CN107486016A - A kind of low-temp desulfurization denitration technology of marine low speed diesel engine suitable for high-sulfur fuel oil - Google Patents

A kind of low-temp desulfurization denitration technology of marine low speed diesel engine suitable for high-sulfur fuel oil Download PDF

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CN107486016A
CN107486016A CN201710722266.0A CN201710722266A CN107486016A CN 107486016 A CN107486016 A CN 107486016A CN 201710722266 A CN201710722266 A CN 201710722266A CN 107486016 A CN107486016 A CN 107486016A
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waste gas
diesel engine
low
fuel oil
sulfur
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CN107486016B (en
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冯永明
骆素爽
朱元清
周松
胡祖康
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Harbin Engineering University
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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
    • B01D53/34Chemical 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
    • B01D53/9404Removing only nitrogen compounds
    • B01D53/9409Nitrogen oxides
    • B01D53/9431Processes characterised by a specific device
    • 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
    • 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2259/00Type of treatment
    • B01D2259/45Gas separation or purification devices adapted for specific applications
    • B01D2259/4566Gas separation or purification devices adapted for specific applications for use in transportation means
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00Road transport of goods or passengers
    • Y02T10/10Internal combustion engine [ICE] based vehicles
    • Y02T10/12Improving ICE efficiencies

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Exhaust Gas After Treatment (AREA)
  • Engine Equipment That Uses Special Cycles (AREA)

Abstract

The present invention proposes a kind of low-temp desulfurization denitration technology of marine low speed diesel engine suitable for high-sulfur fuel oil, including diesel engine, SCR system, SOx oxidators, organic rankine cycle system, Sulfur-Vapor of Lower Temperature acid treatment device, steam-electric power group, condenser, pump etc.;Fumer, evaporation mixer, SCR reactors and turbocharger are sequentially connected after diesel engine, SOx oxidators and exhaust boiler are connected after turbocharger, then waste gas flows through organic rankie cycle, the organic working medium in heating heat exchanger, is generated electricity using its middle-low temperature heat;Sulfur-Vapor of Lower Temperature acid treatment device is finally connected, handles the sulfuric acid generated in waste gas, while reach the purpose of low temperature waste gas desulphurization denitration;Organic rankine cycle system is connected with compressor simultaneously, the gas after cooling compressor compression.

