FI127391B - Exhaust aftertreatment system and method for exhaust aftertreatment - Google Patents

Exhaust aftertreatment system and method for exhaust aftertreatment Download PDF

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Publication number
FI127391B
FI127391B FI20155247A FI20155247A FI127391B FI 127391 B FI127391 B FI 127391B FI 20155247 A FI20155247 A FI 20155247A FI 20155247 A FI20155247 A FI 20155247A FI 127391 B FI127391 B FI 127391B
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Finland
Prior art keywords
exhaust
separator
treatment system
exhaust gas
oxidation catalyst
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FI20155247A
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Finnish (fi)
Swedish (sv)
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FI20155247A (en
Inventor
Plamen Toshev
Andreas Döring
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Man Diesel & Turbo Se
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01D53/02—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 by adsorption, e.g. preparative gas chromatography
    • B01D53/06—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 by adsorption, e.g. preparative gas chromatography with moving adsorbents, e.g. rotating beds
    • B01D53/10—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 by adsorption, e.g. preparative gas chromatography with moving adsorbents, e.g. rotating beds with dispersed adsorbents
    • B01D53/12—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 by adsorption, e.g. preparative gas chromatography with moving adsorbents, e.g. rotating beds with dispersed adsorbents according to the "fluidised technique"
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/022—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
    • F01N3/0224—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous the structure being granular
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D24/00—Filters comprising loose filtering material, i.e. filtering material without any binder between the individual particles or fibres thereof
    • B01D24/28—Filters comprising loose filtering material, i.e. filtering material without any binder between the individual particles or fibres thereof with the filter bed moving during the filtration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D24/00—Filters comprising loose filtering material, i.e. filtering material without any binder between the individual particles or fibres thereof
    • B01D24/36—Filters comprising loose filtering material, i.e. filtering material without any binder between the individual particles or fibres thereof with the filter bed fluidised during the filtration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D24/00—Filters comprising loose filtering material, i.e. filtering material without any binder between the individual particles or fibres thereof
    • B01D24/46—Regenerating the filtering material in the filter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01D53/02—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 by adsorption, e.g. preparative gas chromatography
    • B01D53/06—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 by adsorption, e.g. preparative gas chromatography with moving adsorbents, e.g. rotating beds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75—Multi-step processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8609—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01D53/96—Regeneration, reactivation or recycling of reactants
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
    • F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors, e.g. catalysed diesel particulate filters
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2062—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
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    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/30—Physical properties of adsorbents
    • B01D2253/302—Dimensions
    • B01D2253/304—Linear dimensions, e.g. particle shape, diameter
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/507—Sulfur oxides by treating the gases with other liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
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    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/508—Sulfur oxides by treating the gases with solids

Description

Pakokaasunjälkikäsittelyjärjestelmä (2) polttovoimakonetta varten, jossa on alavirtaan polttovoimakoneesta (1) järjestetty pakokaasunpesuri, tai kalsiumpitoisia rakeita sisältävä erotin (4) rikkioksidien kemisorptiota varten, ja alavirtaan polttovoimakoneesta (1) ja ylävirtaan erottimesta (4) järjestetty hapetuskatalysaattori (3) SO2:n hapettamiseksi SO3:ksi.
20155247 prh 29 -03- 2018
Exhaust gas after-treatment system and method for the exhaust gas after-treatment
The invention relates to an exhaust gas after-treatment system. The invention furthermore relates to a method for the exhaust gas after-treatment.
During combustion processes in stationary internal combustion engines, which are employed for example in power plants, and in combustion processes in nonstationary internal combustion engines, which are employed for example on ships, sulphur oxides such as SO2 and SO3 are created, wherein these sulphur oxides are typically formed during the combustion of sulphur-containing fossil fuels, such as coal, pit coal, brown coal, oil or heavy fuel oil. For this reason, such internal combustion engines are assigned exhaust gas after-treatment systems which in particular serve for the desulphurisation of the exhaust gas leaving the internal combustion engine.
For desulphurising the exhaust gas, absorptive methods are primarily known from the prior art, which as absorbent primarily use quicklime (CaO) or lime hydrate (Ca(OH)2) or calcium carbonate (CaCOs). In the process, dust or granulate is formed, wherein for removing the calcium sulphate dust from the exhaust gas filter devices have to be employed downstream of the desulphurisation.
