AMMONIA PRECURSOR GENERATING SYSTEM FOR USE IN A VEHICLE

Abstract

An ammonia precursor generating system includes: a storage compartment storing at least ammonia precursor granules; a tank storing an ammonia precursor solution; a dissolving compartment configured to store an ammonia precursor solution, and to dissolve ammonia precursor granules in the ammonia precursor solution; a transfer mechanism configured to transfer ammonia precursor granules from the storage compartment to the dissolving compartment; a fluid transfer device configured to transfer the ammonia precursor solution from the tank to the dissolving compartment.

Claims

1. An ammonia precursor generating system comprising: a storage compartment storing at least ammonia precursor granules; a tank storing an ammonia precursor solution; a dissolving compartment adapted for storing the ammonia precursor solution, and for dissolving ammonia precursor granules in the ammonia precursor solution; a transfer means configured for transferring ammonia precursor granules from said storage compartment to said dissolving compartment; a fluid transfer device configured for transferring the ammonia precursor solution from said tank to said dissolving compartment.

2. The ammonia precursor generating system of claim 1, wherein said transfer means is a dosing device configured for dosing a number of ammonia precursor granules to be inserted in the dissolving compartment.

3. The ammonia precursor generating system of claim 1, wherein said dissolving compartment comprises a trigger device arranged for triggering the dissolving the ammonia precursor granules in the ammonia precursor liquid.

4. The ammonia precursor generating system of claim 3, wherein said trigger device is a heater arranged for heating the ammonia precursor solution in the dissolving compartment and configured for dissolving the ammonia precursor granules in the ammonia precursor liquid.

5. The ammonia precursor generating system of claim 1, wherein the storage compartment stores ammonia precursor granules containing solid urea.

6. The ammonia precursor generating system of claim 1, wherein the storage compartment stores ammonia precursor granules having a coating, said coating being adapted to be thermally dissolved in the ammonia precursor liquid.

7. The ammonia precursor generating system of claim 6, wherein the storage compartment stores the ammonia precursor granules in a liquid, and said coating is such that the coating is not dissolved in the liquid in the storage compartment.

8. The ammonia precursor generating system of any one of the previous claims claim 1, further comprising a filler pipe in connection with the storage compartment for filling the storage compartment with ammonia precursor granules; wherein said filler pipe is optionally also intended for filling said storage compartment with an ammonia precursor liquid, and/or wherein the storage compartment is arranged for allowing said ammonia precursor liquid to flow to the dissolving compartment.

9. The ammonia precursor generating system of claim 1, wherein the dissolving compartment is provided with a decomposition activator device configured to convert ammonia precursor solution to ammonia solution in the dissolving compartment.

10. The ammonia precursor generating system of claim 9, wherein the decomposition activator device comprises an enzyme storage unit configured to store an enzyme, and an enzyme transfer means configured for transferring enzyme to the dissolving compartment, said enzyme being adapted to convert ammonia precursor to ammonia.

11. The ammonia precursor generating system of a claim 1, comprising a decomposition compartment provided with a decomposition activator device configured to convert ammonia precursor solution to ammonia solution, and a transfer means configured for transferring ammonia precursor solution from the dissolving compartment to the decomposition compartment; wherein the decomposition activator device optionally comprises an enzyme storage unit configured to store an enzyme, an enzyme transfer means configured for transferring enzyme to the decomposition compartment, said enzyme being adapted to convert ammonia precursor to ammonia, and a heater.

12. The ammonia precursor generating system of claim 9, further comprising a buffer compartment for storing the ammonia solution; wherein the buffer compartment optionally surrounds the dissolving compartment, and/or wherein the buffer compartment and the dissolving compartment are integrated in a single module.

13. The ammonia precursor generating system of claim 1, wherein the storage compartment and dissolving compartment are arranged in a common tank.

14. The ammonia precursor generating system of claim 1, further comprising a conversion unit for converting ammonia into hydrogen; and/or a controller configured for controlling the transfer means such that granules are transferred to the dissolving unit upon request, as needed.

15. SCR system comprising an ammonia precursor generating system according to claim 1.

16. Fuel cell system comprising an ammonia precursor generating system according to claim 1.

17. Granule for use in a vehicle, said granule containing solid ammonia precursor, and having a coating adapted to be dissolved in an ammonia precursor liquid.

