CN104998543A - Ship exhaust gas treatment method and device - Google Patents

Ship exhaust gas treatment method and device Download PDF

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Publication number
CN104998543A
CN104998543A CN201510369761.9A CN201510369761A CN104998543A CN 104998543 A CN104998543 A CN 104998543A CN 201510369761 A CN201510369761 A CN 201510369761A CN 104998543 A CN104998543 A CN 104998543A
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cabinet
waste gas
gas
zeolite
unit
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CN201510369761.9A
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Chinese (zh)
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CN104998543B (en
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刘炳言
杨晓丹
刘伟勋
刘晓翠
曹学磊
曹学良
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青岛海德威科技有限公司
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    • 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
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The invention discloses a ship exhaust gas treatment method and device. The method comprises dust removal by filtration, mixing with methane gas, zeolite-based nitrogen removal and desulphurization, elution, and monitoring and feedback. Methane is used as reduction gas. Through combination of the above steps, ship exhaust gas satisfies discharge standards. The invention also discloses the ship exhaust gas treatment device. The device comprises a control case, a dust collector, a gas mixing cabinet, a methane storage cabinet, a zeolite reaction unit, a heating device, an elution unit, an on-line monitoring unit and a residue recovery tank. The dust collector is connected to the residue recovery tank. The gas mixing cabinet is connected to the zeolite reaction unit. The zeolite reaction unit and the heating unit are arranged in the same cabinet. The zeolite reaction unit is connected to the elution unit. The device has a compact structure, can be operated flexibly, has high catalysis efficiency, has a low cost and can prevent harmful gas diffusion.

Description

A kind of waste gas processing method peculiar to vessel and device thereof

Technical field

The present invention relates to environmental technology field, particularly relate to a kind of waste gas processing method peculiar to vessel and device thereof.

Background technology

The discharge of the harmful substance in marine exhaust is the main source causing atmosphere pollution, and along with the increase increasingly of environmental protection problem importance, the discharge reducing nuisance becomes marine exhaust important development direction in the world today.Therefore, the pollution that marine exhaust brings more and more is subject to the attention of international community, and the MARPOL supplemental provisions V I " preventing boats and ships from causing air pollution rule " that International Maritime Organization (IMO) formulates comes into force on January 1st, 2000.The limitation standard Tier III of more strict NOx discharge capacity also will be formally effective in 2021.The discharge of nitrogen oxide and oxysulfide is subject to more and more stricter control.The current technology for power plant, chemical plant exhaust-gas treatment achieves and is constantly in progress.Desulfur technology mainly comprises: wet desulphurization, dry desulfurization and semi-dry desulphurization; Denitration technology mainly comprises: selective catalytic reduction (SCR) and SNCR method (SNCR).Wherein, selective catalytic reduction (SCR), as a kind of effective technology, is widely used at fixed pollution sources such as boiler, incinerator and power plants.

Due to marine exhaust self, more ripe land waste gas treatment equipment is at present made not directly apply to boats and ships.Be mainly manifested in that boats and ships flue gas scale is less, temperature is low, exhaust fluctuation be large, in flue gas containing the feature such as unburnt oil and carbon black, specific requirement is proposed to treatment facility.Treatment facility must compact, take up space little, lightweight, reactant be easy to store, the power consumption electricity consumption value for the treatment of facility is all low.Above feature makes the process of boats and ships flue gas directly cannot apply the desulphurization denitration technology and equipment of boiler of power plant, one of this professional difficult problem just becoming fume treatment.

