Apparatus for controlled generation of gas from two fluid reagents deposited on a surface

Abstract

An apparatus for the controlled production of gas from first and second liquid reagents which produce gas and non-gaseous by-products upon mixing is provided, the apparatus comprising a reactor surface (14) having a substantially vertical axis of rotation, a shaft (24) which rotates about the axis of rotation and relative to the reactor surface, two nozzles (10, 12) mounted on the shaft configured to spray the first and second reagents, respectively, onto the reactor surface, the two nozzles being angled towards each other such that the first and second reagents are sprayed in intersecting cones onto a common area (16) of the reactor surface, and a scraper (20) mounted on the shaft configured to separate the by-products from the reactor surface while following the nozzles a distance sufficient to cause the reagents to react.

Description

Technical Field

[0001] The present invention relates to hydrogen carrier compounds, more specifically, to the production and collection of hydrogen from liquid hydrogen carriers. The production system can generally be applied to any gas generated by mixing liquid reagents and leaving solid by-products.

Background Art

[0002] Hydrogen carrier compounds can transport large amounts of hydrogen in solid or liquid form, which facilitates the transportation of hydrogen. Such hydrogen carriers can be silylated derivatives, more specifically those of the group of hydrogen-polysiloxanes having the general formula (HRSiO)n. To extract hydrogen, the hydrogen carrier compound is mixed in the presence of a so-called proton source, often water and a catalyst, see for example patent applications WO2010094785 and WO2011098614. After hydrogen is produced, by-products remain that need to be removed from the system and ultimately recycled.

[0003] Particularly when the by-product is solid, there are difficulties in continuously extracting hydrogen from such compounds while removing the by-product. Patent application WO2012151582 discloses a hydrogen generation system based on a solid hydrogen carrier that can remove solid by-products.

[0004] Patent application WO2020 / 187754 discloses a system for the continuous treatment of heavy oil, comprising a substantially horizontal heated rotary reactor, several nozzles configured to evenly distribute oil longitudinally within the reactor, and scraper means configured to maintain the thickness of the solid coke formed on the inner wall of the reactor at a predetermined thickness. The nozzles are distributed so that the spray patterns do not overlap.

Summary of the Invention

[0005] Apparatuses are generally provided for the controlled generation of gases from first and second liquid reagents that produce gases and non-gaseous byproducts upon mixing, the apparatus comprising a reactor surface having a substantially vertical axis of rotation, a shaft rotating relative to the reactor surface with respect to the axis of rotation, and two nozzles mounted on the shaft configured to spray the first and second reagents onto the reactor surface, the two nozzles being inclined toward each other so that the first and second reagents are sprayed into a common area of ​​the reactor surface in intersecting cones, and a scraper mounted on the shaft configured to separate the byproducts from the reactor surface while following the nozzles at a distance sufficient to allow the reagents to react.

[0006] The reactor surface may have an inverted truncated cone structure.

[0007] An inverted frustum of a cone can have a vertex angle of 30 to 120°.

[0008] The leading edge of the scraper may come into contact with the reactor surface at an angle of up to 90° between the scraper and the reactor surface.

[0009] The apparatus may further include a by-product collection area, and the scraper and reactor surface are oriented so that the separated by-products fall into the collection area.

[0010] The scraper may be delayed by at least 270° from the nozzle.

[0011] The first reagent may be a liquid hydrogen carrier, and the second reagent may be a liquid proton source, thereby producing hydrogen as the gas.

[0012] The hydrogen support can be a liquid silylated derivative.

[0013] The hydrogen support may be a liquid dihydrogen-polysiloxane, which produces byproducts that are essentially composed of silicates.

[0014] A method is also provided for the controlled generation of gas from first and second liquid reagents that produce gaseous and non-gaseous byproducts upon mixing, the method comprising: spraying the first and second reagents onto a common area of ​​a reactor surface having substantially vertical axes of rotation along intersecting cones; and scraping the reactor surface to remove any remaining byproducts on the reactor surface. The spraying and scraping are performed with rotational motion around the axes of rotation, with a delay sufficient to allow the reagents to react.

