel oil, is the most direct and effective choice for reducing SOx emission, can directly reduce SOx emission by reducing the sulfur content, and has small change on ships. However, data show that the sulfur content of the fuel oil used by ships is 2.5-3% at present, the desulfurization cost of the fuel oil is very high, the cost of the low-sulfur oil is high, and the low-sulfur fuel oil used by the existing engine has the problems of low viscosity, poor lubricity, easy abrasion and the like, so that the engine is damaged to a certain extent, and the low-sulfur fuel oil can generate a large amount of carbon dioxide in the refining process to aggravate the global greenhouse effect.
The main fuel consumed directly by ship is diesel engine, auxiliary engine and auxiliary boiler. The diesel engine host consumes the most energy, only a part of all heat generated by fuel combustion is converted into mechanical work to be output, and the rest heat is not utilized. If the waste gas of the main engine can be efficiently utilized to generate electricity or be used as an auxiliary heat source to provide steam, the effects of energy conservation and emission reduction can be achieved at the same time.
Organic Rankine Cycle (ORC) is a Rankine Cycle using low-boiling point Organic matter as a working medium, has the advantages of simple structure, high efficiency, environmental friendliness, strong load adaptability and the like, is suitable for low-temperature waste heat sources with the temperature higher than 70 ℃, and is widely applied to medium and low temperature waste heat utilization. The temperature of the outlet of the turbocharger of the diesel engine is about 200 ℃, ORC can effectively utilize waste gas waste heat to drive the steam turbine to do work and drive the generator to generate electricity, and further low-grade energy of the diesel engine is recovered, so that certain waste heat can be recovered while emission is effectively reduced, and the utilization rate of energy is improved.
In the patent document 'an integrated marine diesel engine exhaust treatment device' with chinese patent application number 201621012703.7, an integrated marine diesel engine exhaust treatment device is proposed, and the integrated structural design is adopted, and with all equipment settings in the box, structural design is ingenious, and the area that significantly reduces saves occupation of land space, but the design is comparatively complicated, needs higher technology.
In the patent document 'a ship low-speed diesel engine tail gas aftertreatment composite device' with chinese patent application number 201620400596.9, it is proposed to locate the SCR system at the rear side of the turbocharger, and simultaneously, high-temperature tail gas at the inlet of the bypass turbine is used to raise the temperature of the tail gas before the reactor, and the reflux tail gas is used for afterburning and heating to remove the deposits in the reactor. The scheme adopts bypass high-temperature tail gas under medium and high working conditions, so that the oil consumption of the diesel engine is increased, and the economy is not suitable for ships.
In the patent document 'marine desulfurization circulating spray system based on sodium-alkali method' with Chinese patent application number 201520214247.3, the marine desulfurization circulating spray system based on the sodium-alkali method is provided, but the sodium-alkali method requires a large amount of alkali liquor, consumes a large amount of water, requires a large space, and has great requirements for ship space.
Disclosure of Invention
The invention aims to provide a low-temperature desulfurization and denitrification technology suitable for a low-speed diesel engine for a ship using high-sulfur fuel oil, which can simultaneously realize low emission of NOx and SOx of a low-speed two-stroke diesel engine for the ship on the basis of effectively utilizing the exhaust waste heat energy of the diesel engine.
In order to realize the purpose of the invention, the following technical scheme is implemented:
the invention comprises the following steps: two-stroke diesel engines, high-pressure SCR systems, SOx oxidizers, exhaust gas boilers, sulfuric acid treatment devices, organic rankine cycle systems, and the like. The method is characterized in that:
a low-temperature desulfurization and denitrification technology suitable for a marine low-speed diesel engine of high-sulfur fuel oil specifically comprises the following steps:
(1) waste gas generated by a diesel engine host firstly passes through an exhaust box and then enters a mixing evaporator and an SCR reactor for denitration treatment, and the reacted waste gas is discharged by a turbine;
(2) the exhaust gas discharged from the turbine enters an SOx oxidizer and acts as a catalystSO in the exhaust gas2And O2Reacting at 200-300 ℃ to generate SO3；
(3) The waste gas boiler utilizes the low-temperature waste heat in the exhaust to heat the boiler to supply water and generate steam to work, and part of waste gas energy is recovered; waste gas from a waste gas boiler enters an organic Rankine cycle, exchanges heat with an organic working medium in a heat exchanger, heats the organic working medium to generate gas steam with certain pressure and temperature, and the steam enters a steam turbine power generation set to push a turbine to rotate and drive a power generation device to generate power at low temperature;
(4) finally, the waste enters a low-temperature sulfuric acid treatment device arranged at the tail end of an exhaust system, an alkaline working medium atomizing device in the system sprays a small amount of NaOH into the low-temperature sulfuric acid treatment device, and SO in the waste gas is neutralized3Sulfuric acid generated with water is captured by the demister, and residual liquid is discharged out of the system and stored in the storage tank.
