Oil ammonia column drop ball forming device and method

Abstract

The invention belongs to the field of catalyst carrier preparation, and discloses an oil ammonia column drop ball forming device which comprises a formed oil ammonia column and an oil phase purification device, the forming oil ammonia column comprises a forming container with an opening in the top, and an oil phase area located on the upper portion and a water phase area located on the lower portion are arranged in the forming container. A ball dripping device is arranged above the top opening of the forming container; the oil phase area is provided with an oil phase purification circulation outlet and an oil phase purification circulation return port; an oil phase in the oil phase area enters the oil phase purification device through the oil phase purification circulation outlet to be washed and subjected to ammonia removal, and then returns to the oil phase area through the oil phase purification circulation return port, so that an ammonia-removed oil phase area and a transition oil phase area are formed in the oil phase area from top to bottom; and the oil phase purification circulation outlet and the oil phase purification circulation return port are positioned in the ammonia removal oil phase region. The problems that the water dropper is blocked and cannot work continuously due to gelation of sol at the water dropper are solved. Gel balls with good sphericity and uniformity can be obtained, and a basis is provided for preparing carrier balls with good sphericity and uniformity.

Description

Technical Field

[0001] The invention belongs to the field of catalyst carrier preparation and relates to a device and method for oil-ammonia column drop ball molding. Background Art

[0002] The oil-ammonia column drop ball method is an important method for preparing spherical alumina carriers. The upper layer of the oil-ammonia column is the oil phase, and the lower layer is the ammonia phase. In the process of preparing alumina carrier spheres, a mixed sol liquid containing alumina sol is generally dropped into the oil-ammonia column through a ball dropper. The sol drops in the oil are spherical due to surface tension, and move to the bottom of the column under the action of gravity, passing through the contact surface between different media, and gelling occurs after entering the ammonia water layer, thereby obtaining gel spheres. The gel spheres are further solidified, separated from the ammonia water phase, and dried and calcined to obtain alumina carrier spheres.

[0003] In the aspect of forming drop balls from oil-ammonia columns, oil-ammonia columns require two ball-forming media, oil phase and ammonia water phase. Ammonia water often has a small amount of solubility in the oil phase, which will cause a small amount of ammonia in the ammonia water phase to dissolve into the oil phase during the ball-dropping process, thereby affecting the forming process. On the one hand, the ammonia entering the oil phase will cause the sol on the surface of the sol drop to gel prematurely in the oil phase, causing the sol drop to solidify and form before it becomes a sphere, resulting in a deterioration in the sphericity of the gel ball, and even the formation of water drop-shaped particles. On the other hand, when there is a lot of dissolved ammonia in the oil phase, the ammonia in the oil phase overflows on the surface of the oil phase and gathers at the dripper of the sol dropper, causing the sol surface to gel prematurely and form a gel at the dripper, thereby clogging the dripper, affecting the continuous process of dropping balls. In addition, the oil phase and the ammonia water phase in the oil-ammonia column are two immiscible phases. When the droplets of the sol raw material slurry descend from the oil phase and cross the oil / water interface to form balls, the sol droplets need to overcome the interfacial resistance of the ammonia water. This also causes the spherical sol droplets formed in the oil phase to deteriorate in sphericity due to the interfacial resistance when passing through the interface. The gel droplets with deteriorated sphericity quickly gel after passing through the oil / water interface, which causes the sphericity of the gel balls and products to deteriorate.

[0004] CN218393563U proposes to add an air suction structure at the dripper to deal with the problem of ammonia gas diffusing upwards. The air suction structure includes a main shaft tube and an air suction pipe. The suction port at the top of the main shaft tube is connected to the suction device. One end of the air suction pipe is connected to the main shaft tube and the other end is sealed. The multiple air suction holes arranged on the air suction pipe can suck away the ammonia gas around the dripper, and the gas around the dripper can be sucked out through the suction device connected to the main shaft tube.

[0005] CN109908828A discloses a combined ball dropper for oxide ball drop molding, wherein the dropper of the ball dropper is wrapped by a jacket, an air inlet and an air outlet are arranged in the jacket wall, and the jacket device blows away ammonia near the dropper by ventilation to prevent slurry from adhering to and hanging on the dropper.

[0006] CN109701442A adds an oil chamber to the ball dropper, and the slurry drips out through a dripper with a variable diameter. The protective oil flowing out of the oil chamber wraps the dripping slurry, isolating the slurry droplets from the volatilized ammonia gas, preventing the slurry from sticking and clogging at the dripper outlet.

[0007] CN110871112A proposes a device and method for preparing spherical carriers, wherein the spherical liquid is sucked out from the spherical container and re-injected through a circulation mechanism, and the falling slurry rotates under the lateral force of the spherical liquid, thereby eliminating the tailing phenomenon of the spherical slurry and improving the sphericity and wear resistance of the prepared spherical carrier.

[0008] CN110871111A provides a spherical carrier ball-forming device and preparation method, including a container body for containing a ball-forming liquid and a ball-forming liquid circulation mechanism outside the container body, and the container body is divided into a ball-forming area, a solidification area and a collection area from top to bottom. The carrier slurry is dripped into the top opening of the container body in the form of slurry drops through a ball dropper, contacts with the ball-forming liquid and falls to form balls, and the falling slurry is rotated by the lateral force of the ball-forming liquid, and the horizontal movement is reduced, thereby eliminating the tailing phenomenon caused by the falling slurry drops, and improving the sphericity and wear resistance of the prepared spherical carrier.

