A SELECTIVE CATALYTIC REDUCTION SYSTEM AND A METHOD FOR NOx REDUCTION
20200408128 · 2020-12-31
Inventors
Cpc classification
F01N2370/04
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F01N3/36
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F01N3/035
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F01N2590/02
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F01N3/106
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F01N13/0093
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
Y02T10/12
GENERAL 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
F01N3/103
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F01N2330/06
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F01N3/2066
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F01N5/04
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F01N2610/03
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F01N5/02
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F01N2250/02
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F01N2340/02
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
International classification
F01N3/20
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F01N13/00
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F01N3/035
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F01N3/10
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F01N3/36
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
F01N5/02
MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
Abstract
A selective catalytic reduction system applying diesel oil as reductant for converting nitrogen oxides by a catalyst into diatomic nitrogen and water in a diesel engine is provided. The selective catalytic reduction system includes an oil injection system, a reactor and a number of selective catalytic reduction catalysts provided in a first section. The selective catalytic reduction system includes at least one additional section including a number of selective catalytic reduction catalysts. The at least one additional section is provided in a non-zero distance from the first section.
Claims
1-24. (canceled)
25. A selective catalytic reduction system applying diesel oil as reductant for converting nitrogen oxides in diesel engine exhaust, through a NO reduction process by a catalyst, into diatomic nitrogen and water in a diesel engine, wherein the selective catalytic reduction system is configured to be installed and used in a two-stroke diesel engine or a four-stroke diesel engine for marine purposes, wherein the selective catalytic reduction system comprises: an oil injection system; a reactor; a number of selective catalytic reduction catalysts provided in a section comprising a plurality of layers provided in a non-zero distance from each other, wherein the selective catalytic reduction system comprises a number of selective catalytic reduction catalysts provided in separated layers in a first section, wherein the selective catalytic reduction system comprises at least one additional section comprising a number of selective catalytic reduction catalysts in separated layers, wherein the at least one additional section is provided in a non-zero distance from the first section, wherein the reactor is configured to house the sections in order to facilitate the NO reduction process, wherein the distance between the layers is selected to ensure that a minimum average residence time for the exhaust is provided between each layer, wherein the minimum average residence time for moving a gas molecule from one layer to the next layer is no smaller than 0.025 seconds.
26. A selective catalytic reduction system according to claim 25, wherein the minimum average residence time for moving a gas molecule from one layer to the next layer is no smaller than 0.04 seconds.
27. A selective catalytic reduction system according to claim 25, wherein the minimum average residence time for moving a gas molecule from one layer to the next layer is no smaller than 0.135 seconds.
28. A selective catalytic reduction system according to claim 25, wherein a plate member is provided between at least some of the adjacent sections.
29. A selective catalytic reduction system according to claim 25, wherein the selective catalytic reduction catalysts are arranged in the layers each having a thickness within the range 40-120 mm, or in the range 50-100 mm, or in the range 60-90 mm.
30. A selective catalytic reduction system according to claim 25, wherein the selective catalytic reduction catalysts are selected among the following: Ce/Cu-ZSM-5, CeZr/Cu-ZSM-5, Ce/Fe-ZSM-5 or CeZr/Fe-ZSM-5, Ce/Mg-ZSM-5 or CeZr/Mg-ZSM-5.
31. A selective catalytic reduction system according to claim 25, wherein the selective catalytic reduction system comprises a tubular structure extending centrally along the longitudinal axis of the reactor.
32. A selective catalytic reduction system according to claim 25, wherein the selective catalytic reduction system comprises a diffuser.
33. A selective catalytic reduction system according to claim 25, wherein the selective catalytic reduction system comprises a heat recovering unit.
34. A method for nitrogen oxides reduction in diesel engine exhaust, said method comprising the step of using a selective catalytic reduction system configured to be applied for selective catalytic reduction of NOx in an exhaust stream either after a four-stroke diesel engine or between the exhaust receiver and the exhaust turbine(s) on a two-stroke diesel engine and applying diesel oil as reductant for converting nitrogen oxides through a NO reduction process by a catalyst into diatomic nitrogen and water in a diesel engine, wherein the method comprises the step of providing evaporated diesel oil in a reactor, wherein a NOx conversion is carried out including a NO reduction followed by a heterogeneous catalyzing process followed by a homogeneous catalyzing process by applying a number of selective catalytic reduction catalysts provided in a section having a plurality of layers, and further that the selective catalytic reduction system comprises a number of selective catalytic reduction catalysts provided in separated layers in a first section, wherein the selective catalytic reduction system comprises at least one additional section comprising a number of selective catalytic reduction catalysts in separated layers, wherein the at least one additional section is provided in a non-zero distance from the first section, wherein the reactor is configured to house the sections in order to facilitate the NO reduction process, wherein the distance between the layers is selected to ensure that a minimum average residence time for the exhaust is provided between each layer, wherein the minimum average residence time for moving a gas molecule from one layer to a next layer is no smaller than 0.025 seconds.
35. A method according to claim 34, wherein the minimum average residence time for moving a gas molecule from one layer to a next layer is no smaller than 0.04 seconds.
36. A method according to claim 34, wherein the minimum average residence time for moving a gas molecule from one layer to a next layer is no smaller than 0.135 seconds.
37. A method according to claim 34, wherein the method comprises the step of cracking at least a portion of the evaporated diesel oil, carrying out a heterogeneous NOx conversion that causes formation of the radical NH4.sup.+, wherein the radical NH4.sup.+ is used for carrying out homogeneous NO.sub.x conversion.
