Disclosure of Invention
The invention mainly aims to provide a liquid non-submerged impinging stream reaction device and a reaction method, which aim to solve the problem that the strengthening effect of submerged impinging streams in the prior art on the aspects of destroying the internal energy of molecular structures and promoting the generation of new substances is insufficient.
To achieve the above object, according to one aspect of the present invention, there is provided a liquid non-submerged impinging-stream reaction device comprising: a reaction housing having a cavity; the non-submerged impinging stream reaction assembly is arranged in the cavity and used for enabling the jet fluid of the liquid raw material to complete reaction in the action of non-submerged impingement, cavitation and shearing.
Further, a non-submerged impinging stream reaction assembly comprises: the first barrel is provided with an inlet of liquid raw materials, an inner cavity of the first barrel is used for providing a non-submerged impact place, a plurality of first hole structures are arranged on the barrel wall of the first barrel, and an included angle is formed between the axial direction of each first hole structure and the inlet direction of the liquid raw materials of the first barrel.
Further, the first cylinder body is provided with two opposite side ends, and the side ends are provided with one or more liquid raw material inlets.
Furthermore, inlets of the liquid raw materials are arranged at one side end, and the other side end of the first cylinder body is provided with an impact bottom plate; or the inlets of the liquid raw materials are arranged at one side end, the radial sectional area of the first cylinder body is gradually reduced along the direction far away from the inlets of the liquid raw materials, and the other side end of the first cylinder body is closed; or the part of the liquid raw materials are arranged at one side end, the other part of the liquid raw materials are arranged at the other side end, and at least one of the liquid raw materials at the one side end is overlapped with at least one of the liquid raw materials at the other side end in the material entering direction.
Further, the first cylinder body is a conical cylinder body, a cylinder, a square cylinder or an irregular cylinder body, and the radial sectional area of the irregular cylinder body is gradually reduced from the two ends of the first cylinder body to the middle; alternatively, the radial cross-sectional area of the irregular cylinder is gradually reduced or gradually increased in a direction away from the inlet of the liquid raw material.
Furthermore, the non-submerged impinging stream reaction assembly further comprises a second barrel, the second barrel is sleeved on the periphery of the first barrel, a plurality of second hole structures are arranged on the barrel wall of the second barrel, and an included angle is formed between the axial direction of each second hole structure and the axial direction of each first hole structure.
Furthermore, the non-submerged impinging stream reaction assembly further comprises at least one third cylinder, the third cylinder is sleeved on the periphery of the second cylinder, a plurality of third hole structures are arranged on the cylinder wall of the third cylinder, and an included angle is formed between the axial direction of each third hole structure and the axial direction of each second hole structure.
Further, the first pore structure, the second pore structure and the third pore structure have respective pore diameters independently selected from 1 to 3 mm.
Further, the non-submerged impinging stream reaction assembly further comprises an impingement portion disposed inside the first barrel.
Further, the impingement section comprises a solid component having a pointed end, the pointed end being opposite to the inlet direction of the liquid feedstock.
Further, striking portion still includes the shell, and the shell setting is outside at solid subassembly, and the point form tip passes the shell and extends to the outside of shell, is provided with a plurality of fourth pore structures on the conch wall of shell, and the axial direction of fourth pore structure all has the contained angle with the axial direction of the import direction of liquid raw materials and first pore structure respectively.
Furthermore, the aperture of the fourth pore structure is 1-3 mm.
Further, the reaction device is a heavy oil hydrogenation reaction device.
Further, reaction housing bottom is provided with the liquid phase export, and reaction unit still includes: the inlet of the circulating pipeline is connected with the liquid phase outlet, and the outlet of the circulating pipeline is connected with the inlet of the liquid raw material; and the driving device is arranged on the circulating pipeline.
Furthermore, the reaction device also comprises a mixing unit which is arranged on the circulating pipeline, and the mixing unit is provided with a heavy oil inlet, a hydrogen inlet and a hydrogenation catalyst inlet.
Further, a non-submerged impinging stream reaction assembly is disposed within the interior of the reaction housing proximate the top end.
Further, the reaction device also comprises a hydrogenated product collecting unit which is arranged inside the reaction shell and is positioned above the non-submerged impinging stream reaction assembly.
According to another aspect of the present invention, there is also provided a liquid non-submerged impinging stream reaction method comprising: the liquid raw material is introduced into the reaction device in the form of jet fluid, so that the liquid raw material is reacted in the non-submerged impinging stream reaction assembly through non-submerged impinging, cavitation and shearing actions.
Further, the liquid raw material is a chemical substance which is in a liquid phase under a reaction environment, and the liquid raw material is a simple liquid phase or a multiphase fluid which takes the liquid phase as a dense phase and takes solid and/or gas as a dilute phase; preferably, the non-submerged impinging stream reaction assembly comprises a first cylinder having an inlet for the liquid feedstock, and the axial direction of the first pore structure has an angle with the inlet direction of the liquid feedstock of the first cylinder; the reaction method comprises the following steps: and introducing the liquid raw material into the inner cavity of the first cylinder in a jet fluid mode, carrying out non-submerged impact in the inner cavity, and reacting the impacted material under the cavitation and shearing action of the first hole structure on the cylinder wall.
