Device for controlled gas production from two liquid reagents applied to surface and method for controlled gas production

Abstract

FIELD: production of gas.SUBSTANCE: device and method for controlled production of gas from first and second liquid reagents. Device which comprises a reactor surface (14) having a substantially vertical axis of rotation; a shaft (24) centered on the axis of rotation and rotating relative to the reactor surface; two nozzles (10, 12) attached to the shaft, configured to spray the first and second reagents, respectively, onto the reactor surface. Two nozzles are inclined towards each other in such a way that the spray cones of the first and second reactants intersect in a common area (16) of the reactor surface; and a scraper (20), attached to the shaft, is configured to separate the by-product from the reactor surface, while following the nozzles at a distance sufficient for the reactants to react.EFFECT: provision of the device and the method for the controlled production of gas from first and second liquid reagents, as a result of mixing of which a gas and a non-gaseous by-product are formed.15 cl, 7 dwg

Description

Field of technology

[0001] The present invention relates to hydrogen carrier compounds and, more specifically, to the production of hydrogen from a liquid hydrogen carrier. The production system can be applied, more generally, to any gas that is formed by mixing liquid reactants to produce a solid by-product. The present invention particularly relates to a device for the controlled production of gas from first and second liquid reactants and to a method for the controlled production of gas from first and second liquid reactants.Background of the invention

[0002] Hydrogen carrier compounds are capable of transporting significant volumes of hydrogen in solid or liquid form. This facilitates the hydrogen transfer process. Such hydrogen carriers can belong to the family of silylated derivatives, more specifically, hydrogen-polysiloxanes with the general formula (HRSiO)n. To extract hydrogen, the hydrogen carrier compound is mixed with a so-called proton source, often water, in the presence of catalysts (see, for example, patent applications WO2010094785 and WO2011098614). After hydrogen production, a byproduct remains that must be removed from the system and ultimately recycled.

[0003] The challenge lies in continuously extracting hydrogen from such components while simultaneously removing byproducts, especially when the byproducts are solid. Patent application WO 2012151582 describes a hydrogen production system based on solid carriers capable of removing solid byproducts.

[0004] Patent application WO2020 / 187754 describes a system for the continuous processing of heavy fuel oils, comprising a substantially horizontal heated rotating reactor, a number of nozzles configured to uniformly distribute oil in the longitudinal direction within the reactor, and a scraper device configured to maintain a predetermined thickness of hard coke formed on the inner wall of the reactor. The nozzles are distributed in such a way that the spray areas do not overlap. Summary of the invention

[0005] In essence, in a first aspect of the present invention, for the controlled production of gas from first and second liquid reactants, as a result of mixing of which a gas and a non-gaseous by-product are formed, a device is proposed, comprising: - a reactor surface having a vertical axis of rotation; - a shaft centered on the axis of rotation and rotating relative to the reactor surface; - two nozzles attached to the shaft, configured to spray the first and second reactants, respectively, onto the reactor surface, wherein the two nozzles are inclined to each other in such a way that the spray cones of the first and second reactants intersect in a common area of ​​the reactor surface; and - a scraper attached to the shaft, configured to separate the by-product from the reactor surface, while following the nozzles at a distance sufficient for the reactants to react.

[0006] In a preferred embodiment, the reactor surface has the shape of an inverted truncated cone.

[0007] In a preferred embodiment, the inverse truncated cone has an apex angle of between 30 and 120 degrees

[0008] In a preferred embodiment, the leading edge of the scraper contacts the surface of the reactor at an angle of no more than 90 degrees between the scraper and the surface of the reactor.

[0009] In a preferred embodiment, the device comprises a by-product collection zone, wherein the scraper and the reactor surface are oriented such that the separated by-product falls into the collection zone.

[0010] In a preferred embodiment, the scraper lags behind the nozzles at an angle of at least 270 degrees.

[0011] In a preferred embodiment, the first reactant is a liquid hydrogen carrier and the second reactant is a liquid proton source, and the resulting gas is hydrogen.

[0012] In a preferred embodiment, the hydrogen carrier is a liquid silylated derivative.

[0013] In a preferred embodiment, the hydrogen carrier is a liquid dihydrogenpolysiloxane that forms a by-product mainly consisting of silicate.