[0009] Although the above technical solution can solve the problem of ammonia accumulation at the dripper causing the slurry to stick and clog at the dripper and the uneven sphericity of the carrier, it cannot solve the problem of poor sphericity caused by premature gelation of the slurry after entering the oil phase and the diffusion of ammonia through the oil phase causing the slurry to stick and hang in the ball dropper and unable to produce continuously. Summary of the invention

[0010] The object of the present invention is to provide an oil-ammonia column drop ball forming device and method to solve at least one technical problem existing in the above-mentioned background technology.

[0011] To achieve the purpose of the present invention, the specific technical scheme is as follows: An oil-ammonia column drop ball forming device, comprising a forming oil-ammonia column and an oil phase purification device; The molded oil-ammonia column comprises a molding container with an opening at the top, wherein an oil phase region located at the top and a water phase region located at the bottom are arranged inside the molding container; a ball dropper is arranged above the top opening of the molding container; The oil phase zone is provided with an oil phase purification circulation outlet connected to the liquid inlet of the oil phase purification device and an oil phase purification circulation return port connected to the liquid outlet of the oil phase purification device; The oil phase purification device is used to wash and remove ammonia from the oil phase in the oil phase zone; the oil phase in the oil phase zone enters the oil phase purification device through the oil phase purification circulation outlet for washing and removing ammonia, and then returns to the oil phase zone through the oil phase purification circulation return port, so that the oil phase zone forms an ammonia removal oil phase zone and a transition oil phase zone from top to bottom; The oil phase purification circulation outlet and the oil phase purification circulation return port are located in the ammonia removal oil phase zone.

[0012] Furthermore, the oil phase purification cycle outlet and the oil phase purification cycle return port are respectively provided with one or more; Furthermore, the oil phase purification cycle return port is arranged on the same height plane as the oil phase purification cycle outlet or above it; Furthermore, the oil phase purification circulation outlet is arranged below 1 / 3 of the upper part of the oil phase zone of the oil-ammonia column, and the height of the oil phase zone except ammonia accounts for more than 1 / 3 of the total height of the oil phase zone; Furthermore, the oil phase purification circulation outlet is set at 1 / 2 to 2 / 3 of the height of the oil phase zone; It is further preferred that the oil phase purification circulation outlet is set at 1 / 2 of the height of the oil phase zone.

[0013] Furthermore, the oil phase purification device is a mixer-settler.

[0014] Furthermore, the oil phase purification device includes a first oil phase mixing component and a first oil phase separation component connected to the first oil phase mixing component.

[0015] It is further preferred that the first oil phase mixing component is a stirring mixing tank, and the first oil phase separation component is a clarifying tank.

[0016] Furthermore, in order to increase the content of ammonia (or ammonium salt) in the oil phase in the transition oil phase region, an oil phase ammonia increasing device is also included, and the oil phase ammonia increasing device is used to increase ammonia in the oil phase in the transition oil phase region; The transition oil phase zone is provided with an oil phase ammonia increase circulation outlet connected to the liquid inlet of the oil phase ammonia increase device and an oil phase ammonia increase circulation return port connected to the liquid outlet of the oil phase ammonia increase device; The oil phase in the transition oil phase region enters the oil phase ammonia increase device through the oil phase ammonia increase circulation outlet and then returns to the transition oil phase region through the oil phase ammonia increase circulation return port after ammonia increase, so that the transition oil phase region forms a first transition oil phase region and a second transition oil phase region from top to bottom; The oil phase ammonia increase circulation outlet and the oil phase ammonia increase circulation return port are located in the second transition oil phase zone.

[0017] Furthermore, the oil phase ammonia enhancement device includes a second oil phase mixing component and a second oil phase separation component connected to the second oil phase mixing component.

[0018] It is further preferred that the second oil phase mixing component is a stirring mixing tank, and the second oil phase separation component is a clarifying tank.

[0019] Furthermore, the oil-phase ammonia increase circulation outlet and the oil-phase ammonia increase circulation return port are respectively provided with one or more.

[0020] Furthermore, it is preferred that the oil phase ammonia increase circulation outlet is arranged on the same height plane as or above the oil phase ammonia increase circulation return port; The present invention also discloses a drop ball forming method, using the oil-ammonia column drop ball forming device, comprising the following steps: The molding material is passed into the ball dropper, the washing solution is passed into the oil phase purification device, the oil phase and the water phase are passed into the molding container of the oil-ammonia column, and the ammonia-enhancing solution is passed into the oil phase ammonia-enhancing device; Turn on the ball dropper, oil phase purification device and oil phase ammonia enhancement device; Gel spheres were obtained at the bottom of the aqueous phase region of the forming vessel.

[0021] Furthermore, the molding material is one or more of aluminum oxide, silicon oxide, and molecular sieve sol slurry.

[0022] Furthermore, the oil phase is a liquid organic matter that is immiscible with the aqueous solution; the liquid organic matter is a hydrocarbon or an ether; preferably one or more of petroleum ether, gasoline, kerosene, white oil, diesel, lubricating oil, and liquid paraffin oil.