Furthermore, the first cylinder body is provided with two opposite side ends, and the side ends are provided with one or more inlets for liquid raw materials, wherein when the inlets for the liquid raw materials are arranged at one side end, after the liquid raw materials are introduced into the inner cavity, the jet fluid of the liquid raw materials impacts the impact bottom plate positioned at the other side end of the first cylinder body, so that non-submerged impact is completed; or the radial sectional area of the first cylinder body is gradually reduced along the direction far away from the inlet of the liquid raw material, and after the liquid raw material is introduced into the inner cavity, the jet fluid of the liquid raw material directly impacts the cylinder wall of the first cylinder body to complete non-submerged impact; when part of the liquid raw materials are arranged at one side end and the other part of the liquid raw materials are arranged at the other side end, the liquid raw materials enter the inner cavity through the inlets at the two sides respectively, and the jet fluid of the liquid raw materials entering through the two sides completes non-submerged impact in the inner cavity.
Furthermore, the non-submerged impinging stream reaction assembly also comprises a second cylinder, and after the liquid raw material is subjected to non-submerged impinging in the inner cavity, the impinged material is subjected to first cavitation and shearing under the action of the first hole structure, and then is subjected to second cavitation and shearing of the second hole structure on the cylinder wall of the second cylinder to complete the reaction.
And further, the non-submerged impinging stream reaction assembly also comprises at least one third cylinder, and after the impinged materials are subjected to secondary cavitation and shearing, the reaction is completed under the further cavitation and shearing action of a third hole structure on the cylinder wall of the third cylinder.
Further, the non-submerged impinging stream reaction assembly further comprises an impinging portion, and the impinging portion is arranged inside the first cylinder; after the liquid raw material enters the inner cavity, the jet fluid of the liquid raw material is subjected to non-submerged impact under the action of the impact part.
Further, the impingement section comprises a solid component having a pointed end, the pointed end being opposite to the inlet direction of the liquid feedstock; after the liquid material enters the interior chamber, the jet of liquid material effects non-submerged impingement by interacting with the pointed end.
Further, the impact portion further comprises a housing disposed outside the solid component, and the pointed end extends through the housing to the outside of the housing; after the jet fluid of the liquid raw material is subjected to non-submerged impact with the pointed end, the impacted material is subjected to primary cavitation and shearing under the action of a fourth hole structure on the shell, the material entering the fourth hole structure is subjected to secondary impact, secondary cavitation and shearing are performed through the fourth hole structure again, and finally, further cavitation and shearing are performed through the first hole structure to finish the reaction.
Further, the fluid velocity of the liquid feedstock is 340m/s or less when the liquid feedstock is passed into the non-submerged impinging stream reaction module.
Further, the reaction method is used for hydrogenation reaction of heavy oil; the hydrogenation reaction of heavy oil comprises the following steps: the liquid raw material consisting of heavy oil, hydrogen and hydrogenation catalyst passes through a non-submerged impinging stream reaction component, and the reaction is completed through the actions of non-submerged impinging, cavitation and shearing to form a hydrogenation product.
Further, unreacted raw materials are generated in the reaction process, and the hydrogenation reaction of the heavy oil also comprises the following steps: unreacted raw materials are discharged from the bottom of the reaction shell and are returned to the non-submerged impinging stream reaction component through a circulating pipeline under the driving action of a driving device to carry out circulating reaction.
Further, the non-submerged impinging stream reaction assembly is controlled to be located above the liquid level in the reaction housing during the hydrogenation reaction.
Further, during the hydrogenation reaction, the hydrogenation product generated by the reaction is collected by a hydrogenation product collecting unit arranged above the non-submerged impinging stream reaction assembly.
Further, the temperature of the hydrogenation reaction is 350-410 ℃; the pressure of the hydrogenation reaction is less than or equal to 0.1 MPa.