[0014] In a second aspect, the present invention provides a method for the controlled production of gas from first and second liquid reactants that, when mixed, form a gas and a non-gaseous by-product, comprising the following steps: - spraying the first and second reactants in the form of intersecting cones onto a common area of ​​the surface of a reactor having a vertical axis of rotation; and - scraping the surface of the reactor to remove the by-product remaining on the surface of the reactor; - wherein the spraying and scraping are performed by a rotational movement around the axis of rotation with a delay sufficient for the reactants to react.

[0015] In a preferred embodiment, the reactor surface has the shape of an inverted truncated cone.

[0016] In a preferred embodiment, the inverse truncated cone has an apex angle of between 30 and 120 degrees.

[0017] In a preferred embodiment, scraping is performed at an angle of at least 270 degrees behind spraying.

[0018] In a preferred embodiment, the first reactant is a liquid hydrogen carrier and the second reactant is a liquid proton source, and the resulting gas is hydrogen.

[0019] In a preferred embodiment, the hydrogen carrier is a liquid dihydrogen polysiloxane that forms a by-product mainly consisting of silicate.Brief description of the drawings

[0020] The embodiments presented in the description below are given only as an example in relation to the accompanying graphic materials, in which:

[0021] Fig. 1A to 1C respectively show three stages of the operating principle of the device for producing gas from two liquid reactants.

[0022] Fig. 2A–2C respectively show three stages of operation of a practical embodiment of a device for producing gas from two liquid reactants.

[0023] Fig. 3 is a view of the device during operation at the stage shown in Fig. 2C. Detailed description

[0024] Figures 1A–1C are diagrams illustrating the operating principle of embodiments of a device for producing hydrogen by reacting two reactants, both of which are in liquid form. A by-product removal mechanism is shown, which can be configured to process a solid by-product in a continuous hydrogen production cycle.

[0025] In Fig. 1A, two liquid reactants, such as a hydrogen carrier and a proton source, are sprayed onto the surface 14 of the reactor using respective nozzles 10, 12. Since the two reactants must be mixed to the greatest possible extent, the nozzles are preferably oriented such that the two reactants are sprayed onto a common area 16 of the reactor surface, which can be achieved by tilting the nozzles toward each other, as shown in the illustration.

[0026] In this configuration, the spray cones intersect, as shown by the dotted lines, and mixing of the reagents begins before they reach the surface. To maximize efficiency, the intersection of the spray cones is maximized, which can be achieved by mounting the nozzles as close to each other as possible.

[0027] Furthermore, nozzles 10 and 12 are configured to move together along the reactor surface 14 during reagent spraying, as shown by the arrows, ensuring a uniform film of liquid reagents is applied to the surface. The nozzle speed and flow rate are adjusted depending on the reaction duration and the required gas production volume.

[0028] In Fig. 1B, a film of reagents was applied to a specific area of ​​the reactor surface using nozzles. The applied reagents reacted to form a solid byproduct 18.

[0029] Then, scraper 20, located behind the nozzles, is moved in the direction shown by the arrow. The scraper is designed to process the entire width of the reactor surface onto which the reagents are applied, removing any remaining solid byproduct.

[0030] In Fig. 1C, scraper 20 reaches the opposite end of the reactor surface. Solid byproducts are pushed over the surface edge and then fall into a temporary storage area, such as collection tray 22, located below the reactor surface edge.

[0031] After this step, the scraper and nozzles are returned to the position shown in Fig. 1A to start a new cycle.

[0032] Reactor surface 14 can be made of any material that can withstand the reaction temperature and mechanical stress. Preferably, the byproduct should not adhere to the material, allowing for easy removal. The surface can be further coated with a catalyst to promote the reaction.

[0033] The device in Figs. 1A–1C is shown to illustrate the operating principle. It does not, by itself, provide continuous gas production, as a reset step is required to initiate a new production cycle.

[0034] Figs. 2A-2C show three stages of operation of a practical embodiment of a device that continuously produces gas from two liquid reactants using the principle shown in Figs. 1A-1C.

[0035] In Fig. 2A, the surface 14 of the reactor is formed in the form of a surface of revolution, such as a cylinder. The shaft 24 is configured to rotate around the axis of rotation of the cylinder 14 and comprises nozzles 10, 12 and a scraper 20. In other words, all nozzles and the scraper rotate synchronously, for example counterclockwise in Figs. 2A–2C, as shown by arrow R.