From DE 36 03 365 C2 a method and an exhaust gas after-treatment system for the treatment of exhaust gas containing nitrogen oxides and dust are known
In addition, so-called scrubbers are also employed for desulphurisation, in which SO2 is removed from the exhaust gas with the help of water. The sulphur dioxides contained in the scrubbing water are subsequently neutralised with the help of bases such as for example NaOH. Prior to this neutralisation, oxidation of the scrubbed-out SO2 into SO3 is additionally carried out in most cases, since this promises better separation and allows the use of calcium compounds, which with SO3 form CaSO4 and can thus be precipitated. This is usually achieved by blowing air into the sump (US 4515754 A1).
20155247 prh 29 -03- 2018
Starting out from this, the object of the present invention is based on creating a new type of exhaust gas after-treatment system and a new type of method for the exhaust gas after-treatment.
This object is solved through an exhaust gas after-treatment system according to
Claim 1. The exhaust gas after-treatment system for an internal combustion engine according to the invention comprises a separator having calciumcontaining granulate arranged downstream of an internal combustion engine for the chemisorption of sulphur oxides and an oxidation catalytic converter arranged downstream of the internal combustion engine and upstream of the separator for the oxidation of SO2 into SO3. By using the separator it is possible to omit a filter device for removing calcium sulphate or sodium sulphate dust from the exhaust gas. The sulphur dioxides react with the calcium or sodium or magnesiumcontaining granulate of the separator and can be discharged via the granulate.
The use of the oxidation catalytic converter for oxidation of SO2 into SO3 makes possible a short dwell time of the exhaust gas in the separator since the SO3 react more rapidly with the calcium or sodium or magnesium-containing granulate of the separator than the SO2. The exhaust gas after-treatment system according to the invention makes possible effective desulphurisation of exhaust gas. The exhaust gas after-treatment system comprises a device for introducing NH3-precursor substances (urea) or gaseous NH3 into the exhaust gas, which is arranged downstream of the oxidation catalytic converter. Desulphurisation of the exhaust gas can thereby be further improved.
According to an advantageous further development, the granulate in the separator comprises CaO and/or Ca(OH)2 and/or CaCO3 and/or Na2CO3 and/or MgO, wherein the grain size of the granulate is between 1 mm and 8 mm. Here, the separator is designed in particular as a cross flow separator with moving bed or fluidised bed. This makes possible particularly effective desulphurisation of exhaust gas.
20155247 prh 29 -03- 2018
According to an advantageous further development, a heating device is arranged upstream of the oxidation catalytic converter which heats the exhaust gas to a temperature of more than 350°C, preferably of more than 400°C, particularly preferably of more than 450°C. This makes possible a particularly effective oxidation of SO2 into SO3 and thus effective desulphurisation of exhaust gas.
With an exhaust gas supercharged internal combustion engine, the oxidation catalytic converter is positioned upstream of a turbine of an exhaust gas turbocharger, wherein the separator is positioned downstream of the turbine of the exhaust gas turbocharger. Through the relatively high temperatures and pressures which are present upstream of the turbine the oxidation of SO2 into SO3 in the oxidation catalytic converter is favoured.
The method for the exhaust gas after-treatment according to the invention is defined in Claim 13.
Preferred further developments of the invention are obtained from the subclaims and the following description. Exemplary embodiments of the invention are explained in more detail with the help of the drawing without being restricted to this. There it shows:
Fig. 1: a block diagram of a first exhaust gas after-treatment system according to the invention;
Fig. 2: a block diagram of a second exhaust gas after-treatment system according to the invention;
Fig. 3: a block diagram of a third exhaust gas after-treatment system according to the invention; and
Fig. 4: a block diagram of a fourth exhaust gas after-treatment system according to the invention.
20155247 prh 29 -03- 2018
The present invention relates to an exhaust gas after-treatment system for an internal combustion engine, for example for a stationary internal combustion engine in a power plant or for a non-stationary internal combustion engine employed on a ship. The exhaust gas after-treatment system is employed in particular on a marine diesel engine operated with heavy fuel oil.