[0023] Furthermore, the aqueous phase is an aqueous ammonia solution, an ammonium salt solution, or a mixed aqueous solution of aqueous ammonia and an ammonium salt.

[0024] Furthermore, the washing solution is a solution that is immiscible with the oil phase, preferably water or an aqueous solution containing low ammonia.

[0025] Furthermore, the ammonia-enhanced solution is an aqueous ammonia solution, an ammonium salt solution, or a mixed aqueous solution of ammonia water and an ammonium salt.

[0026] Compared with the prior art, the beneficial effects of the present invention are: (1) The device and method provided in the present invention can eliminate the adverse effects of dissolved ammonia in the oil phase and ammonia / water interface resistance on the sphericity of the product in the oil-ammonia column dropper device, and solve the problem that the dropper cannot work continuously and stably for a long time due to the diffusion of ammonia. (2) The problems of the traditional oil-ammonia column forming device, such as the easy blockage of the ball dropper, easy interruption of production, low production efficiency and poor product uniformity, are overcome. The present invention extracts the oil phase at the top of the oil-ammonia column and uses water or solution to wash and remove ammonia in the oil phase, thereby blocking the diffusion of ammonia in the ammonia aqueous phase at the bottom of the oil-ammonia column through the oil phase to the ball dropper, thereby avoiding the gelation of the sol at the dropper, which causes the gel block to stick or hang at the dropper and the blockage of the dropper, thereby reducing the frequency of cleaning the dropper, achieving continuous production, improving production efficiency, and improving product uniformity.

[0027] (3) The sphericity and uniformity of the product are improved, providing a basis for improving the wear resistance and strength of the product. The present invention extracts the oil phase from the upper part of the oil-ammonia column and uses water or solution to wash and remove ammonia from the oil phase, and returns the oil phase after washing and removing ammonia to the upper part of the oil phase of the oil-ammonia column, thereby avoiding premature gelation of the droplets in the oil phase and facilitating the formation of spherical droplets with good sphericity by the sol droplets in the oil phase. On the other hand, the present invention sets a transition oil phase zone at the lower part of the oil phase zone, and uses a small amount of ammonia dissolved therein to gel the surface of the spherical droplets formed in the ammonia-removing oil phase zone to form a "protective shell" with a certain strength, thereby avoiding the destruction of the sphericity of the droplets by the interfacial resistance when the droplets pass through the oil / water interface.

[0028] (4) The oil phase of the present invention is recycled back to the oil phase for reuse after washing and removing ammonia. The material consumption and cost of producing carrier balls by using the device and method of the present invention are low, and it is easy to combine with the existing drop ball forming equipment and easy to promote and apply. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The accompanying drawings, which constitute a part of the present invention, are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute improper limitations on the present invention.

[0030] Attached Figure 1 A simplified structural diagram of a device for drop ball molding; Attached Figure 2 It is a simplified structural diagram of a drop ball forming device with an ammonia increasing device in an oil phase transition zone; Wherein: 1—ball dropper, 2—oil-ammonia forming container, 21—oil phase area, 211—ammonia removal oil phase area, 212—transition oil phase area, 2121—first transition oil phase area, 2122—second transition oil phase area, 2123—oil phase ammonia increase circulation outlet, 2124—oil phase ammonia increase circulation return port, 213—oil phase purification circulation outlet, 214—oil phase purification circulation return port, 22—ammonia water phase area, 3—oil phase purification device, 31—first oil phase mixing component, 32—first oil phase separation component, 4—oil phase ammonia increase device, 41—second oil phase mixing component, 42—second oil phase separation component. DETAILED DESCRIPTION

[0031] An oil-ammonia column drop ball forming device, comprising a forming oil-ammonia column and an oil phase purification device; The molded oil-ammonia column comprises a molding container with an opening at the top, wherein an oil phase region located at the top and a water phase region located at the bottom are arranged inside the molding container; a ball dropper is arranged above the top opening of the molding container; The oil phase zone is provided with an oil phase purification circulation outlet connected to the liquid inlet of the oil phase purification device and an oil phase purification circulation return port connected to the liquid outlet of the oil phase purification device; The oil phase purification device is used to wash and remove ammonia from the oil phase in the oil phase zone; the oil phase in the oil phase zone enters the oil phase purification device through the oil phase purification circulation outlet, and the oil phase after washing and removing ammonia returns to the oil phase zone through the oil phase purification circulation return port, so that the oil phase zone forms an ammonia removal oil phase zone and a transition oil phase zone from top to bottom; The oil phase purification circulation outlet and the oil phase purification circulation return port are located in the ammonia removal oil phase zone.

[0032] During the use of this device, the hydrophilicity of ammonia and ammonium salt is utilized to extract the oil phase on the upper part of the oil-ammonia column, and the ammonia in the oil phase is removed by washing with water or solution, and the oil phase after washing and removing ammonia is returned to the upper part of the oil phase of the oil-ammonia column, thereby avoiding premature gelation of the droplets, and thus facilitating the formation of spherical droplets with good sphericity by the sol droplets in the oil phase.