38. A method according to claim 34, wherein the method is applied for selective catalytic reduction of NOx in an exhaust stream either after a four-stroke diesel engine or between the exhaust receiver and the exhaust turbine(s) on a two-stroke diesel engine.
39. A selective catalytic reduction system according to claim 25 wherein an oxidation catalyst arranged to oxidise one or more compositions in the exhaust gas.
40. A selective catalytic reduction system according to claim 39, wherein the selective catalytic reduction system comprises a flow-through type diesel oxidation catalyst and a soot particle filter.
41. A selective catalytic reduction system according to claim 39, wherein the oxidation catalyst is a wall flow type particle filter comprising walls coated with a catalyst configured to oxide at least CO or HC.
42. A selective catalytic reduction system according to claim 39, wherein the oxidation catalyst is provided downstream the selective catalytic reduction catalysts and a particulate filter.
43. A selective catalytic reduction system according to claim 39, wherein the selective catalytic reduction system comprises or is connected to a generator.
44. A method according to claim 34 wherein the method comprises the step of applying an oxidation catalyst arranged to oxidise one or more compositions in the exhaust gas.
45. A method according to claim 44, wherein the method comprises the step of applying a wall flow type particle filter comprising walls coated with a catalyst configured to oxide at least CO or HC.
46. A method according to claim 44, wherein the method comprises the step of applying a flow through type diesel oxidation catalyst and a particle filter.
47. A method according to claim 44, wherein the method comprises the step of applying an oxidation catalyst provided between the selective catalytic reduction catalysts and a particulate filter.
48. A method according to claim 44, wherein the method comprises the step of applying a generator connected to a turbine to produce electrical energy.
49. A method according to claim 44, wherein the method comprises the step of applying a distillation apparatus to produce distilled water, wherein the distillation apparatus is connected to the selective catalytic reduction system.
Description
BRIEF DESCRIPTION
[0169] Some of the embodiments will be described in detail, with references to the following Figures, wherein like designations denote like members, wherein:
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[0184] Table 1 shows the Cu percentage in slurry, the slurry loading measured in g/L of a various layer configurations;
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DETAILED DESCRIPTION
[0199] Referring now in detail to the drawings for the purpose of illustrating embodiments of the present invention, a selective catalytic reduction system 2 of embodiments of the present invention is illustrated in
[0200]
[0201] The reactor 10 comprises a cylindrical central portion sandwiched between a lower conical portion 20 and an upper conical portion 20. An end pipe 22 provided with a flange 58 in its distal end is provided in the distal end of the lower conical portion 20. Likewise, an end pipe 22 provided with a flange 58 in its distal end is provided in the distal end of the upper conical portion 20. The doors 18, 18, 18 are moveably attached (e.g. rotatably attached or attachably attached) to the central portion of the reactor 10.
[0202] It is important to underline that the reactor 10 can be oriented both horizontally and vertically. It may also be possible to arrange the reactor 10 in an inclined orientation so that the reactor is angled relative to both horizontal and vertical.
[0203] A pipe 26 provided with a flange 58 in its proximal end is attached to the end pipe 22, by fixing the flanges 58, 58 to each other. Similarly, a bent pipe 26 provided with a flange 58 in its proximal end is attached to the end pipe 22, by fixing the flanges 58, 58 to each other. It is important to underline that the pipe configuration can be different. In one embodiment according to embodiments of the invention, the pipe 26 may be straight.
[0204] An injection unit 24 extends through the wall of the pipe 26 and is configured to inject oil 40 into the pipe 26. The injection unit 24 is configured to inject oil 40 towards the end pipe 22 of the reactor 10. Accordingly, the injected oil 40 will enter the reactor 10, in which the diesel oil is applied as reductant in the selective catalytic reduction system 2.
[0205] When oil (in liquid form) is injected into the exhaust in the pipe 26, the diesel oil droplets will evaporate. Accordingly, in an embodiment according to the invention, the system does not require a separate oil evaporation unit.
[0206] The selective catalytic reduction system 2 comprises a differential pressure sensor 32 connected to a first portion of the reactor 10 by a first conduit 34 and to a second portion of the reactor 10 by a second conduit 34. Hereby, the differential pressure sensor 32 is capable of measuring the differential pressure across that part of the reactor 10 that extends between the first portion and the second portion. For practical reasons it may be an advantage that the differential pressure sensor 32 is connected to a lower portion of the reactor 10 by the first conduit 34 and to an upper portion of the reactor 10 by a second conduit 34. Accordingly, the differential pressure sensor 32 can measure the differential pressure across the central portion of the reactor 10, in which the catalysts are arranged. Therefore, the differential pressure sensor 32 is configured to detect when the differential pressure exceeds a predefined pressure level (e.g. 1-1000 mbar, such as 4-500 mbar, or 8-100 mbar, e.g. 10-20 mbar). The selective catalytic reduction system 2 comprises an alert unit configured to generate an alert when the differential pressure exceeds the predefined pressure level.
[0207] In another embodiment according to the invention, two separated pressure sensors are applied to measure the pressure at two different positions of the reactor 10. By comparing the two detected pressures, it is possible to calculate the pressure difference between the two measurement points. Accordingly, the differential pressure sensor 32 may be replaced with two pressure sensors.
[0208] The selective catalytic reduction system 2 comprises a first temperature sensor 28 arranged and configured to detect the temperature in the lower (inlet) portion of the reactor 10. The selective catalytic reduction system 2 comprises a second temperature sensor 30 arranged and configured to detect the temperature in the upper (outlet) portion of the reactor 10. By comparing the temperatures detected by the first temperature sensor 28 and the second temperature sensor 30, it is possible to measure the temperature increase across the reactor 10.