Description

A kind of low-temp desulfurization denitration technology of marine low speed diesel engine suitable for high-sulfur fuel oil
Technical field
The present invention relates to the marine low speed diesel engine low-temp desulfurization denitration field of high-sulfur fuel oil, and in particular to one kind is applied to The low-temp desulfurization denitration technology of the marine low speed diesel engine of high-sulfur fuel oil.
Technical background
At present, ship turns into China coast, the along the river regional main source of atmospheric pollution.Supervised according to national environmental protection portion The data at control center, the ship in Chinese Port berthing in 2013 discharge 58.8 ten thousand tons of sulfur dioxide altogether, and it is total to account for whole nation discharge The 8.4% of amount, 27.8 ten thousand tons of yard craft nitrogen oxide emission, accounts for the 11.3% of national total emission volumn.International Maritime group Knit IMO promulgations《MARPOL 73/78》Pact, the ship emission request from 1 day January in 2016 in emission control area reach To the discharge standards of Tier III, strict limitation is carried out to harmful components discharge in marine exhaust, therefore carry out ship atmosphere pollution Control technology is extremely urgent.
The sulfur method of boat diesel engine waste gas can be divided into be located after washing desulphurization using after Low Sulfur Fuel Oil and installation waste gas Two kinds of device is managed, and is obtained for real ship checking.Existing waste gas washing desulphurization device mainly uses alkaline working medium (seawater, sodium Alkali and magnesium alkali etc.) carrying out washing treatment is carried out to waste gas, so as to reach the emission control requirement of related SOx as defined in IMO, but desulfurization The actual sex chromosome mosaicisms such as volume big, high energy consumption, water consumption be big be present in device.Comparatively, it is more convenient using Low Sulfur Fuel Oil, can be with Meet requirement of the work to marine fuel oil sulfur content, be to reduce the most directly effective selection of SOx discharges, sulfur content, which reduces, directly to be subtracted Few SOx discharge, ship is changed smaller.But the data shows that fuel oil sulfur content used in global ship mostly exists at present Between 2.5%~3%, the very high low-sulfur oil cost of desulfurization expense of fuel oil is high, while available engine is existed using Low Sulfur Fuel Oil Viscosity is too low, poor lubricity, the problems such as easily wearing, have certain infringement to engine, and Low Sulfur Fuel Oil is in refining process Substantial amounts of carbon dioxide can be produced, aggravates Global Greenhouse Effect.
Mainly diesel main engine, subsidiary engine and donkey boiler etc. of fuel are directly consumed on ship.Wherein, diesel engine disappears Energy consumption is most, fuel oil burn in sent net quantity of heat only some be changed into mechanical work and externally export, its excess heat Without utilizing.If efficiently can be generated electricity using main frame waste gas or provide steam as auxiliary thermal source, can reach simultaneously Energy-conservation and the effect of emission reduction.
Organic Rankine bottoming cycle (Organic Rankine Cycle, abbreviation ORC) is using low-boiling-point organic compound as the bright of working medium Agree circulation, have the advantages that simple in construction, efficiency high, environment-friendly and load performance are strong, be higher than 70 DEG C suitable for temperature Low temperature exhaust heat source above, therefore be widely applied in middle-low temperature heat utilization.And the turbocharger of diesel engine goes out Mouth temperature is about 200 DEG C, and ORC can effectively utilize waste gas residual heat pushing turbine work done, drives electrical power generators, and then return The low-grade energy of diesel engine is received, while ensure that effectively reduction discharge, certain waste heat can be also reclaimed, improve the energy Utilization rate.
" a kind of integrated form marine diesel emission-control equipment " that Chinese Patent Application No. is 201621012703.7 is special In sharp file, it is proposed that a kind of integrated form marine diesel emission-control equipment, designed using integrated structure, by all devices Be arranged in casing, smart structural design, greatly reduce floor space, save space, but design it is complex, it is necessary to Compared with high technology.
" the compound dress of a kind of marine low speed diesel engine vent gas post processing that Chinese Patent Application No. is 201620400596.9 Put " in patent document, propose SCR system being located on rear side of turbocharger, while using the high temperature tail of bypassed turbine porch Gas, exhaust temperature before reactor is raised, using backflow tail gas afterburning heating, to remove the deposit in reactor.The program exists Bypass high-temperature tail gas will be used under middle high operating mode, so as to increase engine fuel consumption, economy is not suitable for ship.
" the desulphurization circulating spray system peculiar to vessel based on sodium alkali " that Chinese Patent Application No. is 201520214247.3 is special In sharp file, it is proposed that the desulphurization circulating spray system peculiar to vessel based on sodium alkali, but the alkali lye amount required for sodium alkali is larger, Water consumption is greatly, it is necessary to which, there is larger requirement in larger space to ship space.
The content of the invention
It is an object of the invention to provide a kind of low-temp desulfurization denitration of the marine low speed diesel engine suitable for high-sulfur fuel oil Technology, on the basis of diesel engine exhaust waste heat energy is sent out in effective utilization, while realize the NOx of Marine Low-Speed Two-Stroke Diesel Engines With SOx low emission.
In order to realize the purpose of the present invention, following technical scheme is carried out:
The present invention includes:Two stroke diesel engine, high pressure SCR system, SOx oxidators, exhaust boiler, sulfuric acid treatment device, Organic rankine cycle system etc..It is characterized in that it is:
A kind of low-temp desulfurization denitration technology of one marine low speed diesel engine suitable for high-sulfur fuel oil, specifically includes following step Suddenly:
(1) waste gas caused by diesel engine enters mixing evaporator after first passing through fumer and SCR reactors are taken off Nitre processing, reacted waste gas are discharged by turbine;
(2) SOx oxidators, in the presence of catalyst, the SO in waste gas are entered from the waste gas of turbine discharge2With O2200 Reaction generation SO at~300 DEG C3
(3) exhaust boiler produces vapor to work done, recovery using the low temperature exhaust heat heating boiler feed water in exhaust A part of exhaust energy;The waste gas come out from exhaust boiler enters organic Rankine bottoming cycle, is carried out in heat exchanger with organic working medium Heat exchange, gas vapor of the heating organic working medium generation with certain pressure and temperature, steam enter steam turbine generation group, pushed away Dynamic turbine rotates, and drives TRT to carry out low-temperature electricity-generating;