[0033] In addition, since the ammonia in the upper oil phase is washed away, the diffusion of ammonia in the oil phase toward the oil phase and the dripper tip is blocked, thereby avoiding the problem of dripper blockage and inability to work continuously caused by the gelation of the sol at the dripper.

[0034] As one of the preferred solutions, the oil phase purification circulation outlet and the oil phase purification circulation return port are respectively provided with one or more.

[0035] As one of the preferred solutions, the oil phase purification circulation return port is arranged on the same height plane as or above the oil phase purification circulation outlet.

[0036] As one of the preferred solutions, the oil phase purification circulation outlet is arranged below 1 / 3 of the upper part of the oil phase zone of the oil-ammonia column, and the height of the oil phase zone except ammonia accounts for more than 1 / 3 of the total height of the oil phase zone.

[0037] As one of the preferred schemes, the oil phase purification circulation outlet is set at 1 / 2~2 / 3 of the height of the oil phase zone; further preferably, the oil phase purification circulation outlet is set at 1 / 2 of the height of the oil phase zone.

[0038] As one of the preferred solutions, the oil phase purification device is a mixer-settler.

[0039] As one of the preferred solutions, the oil phase purification device includes a first oil phase mixing component and a first oil phase separation component connected to the first oil phase mixing component.

[0040] It is further preferred that the first oil phase mixing component is a stirring mixing tank, and the first oil phase separation component is a clarifying tank.

[0041] Specifically, the oil phase at the top of the oil-ammonia column can enter the first oil phase mixing component of the oil phase purification device through the oil phase purification circulation outlet. The first oil phase mixing component contains a washing solution, which can wash the oil phase to remove ammonia. After the mixing and washing in the first oil phase mixing component is completed, the mixed solution is passed into a clarification tank. After separation, the oil phase after washing and removal of ammonia can be obtained (for example, a clarification separation method can be adopted). The oil phase returns to the upper part of the oil phase of the oil-ammonia column through the oil phase purification circulation return port, so that the oil phase area forms an ammonia-removing oil phase area and a transition oil phase area from top to bottom.

[0042] As one of the preferred solutions, in order to increase the content of ammonia (or ammonium salt) in the oil phase in the transition oil phase region, an oil phase ammonia increasing device is further included, wherein the oil phase ammonia increasing device is configured to increase ammonia (ammonium) in the oil phase in the transition oil phase region; The transition oil phase zone is provided with an oil phase ammonia increase circulation outlet connected to the liquid inlet of the oil phase ammonia increase device and an oil phase ammonia increase circulation return port connected to the liquid outlet of the oil phase ammonia increase device; The oil phase in the transition oil phase region enters the oil phase ammonia increase device through the oil phase ammonia increase circulation outlet and then returns to the transition oil phase region through the oil phase ammonia increase circulation return port after ammonia increase, so that the transition oil phase region forms a first transition oil phase region and a second transition oil phase region from top to bottom; The oil phase ammonia increase circulation outlet and the oil phase ammonia increase circulation return port are located in the second transition oil phase zone.

[0043] The present invention is provided with an oil phase ammonia increasing device, the oil phase of the transition oil phase zone is led out from the oil phase ammonia increasing circulation outlet to the oil phase ammonia increasing device for ammonia or ammonium increasing, and the oil phase after ammonia or ammonium salt is increased is returned to the transition oil phase zone through the oil phase ammonia increasing circulation return port. According to the positions of the oil phase ammonia increasing circulation outlet and the oil phase ammonia increasing circulation return port of the transition oil phase zone, the ammonia content in the oil phase of the transition oil phase zone will be different, thereby the transition oil phase zone can be divided from top to bottom into a first transition oil phase zone and a second transition oil phase zone.

[0044] The setting of this component makes full use of the property that a small amount of ammonia (ammonium) is easily dissolved in the oil phase, creating conditions for mixing part of ammonia or ammonium salt into the transition oil phase region in the formed oil-ammonia column, and the oil phase in the transition oil phase region of the formed oil-ammonia column is divided into at least two parts, upper and lower. The upper part of the oil phase in the transition oil phase region basically does not contain ammonia, and the droplets form spherical droplets under the surface tension of the upper oil phase. When the spherical droplets pass through the lower oil phase containing a small amount of ammonia, the surface of the spherical droplets is gelled under the action of a small amount of ammonia dissolved in the oil phase, so that the surface of the droplets has a certain "strength". Since there is no obvious interface between the upper oil phase and the lower oil phase in the transition oil phase region, there is no obvious interface resistance, so the sphericity of the surface gelled droplets can be fully guaranteed. When the surface gelled droplets further descend to the oil / water interface, the gel layer formed on their surface can overcome the destruction of the sphericity of the droplets caused by the interface resistance, so that gel balls with good sphericity and uniformity can be obtained, providing a basis for preparing carrier balls with good sphericity and uniformity.

[0045] As one of the preferred solutions, the oil phase ammonia enhancement device includes a second oil phase mixing component and a second oil phase separation component connected to the second oil phase mixing component.

[0046] It is further preferred that the second oil phase mixing component is a stirring mixing tank, and the second oil phase separation component is a clarifying tank.