18. Granule of claim 17, wherein the granule contains solid urea.

19. Granule of claim 17, wherein the coating is adapted to be thermally dissolved in an ammonia precursor liquid.

20. Granule of claim 17, wherein the granule has dimensions between 0.01 micron and 50 mm, preferably between 100 micron and 5 mm, and more preferably between 500 microns and 5 mm; and/or wherein the granule is substantially ball-shaped; and/or wherein the coating of the ammonia precursor granules is made of any one or more of the following materials: polyvinylidene chloride (PVDC), linear low density polyethylene (LLDPE), certain grades of ethylene vinyl alcohol (EVOH), certain grades of polyvinyl alcohol (PVOH), biaxially oriented polypropylene (BOPP), cyclic olefin polymer (COC), polyethylene naphthalate (PEN), liquid-crystal polymers (LCPs, a class of aromatic polyester polymers), polypropylene (PP), and polyethylene terephthalate blends (PET/PE, PET/PVDC/PE, PET/PVOH/PE, PET/EVOH/PE); and/or wherein the coating is a multi-layer coating.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0030] The accompanying drawings are used to illustrate presently preferred non-limiting exemplary embodiments of devices of the present invention. The above and other advantages of the features and objects of the invention will become more apparent and the invention will be better understood from the following detailed description when read in conjunction with the accompanying drawings, in which:

[0031] FIG. 1 is a diagram illustrating an exemplary embodiment of a vehicle system for generating hydrogen for a hydrogen fuel cell;

[0032] FIGS. 2, 3, 4, 5, and 6 are diagrams illustrating exemplary embodiments of an ammonia precursor generating and decomposition system;

[0033] FIG. 7A-C illustrate two variants of a module for use in an exemplary embodiment of an ammonia precursor generating and decomposition system; and

[0034] FIGS. 8 and 9 are diagrams illustrating further exemplary embodiments of an ammonia precursor generating and decomposition system.

DESCRIPTION OF EMBODIMENTS

[0035] FIG. 1 illustrates a first embodiment of an ammonia precursor booster system as used in a vehicle system for generating hydrogen for a hydrogen fuel cell. The ammonia precursor booster system comprises a storage compartment 110 in the form of an inner chamber of a tank 100, a dissolving compartment 120 in the form of a sub-tank located in the tank 100, and a transfer means 130. The storage compartment 110 is adapted for storing ammonia precursor granules 111. The dissolving compartment 120 is adapted for storing an ammonia precursor solution, and for dissolving ammonia precursor granules in the ammonia precursor solution. The transfer means 130 are configured for transferring ammonia precursor granules from the storage compartment 110 to the dissolving compartment 120. In the embodiment of FIG. 1 the transfer means is a dosing device 130 configured for dosing a number of ammonia precursor granules to be inserted in the dissolving compartment 120.

[0036] The dissolving compartment comprises a trigger device in the form of a heater 140 arranged for triggering the dissolving the ammonia precursor granules 111 in the ammonia precursor liquid in the dissolving compartment 120.

[0037] In the present embodiment the dissolving compartment 120 also functions as a decomposition unit for converting ammonia precursor into ammonia. There is provided a decomposition activator device comprising an enzyme storage unit 160 configured to store an enzyme, and an enzyme transfer means 170, 175 configured for transferring enzyme to the dissolving compartment 120, said enzyme being adapted to convert ammonia precursor to ammonia. The enzyme storage unit 160 has an enzyme access port 162 for filling the enzyme storage unit 160 with enzyme. The heater 140 functions also as a part of the decomposition activator device for activating the enzymatic conversion of ammonia precursor to ammonia in the dissolving compartment 120.

[0038] The system of FIG. 1 further comprises a filler pipe 115 in connection with the storage compartment for filling the storage compartment with ammonia precursor granules, and for filling said storage compartment with a ammonia precursor liquid, wherein the storage compartment 110 is arranged for allowing said ammonia precursor liquid to flow to the dissolving compartment 120, here by providing the storage compartment 110 above the dissolving compartment 120 and by providing the bottom of the storage compartment 110 with through holes allowing the liquid to pass through whilst blocking the granules.

[0039] Also the system of FIG. 1 comprises a buffer compartment 180 for storing converted ammonia, a conversion unit 190 for converting ammonia into hydrogen, and a hydrogen fuel cell 195.