Fig. 1 shows a first exemplary embodiment of an exhaust gas after-treatment system 2 located downstream of an internal combustion engine 1, wherein the exhaust gas after-treatment system 2 comprises an oxidation catalytic converter 3 which is arranged downstream of the internal combustion engine 1. In the oxidation catalytic converter 3, SO2 reacts into SO3 according to the following reaction equation
2SO3+O2 2SO2
The following chemical elements are employed as active components in the oxidation catalytic converter 3 for the oxidation of SO2 into SO3: V (vanadium) and/or K (potassium) and/or Na (sodium) and/or Fe (iron) and/or Ce (cer) and/or Cs (ceasium) and/or oxides of these elements.
The component of vanadium (V) amounts to more than 5 %, preferably more than 7 %, particularly preferably to more than 9 %.
As base material, the oxidation catalytic converter 3 utilises T1O2 (titanium oxide) and/or S1O2 (silicon oxide), preferentially stabilised by WO3 (tungsten oxide).
20155247 prh 29 -03- 2018
In addition, the exhaust gas after-treatment system 2 according to the invention comprises a separator 4 arranged downstream of the oxidation catalytic converter 3 comprising calcium or sodium or magnesium-containing granulate, the separator
4 preferentially being a moving bed reactor or fluidised bed reactor.
The calcium or sodium or magnesium-containing granulate preferentially comprises CaO and/or Ca(OH)2 and/or CaCO3 and/or Na2CO2 or NaHCO3, MgO. Here, the sulphur oxides react with the calcium-containing granulate according to the following reaction equations, namely for Ca(OH)2 according to the following reaction equations
Ca(OH)2+SO2 θ CaSOs + H2O Ca(OH)2+SO2+1/2O2 θ CaSO4 + H2O
Ca(OH)2+CO2 θ CaCOs + H2O 15 Ca(OH)2+SO3 θ CaCO4 + H2O and for CaCO3 according to the following reaction equations
CaCO3+SO2 <-> CaSO3 + CO2
CaCO3+SO2+1/2O2 <-> CaSO4 + CO2
CaCO3+SO3 <-> CaSO4 + CO2 and for Na2CO3 and NaHCO3 according to the following reaction equations
NaCO3 <-> Na2SO3+CO2
Na2CO3+SO3 <-> Na2SO4+CO2
2NaHCO3+SO3 <-> Na2SO4+CO2+2H2O and for MgO according to the following reaction equations
MgO+SO2+O2 —> MgSCU MgO+SO3+1/2O2 —>MgSO4
20155247 prh 29 -03- 2018
Here it is significant according to the invention that SO3 reacts more rapidly with the calcium or sodium or magnesium-containing granulate than SO2, which is why the oxidation catalytic converter 3 for the oxidation of SO2 into SO3 is arranged downstream of the internal combustion engine 1 and upstream of the separator 4. Because of this the effectiveness of desulphurisation can be increased.
Preferentially, oxidation of SO2 into SO3 takes place in the oxidation catalytic converter 3 in such a manner that downstream of the oxidation catalytic converter 3 the component of SO3 in all sulphur oxides (SOx) in the exhaust gas amounts to at least 20 %, preferably to more than 40 %, particularly preferably to more than 60 %.
In the separator 4, the sulphur oxides react with the granulate into calcium or sodium or magnesium sulphate, which can be discharged together with the granulate of the separator 4.
The grain size of the granulate in the separator 4 amount to between 1 mm and 8 mm, preferentially to between 4 mm and 8 mm. Because of the relatively large grain size of the granulate the same, in addition, does not react with the sulphur oxides as far as to the centre, but consists in the core at least partially of components that have not yet reacted with sulphur oxide, which are then surrounded by a shell of calcium sulphate.
The separator 4 is preferentially assigned a device in order to separate from the granulate calcium sulphate intercepted in the moving bed or fluidised bed via the granulate, which is discharged from the moving bed reactor or fluidised bed
20155247 prh 29 -03- 2018 reactor together with the granulate. This device can for example be a drum peeler, a drum screen or a mill. The granulate freed of calcium sulphate can subsequently be returned to the separator 4 in order to thus form a granulate circuit and more effectively utilise the granulate.