The method is characterized in that: the system adopts a high-pressure SCR arrangement mode, namely, the waste gas exhausted by a cylinder before the SCR reactor is arranged in the turbocharger enters the SCR reactor for denitration treatment and then enters the turbocharger.
The method is characterized in that the step (2) specifically comprises the following steps:
the housing of the SOx oxidizer is made of stainless steel, catalysts are stacked on steel grate plates of each layer in a segmented manner, and iron wire nets are arranged on the grate plates to prevent the catalysts from leaking; the catalyst is a vanadium-based catalyst, and the specific chemical reaction is as follows:
the method is characterized in that the step (3) specifically comprises the following steps: the heat exchanger is made of ceramics.
The method is characterized in that the step (3) specifically comprises the following steps: in the organic Rankine cycle, the waste gas of the organic working medium which does work is condensed and cooled by a condenser, and then is pumped into an intercooler by a pump set to exchange heat with the gas compressed by the compressor.
The method is characterized in that the step (4) specifically comprises the following steps: the chemical reaction in the low-temperature sulfuric acid treatment device is specifically as follows:
SO3+H2O→H2SO4；
H2SO4+2NaOH→Na2SO4+2H2O；
H2SO4+NaOH→NaHSO4+H2O。
the invention has the beneficial effects that: according to the invention, the SCR reactor is arranged in front of the turbocharger, so that the inlet temperature of the reactor is increased, and NOx in the exhaust gas can be efficiently removed; SO is oxidized by a SOx oxidizer under the action of a vanadium-based catalyst2Oxidation to SO3(ii) a The organic Rankine cycle reduces the temperature of the waste gas to be below an acid dew point, and meanwhile, the low-temperature waste heat in the part is utilized for power generation, so that the aim of saving energy is fulfilled; a small amount of NaOH solution is sprayed in the sulfuric acid treatment device to treat sulfuric acid generated in the waste gas, so that NOx and SOx emission in the waste gas is reduced, heat in the waste gas is recovered to the maximum extent, and the energy utilization rate of the system is improved.
Drawings
Fig. 1 is a schematic diagram of a low-temperature desulfurization and denitrification technology of a marine low-speed diesel engine suitable for high-sulfur fuel oil.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Because the exhaust gas temperature of the low-speed engine is lower, the requirement on the inlet temperature of the SCR reactor cannot be met, and the inlet temperature of the turbine is 50-175 ℃ higher than the outlet temperature, the SCR reactor is arranged in front of the turbocharger, namely, the high-pressure SCR arrangement mode is adopted, and the exhaust gas discharged by the cylinder enters the SCR reactor to be subjected to denitration treatment and then enters the turbocharger.
Under the condition of high-sulfur fuel oil, sulfur in the fuel oil is combusted to generate a large amount of SO2Part of SO in the exhaust gas at a temperature of 200-560 DEG C2Will be further oxidized into SO3。
Next, an SOx oxidizer is installed at the outlet of the turbocharger, and the exhaust gas temperature is controlled at 200-300 deg.C with a vanadium-based catalystAbout DEG C) of the waste gas2Conversion to SO3Further more SO is formed3And (4) steam. And the waste gas flows through the waste gas boiler to heat the boiler feed water again to form steam which does work externally and then enters the organic Rankine cycle. The temperature of the waste gas is reduced to be lower than the acid dew point, and the organic Rankine cycle can effectively utilize the medium-low temperature waste heat to generate power. Finally, a low-temperature sulfuric acid treatment device is arranged at the tail end of the exhaust system of the main engine, a small amount of NaOH solution and SO in the waste gas are sprayed into the device3Reacting with sulfuric acid generated by water, capturing by a demister, treating the sulfuric acid, and discharging residual liquid out of the system.
In the drawings, since the exhaust gas temperature of the low-speed engine is low, the SCR reactor is placed before the turbocharger, first, the exhaust gas generated by the diesel engine 1 firstly passes through the exhaust box 2 and then enters the mixing evaporator 3 and the SCR reactor 4 to be denitrated, and the reacted exhaust gas is discharged from the turbine 5.
Secondly, the exhaust gas discharged from the turbine 5 enters an SOx oxidizer 7, the housing of the SOx oxidizer is made of stainless steel, catalysts are stacked on grate plates made of steel in each layer in a segmented mode, and iron wires are arranged on the grate plates to prevent the catalysts from leaking. SO in the exhaust gas under the action of a vanadium-based catalyst2And O2Reacting at 200-300 ℃ to generate SO3And reduces SOx emission.
SOxCatalytic oxidation in an oxidizer:
and thirdly, the exhaust gas boiler 8 utilizes the middle-low temperature waste heat of the exhaust gas to heat the boiler feed water to generate steam for doing work, and part of the exhaust gas energy is recovered.