[0040] The tank 100 may be filled with the commercially available liquid ammonia precursor, known as AdBlue and matching the ISO 22241 standard specifications. Such a fluid contains 32.50.7 weight % urea. The tank 100 is equipped with a chamber forming the storage compartment 110 containing small granules, e.g. ball-shaped granules containing solid urea, in order to increase the urea concentration in the solution to be converted into ammonia solution. The urea granules are preferably coated so as to avoid the release of the solid urea in the main chamber 118 of the tank that could result in a premature increase of the urea concentration and precipitates in or freezing of the content of the main chamber 118. Preferably, the size of the ammonia precursor granules is in a range from 0.01 micron to 50 mm, more preferably from 100 micron to 5 mm, and e.g. between 500 microns and 5 mm.

[0041] When conversion from urea to ammonia is needed, the urea solution is transferred from the main chamber 118 to the decomposition unit 120 by a fluid transfer device 122. A fluid transfer device can be for example a pump, a valve, a combination of both, gravity, gravity in combination with a valve, or a valve in combination with whatever system known by the person skilled in the art to transfer liquid. The decomposition unit 120 is equipped with a heater 140 in order to thermally dissolve the coating of the ammonia precursor granules, dissolve the solid urea contained in the granules, and activate the enzymes converting the urea to ammonia. The ammonia precursor granules can be transferred to the decomposition unit 120 by a dosing device 130. The dosing device may be a device as described in US 20070128054A1 in the name of the Applicant, a dosing device as described in FR2911639B or FR2911641B, a powder dosing device, such as described in EP0296632A2, EP0859944B1, EP0973015A1, U.S. Pat. No. 6,701,944B2, US0318218A1 or U.S. Pat. No. 6,510,962B1, etc. When conversion is needed, the dosing device 130 is activated and a small quantity of enzyme is transferred from the enzyme storage unit 160 to the decomposition unit 120 by means of a connecting pipe 170 and a dosing pump 175. The enzyme storage unit 160 contains a bio-agent suitable to convert the urea solution into an ammonia solution. For example, as an enzyme, urease can be used to decompose urea, or any other suitable protein sequence. As the temperature remains relatively high in the decomposition unit 120, no freezing or precipitating of urea occurs. Also, once the urea is converted into ammonia, no freezing occurs either as the freezing temperature of the effluents from the decomposition is even lower.

[0042] When the conversion is complete, for instance, when 50% of the ammonia precursor, typically urea, is converted into an ammonia solution, or ideally when at least 80% or more of the ammonia precursor is converted into aqua ammonia, the resulting effluents are transferred to the buffer tank 180 by a fluid transfer device 124. Thus, the system of the embodiment of FIG. 1 allows increasing the urea concentration in the urea solution to be converted to ammonia and, consequently, increasing the ammonia concentration in the final solution.

[0043] The ammonia solution with increased or boosted concentration in the buffer tank 180 is ready to be sent by a fluid transfer device 182 to a downstream tank, to the exhaust pipe or to any additional system to store or consume ammonia (not illustrated). In the example shown in FIG. 1, the ammonia buffer tank 180 communicates with an ammonia-hydrogen conversion unit 190 that subsequently communicates with a hydrogen fuel cell 195 where the hydrogen is converted into a power source. The ammonia solution could also be used in a direct ammonia fuel cell (not illustrated).

[0044] The filler pipe 115 is connected to an inner chamber forming the storage compartment 110. The inner chamber has holes 112, allowing the liquid ammonia precursor to flow inside the lower part of tank 100 (the main chamber 118) but being too small for letting the granules flow into the main chamber 118 of the tank. The inner chamber 110 is connected to the decomposition unit 120 through the dosing device 130, so that granules containing solid urea can be introduced at the top of the decomposition unit 120. The migration of the granules 111 to the inner chamber 110 can be promoted by the movement of the ammonia precursor liquid when the tank is refilled, but this is not required.

[0045] In an exemplary embodiment, the ammonia precursor granules 111 can be transferred to the decomposition unit 120 after the conversion to ammonia is partially completed, for instance, when at least 30% of the ammonia precursor is converted into ammonia solution. The presence of ammonia in the solution may help to chemically decompose the coating of the granules.