The invention provides a liquid non-submerged impinging stream reaction device which comprises a reaction shell and a non-submerged impinging stream reaction assembly, wherein the reaction shell is provided with a cavity, and the non-submerged impinging stream reaction assembly is arranged in the cavity and is used for enabling jet fluid of liquid raw materials to complete reaction in non-submerged impinging, cavitation and shearing actions. Unlike traditional submerged impinging stream reactors, the present invention utilizes a non-submerged impinging stream reaction assembly to complete the chemical reaction of the liquid feedstock during non-submerged impingement, cavitation, and shear processes. The non-submerged impact can not only improve the chemical reaction rate and the heat transfer, mass transfer or mixing rate of the liquid raw material, but also lead the fluid with high kinetic energy to pass through an impact-based strengthening mode and be accompanied with a series of strengthening means such as cavitation, shearing and the like, and finally achieve the purposes of destroying the molecular structure of the liquid raw material and breaking molecular bonds to obtain new chemical products. In a word, the liquid non-submerged impinging stream reaction device provided by the invention is applied to liquid chemical reaction, and can obviously improve the strengthening effect on liquid raw material fluid, so that the liquid raw material fluid can efficiently react under a mild reaction condition. It should be noted that the liquid raw material in the present invention refers to a chemical substance that is in a liquid phase under the reaction environment and the reaction temperature, and it may be a simple liquid phase or a multiphase fluid in which a dense phase is a liquid phase and a dilute phase is a gas phase, a solid phase or a gas-solid two phase.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As described in the background section, submerged impinging streams in the prior art have insufficient enhancement in disrupting the internal energy of the molecular structure and promoting the production of new species. In order to solve the above problems, the present invention provides a liquid non-submerged impinging stream reaction apparatus, as shown in fig. 1, comprising a reaction housing 10 and a non-submerged impinging stream reaction assembly 20, the reaction housing 10 having a cavity, the non-submerged impinging stream reaction assembly 20 being disposed in the cavity, the non-submerged impinging stream reaction assembly 20 being configured to cause the jet of liquid feedstock to react in a non-submerged impinging, cavitation, shearing action.
Unlike traditional submerged impinging stream reactors, the present invention utilizes a non-submerged impinging stream reaction assembly to complete the chemical reaction of the liquid feedstock during non-submerged impingement, cavitation, and shear processes. The non-submerged impact can not only improve the chemical reaction rate and the heat transfer, mass transfer or mixing rate of the liquid raw material, but also lead the fluid with high kinetic energy to pass through an impact-based strengthening mode and be accompanied with a series of strengthening means such as cavitation, shearing and the like, and finally achieve the purposes of destroying the molecular structure of the liquid raw material and breaking molecular bonds to obtain new chemical products. In a word, the liquid non-submerged impinging stream reaction device provided by the invention is applied to liquid chemical reaction, and can obviously improve the strengthening effect on liquid raw material fluid, so that the liquid raw material fluid can efficiently react under a mild reaction condition. It should be noted that the liquid raw material in the present invention refers to a chemical substance that is in a liquid phase under the reaction environment and the reaction temperature, and it may be a simple liquid phase or a multiphase fluid in which a dense phase is a liquid phase and a dilute phase is a gas phase, a solid phase or a gas-solid two phase.
It is pointed out that when the Reynolds number of the motion of any fluid, for example, a liquid phase fluid, is greater than a certain value (. gtoreq.4000), the motion of the fluid is in a turbulent state. The liquid in a turbulent state has the effects of impact, cavitation, shearing and the like. However, these intensification effects are compared with the intensification effect of the high-speed fluid directly subjected to non-submerged impact, and the difference in efficiency is 106~109An order of magnitude. The use of different enhanced functional modules in the reactor is proposed in Zhengying et al patent No. ZL201710627354.2And (4) combining. The biggest difference between the invention and the method is that: all the modules (including functions of impact, cavitation and shearing) connected in series in the patent can only work in a submerged state no matter how designed, so that the working fluid is difficult to obtain kinetic energy of ultra-high speed motion under the same external force. In the patent, only the fluid at the outlet of the module I is in a non-submerged state, but even if the working fluid obtains high speed and high kinetic energy, the working fluid is only a free falling body with initial speed, non-submerged impact does not occur, and the kinetic energy of the fluid cannot be converted into internal energy which causes molecular bond breakage. In the reaction device provided by the invention, the jet fluid of the raw material liquid can convert high-speed fluid kinetic energy into internal energy which can cause molecular bond fracture through non-submerged impact, cavitation and shearing actions, thereby achieving the purpose of more obviously strengthening the process.
In a preferred embodiment, as shown in fig. 2, 3, 5, 6 and 8, the non-submerged impinging stream reaction assembly 20 comprises a first cylinder 21, the first cylinder 21 has an inlet for liquid raw material, the inner cavity of the first cylinder 21 is used for providing a non-submerged impinging place, a plurality of first hole structures are arranged on the cylinder wall of the first cylinder 21, and the axial direction of the first hole structures forms an angle with the inlet direction of the liquid raw material of the first cylinder 21.