(4) finally, the Sulfur-Vapor of Lower Temperature acid treatment device entered installed in gas extraction system end, the alkaline work of internal system are discarded Matter atomising device sprays a small amount of NaOH thereto, neutralizes SO in waste gas3With water generation sulfuric acid, it is residual after demister is caught Extraction raffinate body discharge system is stored in storage bin.
It is characterized in that:System uses high pressure SCR arrangements, i.e., SCR reactors is placed in into gas before turbocharger After the waste gas of cylinder discharge enters SCR reactors progress denitration process, turbocharger is entered back into.
Characterized in that, described step (2) specifically includes:
SOx oxidator housings are made of stainless steel, and catalyst segments are deposited on the grate plate of each layer steel, in grate plate It is upper to install wire netting to avoid catalyst from leaking down;Used catalyst is catalytic component based on vanadium, and specific chemical reaction is:
Characterized in that, described step (3) specifically includes:Described heat exchanger material is ceramics.
Characterized in that, described step (3) specifically includes:In described organic Rankine bottoming cycle, made organic work of work( Matter waste gas squeezes into charge air cooler, the gas after being compressed with compressor carries out heat exchange after condenser condensation cooling by pump group.
Characterized in that, described step (4) specifically includes:The chemical reaction occurred in Sulfur-Vapor of Lower Temperature acid treatment device is specific For:
SO3+H2O→H2SO4
H2SO4+2NaOH→Na2SO4+2H2O;
H2SO4+NaOH→NaHSO4+H2O。
The beneficial effects of the present invention are:Before SCR reactors are placed in turbocharger by the present invention, reactor is improved Inlet temperature, the NOx that can efficiently go in removing exhaust gas;Using SOx oxidators, by SO in the presence of catalytic component based on vanadium2 It is oxidized to SO3;EGT is reduced under acid dew point by organic Rankine bottoming cycle, while is sent out using this part middle-low temperature heat Electricity, the purpose of energy-conservation is reached;By spraying a small amount of NaOH solution in sulfuric acid treatment device, the sulphur generated in waste gas is handled Acid, so as to both reduce NOx and SOx discharges in waste gas, and the farthest heat in recovery waste gas, improve the energy of system Measure utilization rate.
Brief description of the drawings
Fig. 1 is a kind of schematic diagram of marine low speed diesel engine low-temp desulfurization denitration technology suitable for high-sulfur fuel oil.
Embodiment
The present invention will be described in further detail below in conjunction with the accompanying drawings.
Because low speed machine EGT is relatively low, it is impossible to meet SCR reactor inlet temperature requirements, and turbine-entry temperature ratio Outlet temperature is high 50~175 DEG C, therefore before SCR reactors are placed in into turbocharger, i.e. high pressure SCR arrangements, inblock cylinder After the waste gas gone out enters SCR reactors progress denitration process, turbocharger is entered back into.
Under the conditions of high-sulfur fuel oil, the combustion of sulfur in fuel oil generates substantial amounts of SO2, when 200~560 DEG C of temperature, in waste gas In part SO2SO can be further oxidized to3
Secondly, exported in turbocharger and SOx oxidators are set, in (200 DEG C~300 DEG C of catalytic component based on vanadium, EGT Left and right) under the conditions of by SO in waste gas2It is converted into SO3, and then form more SO3Steam.Waste gas flows through exhaust boiler heating again Boiler feedwater enters organic Rankine bottoming cycle after forming the external work done of steam.EGT is reduced to below acid dew point, organic Rankine Circulation effectively can be generated electricity using this part middle-low temperature heat.Finally, low temperature sulfuric acid is installed in main exhaust system end Processing unit, a small amount of NaOH solution is sprayed to device inside, with SO in waste gas3Reacted with the sulfuric acid of water generation, through demisting After device is caught, sulfuric acid is handled, by residual liquid discharge system.
In Figure of description, because low speed machine EGT is relatively low, therefore by SCR reactors be placed in turbocharger it Before, first, waste gas caused by diesel engine 1 enters mixing evaporator 3 after first passing through fumer 2 and SCR reactors 4 are taken off Nitre processing, reacted waste gas are discharged by turbine 5.
Secondly, the waste gas discharged from turbine 5 enters SOx oxidators 7, and SOx oxidator housings are made of stainless steel, catalyst Segmentation is deposited on the grate plate of each layer steel, and wire netting is installed on grate plate to avoid catalyst from leaking down.It is catalyzed in vanadium base In the presence of agent, the SO in waste gas2With O2The reaction generation SO at 200~300 DEG C3, reduce SOx discharges.
SOxCatalysis oxidation in oxidator:
Again, exhaust boiler 8 produces vapor to work done, recovery using the middle-low temperature heat heating boiler feed water of exhaust A part of exhaust energy.
Then, the waste gas come out from exhaust boiler 8 enters organic Rankine bottoming cycle, is carried out in heat exchanger 9 with organic working medium Heat exchange, gas vapor of the heating organic working medium generation with certain pressure and temperature, steam enter steam turbine generation group 12, Promote turbine to rotate, drive TRT to carry out low-temperature electricity-generating.
Waste gas acid dew-point temperature is relevant with sulfur content, and about between 115~140 DEG C, organic Rankine bottoming cycle is by waste gas temperature Degree is reduced under acid dew point 90~120 DEG C or so, abundant to be generated electricity using waste gas residual heat, while to prevent waste gas heat exchanging The corrosion of device 9, Ceramics heat exchanger.
Finally, gas extraction system end is provided with Sulfur-Vapor of Lower Temperature acid treatment device 10, and internal system sets alkaline working medium atomization dress Put, spray a small amount of NaOH thereto, neutralize SO in waste gas3With water generation sulfuric acid, after demister is caught, residual liquid row Go out system deposit storage bin.
The chemical reaction being related in sulfuric acid treatment device:
The generation of sulfuric acid
SO3+H2O→H2SO4
Sulfuric acid reacts with NaOH:
H2SO4+2NaOH→Na2SO4+2H2O
H2SO4+NaOH→NaHSO4+H2O
In organic Rankine bottoming cycle, made the organic working medium waste gas of work(after the condensation cooling of condenser 13, beaten by pump group 14 Enter charge air cooler 15, the gas after being compressed with compressor 6 carries out heat exchange, the intake air temperature of scavenging air box 16 is lowered into, so as to increase Add cylinder intake air quantity, improve the combustibility of diesel engine.