[0036] Nozzles 10, 12 are aligned axially on shaft 24 and oriented to spray liquid reagents in a radial direction onto a common target area 16 of the inner surface 14 of the cylinder. Scraper 20 is configured to process the inner surface of the cylinder during rotation of the shaft and has a height in contact with the surface of the cylinder, preferably greater than the common target spray area.

[0037] To increase the reaction time at a given rotational speed, scraper 20 is mounted on the shaft so that it begins operation as late as possible after the initial spray. Ideally, the scraper should operate with a rotational lag of 360 degrees behind the nozzles, which would mean that the scraper should be positioned on the shaft in line with the nozzles. In practice, this is not feasible. As shown in the practical example, scraper 20 is mounted on the shaft so that it leads the nozzles by approximately 45 degrees in the direction of rotation, leaving some clearance for the spray cone. This configuration corresponds to a cleaning operation lag of approximately 315 degrees. Satisfactory results can be obtained with a range of lag angles, for example, from 270 to 360 degrees.

[0038] As shown, the leading edge of the scraper contacts the cylinder surface at an angle of approximately 90 degrees. The leading edge preferably has a penetrating profile, meaning the angle between the scraper and the cleaned surface is no more than 90 degrees. This allows the scraper, preferably made of a pliable material, to maintain a scraping effect rather than a layering effect. The trailing edge of the scraper can be beveled, as shown in the illustration.

[0039] Fig. 2A shows the initial phase, in which the cylinder 14 is clean, and the injectors 10, 12 are just beginning to spray the reactants, and the by-product has not yet formed.

[0040] In Fig. 2B, the nozzles and scraper have rotated 180 degrees. The nozzles have applied a uniform layer of reagents to half the cylinder. The applied reagents begin to react, leaving a layer 18 of solid byproduct, which typically thickens over time. Scraper 20 has not yet begun to operate.

[0041] In Fig. 2C, the scraper 20 reaches the point at which the nozzles began to spray in Fig. 1A. At this point, the scraper reaches the first layer of by-product and begins to remove it.

[0042] Figure 3 shows a view of the device during operation at the stage shown in Figure 2C. Here, the design features of the elements are better visible. As mentioned earlier, nozzles 10, 12 are inclined toward each other such that they both spray into the same common region 16 of the cylinder and that their spray cones intersect. Scraper 20 may have a substantially parallelepiped shape.

[0043] Cylinder 14 is preferably vertically positioned so that the removed byproduct falls under gravity into the lower portion of the cylinder, which serves as a storage area. The scraper may be designed so that its edge, which contacts the cylinder surface, is inclined to apply a downward force to the removed byproduct.

[0044] The lower portion of the cylinder can be equipped with a sealed drawer system for regularly removing excess byproduct during the gas production cycle. Once the drawer is completely filled, it contains little or no gas, and removing it will result in very little gas leakage. Alternatively, the lower portion of the cylinder can be large enough to store the entire byproduct of the production cycle.

[0045] This system enables continuous gas production from liquid reagents. The gas production rate in the system increases with increasing flow rate through the nozzles. As the flow rate increases, the system's rotation speed should be increased. However, the rotation speed is limited by the reagent reaction time, although the cylinder diameter and height can be increased.

[0046] In some situations, particularly at higher flow rates and when using low viscosity reactants, the vertical cylinder configuration may cause the reactants to flow down the cylinder surface before they have a chance to react with each other.

[0047] To prevent this, the reactor surface can be shaped like an inverted truncated cone (with an apex and a truncated section at the bottom, the truncated section facing the collection zone). The cone's apex angle is chosen to prevent the reactants from flowing off, or at least to slow the flow down to ensure sufficient time for the reaction between the reactants to occur.

[0048] Good results for hydrogen extraction have been observed with an apex angle of approximately 90 degrees. The minimum angle depends on the nozzle flow rate and the viscosity of the reactants. In practice, this value can be around 30 degrees. The actual apex angle can be chosen higher than this value, with the upper limit being 180 degrees (when the cone becomes a disk). In practice, angles greater than 120 degrees are avoided, as they hinder byproduct removal and make the device too bulky, and angles less than 20 degrees are avoided, as they do not provide sufficient reagent retention.