Here, "axial direction of the first hole structure" means a through hole direction of the first hole structure, that is, an extending direction of the hole. "inlet direction of liquid feedstock" indicates the direction of injection of the liquid feedstock jet fluid. Because the first cylinder 21 is provided with the plurality of first hole structures, after the jet fluid of the raw material liquid enters the inner cavity of the first cylinder to impact, the fluid is discharged through the first hole structures, namely the environment of the inner cavity of the first cylinder 21 is always a gas environment, so that the jet fluid of the raw material is always in a non-submerged impact process. The impact time of the jet is very short, in the order of milliseconds. After the impact happens instantaneously, the flow direction of the fluid is forced to change to a direction approximately orthogonal to the entering direction of the primary jet fluid, and secondary fluid is formed. The secondary fluid forced to change direction still has very high initial speed, after the secondary fluid collides with the first cylinder 21 with a plurality of first hole structures, because the axial direction of the first hole structures and the inlet direction of the liquid raw material of the first cylinder 21 have included angles, the secondary fluid is blocked by the cylinder wall and the first hole structures, and under the action of cavitation, shearing and re-collision, the conversion effect of the collision flow is greatly improved, so that the conversion of the kinetic energy of the fluid to the internal energy of molecules is completed under a high-efficiency state, and the chemical reaction of the liquid raw material is completed. The axial direction of the first hole structure and the inlet direction of the liquid raw material of the first cylinder 21 form an included angle, and the included angle is preferably 165-195 degrees.
Preferably, the first cylinder 21 has two opposite side ends, and the side ends are provided with one or more inlets for liquid raw materials. Thus, the multiple groups of jet fluids complete non-submerged impact, cavitation and shearing in the inner cavity of the first cylinder 21, which is beneficial to further improving the reaction efficiency.
Since the plurality of first hole structures of the first cylinder 21 maintains the gas phase environment in the inner cavity, the non-submerged impact may be a "liquid-liquid collision" or a "liquid-solid collision".
In a typical embodiment, as shown in fig. 8, the inlets for the liquid raw materials are all provided at one side end, and the other side end of the first cylinder 21 is provided with an impingement bottom plate 24. Thus, the jet fluid of the raw material liquid has liquid-solid collision with the collision bottom plate 24, the direction of the fluid is changed, and the formed secondary fluid has cavitation, shearing and re-collision under the action of the first cylinder 21 and the first hole structure thereof, so that the conversion of kinetic energy and molecular internal energy is realized, and the reaction is completed.
In another exemplary embodiment, as shown in fig. 6, the inlets for the liquid raw materials are all disposed at one side end, the radial cross-sectional area of the first cylinder 21 is gradually reduced in a direction away from the inlets for the liquid raw materials, and the other side end of the first cylinder 21 is closed. Thus, the incoming jet fluid can directly impact the inner wall of the first cylinder 21, complete liquid-solid non-submerged impact, and cavitate and shear under the action of the first orifice structure. More preferably, as shown in fig. 6, the inlets of the liquid materials are all arranged at one side end, the radial cross-sectional area of the first cylinder 21 is gradually reduced along the direction far away from the inlets of the liquid materials, the other side end of the first cylinder 21 is closed, and the closed section is provided with an impact bottom plate 24. In this way, fluid exiting the first orifice structure can be subjected to a second non-submerged impact with the impingement baseplate 24 to complete the final conversion.
More preferably, as shown in fig. 6 and 8, the area of the impact floor 24 is larger than the radial cross-sectional area of the first cylinder 21, so that the fluid coming out of the first hole structure can more sufficiently perform secondary impact with the first hole structure, and further improve the conversion degree of the kinetic energy into the molecular internal energy.
In another exemplary embodiment, as shown in fig. 2, 3 and 5, the inlets for a portion of the liquid feedstock are disposed at one side end and the inlets for another portion of the liquid feedstock are disposed at the other side end, wherein at least one of the inlets for the liquid feedstock at the one side end overlaps with the material entry direction of at least one of the inlets for the liquid feedstock at the other side end. Thus, after the liquid-liquid impact of the injected fluids entering from the two side ends of the first cylinder 21 is completed, the secondary fluid with changed direction continues to complete cavitation, shearing and re-impact under the action of the first cylinder 21. In order to more effectively perform fluid collision, it is more preferable that the number of inlets at both side ends of the first cylinder 21 is the same and are formed in a plurality of sets one to one.
The shape of the first cylinder is not limited as long as the second cylinder can block the secondary fluid after the impact. In a preferred embodiment, the first cylinder 21 is a conical cylinder (fig. 6), a cylinder (fig. 2), a square cylinder (not shown) or an irregular cylinder, and the radial cross-sectional area of the irregular cylinder is gradually reduced from the two ends of the first cylinder 21 to the middle (fig. 3 and 5); alternatively, the radial cross-sectional area of the irregular cylinder may be gradually reduced (fig. 8) or gradually increased (not shown) in a direction away from the inlet of the liquid feedstock. Compared with a cylinder, the irregular cylinder shown in fig. 3 is more beneficial to improving the shearing effect of the first hole structure, as shown in fig. 4, the secondary fluid a impacts against the cylinder wall of the first cylinder 21 at a certain angle, and is divided into a first third fluid b parallel to the cylinder wall direction and a second third fluid c parallel to the axial direction of the first hole structure under the shearing and re-impacting effects of the first hole structure, the outer edge of the first hole structure is an impact and shearing effect point, and the inner cavity of the first hole structure is a cavitation effect point. The non-submerged impinging stream reaction assembly 20 shown in fig. 2 and 3 is more suitable for the impinging stream with a low impinging velocity in liquid-liquid impingement, and the jet fluid velocity is generally 10-100 m/s. As shown in figures 6 and 7, a plurality of jets are vertically jetted along the bottom end of the conical cylinder, directly collide with the cylinder wall of the conical cylinder and simultaneously generate cavitation, shearing and impact effects instantly, and kinetic energy carried by high-speed fluid is blocked by a member and converted into internal energy for destroying the structure of the high-speed fluid, so that the aim of cutting off molecular bonds of continuous phase materials is fulfilled. And the fluid from the first hole structure continues to move and collides with an impact bottom plate arranged at the top of the conical cylinder body, so that the final kinetic energy absorption is completed.