Fig. 2 shows a version of the invention in which the internal combustion engine 1 is shown as an exhaust gas supercharged internal combustion engine, in which the exhaust gas after-treatment system 2 accordingly comprises a turbine 5 of an exhaust gas turbocharger, in which exhaust gas leaving the internal combustion engine 1 is expanded for extracting mechanical energy. In the case of such an exhaust gas supercharged internal combustion engine, the oxidation catalytic converter 3 is arranged seen in flow direction of the exhaust gas upstream of the turbine 5, wherein the separator 4 is arranged downstream of the turbine 6. The high pressures and temperatures in the exhaust gas flow which are present upstream of the turbine 5 favour the oxidation of SO2 into SO3 in the oxidation catalytic converter 3.
A further exemplary embodiment of an exhaust gas after-treatment system 2 according to the invention for an internal combustion engine is shown by Fig. 3, wherein the exhaust gas after-treatment system 2 of Fig. 3 just like the exhaust gas after-treatment system 2 of Fig. 1 comprises the oxidation catalytic converter 3 and the separator 4. In addition, the exhaust gas after-treatment system 2 of Fig.
comprises a heating device 6 arranged upstream of the oxidation catalytic converter 3, which heats the exhaust gas upstream of the oxidation catalytic converter 3 to a temperature of more than 350°C, preferably of more than 400°C, particularly preferably of more than 450°C. This favours the oxidation of SO2 into SO3 in the oxidation catalytic converter 3.
A further exemplary embodiment of an exhaust gas after-treatment system 2 according to the invention for an internal combustion engine is shown by Fig. 4, wherein the exhaust gas after-treatment system 2 of Fig. 4 just like the exhaust
20155247 prh 29 -03- 2018 gas after-treatment system 2 of Fig. 2 comprises the oxidation catalytic converter 3, the turbine 5, the separator 4 and additionally a device 7 for introducing gaseous NH3 into the exhaust gas, wherein this device 7 for introducing the gaseous NH3 into the exhaust gas is arranged downstream of the oxidation catalytic converter 3, so that accordingly NH3 is introduced into the exhaust gas of the internal combustion engine 1 downstream of the oxidation catalytic converter
3. In the process it can be provided to introduce the NH3 into the exhaust gas flow either directly in gaseous form or to inject an NFb-precursor substance such as for example urea into the exhaust gas flow and evaporate the same in the exhaust gas flow into NH3. Introducing gaseous NH3 into the exhaust gas flow downstream of the oxidation catalytic converter 3 has the advantage that the subsequent desulphurisation can thereby be improved because of this.
With the exhaust gas after-treatment systems 2 shown in Fig. 1 to 4 a multi-stage separator 4 preferentially designed as moving bed reactor or fluidised bed reactor can be employed in order to improve the separation of calcium or sodium or magnesium sulphate, wherein in particular when a multi-stage separator 4 is used, granulate of different grain size is used in the individual stages of the separator 4.
Preferentially, a separator 4 designed as a cross flow separator is utilised.
The exhaust gas after-treatment system 1 according to the invention allows effective desulphurisation of exhaust gas by way of the method for the exhaust gas after-treatment according to the invention. For desulphurising exhaust gas with the help of the exhaust gas after-treatment system 2 according to the invention, exhaust gas leaving the internal combustion engine is initially conducted via an oxidation catalytic converter 3 in order to make possible oxidation of SO2 into SO3. Following this, the exhaust gas is conducted via a separator 4 comprising calcium-containing granulate. As described, desulphurisation of the exhaust gas can be improved by introducing NH3 into the exhaust gas. Oxidation of SO2 into SO3 can be improved by providing or utilising a high exhaust gas temperature. Reference is made to the explanations regarding Fig. 1 to 4.
In addition to the use of granulate the separation with the help of exhaust gas 5 scrubbers is also expedient, which are arranged downstream of a catalytic converter for the SO2-oxidation. Because of this, the separation rate in the exhaust gas scrubber on the one hand is increased since SO3 is significantly better soluble in water than SO2, as a result of which either the separation performance can be improved and/or the scrubber reduced in size. In addition, blowing air into the sump for the oxidation of SO2, as described in US 4515754 A1 can be omitted.