[0047] Specifically, the oil phase in the transition oil phase zone can enter the second oil phase mixing component of the oil phase ammonia increase device through the oil phase ammonia increase circulation outlet. The second oil phase mixing component contains an ammonia increase solution, that is, an aqueous solution containing ammonia or ammonium salt (preferably a solution with the same ammonia aqueous phase as used in the formed oil-ammonia column). After the ammonia (ammonium) is mixed in the second oil phase mixing component, the mixed solution is passed into the second oil phase separation component. After separation, the ammonia (ammonium) oil phase can be obtained (for example, a clarification separation method can be adopted). The oil phase returns to the transition oil phase zone through the oil phase ammonia increase circulation return port, so that the transition oil phase zone forms a first transition oil phase zone and a second transition oil phase zone from top to bottom.

[0048] As one of the preferred solutions, the oil-phase ammonia increase circulation outlet and the oil-phase ammonia increase circulation return port are respectively provided with one or more.

[0049] As one of the preferred schemes, the oil-phase ammonia increase circulation outlet is preferably arranged on the same height plane as or above the oil-phase ammonia increase circulation return port.

[0050] It should be noted that: in the actual operation of the present application, the flow rate of the organic phase extracted from the ammonia removal oil phase area and the second transition oil phase area will be kept consistent with the flow rate of the organic phase after washing returned. The boundary between different phase areas will maintain dynamic balance, the height of each phase area is dynamically stable, and the division of the area is divided by the plane where the outlet or return port is located, such as: the boundary between the ammonia removal oil phase area and the transition oil phase area is the plane where the oil phase purification cycle outlet is located, and the boundary between the first transition oil phase area and the second transition oil phase area is the plane where the oil phase ammonia increase cycle return port is located.

[0051] The present invention also discloses a drop ball forming method, using the oil-ammonia column drop ball forming device, comprising the following steps: The molding material is passed into the ball dropper, the washing solution is passed into the oil phase purification device, the oil phase and the water phase are passed into the molding container of the oil-ammonia column, and the ammonia-enhancing solution is passed into the oil phase ammonia-enhancing device; Turn on the ball dropper, oil phase purification device and oil phase ammonia enhancement device; Gel spheres were obtained at the bottom of the aqueous phase region of the forming vessel.

[0052] As one of the preferred solutions, the molding material is one or more of aluminum oxide, silicon oxide, and molecular sieve sol slurry.

[0053] As one of the preferred schemes, the oil phase is a liquid organic matter that is immiscible with the aqueous solution; the liquid organic matter is a hydrocarbon or an ether; preferably one or more of petroleum ether, gasoline, kerosene, white oil, diesel, lubricating oil, and liquid paraffin oil.

[0054] As one of the preferred embodiments, the aqueous phase is an aqueous ammonia solution, an ammonium salt solution, or a mixed aqueous solution of an ammonia solution and an ammonium salt; As one of the preferred solutions, the washing solution is a solution that is immiscible with the oil phase, preferably water or an aqueous solution low in ammonia.

[0055] As one of the preferred solutions, the ammonia-enhanced solution is an aqueous ammonia solution, an ammonium salt solution, or a mixed aqueous solution of ammonia water and an ammonium salt.

[0056] The present invention is described in detail below in conjunction with the accompanying drawings. The description in this part is only exemplary and explanatory and should not have any limiting effect on the scope of protection of the present invention. In addition, those skilled in the art can make corresponding combinations of the features in the embodiments and in different embodiments in this document based on the description of this document.

[0057] Example 1 An oil-ammonia column drop ball forming device, such as Figure 1As shown, it includes a formed oil-ammonia column and an oil phase purification device 3; the formed oil-ammonia column includes a forming container 2 with an opening at the top, and an oil phase area 21 located at the upper part and a water phase area 22 located at the lower part are arranged inside the forming container 2; a ball dropper 1 is arranged above the top opening of the forming container 2; the oil phase area 21 is provided with an oil phase purification circulation outlet 213 connected to the liquid inlet end of the oil phase purification device 3 and an oil phase purification circulation return port 214 connected to the liquid outlet end of the oil phase purification device 3; the oil phase purification device 3 is used to wash and remove ammonia from the oil phase in the oil phase area 21; the oil phase in the oil phase area 21 enters the oil phase purification device 3 through the oil phase purification circulation outlet 213 for washing and removing ammonia, and then returns to the oil phase area 21 through the oil phase purification circulation return port 214, so that the oil phase area 21 forms an ammonia removal oil phase area 211 and a transition oil phase area 212 from top to bottom; the oil phase purification circulation outlet 213 and the oil phase purification circulation return port 214 are located in the ammonia removal oil phase area 211.

[0058] In this embodiment, there are two oil phase purification circulation outlets 213 and two oil phase purification circulation return ports 214 , which are symmetrically distributed along the outer wall of the molding container 2 in the same plane.

[0059] In this embodiment, the oil phase purification circulation return port 214 is arranged above the height plane where the oil phase purification circulation outlet 213 is located. Specifically, the oil phase purification circulation outlet 213 is arranged in the middle of the oil phase area 21 (i.e., 1 / 2 of the height of the oil phase area), and the oil phase purification circulation return port 214 is arranged 5 cm below the upper liquid surface of the oil phase.