[0209] The selective catalytic reduction system 2 comprises a pump 48 connected to a diesel tank 50 via a pipe 54. The pump 48 is a pump configured to generate a sufficiently high pressure. The pump 48 is in fluid communication with the injection unit 24. The pump 48 is connected to a flow sensor 46 through a pipe 54. A control valve 44 is connected to the flow sensor 46 via a pipe 54 and the control valve 44 is connected to the injection unit 24 via a pipe 36. A pipe 55 extends between the pipe 54 and the tank diesel tank 50. Accordingly, diesel oil can be returned from the pipe 54 to the tank diesel tank 50. In one embodiment according to the invention, the selective catalytic reduction system 2 comprises two pumps 48 (a first pump and a second pump) connected in parallel. Hereby, it is possible to apply the second pump in case that the first pump is malfunctioning, needs to be serviced or be replaced, or vice versa.
[0210] A tray (for collecting oil) may be arranged under the injection unit 24. Likewise, a tray may be arranged under the pump for collection of leaking oil. The system 2 may comprise a sensor arranged and configured to generate an alert in case of a sufficiently large leakage.
[0211] The selective catalytic reduction system 2 comprises a programmable logic controller 60. The differential pressure sensor 32, the temperature sensors 28, 30, pump 48, the flow sensor 46 and the control valve 44 are connected to the programmable logic controller 60 by cables 52, 52, 52. However, it is possible to replace this wired connection with a wireless connection (by applying corresponding transmitters and receivers). The programmable logic controller 60 receives the measurements (sensor inputs) detected by the differential pressure sensor 32, the temperature sensors 28, 30, the pump 48, the flow sensor 46 and the control valve 44. The programmable logic controller 60 is configured to control the pump 48 and the control valve 44 on the basis of the sensor inputs of the differential pressure sensor 32, the temperature sensors 28, 30 and the flow sensor 46. The programmable logic controller 60 may be configured to generate an alert when the difference between the detected temperatures exceeds a predefined temperature level or when the difference between the detected temperatures is lower than a predefined temperature level.
[0212]
[0213] The selective catalytic reduction system 2 comprises an oil pump 48, an oil injector 6 and a reactor 10. The pump 48 is arranged to deliver pressurised oil to the oil injector 6. The oil injector 6 is arranged and configured to inject pressurised oil into the reactor 10. A blower 72 is arranged to blow (compressed) air into the reactor 10. In an embodiment according to the invention, the blower 72 is configured to blow air under the first catalyst layer in every section of the catalyst in a predefined manner, with fixed time intervals to keep the catalyst entrance surface clean.
[0214] The reactor 10 is arranged between the outlet of the exhaust gas receiver 78 and the exhaust turbine 82. An oil injection system 6 is arranged between the exhaust gas receiver 78 and the reactor 10.
[0215] The selective catalytic reduction system 2 comprises a control valve 68 arranged between the exhaust gas receiver 78 and the oil injection system 6.
[0216] In one embodiment according to the invention, the blower 72 may be an integrated part of the selective catalytic reduction system 2.
[0217] In another embodiment according to the invention, the blower 72 may be a separate unit not being an integrated part of the selective catalytic reduction system 2.
[0218] A control valve 68 is arranged after the outlet of the reactor 10. The control valve 68 is configured to regulate the flow from the reactor 10.
[0219] The scavenge air receiver 76 is connected to the exhaust turbine 82. A control valve 74 is provided between the scavenge air receiver 76 and the exhaust turbine 82. The control valve 74 may be of any suitable type and size.
[0220] The selective catalytic reduction system 2 comprises a control unit 62 configured to control a number of units of the selective catalytic reduction system 2. In one embodiment according to the invention, the selective catalytic reduction system 2 comprises a control unit 62 configured to control the pump 48, and at least a selection of the control valves 68, 68, 68, 68 and the brake resistor 74. In an embodiment according to the invention, the selective catalytic reduction system 2 comprises a control unit 62 configured to control the pump 48, the control valves 68, 68, 68, 68 and the brake resistor 74 and the oil injection system 6.
[0221] The selective catalytic reduction system 2 may comprise a number of sensors (e.g. as shown in
[0222] As shown in
[0223]
[0224] The exhaust gas leaves the cylinder 66 via a pipe that is connected to an exhaust gas receiver 78. The exhaust gas receiver 78 is connected to an exhaust turbine 82.
[0225] The reactor 10 is arranged after the exhaust turbine 82. The selective catalytic reduction system 2 comprises an oil injector 6 and a reactor 10. A diesel tank 50 is in fluid communication with the oil injector 6. Accordingly, the tank 50 is configured to deliver oil to the oil injector 6. The exhaust turbine 82 is connected to the oil injector 6, which is arranged and configured to inject pressurised oil into the reactor 10. A blower 72 is arranged to blow (compressed) air into the reactor 10. In an embodiment according to the invention, the blower 72 is configured to blow air under the first catalyst layer in every section of the catalyst in a predefined manner, with fixed time intervals to keep the catalyst entrance surface clean.
[0226] In one embodiment according to the invention, the blower 72 may be an integrated part of the selective catalytic reduction system 2.
[0227] In another embodiment according to the invention, the blower 72 may be a separate unit not being an integrated part of the selective catalytic reduction system 2.
[0228] The selective catalytic reduction system 2 comprises a control unit 62 configured to control a number of units of the selective catalytic reduction system 2. In one embodiment according to the invention, the selective catalytic reduction system 2 comprises a control unit 62 configured to control the oil injection system 6 as well as one or more structures of the selective catalytic reduction system 2.