20155247 prh 29 -03- 2018
List of reference numbers
Internal combustion engine
Exhaust gas after-treatment system
3 Oxidation catalytic converter
Separator
Turbine
Heating device
Device

Claims (14)

PatenttivaatimuksetThe claims 20155247 prh 29 -03- 201820155247 prh 29 -03- 2018 1. Pakokaasunjälkikäsittelyjärjestelmä (2) polttovoimakonetta varten, jossa on alavirtaan polttovoimakoneesta (1) järjestetty pakokaasunpesuri, taiAn exhaust after-treatment system (2) for a combustion engine having an exhaust scrubber provided downstream of the combustion engine (1), or 5 kalsium- ja/tai natrium- ja/tai magnesiumpitoisia rakeita sisältävä erotin (4) rikkioksidien kemisorptiota varten, ja alavirtaan polttovoimakoneesta (1) ja ylävirtaan erottimesta (4) järjestetty hapetuskatalysaattori (3) SChm hapettamiseksi SO3:ksi, tunnettu laitteesta (7) kaasumaisen NH3:n tuomiseksi pakokaasuvirtaan, joka laite on järjestetty ylävirtaan hapetuskatalysaattorista (5).Separator (4) for calcium and / or sodium and / or magnesium containing granules for chemisorption of sulfur oxides, and an oxidation catalyst (3) arranged downstream of the combustion engine (1) and upstream of the separator (4) for oxidizing SChm to SO3, known from the device (7) for introducing gaseous NH3 into the exhaust stream arranged upstream of the oxidation catalyst (5). 2. Patenttivaatimuksen 1 mukainen pakokaasunjälkikäsittelyjärjestelmä, tunnettu siitä, että rakeet erottimessa (4) käsittävät CaO:a ja/tai Ca(OH)2:a ja/tai CaCCKa ja/tai Na2COExhaust after-treatment system according to claim 1, characterized in that the granules in the separator (4) comprise CaO and / or Ca (OH) 2 and / or CaCCK and / or Na2CO 3:a ja/tai NaHCO3:a.3 and / or NaHCO3. 15 3. Patenttivaatimuksen 1 tai 2 mukainen pakokaasunjälkikäsittelyjärjestelmä, tunnettu siitä, että rakeiden raekoko on välillä 1 - 8 mm.Exhaust after-treatment system according to claim 1 or 2, characterized in that the granules have a grain size of between 1 and 8 mm. 4. Jonkin patenttivaatimuksen 1 - 3 mukainen pakokaasunjälkikäsittelyjärjestelmä, tunnettu siitä, että erotin (4) on muodostettu liikkuvakerros20 reaktorina tai fluidikerrosreaktorina.Exhaust after-treatment system according to one of claims 1 to 3, characterized in that the separator (4) is formed as a moving bed 20 reactor or a fluid bed reactor. 5. Jonkin patenttivaatimuksen 1 - 4 mukainen pakokaasunjälkikäsittelyjärjestelmä, tunnettu siitä, että erotin (4) on muodostettu poikkivirtauserottimena.Exhaust after-treatment system according to one of claims 1 to 4, characterized in that the separator (4) is formed as a cross-flow separator. 6. Jonkin patenttivaatimuksen 1 - 5 mukainen pakokaasunjälkikäsittelyjärjestelmä, tunnettu siitä, että erotin (4) on muodostettu useampiportaisena, jolloin rakeiden raekoot poikkeavat erottimen (4) yksittäisissä portaissa.Exhaust after-treatment system according to one of claims 1 to 5, characterized in that the separator (4) is formed in several steps, whereby the grain size of the granules differs in the individual steps of the separator (4). 3030 7. Jonkin patenttivaatimuksen 1 - 6 mukainen pakokaasunjälkikäsittelyjärjestelmä, tunnettu siitä, että hapetuskatalysaattori (3) käsittää aktiivikomponenttina SChm hapettamisessa SCKksi vanadiumia ja/tai kaliumia ja/tai natriumia ja/tai rautaa ja/tai ceriumia ja/tai cesiumia ja/tai näiden elementtien oksideja, jolloin hapetuskatalysaattori käyttää perusmateriaalina titaanioksidiaExhaust aftertreatment system according to one of claims 1 to 6, characterized in that the oxidation catalyst (3) comprises vanadium and / or potassium and / or sodium and / or iron and / or cerium and / or cesium and / or oxides of these elements as the active component in oxidizing SChm to SCK. , wherein the oxidation catalyst uses titanium oxide as the base material 35 ja/tai piioksidia edullisesti volframioksidilla stabiloituna.And / or silica, preferably stabilized with tungsten oxide. 