[0046] In variants of the embodiment of FIG. 1 other means for releasing the solid urea contained in the granules may be used, in addition or as an alternative to temperature and chemical attack. Possible other means comprise the use of a mechanical force, or a pressure, or a combination of any of those forms or any other means known in the art.

[0047] FIG. 2 illustrates a second embodiment in which ammonia precursor granules 211 are transferred from a storage compartment 210 of a tank 200 to a dissolving compartment in the form of a warm chamber 220 to be dissolved, before being decomposed in a decomposition unit 250. The warm chamber 220 is equipped with a heater 240 in order to thermally dissolve the coating material and release the urea content, and the decomposition unit 250 is provided with a further heater 245 for the conversion into ammonia. This physical separation between the dissolving compartment 220 and the decomposition unit 250 limits the temperature interference that can happen between the two different compartments, since the temperature for enzyme activation and coating dissolution may be different: for instance, the dissolution temperature of the coating may be 70 C., while the optimum temperature for the decomposition unit may be 50 C. The boosted ammonia solution may be cooled down by a cooling device, which can be natural heat dissipation occurring between the warm chamber 220 and the decomposition unit 250 at the level of a fluid transfer device 226, and then transferred to the decomposition unit 250 by the fluid transfer device 226. Dosing device 230 transfers both granules and ammonia precursor liquid to the warm chamber 220. Further, ammonia precursor liquid may be fed into the decomposition unit 250 via an optional fluid transfer device 214. Next the ammonia solution may be transferred to a buffer compartment 280 via a further fluid transfer device 252, and from there via a fluid transfer device 282 to e.g. the exhaust pipe of a vehicle. In a possible embodiment fluid transfer device 214 is used to transfer some ammonia precursor liquid to start the decomposition in decomposition unit 250, whereupon, step by step, urea boosted solution may be added by fluid transfer device 226.

[0048] FIG. 3 describes another exemplary embodiment of the invention. Here a dissolving and decomposition unit 320 and a buffer tank 380 are integrated into a single cylinder module located in a tank 300. The dissolving and decomposition unit 320 is located in the core of the module and is surrounded by the buffer tank 380. When needed, ammonia precursor granules 311 (optionally with liquid) in a storage compartment 310 can be added to the urea solution in the dissolving and decomposition unit 320 by means of a dosing device 330 to be dissolved and further converted. The urea solution can be transferred from a main chamber 318 of the tank 300 to the dissolving and decomposition unit 320 by a fluid transfer device 322. When the conversion is complete, the resulting effluents are transferred to the buffer tank 380 by a fluid transfer device 324. The ammonia solution with increased concentration in the buffer tank 380 is ready to be sent by a fluid transfer device 382 to e.g. a downstream tank, to the exhaust pipe or to any additional system to store or consume ammonia (not illustrated).

[0049] FIG. 4 shows another exemplary embodiment. The ammonia precursor granules are stored in a storage compartment 410 in the form of a separated urea storage unit inside a tank 400. When needed, the granules are dispensed into a dissolving and decomposition unit 420 by a dosing device 430. The granules can be prepared as thin particles and may be dissolved at the same temperature as needed for the conversion to ammonia. The granules may be added to the urea storage unit 410 via a filler pipe 415. Enzyme may be added to the dissolving and decomposition unit 420 by a pipe 470. Main chamber 418 is filled with urea solution via filler pipe 417. The urea solution can be transferred from the main chamber 418 of the tank 400 to the dissolving and decomposition unit 420 by a fluid transfer device 422. When the conversion is complete, the resulting effluents are transferred to the buffer tank 480 by a fluid transfer device 424. The ammonia solution with increased concentration in the buffer tank 480 is ready to be sent by a fluid transfer device 482 to e.g. a downstream tank, to the exhaust pipe or to any additional system to store or consume ammonia (not illustrated).

[0050] FIG. 5 shows a variant of the embodiment of FIG. 4 where a tank 500 comprises a urea storage unit 510, a dissolving and decomposition unit 520 and a buffer tank 580 which are integrated into a single cylinder module. There is provided a first filler pipe 515 for adding dry ammonia precursor to the urea storage unit 510, and a second filler pipe 517 for filing ammonia precursor liquid to the tank 500. There is provided a dosing device 530 for dosing solid ammonia precursor of the urea storage unit 510 into the decomposition unit 520, and an enzyme transfer pipe 570 for transporting enzyme to the decomposition unit 520. A first fluid transfer device 522 transports ammonia precursor liquid from the tank 500 to the decomposition unit 520, and a second fluid transfer device 524 transfers converted ammonia solution to the buffer tank 580, from where the ammonia solution may be transported by means of a fluid transfer device 582 to any location in the vehicle where the solution is needed.