The zeolite molecular sieve catalyst developed for selective catalytic reduction (SCR) has showed excellent activity in desulphurization denitration aspect at the same time, finds Cu from Iwamoto in 1986 etc. 2+since the effective catalytic decomposition NO of crossover zeolite molecular sieve catalyst Cu/ZSM-5 energy, the structure, preparation, catalytic mechanism, modification etc. of Chinese scholars to ZSM-5 catalyst have carried out large quantity research.Zeolite molecular sieve catalyst generally can apply CH4 that traditional NH3 adopts as reducing agent, this patent as reducibility gas, and the catalytic activity that CH4 possesses is high, effectively prevent ammonium salt corrosion equipment that NH3 causes as reducing agent and causes catalyst poisoning.Further, CH4 is as the main component of natural gas, and cost is low, rich reserves, is easy to obtain.Zeolite molecular sieve possesses that silica alumina ratio excursion is wide, specific area is large, degree of crystallinity and total acid content is high, hydrothermal stability and absolute acid stability is strong, the life-span longly adds its advantage such as superior shape selective catalysis effect and lower knot carbon amounts, at present, both at home and abroad the research of zeolite molecular sieve desulphurization denitration is also being carried out in a deep going way, comprising the exploitation etc. of the exploitation of various high effective zeolite molecular sieve, the research of desulfurization removing nitric mechanism and low-temperature catalyzed zeolite.Zeolite molecular sieve, as the efficient new catalytic material of one, shows good effect in exhuast gas desulfurization denitration, and being expected to becomes a kind of important catalyst for treating waste gas.

Summary of the invention

The present invention is intended to solve the problem, and provides a kind of emission-control equipment peculiar to vessel.

A kind of waste gas processing method peculiar to vessel, comprises the steps:

1) dust removal by filtration: waste gas peculiar to vessel is led in dust arrester the solid suspended particle removed in waste gas, and collect residue to Slag recovering groove;

2) gas and vapor permeation: the gas after filtering is passed in the methane storing cabinet containing less than 1% methane, waste gas is fully mixed with methane;

3) zeolite nitrogen and desulfurization is adopted: by being passed in the reaction cabinet of Zeolite catalytic materials with the well-mixed waste gas of methane, carrying out desulfurization, denitrogenation, denitration process at a certain temperature, reacting as follows:

a) 2NO=N2+O2

b) 2NO+O 2=2NO 2

c) 2SO 2+O 2=2SO 3

d) CH 4+2O 2=CO 2+2H 2O

e) CH 4+2NO 2=N 2+CO 2+2H 2O;

4) wash-out: adopt spray mode again to carry out waste gas absorption wash-out, removing SO 3with part CO 2, cool high-temperature flue gas simultaneously, complete waste gas purification, reaction principle is as follows:

a) SO 3+OH =H ++ SO 4 2—

b) CO 2+OH =HCO 3

c) HCO 3 = H ++ CO 3 2—

5) monitoring feedback: the air purified is passed into monitoring means, and result is presented on control cabinet by monitoring means, and when reaching the discharge standard of waste gas, according to the related request of IMO, toxic emission should reach SO 2(ppm)/CO 2(%v/v) less than 21.7, according to Tier III ,emission control district (ECAs) intrinsic motivation rotating speed lower than the ship NOx emission of 130rpm lower than the ship NOx emission of 3.4g/KWh, 130rpm-2000rpm lower than 9*n (-0.2)g/KWh, is greater than the ship NOx emission of 2000rpm lower than 2.0 g/KWh), it is punctual that the result detected when detecting unit reaches above row's subscript; Control cabinet will open air bleeding valve combustion gas automatically, if standard not up to standard circular treatment waste gas again.

Further, solid particle residue in described step (1), unification ashore processes.

Further, in described step (3), artificial zeolite can be one or more in ZSM-5 type, beta type, A type, X-type, Y type, mordenite molecular sieve, and on zeolite, load has one or more in Cu, Ni, Mn, Co, Fe, Ce, Cr, Zn, Ga, Mo, Ru, Rh, Pd, Ag, In, Sn, Re, Ir and Pt.

Further, in described step (3), uniform temperature is between 300 DEG C ~ 600 DEG C.

Further, what the middle eluting liquid of described step (4) adopted is natural sea-water.