[0229] The selective catalytic reduction system 2 may comprise one or more control valves (not shown) and the control unit 62 may be configured to control one or more of these control valves. In one embodiment according to the invention, the control unit 62 is configured to receive one or more signals from one or more sensors and to regulate one or more devices on the basis of the received signal(s). The control unit 62 may be configured to control one or more valves and/or the oil injection system 6 on the basis of temperature and/or differential pressure detections.
[0230] The selective catalytic reduction system 2 may comprise a number of sensors (e.g. as shown in
[0231] The central portion is sandwiched between a lower conical portion 20 and an upper conical portion 20. An end pipe 22 provided with a flange 58 in its distal end is provided in the distal end of the lower conical portion 20. Likewise, an end pipe 22 provided with a flange 58 in its distal end is provided in the distal end of the upper conical portion 20.
[0232] A bent pipe 26 provided with a flange 58 in its proximal end is attached to the end pipe 22, by attachment of the adjacent flanges 58, 58 to each other. The pipe 26 may have another configuration. The pipe 26 may by way of example be straight.
[0233] A pressure tank 31 configured to deliver pressurised air is connected to the reactor 10 by a first conduit and a second conduit. A valve 33 is arranged in the first conduit between the pressure tank 31 and the reactor 10, whereas another valve 33 is arranged in the second conduit between the pressure tank 31 and the reactor 10.
[0234] The reactor 10 is provided with a first support leg 90, a second support leg 90 and a third support leg (not shown). The reactor 10 may be applied in a selective catalytic reduction system that comprises a control unit configured to control the one or more oil injectors and/or one or more control valves (not shown). The control unit may be configured to receive information from one or more sensors including the differential pressure sensor 32.
[0235]
[0236] Inside the interior of the cylindrical central portion a first section 14 and an additional section 16 are provided in a non-zero distance D.sub.3 from the first section 14. A plate member is provided between the first section 14 and the additional section 16. The plate member 84 is configured to disperse the oil injected into the interior of the reactor 10.
[0237] Each section 14, 16 comprises several layers S.sub.1, S.sub.2, S.sub.3 and S.sub.1, S.sub.2, S.sub.3, respectively. The distance between adjacent layers S.sub.1, S.sub.2, S.sub.3, S.sub.1, S.sub.2, S.sub.3 and the distance D.sub.3 between the first section 14 and the additional section 16 provides time for the generated free radical NH.sub.4.sup.+ to have an impact through its reaction during the previously mentioned homogeneous catalyzing step:
NH.sub.4.sup.++NO.sub.2.Math.N.sub.2+2H.sub.2O(5)
[0238] Accordingly, by providing a non-zero distance between adjacent layers S.sub.1, S.sub.2, S.sub.3, S.sub.1, S.sub.2, S.sub.3 and between the first section 14 and the additional section 16, it is possible to increase the effect and efficiently of the reactor 10. The distance between adjacent layers S.sub.1, S.sub.2, S.sub.3, S.sub.1, S.sub.2, S.sub.3 and the distance D.sub.3 between the first section 14 and the additional section 16 is selected in such a manner that maximum effect of the free radical NH.sub.4.sup.+ can be achieved. The distance D.sub.3 is between 5-1000 mm, or in the range 50-500 mm, such as 100-400 mm.
[0239] A diffuser 88 is provided in the lower conical portion 20. The diffuser is configured to mix and diffuse the injected oil 40 towards and onto the first layer S.sub.1 of the first section 14.
[0240] The exhaust to be treated enters the reactor 10 through the inlet provided in the first end 92, passes the first section 14, the second section 16 and leaves the reactor 10 through the outlet provided in the second end 94. The exhaust carries the injected oil 40 in gaseous form. The gaseous oil 40 is initially guided outwardly by the diffuser 88. A closing structure 134, 134, 134 extends radially in extension of each layer S.sub.1, S.sub.2, S.sub.3. Accordingly, the closing structures 134, 134, 134 force the evaporated diesel oil 40 to pass (axially) through the passages provided in the layer S.sub.1, S.sub.2, S.sub.3.
[0241] The first section 14 comprises three layers S.sub.1, S.sub.2, S.sub.3 arranged above each other separated by a gap. Likewise, the second section 16 comprises three layers S.sub.1, S.sub.2, S.sub.3 arranged above each other, wherein a distance is provided between adjacent layers S.sub.1, S.sub.2, S.sub.3.
[0242] The layers S.sub.1, S.sub.2, S.sub.3 of the first section 14 and the layers S.sub.1, S.sub.2, S.sub.3 of the second section 16 may form a Ce/Cu-ZSM-5 type catalyst or a CeZr/Cu-ZSM-5 type catalyst.
[0243] When a Ce/Cu-ZSM-5 type catalyst is used, the catalyst may be calcinated respectively after Cu adding and after Ce and Zr adding.
[0244] When a CeZr/Cu-ZSM-5 type catalyst is used, Cu and Ce and Zr may be added at same time and powder may be calcined after the adding of Cu and Ce and Zr.
[0245] For both types, TiO.sub.2 may be added to the binder, binding the catalyst powder to the substrate. The substrate may consist of either corrugated steel plates or corrugated ceramic plates with a CPSI (Cells Per Square Inch) in the range 81-256.
[0246] The layers S.sub.1, S.sub.2, S.sub.3 of the first section 14 and the layers S.sub.1, S.sub.2, S.sub.3 of the second section 16 may have essentially the same thickness. The thickness of each layer may be 5-500 mm, or 10-250 mm such as 40-150 mm, e.g. 75 mm.