[0051] FIG. 6 illustrates a preferred embodiment where an enzyme storage unit 660, a decomposition unit 620 and a buffer tank 680 are part of the same module which is arranged in a tank 600. The urea solution is transferred from a main chamber 618 of the tank 600 to the decomposition unit 620 by a fluid transfer device 622. The tank 600 is filled with ammonia precursor liquid and granules via a filler pipe 615. In other words, the main chamber 618 of the tank 600 functions as the storage compartment for storing granules. The enzyme storage unit 660 is filled for example through a filler pipe 670 and contains a bio-agent in suitable form to convert the urea solution into an ammonia solution. For example, as an enzyme, urease can be used to decompose urea, or any other suitable protein sequence. When the conversion is needed, the decomposition unit 620 is filled with the ammonia precursor by the fluid transfer device 622. The ammonia precursor granules 611 can be transferred to the decomposition unit 620 through a channel equipped with a heated transfer tube 632 with a heater 636 in order to generate a flow of liquid and entrain the granules near the dosing device 630 by heat convection or by a thermo-siphon effect. The granules are circulated together with the liquid and are trapped at the end on the tube. The tube is closed at one side by a strainer 634 that allows the liquid to flow, but blocks the passage of the granules. The granules trapped at the end of the tube are then transferred to the decomposition unit 620 by the dosing device 630. Subsequently, a small quantity of enzyme is transferred from the enzyme storage unit 660 to the decomposition unit 620 by an enzyme dosing device 675. Optionally the enzyme storage unit 660 may be provided with thermal conditioning element. When the conversion is complete, the resulting effluents are transferred to the buffer tank 680 by a fluid transfer device 624.

[0052] The solution in the buffer tank 680 is ready to be sent by a fluid transfer device 682 to a downstream tank, to the exhaust pipe or to any additional system to store or consume ammonia (not illustrated). The ammonia buffer tank 680 can also communicate with an ammonia-hydrogen conversion unit that subsequently communicates with a hydrogen fuel cell where the hydrogen is then converted into a power source such as electricity (not illustrated), as in the embodiment of FIG. 1. Alternatively, the ammonia solution can be used in a direct ammonia fuel cell (not illustrated).

[0053] According to a variant of the embodiments of FIG. 1-6, fluid transfer device 122, 322, 422, 522, 622 and the dosing device 130, 330, 430, 530, 630 can be combined in a single component to feed continuously liquid ammonia precursor and granules in a given proportion, simplifying the setup.

[0054] FIGS. 7A and 7B illustrate two variants of a suitable module in which the dissolving and decomposition compartment and buffer compartment may be arranged. The module can be designed as a multi-compartment container with different shapes, such as a barrel shape illustrated in FIG. 7A or a tower shape illustrated in FIG. 7B. For a typical barrel shape the height will be less than the diameter. Both shapes may be composed of a central cylindrical compartment forming the decomposition unit 720 and a surrounding compartment forming the buffer tank 780, as illustrated in FIG. 7C. This has the advantage that the warm decomposition unit 720 is separated from the cold main chamber by the buffer compartment 780. In addition, with the preferred setup, the effluents in buffer tank 780 will be at an intermediate temperature between the temperature of the cold chamber of the main tank and the temperature of the decomposition unit 720, and will also contribute to limit the heat losses from the decomposition unit 720. Also, in case of leakage of the buffer solution containing ammonia, this irritating substance will stay in the main tank containing urea. The more diluted ammonia solution is then less dangerous to the environment. An enzyme storage unit and/or a urea storage unit may be located on the top of the module and may be integrated in the module.