[0060] In this embodiment, the height of the oil phase region 21 is 40 cm, and the height of the water phase region 22 is 20 cm; the height of the ammonia-removing oil phase region 211 accounts for 1 / 3 of the total height of the oil phase region.

[0061] In this embodiment, the oil phase purification device 3 includes a first oil phase mixing component 31 and a first oil phase separation component 32 connected to the first oil phase mixing component 31; the first oil phase mixing component 31 is a stirring mixing tank, and the first oil phase separation component 32 is a clarifier.

[0062] In this embodiment, the oil phase of the molding container is petroleum ether (distillation range is 60-90° C.), the water phase is 20% ammonia water, and the oil phase washing solution is pure water.

[0063] This embodiment also discloses a method for forming oil-ammonia column drop balls, using the above-mentioned oil-ammonia column drop ball forming device, comprising the following steps: Pseudo-boehmite with a peptization index of 96% is used as a raw material, and water and hydrochloric acid are used to prepare an alumina sol slurry with an alumina content of 24%. The alumina sol raw material used as a ball dropper is placed in a ball dropper.

[0064] The oil-ammonia column drop ball forming device described above was used, and the oil phase purification device was started at the same time. The circulation flow rate of the purified oil phase was controlled according to the oil phase in the purified oil phase zone circulating once every 15 minutes. The average drop ball speed was controlled to be about 20 mL / min·drip head. The drop balls were continuously dropped for 4 hours. No obvious gel blocks were seen at the drip head of the drop ball device, and there was no obvious tailing phenomenon after the sol droplets entered the oil phase.

[0065] Gel balls in different time periods were taken, and alumina carrier balls were obtained after aging, drying and calcination. The sphericity of the carrier balls was analyzed by a particle size and particle shape analyzer. The average sphericity of the alumina carrier balls obtained 25 minutes before dropping the balls was 0.97, the average particle size of the carrier balls was 1.6 mm, and the standard deviation was 0.1 mm. The average sphericity of the alumina carrier balls obtained from 30 to 40 minutes was 0.98, the average particle size was 1.60 mm, and the standard deviation was 0.06 mm. The average sphericity of the alumina carrier balls obtained from 40 to 120 minutes was 0.98, the average particle size was 1.61 mm, and the standard deviation was 0.07 mm. The average sphericity of the alumina carrier balls obtained from 120 to 240 minutes was 0.97, the average particle size was 1.60 mm, and the standard deviation was 0.08 mm.

[0066] Comparative Example 1 This comparative example 1 is basically the same as the example 1, except that the oil-ammonia column drop ball forming device of the comparative example 1 is not provided with the oil phase purification device 3.

[0067] The conditions of alumina sol and ball dropping speed are the same as those in Example 1.

[0068] Using the above-mentioned ball dropping device, after 30 minutes of ball dropping, gel blocks began to appear at the needle tube of the ball dropper. After 40 minutes of ball dropping, the gel blocks at the needle tube of the dropper increased to more than 2 mm, and the sol droplets falling at the dropper increased significantly, seriously affecting the normal operation of the dropper. In addition, after 25 minutes of ball dropping, the alumina sol droplets entered the oil phase and tailing occurred. After 40 minutes, the tailing was serious, and the sol droplets entered the ammonia phase to form water drop-shaped gel balls. After aging, drying and calcining, the gel balls were obtained to obtain alumina carrier balls. The sphericity of the carrier balls was analyzed by a particle size and particle shape analyzer. The sphericity of the alumina carrier balls obtained 25 minutes before the ball dropping accounted for 90% of the sphericity greater than 0.95, the average sphericity (the sum of the sphericity of each particle / the number of particles) was 0.96, the average particle size of the carrier balls was 1.6 mm, and the standard deviation was 0.1 mm. The average sphericity of the alumina carrier spheres obtained in 30-40 minutes was 0.90, the average particle size was 1.8 mm, and the standard deviation was 0.3 mm. After 40 minutes, the particles were pear-shaped and had very poor sphericity.

[0069] Example 2 An oil-ammonia column drop ball forming device, such as Figure 2As shown, it includes a formed oil-ammonia column and an oil phase purification device 3; the formed oil-ammonia column includes a forming container 2 with an opening at the top, and an oil phase area 21 located at the upper part and a water phase area 22 located at the lower part are arranged inside the forming container 2; a ball dropper 1 is arranged above the top opening of the forming container 2; the oil phase area 21 is provided with an oil phase purification circulation outlet 213 connected to the liquid inlet end of the oil phase purification device 3 and an oil phase purification circulation return port 214 connected to the liquid outlet end of the oil phase purification device 3; the oil phase purification device 3 is used to wash and remove ammonia from the oil phase in the oil phase area 21; the oil phase in the oil phase area 21 enters the oil phase purification device 3 through the oil phase purification circulation outlet 213 for washing and removing ammonia, and then returns to the oil phase area 21 through the oil phase purification circulation return port 214, so that the oil phase area 21 forms an ammonia removal oil phase area 211 and a transition oil phase area 212 from top to bottom; the oil phase purification circulation outlet 213 and the oil phase purification circulation return port 214 are located in the ammonia removal oil phase area 211.

[0070] In this embodiment, there are two oil phase purification circulation outlets 213 and two oil phase purification circulation return ports 214 , which are symmetrically distributed along the outer wall of the molding container 2 in the same plane.