[0247] In an embodiment according to the invention, the layer S.sub.1 has a thickness of 5-500 mm, or 10-250 mm such as 40-150 mm, e.g. 75 mm. In an embodiment according to the invention, the layer S.sub.2 has a thickness of 5-500 mm, or 10-250 mm such as 40-150 mm, e.g. 75 mm. In an embodiment according to the invention, the layer S.sub.3 has a thickness of 5-500 mm, or 10-250 mm such as 40-150 mm, e.g. 75 mm.
[0248] In an embodiment according to the invention, the layers S.sub.1, S.sub.2 and S.sub.3 have a thickness of 5-500 mm, or 10-250 mm such as 40-150 mm, e.g. 75 mm.
[0249] In an embodiment according to the invention, the layers S.sub.1, S.sub.2, S.sub.3 are of equal type and dimension.
[0250] In another embodiment according to the invention, the layers S.sub.1, S.sub.2, S.sub.3 are of different equal type and/or thickness.
[0251] A plate member 84 is arranged between the first section 14 and the second section 16. A tubular structure 86 formed as a centrally arranged tube extends along the longitudinal axis of the lower conical portion 20 of the reactor 10. Evaporated oil 40 is introduced into the space between the two sections 14, 16. The distal end of the tubular structure 86 is provided in a distance h to the plate member 84. The plate member 84 is configured and arranged to guide the evaporated diesel oil 40 radially towards the periphery of the reactor 10, from which the evaporated diesel oil 40 is guided towards the first layer S.sub.1 of the second section 16.
[0252] The selective catalytic reduction system according to embodiments of the invention may comprise an additional oxidation catalyst reactor (not shown) configured to oxidize CO to CO.sub.2 and HC to CO.sub.2 and H.sub.2O. The additional oxidation catalyst reactor may be arranged after the reactor 10.
[0253] Under the first catalyst layer S.sub.1 (arranged closest to the inlet 92 of the reactor 10) in the first section 14 and the first catalyst layer S.sub.1 in the second section 16, air may be blown with fixed time intervals to keep the catalyst entrance surface clean. This may be done by a blower (as illustrated in
[0254] The catalysts of the sections 14, 16 ensure three integrated catalyzing processes including: [0255] Cracking of oil; [0256] Heterogeneous NOx conversion and formation of radicals used for a following reaction; [0257] Homogeneous NOx conversion downstream the catalyst.
[0258] The temperature increases across the first section 14. This temperature increase T.sub.1 is indicated in
[0259] In one embodiment according to the invention, the selective catalytic reduction system comprises a waste heat recovering system arranged after the reactor 10. Hereby, the waste heat recovering system can recover the heat released in the catalysts of the reactor 10.
[0260] The recovered heat may be used for producing steam for production of drinking water or electricity (that may be used onboard if the selective catalytic reduction system is applied for selective catalytic reduction of NOx in an exhaust stream in a marine diesel engine).
[0261]
[0262] Inside the interior of the cylindrical central portion, however, a first section 14 and an additional section 16 are provided in a non-zero distance D.sub.1 from the first section 14. A second plate member 84 is provided in a non-zero distance D.sub.2 between the additional (second) section 16 and the third section 16. The plate members 84, 84 are configured to disperse the oil 40 injected into the interior of the reactor 10.
[0263] The distance D.sub.1 between the first section 14 and the additional section 16 as well as the distance between adjacent layers S.sub.1, S.sub.2, S.sub.3, S.sub.1, S.sub.2, S.sub.3 provides time for the generated free radical NH.sub.4 to have an impact through its reaction with nitrogen dioxide (NO.sub.2) forming diatomic nitrogen gas (N.sub.2) and water (H.sub.2O). Likewise, the distance D.sub.2 between the additional section 16 and the third section 16 as well as the distance between adjacent layers S.sub.1, S.sub.2, S.sub.3 provides time for the generated free radical NH.sub.4.sup.+ to have an impact through the above-mentioned reaction with nitrogen dioxide (NO.sub.2).
[0264] By providing a non-zero distance D.sub.1, D.sub.2 between the adjacent sections 14, 16, 16 and between adjacent layers S.sub.1, S.sub.2, S.sub.3, S.sub.1, S.sub.2, S.sub.3, S.sub.1, S.sub.2, S.sub.3, it is possible to improve the effect and efficiently of the reactor 10. Said distances may be selected in such a manner that maximum effect of the free radical NH.sub.4.sup.+ can be achieved. The distances D.sub.1, D.sub.2 may be between 5-1000 mm, or in the range 50-500 mm, such as 100-400 mm. In one embodiment according to the invention, the distances D.sub.1, D.sub.2 are equal. The distance between adjacent layers S.sub.1, S.sub.2, S.sub.3, S.sub.1, S.sub.2, S.sub.3, S.sub.1, S.sub.2, S.sub.3 may be between 5-1000 mm, or in the range 25-500 mm, such as 50-400 mm.
[0265] A tubular structure 86 extends centrally along the longitudinal axis of the lower conical portion 20 of the reactor 10. The tubular structure 86 extends through the first section 14 and protrudes therefrom. A diffuser 88 is arranged at the inlet portion of the tubular structure 86. The diffuser 88 is adapted and arranged to mix and diffuse injected oil towards and onto the first layer C.sub.1 of the first section 14.
[0266] Exhaust from the engine in which the selective catalytic reduction system is installed, enters the reactor 10 through the inlet provided in the first end 92, passes the first section 14, the second section 16, the third section 16 and leaves the reactor 10 through the outlet provided in the second end 94.