[0055] FIG. 8 illustrates a further embodiment where ammonia precursor granules stored into a urea storage unit 810, are transferred into a warm dissolving compartment 820 by a dosing device 830 where the granules can be thermally dissolved in a urea solution. The urea storage unit 810 and the dissolving compartment 820 are arranged in a tank 800 which can be filled with an aqueous urea solution which is transferred by a liquid transfer device 822 to the dissolving compartment 820. The boosted urea solution in the dissolving compartment 820 can be transferred by a further liquid transfer device 824 to a location in a vehicle where the boosted urea solution is needed. Alternatively, as illustrated in FIG. 9, ammonia precursor granules can be transferred to a warm chamber 920 through a channel equipped with a heated transfer tube 932 in order to generate liquid circulation by convection or by a thermo-siphon method. The granules are circulated together with the liquid and trapped at the end on the tube by a strainer 934. The granules 911 are transferred to the warm chamber 920 by a dosing device 930. The boosted (or more concentrated) urea solution in the warm chamber is ready to be sent by a fluid transfer device 924 to the exhaust pipe and SCR catalyst or to any additional system to store or consume urea (not illustrated). Optionally, the dosing device 930 and the fluid transfer device 922 may be combined in a single component arranged to send granules and liquid ammonia precursor according to a set proportion to the warm chamber 920, simplifying the setup.

[0056] In the exemplary embodiments illustrated above, when using AdBlue as the ammonia precursor liquid, the total urea concentration in the dissolving compartment may be progressively increased to 55% by weight after dissolution of the granules in AdBlue. In other words, 1 kg of solution contains 450 g of water and 550 g of urea, from which 217 g (32.5% of (450 g+217 g)) originate from the eutectic AdBlue and 333 g have been added in the form of solid ammonia precursor granules per kg of solution. While a conventional SCR system would require 45 litre useful volume to reach a driving range of 30000 km (corresponding for instance to the maintenance interval) with a consumption of 0.15 litre of AdBlue per 100 km, embodiments of a system boosted with granules would require only about 27 litre of useful volume for the same driving range. Accordingly, the weight of the full system would be reduced by about 20 kg.

[0057] In another exemplary embodiment, the total urea concentration may be progressively increased to 76.9% by weight after dissolution of the granules in AdBlue. So 1 kg of solution contains 231 g of water and 769 g of urea, from which 111 g (32.5% of (231 g+111 g)) originate from the eutectic AdBlue and 658 g have been added in the form of solid ammonia precursor granules per kg of solution. While a conventional SCR system would require 45 litre useful volume to reach a driving range of 30000 km (corresponding for instance to the maintenance interval) with a consumption of 0.15 litre of AdBlue per 100 km, embodiments of the system boosted with granules would only require about 20 litre of useful volume for the same driving range. Accordingly, the weight of the full system would be reduced by about 25 kg.

[0058] In the example of a fuel cell feeding system, a vehicle equipped with a prior art system of 70 litre useful volume based on AdBlue and consuming 28 litre/100 km has a driving range of 250 km, while a system of the same useful volume in accordance with embodiments of the invention and filled with the boosted solution having an urea concentration boosted at 55% in weight as set out above, will reach a driving range of about 420 km, and a system filled with the boosted solution having an urea concentration boosted at 76.9% in weight as set out above, will reach a driving range close to 600 km.

[0059] In an exemplary embodiment a granule contains solid ammonia precursor, and has a coating adapted to be dissolved in an ammonia precursor liquid. The solid ammonia precursor is preferably solid urea, but ammonia precursor granules may contain other materials than urea, such as ammonium carbamate which is also a solid that can dissolve in water and generate ammonia, and more generally ammonia salts. Preferably the coating is adapted to be thermally dissolved in an ammonia precursor liquid. The coating of the ammonia precursor granules may be made of any one or more of the following materials: polyvinylidene chloride (PVDC), linear low density polyethylene (LLDPE), certain grades of ethylene vinyl alcohol (EVOH), certain grades of polyvinyl alcohol (PVOH), biaxially oriented polypropylene (BOPP), cyclic olefin polymer (COC), polyethylene naphthalate (PEN), liquid-crystal polymers (LCPs, a class of aromatic polyester polymers), polypropylene (PP), and polyethylene terephthalate blends (PET/PE, PET/PVDC/PE, PET/PVOH/PE, PET/EVOH/PE). Whilst the principles of the invention have been set out above in connection with specific embodiments, it is to be understood that this description is merely made by way of example and not as a limitation of the scope of protection which is determined by the appended claims.