In order to absorb the kinetic energy of the injected fluid to a greater extent, in a preferred embodiment, as shown in fig. 5, the non-submerged impinging stream reaction assembly 20 further includes a second cylinder 22, the second cylinder 22 is sleeved on the periphery of the first cylinder 21, and the cylinder wall of the second cylinder 22 is provided with a plurality of second hole structures, and the axial directions of the second hole structures and the axial directions of the first hole structures have an included angle. Thus, the tertiary fluid exiting the first orifice structure is trapped by the second cylinder 22 and is further absorbed by the secondary shear and cavitation of the second orifice structure. Similarly, the non-submerged impinging stream reaction assembly 20 further comprises at least one third cylinder, the third cylinder is sleeved on the periphery of the second cylinder 22, a plurality of third hole structures are arranged on the cylinder wall of the third cylinder, and an included angle is formed between the axial direction of the third hole structure and the axial direction of the second hole structure. Such a non-submerged impinging stream reactor assembly 20 is preferably adapted to handle initially higher velocity jets, such as those having a velocity of 100m/s or more. Moreover, the non-submerged impinging stream reaction assembly 20 is more suitable for processing liquid raw materials with higher molecular internal energy and larger chemical reaction molecular internal energy conversion, so that the kinetic energy of the jet fluid with high-speed kinetic energy can be converted into the molecular internal energy as much as possible by utilizing a multi-layer cylinder and a hole structure, and the reaction is finished. In fact, when the initial velocity u of the impinging stream is0And more than or equal to 340m/s, and the fluid kinetic energy enters the hydraulic cutting speed range. Thus when the initial velocity u of the impinging stream0At 340m/s or more, the kinetic energy of the working fluid can be reduced to a range that can be tolerated by the metal member only by direct liquid-liquid collision in general. In general, it is preferred notThe submerged impinging stream reaction assembly 20 comprises 1 to 5 layers of cylinders arranged from inside to outside, a plurality of hole structures are arranged on each layer of cylinder, and the axial directions of the hole structures of the two adjacent layers of cylinders have included angles.
In order to further improve the shearing and cavitation effects of the pore structure, in a preferred embodiment, the pore diameters of the first pore structure, the second pore structure and the third pore structure are respectively and independently selected from 1-3 mm.
To further enhance the effect of non-submerged impingement, in a preferred embodiment, as shown in fig. 8, the non-submerged impinging stream reaction assembly 20 further comprises an impingement portion 23, the impingement portion 23 being disposed inside the first cylinder 21. The non-submerged impinging stream reactor 20 is more suitable for ultra-high flow velocity conditions, and when the impinging flow velocity is close to 340m/s, the liquid phase continuous fluid has enough kinetic energy to cut the solid, and at this time, the kinetic energy of the continuous phase fluid is preferably reduced by liquid-liquid impingement and then contacts with the metal member, so as to protect the member from rapid damage. However, if the conditions of the liquid-liquid collision cannot be met0When the jet speed is less than or equal to 340m/s or even higher, the impact part 23 is arranged to be more beneficial to non-submerged impact of ultra-high-speed jet fluid. More preferably, as shown in fig. 8, the impingement section 23 comprises a solid member 231 having a pointed end portion opposite to the inlet direction of the liquid raw material. The solid component 231 is provided to help maintain the stability and life of the construction itself, and by the collision of the pointed end with the injected fluid, the fluid will disperse 360 degrees around the pointed end, helping to absorb its kinetic energy more fully.