[0267] The first section 14 comprises three layers S.sub.1, S.sub.2, S.sub.3 arranged above each other, wherein adjacent layers are axially spaced from each other. The second section 16 comprises several layers S.sub.1, S.sub.2, S.sub.3 arranged above each other and are spaced from each other. The third section 16 comprises several layers S.sub.1, S.sub.2, S.sub.3 spaced from each other.
[0268] The sections 14, 16, 16 may be of the same type as the sections explained with reference to
[0269] The temperature increases across all sections 14, 16, 16. The temperature increase T.sub.3, T.sub.4, T.sub.5 across each of the segments 14, 16, 16, is indicated in
[0270] In one embodiment according to the invention, the selective catalytic reduction system comprises a waste heat recovering system (not shown) arranged after the reactor 10. Hereby, the waste heat recovering system can recover the heat released in the catalysts of the reactor 10. Accordingly, the recovered heat may be used for producing steam for production of drinking water or electricity (that may be used onboard if the selective catalytic reduction system is applied for selective catalytic reduction of NOx in an exhaust stream in a marine diesel engine).
[0271]
[0272] The cracking process represents the first process step inside the reactor. The diesel oil used as reactant is injected into the exhaust as small droplets upstream (in the direction indicated by the arrow) the catalyst layer of the first layer S.sub.1. The injection of oil is carried out in such a manner that minimum 80% of the oil droplets are evaporated before reaching the first catalyst layer S.sub.1. The selective catalytic reduction system is configured to evenly disperse the oil into the exhaust.
[0273] The evaporated oil is cracked on the surface of the catalyst layer S.sub.1. Accordingly, cracked oil 110 will be present on the distal portion of the substrate 108, 108. A portion of the oil may flow un-cracked towards the passages 112, 112 of the first catalyst layer S.sub.1 and the second catalyst layer S.sub.2. Due to the increased temperature (as explained with reference to
[0274] When the selective catalytic reduction system is used in marine engines, the diesel oil contains relative long-chained hydrocarbon (HC) connections. These connections are cracked to short-chained HC connections during the catalyst process. Accordingly, the short-chained HC connections will be short enough to enter the catalyst layer and convert NO to N.sub.2 and H.sub.2O and further produce radicals (NH4.sup.+). The chemical reactions (of the NOx conversion) are show in the following.
[0275] The NO oxidation carried out may be expressed as:
NO+O.sub.2.Math.NO.sub.2(1)
NO+NO.sub.2+2H.sup.+.Math.2NO++H.sub.2O(2)
[0276] The heterogeneous catalyzing carried out may be expressed as:
2C.sub.4H.sub.8+10O.sub.2+2NO.sup.+.Math.N.sub.2+2CO+6CO.sub.2+8H.sub.2O(3)
C.sub.3H.sub.6+NO.sup.+2,5O.sub.2.Math.NH.sub.4.sup.+CO+2CO.sub.2+H.sub.2O(4)
[0277] The homogeneous catalyzing carried out may be expressed as:
NH.sub.4.sup.++NO.sub.2.Math.N.sub.2+2H.sub.2O(5)
[0278]
[0279] The manifold 100 comprises a cylindrical tubular body portion that is provided with a first flange 102 in the inlet end of the manifold 100 and a second flange 104 in the opposite outlet end of the manifold 100. The flanges 102, 104 are configured to be attached to an adjacent pipe (not shown) provided with a matching flange.
[0280] The manifold 100 comprises four connection pipes 96, 96, 96, 96 evenly distributed along the circumference of the manifold 100. The connection pipes 96, 96, 96, 96 are angled relative to the longitudinal axis of the cylindrical tubular body portion.
[0281] Each connection pipes 96, 96, 96, 96 is provided with a flange 98 in its distal end. A nozzle 106 extends through the interior of each connection pipes 96, 96, 96, 96. The nozzles 106 are arranged and configured to inject oil into the upper, central portion of the manifold 100.
[0282]
[0283]
[0284] The uppermost graph comprises points 122 representing the activity when two layers of different types are applied. The activity is measured relative to a reference activity in a reactor comprising only a single layer.
[0285] The lowermost graph comprises points 120 representing the activity when the catalyst layer thickness is low. The activity is measured relative to the activity in a reactor comprising only a single section.
[0286] It can be seen that the relative activity 118 is very low compared to the situation wherein the catalyst layer thickness is larger. Both graphs increase as function of residence time 116. Accordingly, it is possible to achieve an increased efficiency of the selective catalytic reduction system according to embodiments of the invention by introducing two sections being provided in a non-zero distance from each other.
[0287] The lowermost graph, however, illustrates that the effect of several layers is minimal when the catalyst layer is thin. Accordingly, it is desirable that the catalyst layer exceeds a predefined minimum layer thickness. The predefined minimum catalyst layer thickness may depend on the relative content of Cu, Fe or Mg.
[0288]
[0289]
[0290] The height H of the layer S.sub.1 may be in the range 20-300, such as 40-150 mm, e.g. 60-120 mm.
[0291] Table 1 illustrates the Cu percentage in slurry, the slurry loading measured in g/L of a first layer configuration called 1A-1B, a second layer configuration called 1Bb and a third layer configuration called 1B-1C. In the first layer configuration, 1A-1B, the layers are arranged on the top of each other in the two sections. In the second layer configuration, 1Bb, there is no space between the layers in two sections, whereas the third layer configuration, 1B-1C, a space between adjacent layers.
[0292]
[0293]
[0294] In
[0295] Type 1B and 1C are placed in one section with space in between. An increase in activity due to the homogeneous catalysing process after the catalyst can be observed.