A kind of emission-control equipment peculiar to vessel, it is characterized in that, comprise: dust arrester, gas and vapor permeation cabinet, methane storing cabinet, zeolite reaction member, heater, wash-out unit, on-line monitoring unit, control cabinet and air bleeding valve, described methane storing cabinet, zeolite reaction member, heater, wash-out unit, on-line monitoring unit are all placed in control cabinet, and dust arrester is connected with Slag recovering groove; Gas and vapor permeation cabinet is connected by gas pipeline with zeolite reaction member; Zeolite reaction member is connected with wash-out unit, and zeolite reaction member and heater are in same cabinet, and described heater can be electric heating tube or the common electric heater unit of electrical heating wire; Described wash-out unit is sprayed sea water wash-out.

Further, described control cabinet can be the one in PLC, DSP, ARM, single-chip microcomputer.

Further, control cabinet, according to the feedback of monitoring means monitoring result, regulates the intake of methane in methane cabinet, and whether the heating-up temperature of heater, wash-out unit spray amount and exhaust emission valve are opened, and below standardly carries out after-treatment.

The invention has the beneficial effects as follows:

The advantages such as this equipment has that operation is flexible, and catalytic efficiency is high, compact conformation, prevents the diffusion of pernicious gas, and environmental protection, cost are low.The present invention adopts methane fully to mix with the gas after dust removal by filtration first, methane is made to become the reducing agent of lower reaction together, mixed gas is again through zeolite reaction member, catalytic reaction is carried out at the temperature be applicable to, then natural sea-water is adopted to carry out wash-out, finally also carry out through wasted nickel catalyst, qualified discharge, not up to standardly again to process.Denitration rate of the present invention is stabilized in 98%, and desulfurization degree is stabilized in more than 95%, finally realizes the discharge standard that combustion gas reaches IMO and national regulation.

Accompanying drawing explanation

Below in conjunction with accompanying drawing, the present invention is described in further detail.

Fig. 1 is principle of the present invention and process chart

In figure: 1-control cabinet; 2-dust arrester; 3-gas and vapor permeation cabinet; 4-methane storing cabinet; 5-zeolite reaction member; 6-heater; 7-wash-out unit; 8-monitoring means; 9-Slag recovering groove; A-stube cable; B-exhaust gas entrance pipeline; C-controlled valve; D-liquid inlet; E-liquid outlet; F-gas vent; G-connection cable; Residue after H-filters.

Detailed description of the invention

Embodiment 1

As shown in Figure 1, marine exhaust processing method in the present invention, its course of work is: waste gas enters dust arrester by exhaust gas entrance, in dust arrester, solid suspended particle is removed and enters Slag recovering groove, after after dedusting, waste gas then fully mixes with the methane in methane storing cabinet in gas and vapor permeation cabinet, in methane cabinet, the preferred value of methane content is 0.2%--0.5%, the gas of mixing enters zeolite reaction member, device for simultaneous heating heats zeolite reaction member, reaction temperature is heated to 300 ~ 400 DEG C, under zeolite catalysis, nitrogen oxide and sulfur dioxide are converted removal, exhaust gas products after conversion enters wash-out unit, SO in waste gas 3with part CO 2again by Absorption by Sea Water, waste gas peculiar to vessel is purified.Waste gas after purification enters monitoring means and carries out on-line monitoring.Monitoring result is presented at control cabinet by on-line monitoring unit, and control cabinet opens air bleeding valve automatically, toxic emission up to standard.

Embodiment 2

Waste gas enters dust arrester by exhaust gas entrance, removes the solid suspended particle in waste gas in dust arrester, and the particle screened out directly is discharged in Slag recovering groove.After dedusting, waste gas enters gas and vapor permeation cabinet and methane blended.