[0071] In this embodiment, the oil phase purification circulation return port 214 is arranged above the height plane where the oil phase purification circulation outlet 213 is located. Specifically, the oil phase purification circulation outlet 213 is arranged at 20 cm from the upper liquid surface of the oil phase (i.e., 1 / 3 of the height of the oil phase), and the oil phase purification circulation return port 214 is arranged at 5 cm below the upper liquid surface of the oil phase.

[0072] In this embodiment, the height of the oil phase region 21 is 60 cm, and the height of the water phase region 22 is 30 cm; the height of the ammonia-removing oil phase region 211 accounts for 1 / 3 of the total height of the oil phase region.

[0073] In this embodiment, the oil phase purification device 3 includes a first oil phase mixing component 31 and a first oil phase separation component 32 connected to the first oil phase mixing component 31; the first oil phase mixing component 31 is a stirring mixing tank, and the first oil phase separation component 32 is a clarifier.

[0074] In the present embodiment, an oil phase ammonia increase device 4 is also included, and the oil phase ammonia increase device 4 is used to increase ammonia for the oil phase in the transition oil phase zone 212; the transition oil phase zone 212 is provided with an oil phase ammonia increase circulation outlet 2123 connected to the liquid inlet end of the oil phase ammonia increase device 4 and an oil phase ammonia increase circulation return port 2124 connected to the liquid outlet end of the oil phase ammonia increase device 4; the oil phase in the transition oil phase zone 212 enters the oil phase ammonia increase device 4 through the oil phase ammonia increase circulation outlet 2123 and returns to the transition oil phase zone 212 through the oil phase ammonia increase circulation return port 2124 after ammonia increase, so that the transition oil phase zone 212 forms a first transition oil phase zone 2121 and a second transition oil phase zone 2122 from top to bottom; the oil phase ammonia increase circulation outlet 2123 and the oil phase ammonia increase circulation return port 2124 are located in the second transition oil phase zone 2122.

[0075] In this embodiment, the oil phase ammonia enhancement device 4 comprises a second oil phase mixing component 41 and a second oil phase separation component 42 disposed in the second oil phase mixing component 41. The second oil phase mixing component 41 is a stirring mixing tank, and the second oil phase separation component 42 is a clarifier.

[0076] In this embodiment, the oil phase ammonia increase circulation outlet 2123 is set 10 cm below the plane where the oil phase purification circulation outlet 213 is located, and the oil phase ammonia increase circulation return port 2124 is set 10 cm above the lower interface of the oil phase (oil-water interface).

[0077] In this embodiment, two oil-phase ammonia increase circulation outlets 2123 and two oil-phase ammonia increase circulation return ports 2124 are respectively provided, and are symmetrically distributed along the outer wall of the oil-ammonia column in the same plane.

[0078] In this embodiment, the oil phase of the molding container is petroleum ether (distillation range is 60-90° C.), the water phase is 20% ammonia water, and the oil phase washing solution is pure water.

[0079] This embodiment also discloses a method for forming oil-ammonia column drop balls, using the above-mentioned oil-ammonia column drop ball forming device, comprising the following steps: Pseudo-boehmite with a peptization index of 96% is used as a raw material, and water and hydrochloric acid are used to prepare an alumina sol slurry with an alumina content of 24%, which is used as the alumina sol raw material for the drop ball.

[0080] The oil-ammonia column drop ball forming device described above is used to start the oil phase purification device and the oil phase ammonia increase device in the transition zone at the same time. The oil phase circulation flow rate of the oil phase purification device and the oil phase ammonia increase device is controlled to circulate once every 15 minutes on average (that is, the oil phase circulates once every 15 minutes between the circulation outlet and the return port on average). The ball dropping speed is controlled to be about 20 mL / min·drip head on average. After continuous ball dropping for 4 hours, no obvious gel blocks are seen at the dropper of the ball dropper, and there is no obvious tailing phenomenon after the sol drops enter the oil phase. The ball dropping time is increased to 6 hours, and the ball can still be dropped continuously. There is still no obvious gel block at the dropper of the ball dropper, and there is no obvious tailing phenomenon after the sol drops enter the oil phase.

[0081] Gel balls in different time periods were taken, and alumina carrier balls were obtained after aging, drying and calcination. The sphericity of the carrier balls was analyzed by a particle size and shape analyzer. The average sphericity of the alumina carrier balls obtained 1 hour before dropping the balls was 0.99, the average particle size of the carrier balls was 1.60 mm, and the standard deviation was 0.06 mm. The average sphericity of the alumina carrier balls obtained 1 to 2 hours was 0.99, the average particle size was 1.60 mm, and the standard deviation was 0.07 mm. The average sphericity of the alumina carrier balls obtained 2 to 4 hours was 0.99, the average particle size was 1.60 mm, and the standard deviation was 0.07 mm. The average sphericity of the alumina carrier balls obtained 4 to 6 hours was 0.98, the average particle size was 1.60 mm, and the standard deviation was 0.08 mm.