[0015] Embodiments are shown in the following description, which is provided for illustrative purposes only in connection with the accompanying drawings. [Brief explanation of the drawing]

[0016] [Figure 1A-C] The three stages of the operating principle of a device for generating gas from two liquid reagents are shown below. [Figure 2A-C] The three operating stages of an embodiment of a device for generating gas from two liquid reagents are shown below. [Figure 3] Figure 2C shows a perspective view of the device in operation at that stage. [Modes for carrying out the invention]

[0017] Figures 1A-1C illustrate the operating principle of an embodiment of an apparatus for producing hydrogen from the reaction of two reagents, both provided in liquid form. A byproduct removal mechanism is shown, which can be configured to process solid byproducts during a continuous hydrogen production cycle.

[0018] In Figure 1A, two liquid reagents, such as a hydrogen carrier and a proton source, are sprayed onto the reactor surface 14 by their respective nozzles 10 and 12. Since the two reagents should be mixed to the greatest extent possible, the nozzles are preferably oriented so that the two reagents are sprayed onto a common area 16 of the reactor surface, which can be achieved by tilting the nozzles toward each other, as shown.

[0019] In such a configuration, the spray cones intersect as shown by the dotted lines, and the mixing of the reagents starts before they reach the surface. To enhance efficiency, the intersection volume of the spray cones is made as large as possible, which can be achieved by fixing the nozzles as close to each other as possible.

[0020] Furthermore, the nozzles 10, 12 are configured to move together along the reactor surface 14 as indicated by the arrows when spraying the reagents, thus depositing a uniform thin film of the liquid reagent on the surface. The moving speed and flow rate of the nozzles are adjusted as a function of the reaction time and the desired gas generation rate.

[0021] In Figure 1B, the nozzles pass a certain extent of the reactor surface and deposit a thin film of the reagent. The deposited reagent has reacted leaving solid by-products 18.

[0022] Then, the scraper 20 is moved from behind the position of the nozzles as indicated by the arrow. The scraper is configured to pass through the entire reactor surface where the reagent has been deposited and discharge the remaining solid by-products.

[0023] In Figure 1C, the scraper 20 reaches the opposite side of the reactor surface. The solid by-products are pushed out from the edge of the surface and fall into a temporary storage area such as the collection tray 22 placed under the edge of the reactor surface.

[0024] After this stage, the scraper and the nozzles are returned to the position in Figure 1A to start a new cycle.

[0025] The reactor surface 14 can be made of any material that withstands the reaction temperature and mechanical stress. Preferably, the material does not adhere to the by-products and enables easy removal of the by-products. The surface can further be coated with a catalyst to promote the reaction.

[0026] The device of FIGS. 1A-1C is shown for purposes of explaining the operating principle. Therefore, it does not enable continuous generation of gas because it requires a reset stage to start a new generation cycle.

[0027] FIGS. 2A-2C show three operating stages of an embodiment of a device for continuously generating gas from two liquid reagents using the principle described in FIGS. 1A-1C.

[0028] In FIG. 2A, the reactor surface (14) is in the form of a rotating surface such as a cylinder. The shaft (24) is configured to rotate about the axis of rotation of the cylinder (14) and has nozzles (10, 12) and a scraper (20). In other words, all of the nozzles and the scraper rotate synchronously, for example, counterclockwise as indicated by arrow R in FIGS. 2A-2C.

[0029] The nozzles (10, 12) are axially aligned on the shaft (24) and are oriented to spray the liquid reagents radially into a common target area (16) on the inner surface of the cylinder (14). The scraper (20) is configured to sweep the inner surface of the cylinder when the shaft rotates and has a height of contact with the cylinder surface that is preferably greater than the height of the common target spray area.