[0296]
[0297]
[0298] In
[0299] In the embodiment shown in
[0300]
[0301] An example of measures for a cassette adapted for a specific catalytic reduction system is provided in
[0302] In the cross section of a part of a section of a reactor disclosed in 3D view in
Q=A.Math.v(1)
[0303] Here A is the cross-sectional area through which the gas flows and perpendicular to the gas flow direction. The average velocity v is calculated as the distance between layers d divided by the average residence time t between one layer and the next:
[0304] Where d is the distance between one layer and the next, and t is the average residence time of gas particles between one layer and the next. It is here assumed, that the gas flow is uniform across the cross section of the reactor, and that there are no significant changes in temperature during the gas passage over the distance d. This may not be entirely true in real life and a minor compensation for rising temperature and thus increase volumetric gas flow may have to be made.
[0305] From the above, it follows that:
[0306] When the desired minimum residence time has been determined experimentally, the minimum distance may be calculated as:
[0307] Experiments have shown that by choosing non-zero distances defined by the above-mentioned times and defined in the above-mentioned manner, provides a very efficient selective catalytic reduction system.
[0308] In example 1, d is chosen to be 40 mm, and with area A of 0.78 m.sup.2 and Q at 921 Nm.sup.3/h a residence time of 0.04 seconds are arrived at.
[0309] In example 2, the distance d is 110 mm which yields a residence time of 0.135 seconds given the same area A and flow Q as in example one.
[0310] In
G.sub.total=G+G(1G)+G(1(G(1G)))+ . . . (5)
[0311] If a cracking degree of a minimum size is desired, and the cracking fraction in each layer is known, this will then demand a given number N of layers. N may easily be determined, once the property of the individual layers are known.
[0312] It has been determined, that with the layers as indicated above, a minimum number of 3 layers will provide the desired cracking. In one embodiment, the reactor comprises four or more layers. In an embodiment, the reactor comprises five or more layers. In an embodiment, the reactor comprises six or more layers.
[0313]
[0314] The selective catalytic reduction system 2 comprises a reactor 10, an oxidation catalyst 136 and a particulate filter 138. The reactor 10 is provided with an opening in its distal end, wherein the oxidation catalyst 136 is arranged in the proximal end of the reactor 10. The particulate filter 138 is arranged in the distal end of the oxidation catalyst 136 above the oxidation catalyst 136.
[0315] The selective catalytic reduction system 2 is configured to receive exhaust through the opening in the reactor 10. The reactor 10 is configured to break down long-chain hydrocarbons into simpler molecules such as light hydrocarbons. The reactions carried out in the reactor 10 will be explained in further detail in the following.
[0316] The oxidation catalyst 136 is configured to oxidise nitrogen monoxide, NO to nitrogen dioxide, NO.sub.2 through a process as expressed in the following:
NO+O.sub.2=NO.sub.2
[0317] Wall-flow type particulate filters usually remove 85-100% of the soot. In an embodiment, the particulate filter 138 is designed to burn off the accumulated particulate either. This can be accomplished by heating the particulate filter 138 to soot combustion temperatures. The NOx reduction process carried out in the reactor 10 causes the temperature to raise to the required level. Thus, the combustion process in the particulate filter 138 will cause production of additional heat.
[0318] Accordingly, the selective catalytic reduction system 2 is capable of producing an enlarge quantity of heat compared to conventional art selective catalytic reduction systems. The heat may be applied to produce electricity by using a turbine (see
[0319] The reactor 10 makes it possible to break down long-chain hydrocarbons into simpler molecules such as light hydrocarbons. Hereby, an increased heat production can be achieved.
[0320] The exhaust enters from the bottom side of the reactor 10. Diesel oil is injected into the reactor 10. The oil is evaporated due to the elevated temperature inside the reactor 10. The evaporated oil consisting primarily of long-chained hydrocarbons. These long-chained hydrocarbons are cracked to shorter-chained hydrocarbons. Un-cracked oil vapor continues to higher parts of the reactor 10. The short-chained hydrocarbons are used for NOx conversion. The cracking takes place on the outside of the catalyst, and the short-chained hydrocarbons penetrate the catalyst and the NOx conversion can take place.
[0321] Tests have shown that introducing an oxidation catalyst and a particulate filter makes it possible to achieve a heat recovery in the range of up to 100% of the lower heat value in the diesel oil injected. If the heat can be recovered and used on board on a ship in case the selective catalytic reduction system 2 is installed on a ship. Accordingly, there is no extra cost for reactant and no extra production of CO.sub.2.
[0322] The NOx conversion process carried out in the selective catalytic reduction system 2 contains several steps, including:
[0323] Cracking
C.sub.12H.sub.23.Math.C.sub.3H.sub.6+4C.sub.2H.sub.4+H.sup.++C(1)
[0324] NO Oxidation
NO+O.sub.2.Math.NO.sub.2(2)
NO+NO.sub.2+2H.sup.+.Math.2NO++H.sub.2O(3)
[0325] Heterogeneous Catalyzing
4C.sub.2H.sub.4+10O.sub.2+2NO+.Math.N.sub.2+2CO+6CO.sub.2+8H.sub.2O(4)
C.sub.3H.sub.6+NO++2.5O.sub.2.Math.NH.sub.4++CO+2CO.sub.2+H.sub.2O(5)
[0326] Homogeneous Process:
NH.sub.4++NO.sub.2.Math.N.sub.2+2H.sub.2O(6)
[0327] When injecting diesel oil into the exhaust, having a temperature of at least 350 C., the diesel oil will be at least partly evaporated. The first step is the step of cracking of diesel oil to ethylene and propylene and other connections as defined by equation (1). Equations (4) and (5) illustrates that ethylene and propylene is oxidized and that N.sub.2, CO and CO.sub.2 is formed. This implies that heat is created.