[0082] Compared with Example 1, the alumina carrier balls prepared in Example 2 in which the oil-phase ammonia addition device is set have higher average sphericity and smaller standard deviation, and maintain high sphericity and low standard deviation longer, which proves that the oil-phase ammonia addition device can improve the sphericity and uniformity of the prepared alumina carrier balls, extend the stable working time of the ball dropper, and improve production efficiency.

[0083] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. An oil-ammonia column drop ball forming device, characterized in that: It includes a formed oil-ammonia column and an oil phase purification device; The molded oil-ammonia column comprises a molding container with an opening at the top, wherein the interior of the molding container comprises an oil phase region located at the top and a water phase region located at the bottom; a ball dropper is arranged above the top opening of the molding container; The oil phase zone is provided with an oil phase purification circulation outlet connected to the liquid inlet of the oil phase purification device and an oil phase purification circulation return port connected to the liquid outlet of the oil phase purification device; The oil phase purification device is configured to wash and remove ammonia from the oil phase in the oil phase zone; after the oil phase in the oil phase zone enters the oil phase purification device through the oil phase purification circulation outlet for washing and removing ammonia, it returns to the oil phase zone through the oil phase purification circulation return port, so that the oil phase zone forms an ammonia removal oil phase zone and a transition oil phase zone from top to bottom; The oil phase purification circulation outlet and the oil phase purification circulation return port are located in the ammonia removal oil phase zone.

2. The oil-ammonia column drop ball forming device according to claim 1, characterized in that: The oil phase purification circulation outlet and the oil phase purification circulation return port are respectively provided with one or more; Preferably, the oil phase purification circulation return port is arranged on the same height plane as the oil phase purification circulation outlet or above it; Preferably, the oil phase purification circulation outlet is arranged below 1 / 3 of the upper part of the oil phase zone of the oil-ammonia column, and the height of the oil phase zone except ammonia accounts for more than 1 / 3 of the total height of the oil phase zone; The oil phase purification circulation outlet is preferably set at 1 / 2 to 2 / 3 of the height of the oil phase zone; More preferably, the oil phase purification circulation outlet is set at 1 / 2 of the height of the oil phase zone.

3. The oil-ammonia column drop ball forming device according to claim 1, characterized in that: The oil phase purification device comprises a first oil phase mixing component and a first oil phase separation component arranged in the first oil phase mixing component; Preferably, the first oil phase mixing component is a stirring mixing tank, and the first oil phase separation component is a clarifying tank.

4. The oil-ammonia column drop ball forming device according to claim 1, characterized in that: It also includes an oil phase ammonia increasing device, which is used to increase the ammonia of the oil phase in the transition oil phase zone.

5. The oil-ammonia column drop ball forming device according to claim 4, characterized in that: The transition oil phase zone is provided with an oil phase ammonia increase circulation outlet connected to the liquid inlet of the oil phase ammonia increase device and an oil phase ammonia increase circulation return port connected to the liquid outlet of the oil phase ammonia increase device; The oil phase in the transition oil phase region enters the oil phase ammonia increase device through the oil phase ammonia increase circulation outlet and then returns to the transition oil phase region through the oil phase ammonia increase circulation return port after ammonia increase, so that the transition oil phase region forms a first transition oil phase region and a second transition oil phase region from top to bottom; The oil phase ammonia increase circulation outlet and the oil phase ammonia increase circulation return port are located in the second transition oil phase zone.

6. The oil-ammonia column drop ball forming device according to claim 5, characterized in that: The oil phase ammonia increase circulation outlet and the oil phase ammonia increase circulation return port are respectively provided with one or more; Preferably, the oil-phase ammonia-enriched circulation outlet is arranged on the same height plane as or above the oil-phase ammonia-enriched circulation return port.

7. The oil-ammonia column drop ball forming device according to claim 4, characterized in that: The oil phase ammonia enhancement device comprises a second oil phase mixing component and a second oil phase separation component arranged in the second oil phase mixing component; Preferably, the first oil phase mixing component is a stirring mixing tank, and the first oil phase separation component is a clarifying tank.

8. A method for forming a drop ball, characterized in that: The oil-ammonia column drop ball forming device according to any one of claims 1 to 7 comprises the following steps: The molding material is passed into the ball dropper, the washing solution is passed into the oil phase purification device, the oil phase and the water phase are passed into the molding container of the oil-ammonia column, and the ammonia-enhancing solution is passed into the oil phase ammonia-enhancing device; Turn on the ball dropper, oil phase purification device and oil phase ammonia enhancement device; Gel spheres were obtained at the bottom of the aqueous phase region of the forming vessel.

9. The method according to claim 8, characterized in that The molding material is one or more of aluminum oxide, silicon oxide, and molecular sieve sol slurry; The oil phase is a liquid organic matter that is immiscible with the aqueous solution; the liquid organic matter is a hydrocarbon or an ether; the liquid organic matter is preferably one or more of petroleum ether, gasoline, kerosene, white oil, diesel, lubricating oil, and liquid paraffin oil; The aqueous phase is an aqueous ammonia solution, an ammonium salt solution, or a mixed aqueous solution of an ammonia solution and an ammonium salt; The washing solution is a solution immiscible with the oil phase, preferably water or an aqueous solution containing low ammonia; The ammonia-enhanced solution is an aqueous ammonia solution, an ammonium salt solution, or a mixed aqueous solution of ammonia water and an ammonium salt.

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