More preferably, as shown in fig. 8, the striking part 23 further includes a housing 232, the housing 232 is disposed outside the solid component 231, the pointed end extends to the outside of the housing 232 through the housing 232, a plurality of fourth hole structures are disposed on a wall of the housing 232, and axial directions of the fourth hole structures respectively form an angle with an inlet direction of the liquid material and an axial direction of the first hole structure. Thus, after the pointed end part collides with the sprayed fluid, the fluid is dispersed by 360 degrees along the periphery of the pointed end part, and the dispersed fluid is subjected to shearing and cavitation through the fourth hole structure on the shell wall of the shell 232, so that the absorption of the kinetic energy of the fluid is more favorably enhanced. Most preferably, as shown in fig. 8, the conical casing of the casing 232 has a top portion which is a pointed end portion of the solid component 231, the other end of the first cylinder 21 opposite to the liquid material inlet is provided with an impact bottom plate 24, the impact portion 23 is fixed on the impact bottom plate 24 by welding, the first cylinder 21 and the casing 232 are not in contact with each other, and the radial cross-sectional area of the first cylinder 21 is gradually reduced along the direction from the liquid material inlet to the impact bottom plate 24. Thus, when the high-speed continuous phase fluid contacts the cone of the metal member, the fluid is forced to disperse toward the four sides 3600 and flow at high speed in the form of a liquid film on the aperture plate of the cone. The conical metal orifice plate causes shearing and cavitation effects on the liquid film. The liquid entering the cavitation small hole impacts the final plate surface of the component with the residual kinetic energy, and is forced to change the direction to penetrate out of the small hole of the conical component to generate secondary shearing, cavitation and impact, and almost all the kinetic energy is converted into internal energy for destroying the structure of the component. The cavitation component on the outer layer can perform final interception and final kinetic energy-internal energy conversion on the continuous phase liquid flow.
It should be noted that when the fluid is ejected by processing the liquid material with the flow rate close to 340m/s or even higher, the vicinity of the nozzle opening of the high-speed fluid is the hydraulic cutting area, so the collision distance between the ejected fluid and the striking part 23 should avoid the cutting area with the highest kinetic energy of the liquid, and the stability and the service life of the component are exchanged by sacrificing part of the kinetic energy.
In the same way, in order to further enhance the shearing and cavitation effects, the aperture of the fourth pore structure is preferably 1-3 mm.
The liquid non-submerged impinging stream reactor provided by the invention is suitable for chemical reactions of various liquid phase raw materials, such as heavy oil hydrogenation reactions. In a typical embodiment, the reaction apparatus is a heavy oil hydrogenation reaction apparatus. The existing vacuum residue hydrogenation reactor mostly adopts a suspension bed (slurry bed), adopts high temperature of 420-470 ℃, high pressure of 15-40 MPa and high hydrogen-oil ratio (1000 cubic hydrogen is pressed into 1 cubic residue), can obtain good hydrogenation effect, but also becomes a typical process with high investment, high cost and high risk in a refinery. The liquid non-submerged impinging stream reaction device provided by the invention utilizes the concept of fracture and damage caused by local stress concentration in the mechanical principle, and cuts off the molecular bond of heavy oil by local and microcosmically generated high-temperature and high-pressure stress concentration. The process is repeated repeatedly and continuously circularly, the effect of lightening the vacuum residue can be achieved, and the investment and the cost of the process are greatly smaller than those of a suspension bed process and are only one tenth to one dozen tenths of those of the process. The integral pressure of the reactor is less than or equal to 0.1MPa, and is 1/150-1/400 of the suspension bed, so that the danger of high risk caused by high temperature, high pressure and high hydrogen of the suspension bed is avoided.
In a preferred embodiment, as shown in fig. 1, the reaction shell 10 is provided with a liquid phase outlet at the bottom, the reaction device further comprises a circulation pipeline 30 and a driving device 40, an inlet of the circulation pipeline 30 is connected with the liquid phase outlet, and an outlet is connected with an inlet of the liquid raw material; the driving device 40 is provided on the circulation line 30. In the actual reaction process, after the heavy oil raw material carries with hydrogen and the hydrogenation catalyst to complete the reaction in the non-submerged impinging stream reaction assembly 20 through non-submerged impinging, cavitation and shearing, the reaction lightening product is in a gaseous state and is discharged out of the reaction shell 10, the unreacted heavy oil falls to the bottom of the reaction shell 10, and then the unreacted material is returned and recycled by using the driving device 40 and the recycling pipeline 30. Preferably, an injection nozzle is provided at the outlet of the circulation line 30 to inject the liquid material to convert it into an injection fluid.
In a preferred embodiment, the reaction apparatus further includes a mixing unit 50 disposed on the circulation line 30, and the mixing unit 50 is provided with a heavy oil inlet, a hydrogen inlet, and a hydrogenation catalyst inlet. The feedstock can be replenished through a heavy oil inlet, a hydrogen inlet, and a hydrogenation catalyst inlet.
In a preferred embodiment, the non-submerged impinging stream reaction module 20 is disposed within the interior of the reaction shell 10 near the top end. This advantageously maintains the non-submerged impinging stream reaction assembly 20 above the internal liquid level of the reaction housing 10, and maintains a gaseous environment within the interior of the non-submerged impinging stream reaction assembly 20 to maintain non-submerged impingement of the injected fluid.
Preferably, the reaction apparatus further comprises a hydrogenated product collection unit disposed inside the reaction housing 10 and above the non-submerged impinging-flow reaction assembly 20. The lighter products may be collected by a hydrogenated product collection unit after exiting the non-submerged impinging stream reaction module 20 in gaseous form upwardly.