Claims (6)

1. a kind of low-temp desulfurization denitration technology of marine low speed diesel engine suitable for high-sulfur fuel oil, specifically comprises the following steps:
(1) waste gas caused by diesel engine enters mixing evaporator after first passing through fumer and SCR reactors are carried out at denitration Reason, reacted waste gas are discharged by turbine;
(2) SOx oxidators, in the presence of catalyst, the SO in waste gas are entered from the waste gas of turbine discharge2With O2200~ Reaction generation SO at 300 DEG C3
(3) exhaust boiler produces vapor to work done using the low temperature exhaust heat heating boiler feed water in exhaust, reclaims one Divide exhaust energy;The waste gas come out from exhaust boiler enters organic Rankine bottoming cycle, and hot friendship is carried out with organic working medium in heat exchanger Change, gas vapor of the heating organic working medium generation with certain pressure and temperature, steam enters steam turbine generation group, promoted saturating Flat turn is moved, and drives TRT to carry out low-temperature electricity-generating;
(4) finally, the Sulfur-Vapor of Lower Temperature acid treatment device entered installed in gas extraction system end, the alkaline working medium mist of internal system are discarded Makeup is put sprays a small amount of NaOH thereto, neutralizes SO in waste gas3With water generation sulfuric acid, after demister is caught, residual solution Body discharge system is stored in storage bin.
A kind of 2. low-temp desulfurization denitration skill of marine low speed diesel engine suitable for high-sulfur fuel oil according to claim 1 Art, it is characterised in that:System uses high pressure SCR arrangements, i.e., cylinder is discharged before SCR reactors being placed in into turbocharger Waste gas enter SCR reactors carry out denitration process after, enter back into turbocharger.
A kind of 3. low-temp desulfurization denitration skill of marine low speed diesel engine suitable for high-sulfur fuel oil according to claim 1 Art, it is characterised in that described step (2) specifically includes:
SOx oxidator housings are made of stainless steel, and catalyst segments are deposited on the grate plate of each layer steel, are filled on grate plate If wire netting is to avoid catalyst from leaking down;Used catalyst is catalytic component based on vanadium, and specific chemical reaction is:
A kind of 4. low-temp desulfurization denitration skill of marine low speed diesel engine suitable for high-sulfur fuel oil according to claim 1 Art, it is characterised in that described step (3) specifically includes:Described heat exchanger material is ceramics.
A kind of 5. low-temp desulfurization denitration skill of marine low speed diesel engine suitable for high-sulfur fuel oil according to claim 1 Art, it is characterised in that described step (3) specifically includes:In described organic Rankine bottoming cycle, made the organic working medium waste gas of work( After condenser condensation cooling, charge air cooler is squeezed into by pump group, the gas after being compressed with compressor carries out heat exchange.
A kind of 6. low-temp desulfurization denitration skill of marine low speed diesel engine suitable for high-sulfur fuel oil according to claim 1 Art, it is characterised in that described step (4) specifically includes:The chemical reaction of generation is specially in Sulfur-Vapor of Lower Temperature acid treatment device:
SO3+H2O→H2SO4
H2SO4+2NaOH→Na2SO4+2H2O;
H2SO4+NaOH→NaHSO4+H2O。
CN201710722266.0A 2017-08-22 2017-08-22 Low-temperature desulfurization and denitrification technology applicable to high-sulfur fuel oil for marine low-speed diesel engine Active CN107486016B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114686281A (en) * 2022-03-17 2022-07-01 中国华能集团清洁能源技术研究院有限公司 Low-carbon heat recovery and trapping device

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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
CN107035477A (en) * 2017-05-12 2017-08-11 哈尔滨工程大学 In a kind of low-speed diesel engine matching high pressure SCR system, underload energy recycle device and recovery method

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CN102600903A (en) * 2012-02-28 2012-07-25 中国科学院过程工程研究所 Vanadium-based liquid-phase catalyst and preparation method thereof
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CN114686281B (en) * 2022-03-17 2023-06-06 中国华能集团清洁能源技术研究院有限公司 Low-carbon heat recovery trapping device

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