Then, the waste gas from the waste gas boiler 8 enters an organic Rankine cycle, exchanges heat with the organic working medium in a heat exchanger 9, heats the organic working medium to generate gas steam with certain pressure and temperature, and the steam enters a steam turbine power generation set 12 to push a turbine to rotate and drive a power generation device to generate power at low temperature.
The acid dew point temperature of the waste gas is related to the sulfur content and is about 115-140 ℃, the organic Rankine cycle reduces the temperature of the waste gas to about 90-120 ℃ below the acid dew point, the waste heat of the waste gas is fully utilized for power generation, and meanwhile, a ceramic heat exchanger is selected for preventing the waste gas from corroding the heat exchanger 9.
Finally, the tail end of the exhaust system is provided with a low-temperature sulfuric acid treatment device 10, an alkaline working medium atomization device is arranged in the system, a small amount of NaOH is sprayed into the system, and SO in the waste gas is neutralized3Sulfuric acid generated with water is captured by the demister, and residual liquid is discharged out of the system and stored in the storage tank.
Chemical reactions involved in the sulfuric acid treatment plant:
formation of sulfuric acid
SO3+H2O→H2SO4
Reaction of sulfuric acid with NaOH:
H2SO4+2NaOH→Na2SO4+2H2O
H2SO4+NaOH→NaHSO4+H2O
in the organic Rankine cycle, after the waste gas of the organic working medium which does work is condensed and cooled by the condenser 13, the waste gas is pumped into the intercooler 15 by the pump unit 14 to exchange heat with the gas compressed by the gas compressor 6, so that the temperature of the inlet gas entering the scavenging box 16 is reduced, the air inlet amount of the cylinder is increased, and the combustion performance of the diesel engine is improved.
Claims (1)
1. A low-temperature desulfurization and denitrification method applicable to a marine low-speed diesel engine of high-sulfur fuel oil specifically comprises the following steps:
(1) waste gas generated by a diesel engine host firstly passes through an exhaust box and then enters a mixing evaporator and an SCR reactor for denitration treatment, and the reacted waste gas is discharged by a turbine;
(2) the exhaust gas discharged from the turbine enters an SOx oxidizer, and SO in the exhaust gas is generated under the action of a catalyst2And O2Reacting at 200-300 ℃ to generate SO3；
(3) The waste gas boiler utilizes the low-temperature waste heat in the exhaust to heat the boiler water supply to generate steam for doing work and recycling a part of waste gas energy; waste gas from a waste gas boiler enters an organic Rankine cycle, exchanges heat with an organic working medium in a heat exchanger, heats the organic working medium to generate gas steam with certain pressure and temperature, and the gas steam enters a steam turbine power generation set to push a turbine to rotate and drive a power generation device to generate power at low temperature;
(4) finally, the waste gas enters a low-temperature sulfuric acid treatment device arranged at the tail end of an exhaust system, an alkaline working medium atomizing device in the system sprays a small amount of NaOH into the low-temperature sulfuric acid treatment device, and SO in the waste gas is neutralized3Sulfuric acid generated by water is captured by a demister, and residual liquid is discharged out of the system and stored in a storage tank;
the step (2) specifically comprises the following steps:
the housing of the SOx oxidizer is made of stainless steel, catalysts are stacked on steel grate plates of each layer in a segmented manner, and iron wire nets are arranged on the grate plates to prevent the catalysts from leaking; the catalyst is a vanadium-based catalyst, and the specific chemical reaction is as follows:
the step (3) specifically comprises the following steps: the heat exchanger is made of ceramics;
in the organic Rankine cycle, after the waste gas of the organic working medium which does work is condensed and cooled by a condenser, the waste gas is pumped into an intercooler by a pump set and exchanges heat with the gas compressed by a gas compressor;
the step (4) specifically comprises the following steps: the chemical reaction in the low-temperature sulfuric acid treatment device is specifically as follows:
SO3+H2O→H2SO4；
H2SO4+2NaOH→Na2SO4+2H2O；
H2SO4+NaOH→NaHSO4+H2O。
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| CN102600903B (en) * | 2012-02-28 | 2015-07-01 | 中国科学院过程工程研究所 | Vanadium-based liquid-phase catalyst and preparation method thereof |
| CN102628412A (en) * | 2012-04-20 | 2012-08-08 | 江苏科技大学 | Waste heat power generation system of marine diesel engine based on organic Rankine cycle |
| CN104265427A (en) * | 2014-08-07 | 2015-01-07 | 哈尔滨工程大学 | Medium speed diesel engine waste gas desulfurization and waste heat recovery combined cycle system for ship |
| CN105797553A (en) * | 2016-05-06 | 2016-07-27 | 哈尔滨工程大学 | Desulfurization and denitration combined treatment device of tail gas of marine diesel engine |
| CN107035477B (en) * | 2017-05-12 | 2020-01-17 | 哈尔滨工程大学 | Medium-load and low-load energy recovery device and method for low-speed diesel engine matched with high-pressure SCR system |
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