According to another aspect of the present invention, there is also provided a liquid non-submerged impinging stream reaction method, wherein a liquid feedstock is introduced into the reaction apparatus as a jet of fluid, and the reaction is carried out in the non-submerged impinging stream reaction module 20 by non-submerged impinging, cavitation and shearing. As previously described, the present invention utilizes a non-submerged impinging stream reaction assembly to effect chemical reactions of a liquid feedstock during non-submerged impingement, cavitation, and shear. The non-submerged impact can not only improve the chemical reaction rate and the heat transfer, mass transfer or mixing rate of the liquid raw material, but also lead the fluid with high kinetic energy to pass through an impact-based strengthening mode and be accompanied with a series of strengthening means such as cavitation, shearing and the like, and finally achieve the purposes of destroying the molecular structure of the liquid raw material and breaking molecular bonds to obtain new chemical products. In a word, the liquid non-submerged impinging stream reaction device provided by the invention is applied to liquid chemical reaction, the strengthening effect on liquid raw material fluid can be obviously improved, and the liquid raw material fluid has high fluid kinetic energy under mild reaction conditions and can be efficiently reacted.
In a preferred embodiment, the non-submerged impinging stream reaction assembly 20 comprises a first barrel 21, the first barrel 21 having an inlet for the liquid feedstock, and the axial direction of the first hole structure being at an angle to the direction of the inlet for the liquid feedstock of the first barrel 21; the reaction method comprises the following steps: the liquid raw material is introduced into the inner cavity of the first cylinder 21 in a form of jet fluid, non-submerged impact is carried out in the inner cavity, and the impacted material completes reaction under the action of cavitation and shearing of the first hole structure on the cylinder wall.
In a preferred embodiment, the first cylinder 21 has two opposite side ends, and the side ends are provided with one or more inlets for liquid raw materials, wherein when the inlets for liquid raw materials are arranged at one side end, after the liquid raw materials are introduced into the inner cavity, the jet fluid of the liquid raw materials is made to impact the impact bottom plate 24 at the other side end of the first cylinder 21, so that non-submerged impact is completed; or, the radial sectional area of the first cylinder 21 is gradually reduced along the direction away from the inlet of the liquid raw material, and after the liquid raw material is introduced into the inner cavity, the jet fluid of the liquid raw material directly impacts the cylinder wall of the first cylinder 21 to complete non-submerged impact; when part of the liquid raw materials are arranged at one side end and the other part of the liquid raw materials are arranged at the other side end, the liquid raw materials enter the inner cavity through the inlets at the two sides respectively, and the jet fluid of the liquid raw materials entering through the two sides completes non-submerged impact in the inner cavity.
In a preferred embodiment, the non-submerged impinging stream reaction assembly 20 further comprises a second cylinder 22, wherein after the liquid feedstock undergoes non-submerged impingement in the inner chamber, the impinged material undergoes a first cavitation and shearing action under the action of the first hole structure, and then undergoes a second cavitation and shearing action under the action of the second hole structure located in the wall of the second cylinder 22.
In a preferred embodiment, the non-submerged impinging stream reaction module 20 further comprises at least one third cylinder, and after the impinging material undergoes a second cavitation and shearing, the reaction is completed under the further cavitation and shearing action of the third hole structures located in the wall of the third cylinder.
In a preferred embodiment, the non-submerged impinging stream reaction assembly 20 further comprises an impingement portion 23, the impingement portion 23 being disposed inside the first cylinder 21; after the liquid material enters the inner cavity, the jet of liquid material is subjected to non-submerged impingement by the impingement section 23.
In a preferred embodiment, the impingement section 23 comprises a solid member 231 having a pointed end opposite to the direction of entry of the liquid feedstock; after the liquid material enters the interior chamber, the jet of liquid material effects non-submerged impingement by interacting with the pointed end.
In a preferred embodiment, the impingement section 23 further comprises a housing 232, the housing 232 being disposed outside the solid block 231, and the pointed end extending through the housing 232 to the outside of the housing 232; after the jet fluid of the liquid raw material is subjected to non-submerged impact with the pointed end, the impacted material is subjected to primary cavitation and shearing under the action of the fourth hole structure on the shell 232, the material entering the fourth hole structure is subjected to secondary impact, secondary cavitation and shearing are performed through the fourth hole structure again, and finally, further cavitation and shearing are performed through the first hole structure to complete the reaction.
In a preferred embodiment, the fluid velocity of the liquid feedstock as it is passed into the non-submerged impinging stream reaction module 20 is 340m/s or less.
In a preferred embodiment, the reaction process is used for the hydrogenation of heavy oils; the hydrogenation reaction of heavy oil comprises the following steps: the liquid raw material consisting of heavy oil, hydrogen and hydrogenation catalyst passes through the non-submerged impinging stream reaction component 20, and the reaction is completed through the actions of non-submerged impinging, cavitation and shearing to form a hydrogenation product.