In described zeolite reaction member, ZSM-5 artificial zeolite molecular sieve, loaded Cu, Ni on this zeolite, at the temperature of 530 DEG C, containing NO, the SO2 of 0.15%, the O2 of 0.25% of 0.2% in simulated exhaust, in methane storing cabinet, pass into the CH4 of 0.35%, can simultaneous SO_2 and NO removal.Through wasted nickel catalyst, denitration rate is stabilized in 98%, and desulfurization degree is stabilized in more than 95%.Key reaction principle is:

2NO=N 2+O 2

2NO+O 2=2NO 2

2SO 2+O 2=2SO 3

CH 4+2O 2=CO 2+2H 2O

CH 4+2NO 2=N 2+CO 2+2H 2O

In described wash-out unit, main component is natural sea-water, adopts spray mode to absorb exhaust-gas treatment product, produces a small amount of acid solution.Cool high-temperature flue gas, key reaction principle is simultaneously:

SO 3+OH =H ++ SO 4 2—

CO 2+OH =HCO 3

HCO 3 = H ++ CO 3 2—

Described Slag recovering groove, Main Function is the solid particle residue in collecting dust-removing device, is unified in and processes on the bank.

Other embodiments are the same.

Above-mentioned explanation is not limitation of the present invention, and the present invention is also not limited in above-mentioned citing, and the change that those skilled in the art make in essential scope of the present invention, remodeling, interpolation or replacement also should belong to protection scope of the present invention.

Claims (8)

1. a waste gas processing method peculiar to vessel, comprises the steps:
(1) dust removal by filtration: waste gas peculiar to vessel is led in dust arrester the solid suspended particle removed in waste gas, and collect residue to Slag recovering groove;
(2) gas and vapor permeation: the gas after filtering is passed in the methane storing cabinet containing less than 1% methane, waste gas is fully mixed with methane;
(3) zeolite nitrogen and desulfurization is adopted: by being passed in the reaction cabinet of Zeolite catalytic materials with the well-mixed waste gas of methane, carrying out desulfurization, denitrogenation, denitration process at a certain temperature, reacting as follows:
2NO=N 2+O 2
2NO+O 2=2NO 2
2SO 2+O 2=2SO 3
CH 4+2O 2=CO 2+2H 2O
CH 4+2NO 2=N 2+CO 2+2H 2O;
(4) wash-out: adopt spray mode again to carry out waste gas absorption wash-out, removing SO 3with part CO 2, cool high-temperature flue gas simultaneously, complete waste gas purification, reaction principle is as follows:
SO 3+OH =H ++ SO 4 2—
CO 2+OH =HCO 3
HCO 3 = H ++ CO 3 2—
(5) monitoring feedback: the air purified is passed into monitoring means, and result is presented on control cabinet by monitoring means, and when reaching the discharge standard of waste gas, control cabinet will open air bleeding valve combustion gas automatically, if standard not up to standard circular treatment waste gas again.
2. a kind of waste gas processing method peculiar to vessel according to claim 1, is characterized in that, solid particle residue in described step (1), unifiedly ashore processes.
3. a kind of waste gas processing method peculiar to vessel according to claim 1, it is characterized in that, in described step (3), artificial zeolite can be one or more in ZSM-5 type, beta type, A type, X-type, Y type, mordenite molecular sieve, and on zeolite, load has one or more in Cu, Ni, Mn, Co, Fe, Ce, Cr, Zn, Ga, Mo, Ru, Rh, Pd, Ag, In, Sn, Re, Ir and Pt.
4. a kind of waste gas processing method peculiar to vessel according to claim 1, is characterized in that, in described step (3), uniform temperature is between 300 DEG C ~ 600 DEG C.
5. a kind of waste gas processing method peculiar to vessel according to claim 1, is characterized in that, what in described step (4), eluting liquid adopted is natural sea-water.
6. an emission-control equipment peculiar to vessel, it is characterized in that, comprise: dust arrester, gas and vapor permeation cabinet, methane storing cabinet, zeolite reaction member, heater, wash-out unit, on-line monitoring unit, control cabinet and air bleeding valve, described methane storing cabinet, zeolite reaction member, heater, wash-out unit, on-line monitoring unit are all placed in control cabinet, and dust arrester is connected with Slag recovering groove; Gas and vapor permeation cabinet is connected by gas pipeline with zeolite reaction member; Zeolite reaction member is connected with wash-out unit, and zeolite reaction member and heater are in same cabinet, and described heater can be electric heating tube or the common electric heater unit of electrical heating wire; Described wash-out unit is sprayed sea water wash-out.
7. a kind of emission-control equipment peculiar to vessel according to claim 5, it is characterized in that, described control cabinet can be the one in PLC, DSP, ARM, single-chip microcomputer.
8. a kind of emission-control equipment peculiar to vessel according to claim 5, it is characterized in that, control cabinet is according to the feedback of monitoring means monitoring result, regulate the intake of methane in methane cabinet, whether the heating-up temperature of heater, wash-out unit spray amount and exhaust emission valve are opened, and below standardly carry out after-treatment.
CN201510369761.9A 2015-06-30 2015-06-30 A kind of waste gas processing method peculiar to vessel and its device CN104998543B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106196013A (en) * 2016-07-30 2016-12-07 史默迪 Use the pluralities of fuel high-temperature gasification boiler of reducing process denitration
CN106914272A (en) * 2017-03-08 2017-07-04 湖南云平环保科技有限公司 Desulphurization denitration catalyst of CuMnCePt/ZSM 5 and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006026525A (en) * 2004-07-15 2006-02-02 Babcock Hitachi Kk Exhaust gas treatment system
CN201940168U (en) * 2011-02-17 2011-08-24 大连海事大学 Marine desulfurization system using magnesium-based seawater method
CN102364068A (en) * 2011-06-28 2012-02-29 顾忠华 Tail gas exhausting and processing system for ship
CN102989466A (en) * 2012-12-27 2013-03-27 北京石油化工学院 Flue gas desulfurization and denitrification catalyst for reduction method and applications of catalyst
CN103480272A (en) * 2013-10-01 2014-01-01 王脯胜 Dust-removing, denitration and desulfurization process and device for flue gas of glass kiln
CN204816228U (en) * 2015-06-30 2015-12-02 青岛海德威科技有限公司 Marine exhaust treatment device