8. Jonkin patenttivaatimuksen 1 - 7 mukainen pakokaasunjälkikäsittelyjärjestelmä, tunnettu siitä, että hapetuskatalysaattori (3) käsittääExhaust after-treatment system according to one of claims 1 to 7, characterized in that the oxidation catalyst (3) comprises: 20155247 prh 29 -03- 2018 aktiivikomponenttina vanadiumia osuuden, joka on enemmän kuin 5 %, edullisesti enemmän kuin 7 %, erityisen edullisesti enemmän kuin 9 %.20155247 prh 29 -03-2018 as the active component, a proportion of vanadium of more than 5%, preferably more than 7%, particularly preferably more than 9%. 9. Jonkin patenttivaatimuksen 1 - 8 mukainen pakokaasunjälkikäsittely5 järjestelmä, tunnettu siitä, että pakokaasuahdetun polttovoimakoneen yhteydessä hapetuskatalysaattori (3) on sijoitettu ylävirtaan pakokaasuturboahtimen turbiinista (5), jolloin erotin (4) on sijoitettu alavirtaan pakokaasuturboahtimen turbiinista (5).Exhaust after-treatment system according to one of Claims 1 to 8, characterized in that the oxidation catalyst (3) is disposed upstream of the turbocharger (5) of the exhaust gas turbine, with the separator (4) located downstream of the turbine (5). 10 10. Jonkin patenttivaatimuksen 1 - 9 mukainen pakokaasunjälkikäsittelyjärjestelmä, tunnettu siitä, että ylävirtaan hapetuskatalysaattorista (5) on järjestetty lämmityslaite (6), joka kuumentaa pakokaasun lämpötilaan, joka yli 350°C, edullisesti yli 400°C, erityisen edullisesti yli 450°C.Exhaust after-treatment system according to one of claims 1 to 9, characterized in that a heating device (6) is provided upstream of the oxidation catalyst (5), which heats the exhaust gas to a temperature above 350 ° C, preferably above 400 ° C, particularly preferably above 450 ° C. . 1515 11. Jonkin patenttivaatimuksen 1 - 10 mukainen pakokaasunjälkikäsittelyjärjestelmä, tunnettu siitä, että SO3/SOx-suhde alavirtaan SO2-hapetuskatalysaattorista on vähintään 0,4, edullisesti vähintään 0,5, erityisen edullisesti 0,6.11 in any one of claims 1 to 10 the exhaust gas after-treatment system, characterized in that the SO 3 / SO x ratio downstream of the SO 2 Oxidation catalyst is at least 0.4, preferably at least 0.5, particularly preferably 0.6. 2020 12. Jonkin patenttivaatimuksen 1-11 mukainen pakokaasunjälkikäsittelyjärjestelmä, tunnettu siitä, että rakeiden sulfaattikerros poistetaan ja nämä rakeet johdetaan takaisin ylävirtaan erottimesta ja/tai erottimeen.An exhaust after-treatment system according to any one of claims 1 to 11, characterized in that the sulfate layer of the granules is removed and these granules are recycled upstream of the separator and / or separator. 13. Menetelmä polttovoimakoneen luovuttaman pakokaasun jälkikäsit25 telemiseksi, jolloin pakokaasu johdetaan hapetuskatalysaattorin (3) kautta SO2:n hapettamiseksi SCUksi ja sen jälkeen kalsiumpitoisia rakeita sisältävän erottimen (4) kautta rikkioksidien kemisorptiota varten.A process for treating exhaust gas emitted by a combustion engine, wherein the exhaust gas is passed through an oxidation catalyst (3) to oxidize SO 2 to SCU and then through a calcium-containing granule separator (4) for the chemisorption of sulfur oxides. 14. Patenttivaatimuksen 13 mukainen menetelmä, tunnettu siitä,Method according to claim 13, characterized in that 30 että se suoritetaan jonkin patenttivaatimuksen 1-12 mukaisella pakokaasunjälkikäsittelyjärjestelmällä.30 that it is performed by an exhaust after-treatment system according to any one of claims 1 to 12.
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