In a preferred embodiment, an unreacted feedstock is also produced during the reaction, and the hydrogenation of the heavy oil further comprises: unreacted raw materials are discharged from the bottom of the reaction shell 10 and returned to the non-submerged impinging stream reaction assembly 20 for circular reaction through the circulating pipeline 30 under the driving action of the driving device 40.
In a preferred embodiment, the non-submerged impinging stream reaction module 20 is controlled to be above the liquid level in the reaction housing 10 during the hydrogenation reaction.
In a preferred embodiment, the hydrogenation product produced by the reaction is collected during the hydrogenation reaction by a hydrogenation product collection unit disposed above the non-submerged impinging stream reaction assembly 20.
In order to be able to break the molecular bonds, the flow rate of the jetting fluid is preferably in the high-speed or overspeed range of 10m/s to 1000 m/s; the fluid temperature is generally between 50 ℃ and 450 ℃. When the catalyst is applied to catalytic hydrogenation of heavy oil, in order to improve the fluid strengthening effect and avoid energy waste as much as possible, in a preferred embodiment, the temperature of the hydrogenation reaction is 350-410 ℃; the pressure of the hydrogenation reaction is less than or equal to 0.1 MPa.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
By adopting the reaction device shown in FIG. 1, wherein the non-submerged impinging stream reaction component is shown in FIG. 2, the catalytic hydrogenation of the vacuum residue is carried out to prepare light oil (gasoline and diesel oil), and the process conditions are as follows:
the liquid mixed raw material of vacuum residue, hydrogen and catalyst is sprayed into the inlets of two sides of non-submerged impinging stream reaction component by means of spray nozzle, and two sides are respectively single-stranded spray fluid, and their directions are opposite and overlapped, after the non-submerged impingement is implemented in the component internal cavity, the secondary fluid and raw material are diffused in 90 deg. direction, and can produce secondary impingement with cylinder body and several hole structures set on the cylinder body, and produce cavitation and shearing effect to break molecular bond, so that the gas-phase light product can be collected from the upper portion of reaction shell. The material which is still unreacted after being strengthened or still belongs to the heavy part after being reacted falls into the bottom of the reaction shell in a liquid phase and returns to the bottom of the reaction shell through the driving device and the circulating pipeline for reaction. Wherein the reaction temperature of the vacuum residue is 350-410 ℃ (the vacuum residue is solid at room temperature, liquid at 200-250 ℃ and has better fluidity at more than 300 ℃), the overall pressure of the reactor is less than or equal to 0.1MPa, and the hydrogen-oil ratio is (20-100): 1.
The reaction results were as follows:
TABLE 1
Oil sample
|
Fraction of saturation/%)
|
Fraction of aroma/%)
|
Percent of pectin
|
Asphaltene/%
|
Vacuum residuum (feedstock)
|
1.6
|
58.6
|
23.7
|
14.1
|
Light oil (product)
|
72.5
|
21.8
|
4.6
|
1.1 |
In table 1, saturated hydrocarbons (alkanes, cycloalkanes) are the basic components of gasoline and diesel, while the saturated hydrocarbons in the feed oil are substantially zero, and the aromatic hydrocarbons with rings account for the largest proportion. It is thus known that this vacuum residue is a low value waste.
The saturated hydrocarbon of the product after the light conversion reaches 72.5 percent, occupies most of the product oil, and is a high-value oil product mainly comprising gasoline and diesel oil; according to the test results, the impinging stream multifunctional strengthening reactor utilizes the effects of impingement, cavitation and shearing to destroy aromatic hydrocarbon, colloid and asphaltene structures in the raw oil, and cut off carbon bonds on the cyclic hydrocarbon, so that the cyclic hydrocarbon with a stable structure is changed into saturated hydrocarbon after molecular bond breakage.
And (3) distillation range analysis: different saturated vapor pressure components in the raw material and the product are separated by heating and distillation, and the content of light and heavy components in the material can be examined by distillation range analysis, which is shown in table 2.
TABLE 2
As can be seen from Table 2, the raw vacuum residue is low-value heavy oil, wherein the content percentage of gasoline and diesel oil is zero, the component which can be used as boiler fuel at 350 ℃ and 500 ℃ only accounts for 8.5 percent, and the remaining 91.5 percent can be used as road asphalt only through blending. As can be seen from the product distillation range of table 2, the gasoline and diesel fractions were about 60%, the boiler fuel was 32.3%, and the asphaltenes were only 7.5%. The weight-reducing effect is obvious.
The above tests are the results of the primary reaction, and if the secondary reaction is combined with other processes of a refinery, the overall benefits are more prominent, and the following can be achieved: 73 percent of gasoline and diesel oil, the total yield of gasoline and diesel oil reaches 86.8 percent, and only 8.1 percent of the produced product is solid petroleum coke. Recent refining scales have increased, with a 100-ten-thousand-ton refinery scale being common, and a 1% increase being a ten-thousand-ton scale, so the above tests are sufficient to show that the benefits obtainable by the present invention are exceptionally significant.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.