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006026525A (en) * 2004-07-15 2006-02-02 Babcock Hitachi Kk Exhaust gas treatment system
CN201940168U (en) * 2011-02-17 2011-08-24 大连海事大学 Marine desulfurization system using magnesium-based seawater method
CN102364068A (en) * 2011-06-28 2012-02-29 顾忠华 Tail gas exhausting and processing system for ship
CN102989466A (en) * 2012-12-27 2013-03-27 北京石油化工学院 Flue gas desulfurization and denitrification catalyst for reduction method and applications of catalyst
CN103480272A (en) * 2013-10-01 2014-01-01 王脯胜 Dust-removing, denitration and desulfurization process and device for flue gas of glass kiln
CN204816228U (en) * 2015-06-30 2015-12-02 青岛海德威科技有限公司 Marine exhaust treatment device

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106196013A (en) * 2016-07-30 2016-12-07 史默迪 Use the pluralities of fuel high-temperature gasification boiler of reducing process denitration
CN106914272A (en) * 2017-03-08 2017-07-04 湖南云平环保科技有限公司 Desulphurization denitration catalyst of CuMnCePt/ZSM 5 and preparation method thereof

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Address after: 266100 No.32 Keyuan Jingliu Road, Laoshan District, Qingdao, Shandong Province

Patentee after: Heideway Technology Group (Qingdao) Co., Ltd.

Address before: 266000, 4 floor, building 177, 5 Zhuzhou Road, Laoshan District, Shandong, Qingdao

Patentee before: Qingdao Headway Technology Co., Ltd.