[0030] To increase the reaction time for a given rotational speed, the scraper (20) is attached to the shaft so as to start operating as late as possible after the initial spraying. Ideally, the scraper operates with a 360° rotational delay after the nozzle, which would mean that the scraper is aligned with the nozzle on the shaft. This is not actually achievable. As shown as an example, the scraper (20) is attached to the shaft so as to precede the nozzle by about 45° in the rotational direction, providing some spacing with respect to the spray cone. Such a configuration corresponds to a scraping operation delay of about 315°. Satisfactory results can be obtained within a delay angle range of, for example, 270 to 360°.

[0031] As shown, the leading edge of the scraper contacts the cylindrical surface at an angle of approximately 90°. The leading edge preferably has a recessed shape, i.e., the angle between the scraper and the surface being cleaned is 90° or less, and as a result, the scraper, preferably made of a suitable material, maintains a scraping effect against the lamination effect. The trailing edge of the scraper may be tapered, as shown.

[0032] Figure 2A shows the initial stage, where cylinder 14 is clean, nozzles 10 and 12 have just begun spraying the reagent, and no byproducts have formed.

[0033] In Figure 2B, the nozzle and scraper are rotated 180°. The nozzle deposits a uniform layer of reagent onto half of the cylinder. The deposited reagent initiates the reaction, leaving a solid byproduct layer 18, which typically thickens over time. The scraper 20 has not yet started operating.

[0034] In Figure 2C, the scraper 20 reaches the point in Figure 1A where the nozzle began spraying. At this point, the scraper reaches the initial byproduct formation and begins to remove it.

[0035] Figure 3 shows a perspective view of the apparatus in operation at the stage shown in Figure 2C. Various structural details of the elements are more clearly visible. As previously mentioned, the nozzles 10 and 12 are inclined toward each other so that both spray into the same common area 16 of the cylinder and their spray cones intersect. The scraper 20 may have a substantially parallelepiped shape.

[0036] The cylinder 14 is preferably vertical, so that the detached by-products fall by gravity into the lower part of the cylinder, which serves as a storage area. The scraper may be configured so that its contact end with the cylindrical surface is inclined to push the deposited by-products downward.

[0037] The bottom of the cylinder may be equipped with an airtight drawer system for periodically removing excess by-products during the gas generation cycle. Once the drawer is full, it will contain little to no gas, so its removal will cause little to no gas leakage. Alternatively, the bottom of the cylinder may be large enough to store all of the by-products of the generation cycle.

[0038] Such a system achieves gas generation from liquid reagents in continuous mode. The gas generation rate of the system increases with the nozzle flow rate. As the flow rate increases, the rotation speed of the system should also increase, but since the rotation speed is limited by the reaction time of the reagents, the diameter and height of the cylinder may be increased.

[0039] In some situations, particularly when using low-viscosity reagents at higher flow rates, a vertical cylindrical configuration can cause the reagents to flow downwards and drip from the cylindrical surface before they have finished reacting together.

[0040] To prevent this, the reactor surface may have an inverted frustoconical structure (with a vertex and a truncated apex at the base, the latter facing the collection area). The angle of the cone's apex is chosen to prevent the reagent from flowing, or at least slow down the flow rate, to provide sufficient time for the reagents to react together.

[0041] Good results for hydrogen extraction applications were observed at a apex angle of approximately 90°. The minimum angle value depends on the nozzle flow rate and the viscosity of the reagent. In practice, this value can be approximately 30°. The actual apex angle can be selected somewhere above this value, with the upper limit being 180° (where the cone becomes a disk). In practice, angles greater than 120° are avoided because they hinder the extraction of by-products and make the apparatus too difficult to handle, and angles less than 20° are avoided because they do not provide sufficient retention of the reagent.

[0042] The use of a vertical axis cone is preferable to an inclined cylinder, such as the one disclosed in patent application WO2020 / 187754. Indeed, since a vertical axis cone provides a uniformly inclined surface at any angular position, uniform reaction conditions for two sprayed reagents are provided across the entire spraying area.