[0049] It is preferable to use a cone with a vertical axis rather than an inclined cylinder as described in patent application WO2020 / 187754. Moreover, a cone with a vertical axis provides a uniform inclined surface at any angular position, thereby ensuring conditions for a uniform reaction of the two sprayed reagents over the entire spray area.

[0050] As mentioned earlier, the hydrogen carrier reagent can belong to the family of hydrogen methylpolysiloxanes, which have the general formula (HRSiO) n , which are available in liquid form. The proton source reagent can be, among other things, simple water. However, the resulting byproduct is difficult to recycle.

[0051] The preferred hydrogen carrier is the dihydrogenpolysiloxane family, which has the general formula (H2SiO) n, since their byproduct essentially corresponds to a silicate, which can be easily recycled back into a hydrogen carrier. This compound also reacts with water as a source of protons, among other things.

[0052] Dihydrogenpolysiloxanes were discovered only in solid form and were difficult to produce on an industrial scale. However, patent application EP 18305549 describes a method for the industrial production of dihydrogenpolysiloxanes in liquid form, making them particularly suitable for use in the present system.

[0053] The system described in this document is applicable to gas production from any liquid reactants that leave a solid byproduct. Although the device was specifically designed for processing solid byproducts, it can also be used to process liquid byproducts in a very similar manner.

[0054] Spray nozzles 10, 12 have been described as a preferred embodiment for distributing liquid reactants over the reactor surface. More broadly, liquid distribution can be achieved using alternative technologies, such as a liquid-distributing paddle, a brush equipped with a liquid dispenser, or a dome-shaped liquid deflector to create a falling liquid layer.

Claims

1. A device for the controlled production of gas from first and second liquid reactants which, when mixed, form a gas and a non-gaseous by-product, comprising: surface (14) of the reactor having a vertical axis of rotation; shaft (24), centered on the axis of rotation and rotating relative to the surface of the reactor; two nozzles (10, 12) attached to the shaft, configured to spray the first and second reactants, respectively, onto the surface of the reactor, wherein the two nozzles are inclined towards each other in such a way that the spray cones of the first and second reactants intersect in a common area (16) of the surface of the reactor; and a scraper (20) attached to the shaft, configured to separate the by-product from the surface of the reactor, while following the nozzles at a distance sufficient for the reactants to react.

2. The device according to claim 1, wherein the surface of the reactor has the shape of an inverted truncated cone.

3. The device according to claim 2, wherein the inverse truncated cone has an angle at the apex from 30 to 120 degrees.

4. The device according to claim 1, in which the front edge of the scraper (20) contacts the surface (14) of the reactor at an angle of no more than 90 degrees between the scraper and the surface of the reactor.

5. The device according to claim 1, comprising a by-product collection zone (22), wherein the scraper (20) and the surface (14) of the reactor are oriented in such a way that the separated by-product falls into the collection zone.

6. The device according to claim 1, in which the scraper lags behind the nozzles at an angle of at least 270 degrees.

7. The device of claim 1, wherein the first reactant is a liquid hydrogen carrier and the second reactant is a liquid proton source, and the resulting gas is hydrogen.

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

9. The device of claim 7, wherein the hydrogen carrier is liquid dihydrogenpolysiloxane, which forms a by-product consisting mainly of silicate.

10. A method for the controlled production of gas from first and second liquid reactants which, when mixed, form a gas and a non-gaseous by-product, comprising the following steps: spraying (10, 12) the first and second reactants in the form of intersecting cones onto a common area (16) of the surface (14) of the reactor having a vertical axis of rotation; and scraping the surface of the reactor with a scraper (20) to remove the by-product remaining on the surface of the reactor; wherein the spraying and scraping are carried out by a rotational movement around the axis of rotation with a delay sufficient for the reagents to react.

11. The method according to claim 10, wherein the surface of the reactor has the shape of an inverted truncated cone.

12. The method according to claim 11, wherein the inverse truncated cone has an apex angle of 30 to 120 degrees.

13. The method according to claim 10, wherein the scraping is performed with a lag behind the spraying by an angle of at least 270 degrees.

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

15. The method of claim 14, wherein the hydrogen carrier is liquid dihydrogenpolysiloxane, which forms a by-product consisting primarily of silicate.

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