[0328] Since the heating value of short-chained HC-connections is larger, than the heating value of long-chained HC-connections (see Table A below). The heating value of the cracked connections can be calculated by using equation (1):
42.8 MJ/kg.Math.[(42/167).Math.45.66+(112/167).Math.47.74+(1/167).Math.120.1+12/167.Math.29.5]MJ/kg(7)
42.8 MJ/kg.Math.46.3 MJ/kg (with the oxidation catalyst 136 and particulate filter 138)(8)
42.8 MJ/kg.Math.44.2 MJ/kg(with the oxidation catalyst 136)(9)
TABLE-US-00001 TABLE A Diesel oil Propylene Ethylene Hydrogen Carbon Heating values [MJ/kg] 42.8 45.7 47.7 120 29.5
[0329] From equation (8) it can be seen that the heating value (when applying the oxidation catalyst 136 and particulate filter 138) is increased to 46.3 MJ/kg, which is larger than the heating value of (42.8 MJ/kg) of diesel oil. From equation (9) it can be seen that the heating value (when applying the oxidation catalyst 136) is increased to 44.2 MJ/kg, which is larger than the heating value of (42.8 MJ/kg) of diesel oil. Accordingly, by introducing an oxidation catalyst 136 and a particulate filter 138 it is possible to an increased heat production. The cracking process is essential and required to achieve this increased heat production.
[0330]
[0331]
[0332]
[0333] Although the present invention has been disclosed in the form of preferred embodiments and variations thereon, it will be understood that numerous additional modifications and variations could be made thereto without departing from the scope of the invention.
[0334] For the sake of clarity, it is to be understood that the use of a or an throughout this application does not exclude a plurality, and comprising does not exclude other steps or elements. The mention of a unit or a module does not preclude the use of more than one unit or module.
LIST OF REFERENCE NUMERALS
[0335] 2 Selective catalytic reduction system [0336] 4 Diesel engine [0337] 6 Oil injection system [0338] 10 Reactor [0339] 11, 11, 11 Selective catalytic reduction catalyst [0340] 12, 12, 12 Selective catalytic reduction catalyst [0341] 14 First section [0342] 16, 16 Additional section [0343] 18, 18, 18 Door [0344] 20, 20 Conical portion [0345] 22, 22 End pipe [0346] 24 Injection unit [0347] 26, 26 Pipe [0348] 28 Temperature sensor [0349] 30 Temperature sensor [0350] 31 Pressure tank [0351] 32 Differential pressure sensor [0352] 33, 33 Valve [0353] 34, 34 Conduit [0354] 36 Pipe [0355] 38 Cable [0356] 40 Oil [0357] 42 Cable [0358] 44 Control valve [0359] 46 Flow sensor [0360] 48 Pump [0361] 50 Diesel tank [0362] 52, 52, 52 Cable [0363] 54, 54, 54 Pipe [0364] 55 Pipe [0365] 56 Cable [0366] 58, 58 Flange [0367] 60 Programmable Logic Controller (PLC) [0368] 62 Control unit [0369] 64 Air cooler [0370] 66 Cylinder [0371] 68, 68, 68, 68 Valve [0372] 70 Piston [0373] 72 Blower [0374] 74 Control valve [0375] 76 Scavenge air receiver [0376] 78 Exhaust gas receiver [0377] 80 Compressor [0378] 82 Exhaust turbine (expander) [0379] 84, 84 Plate member [0380] 86 Tubular structure [0381] 88 Diffuser [0382] 90, 90 Support leg [0383] 92 First end [0384] 94 Second end [0385] 96, 96, 96, 96 Connecting pipe [0386] 98 Flange [0387] 100 Manifold [0388] 102 Flange [0389] 104 Flange [0390] 106 Nozzle [0391] 108, 108 Substrate [0392] 109, 109 Catalyst [0393] 110 Cracked diesel oil [0394] 112, 112 Passage [0395] 114 Graph [0396] 116 Residence time between the catalyst layers [0397] 118 Relative activity (two layers relative to one layer) [0398] 120 Point [0399] 122 Point [0400] 124 Number of layers [0401] 126 Activity (NOx reduction [ppm]) [0402] 134, 134, 134 Closing structure [0403] 136 Oxidation catalysts [0404] 138 Particulate filter [0405] 140 Cubic cassette [0406] 144 Generator [0407] 150 Distillation apparatus [0408] 172 Drinking water outlet [0409] 174 Feed water (seawater) inlet [0410] 188 Boiler [0411] 190 Exhaust gas [0412] 210 Steam [0413] 230 Steam turbine [0414] 232 Gas turbine [0415] D.sub.1, D.sub.2, D.sub.3 Distance [0416] d.sub.1, d.sub.2, d.sub.3, d.sub.4 Distance [0417] T.sub.1, T.sub.2, T.sub.3 Temperature increase [0418] T.sub.4, T.sub.5 Temperature increase [0419] S.sub.1, S.sub.2, S.sub.3, S.sub.4, S.sub.5 Layer of selective catalytic reduction catalysts [0420] S.sub.1, S.sub.2, S.sub.3, S.sub.4, S.sub.5 Layer of selective catalytic reduction catalysts [0421] S.sub.1, S.sub.2, S.sub.3 Layer of selective catalytic reduction catalysts [0422] S.sub.4, S.sub.5, E.sub.1, E.sub.2 Layer of selective catalytic reduction catalysts [0423] L.sub.1, L.sub.2, L.sub.3, L.sub.4, L.sub.5 Thickness [0424] h Distance [0425] H Height [0426] W Arrow [0427] W.sub.Q Arrow [0428] N Number of layers