[0043] As mentioned above, the hydrogen carrier reagent is available in liquid form and has the general formula (HRSiO) n It may be a group of hydrogen-methyl-polysiloxanes having the following properties. The proton source reagent can be simply water, among other possibilities. However, the resulting by-products are difficult to recycle.

[0044] A preferred hydrogen carrier is one with the general formula (H2SiO) n These are dihydrogen-polysiloxanes, which correspond to silicates whose byproducts can be readily recycled back into hydrogen carriers. Such compounds also react with water as a proton source, among other possibilities.

[0045] Dihydrogen-polysiloxanes have only been found in solid form and are difficult to produce industrially. However, patent application EP18305549 discloses a method for industrially producing dihydrogen-polysiloxanes in liquid form, which makes dihydrogen-polysiloxanes particularly well suited for use in this system.

[0046] The system disclosed herein is applicable to the production of gases from any liquid reagents that leave solid byproducts. Although the apparatus is specifically designed for processing solid byproducts, it can also be used to process liquid byproducts in a very similar manner.

[0047] Spray nozzles 10 and 12 are disclosed as preferred embodiments for spreading liquid reagents across the reactor surface. More generally, spreading liquids can be achieved by alternative techniques such as liquid-spreading blades, brushes with liquid dispensers, or dome-shaped liquid deflectors for creating a flowing liquid layer.

Claims

1. An apparatus for the controlled generation of gas from first and second liquid reagents that produce gas and non-gaseous by-products during mixing, - A reactor surface having a substantially vertical axis of rotation, - A shaft that rotates around the aforementioned axis of rotation and relative to the surface of the reactor, Two nozzles mounted on the shaft, configured to spray the first and second reagents onto the reactor surface, wherein the two nozzles are inclined toward each other so that the first and second reagents are sprayed onto a common area of ​​the reactor surface in intersecting cones, - A scraper attached to the shaft, configured to separate the by-product from the reactor surface while following the nozzle at a distance sufficient to allow the reagent to react, A device equipped with the following features.

2. The apparatus according to claim 1, wherein the reactor surface has an inverted frustoconical structure.

3. The apparatus according to claim 2, wherein the inverted frustum of a cone has a vertex angle of 30 to 120°.

4. The apparatus according to claim 1, wherein the leading edge of the scraper contacts the reactor surface at an angle of up to 90° between the scraper and the reactor surface.

5. The apparatus according to claim 1, comprising a by-product collection area, wherein the scraper and the reactor surface are oriented so that the separated by-products fall into the collection area.

6. The apparatus according to claim 1, wherein the scraper is delayed by at least 270° from the nozzle.

7. The apparatus according to claim 1, wherein the first reagent is a liquid hydrogen carrier, and the second reagent is a liquid proton source, and thereby the generated gas is hydrogen.

8. The apparatus according to claim 7, wherein the hydrogen carrier is a liquid silylated derivative.

9. The apparatus according to claim 7, wherein the hydrogen carrier is a liquid dihydrogen-polysiloxane and produces a by-product that is essentially composed of silicates.

10. A method for the controlled generation of gas from first and second liquid reagents that produce gas and non-gaseous by-products upon mixing, wherein the method is as follows: - A step of spraying the first and second reagents onto a common area of ​​the reactor surface having substantially vertical axes of rotation along intersecting cones, - A step of scraping the reactor surface in order to remove the by-products remaining on the reactor surface. Includes, The spraying and scraping are performed by rotational motion around the rotating shaft, with a delay sufficient to allow the reagent to react. method.

11. The method according to claim 10, wherein the reactor surface has an inverted frustoconical structure.

12. The method according to claim 11, wherein the inverted frustum of a cone has a vertex angle of 30 to 120°.

13. The method according to claim 10, wherein the scraping is delayed by at least 270° from the spraying.

14. The method according to claim 10, wherein the first reagent is a liquid hydrogen carrier, and the second reagent is a liquid proton source, and thereby the generated gas is hydrogen.

15. The method according to claim 14, wherein the hydrogen carrier is a liquid dihydrogen-polysiloxane and produces a byproduct that is essentially composed of silicates.

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