阅读说明：本技术 一种球形载体的成球装置和制备方法 (Balling device and preparation method of spherical carrier ) 是由 于宁 臧高山 王嘉欣 张玉红 王涛 丁璟 于 2018-08-31 设计创作，主要内容包括：本发明涉及一种球形载体的成球装置和制备方法,该装置包括用于容纳成球液的容器本体和位于所述容器本体外部的成球液循环机构,所述容器本体从上至下分为成球区、固化区和收集区,顶部设置有用于滴入浆液滴的顶部开口；在所述容器本体固化区相对两侧的侧壁上沿垂直方向交替设置多排液体入口和液体出口,成球液通过管线由液体入口进入容器本体,由液体出口排出容器本体,再返回液体入口,通过一个成球液循环机构进行循环。采用本发明提供的成球装置和方法进行制备球形载体,能够提高球形载体的球形度和耐磨损性。(The invention relates to a balling device and a preparation method of a spherical carrier, the device comprises a container body for containing balling liquid and a balling liquid circulating mechanism positioned outside the container body, the container body is divided into a balling area, a solidification area and a collection area from top to bottom, and the top of the container body is provided with a top opening for dropping slurry drops; the side walls of the two opposite sides of the container body solidification area are alternately provided with a plurality of rows of liquid inlets and liquid outlets along the vertical direction, the balling liquid enters the container body from the liquid inlets through pipelines, is discharged out of the container body from the liquid outlets, returns to the liquid inlets and is circulated through a balling liquid circulating mechanism. The spherical carrier prepared by the balling device and the method provided by the invention can improve the sphericity and the wear resistance of the spherical carrier.)

1. A balling device for spherical carriers comprises a container body (1) for containing balling liquid and a balling liquid circulating mechanism (2) positioned outside the container body (1), wherein the container body (1) is divided into a balling area (31), a curing area (32) and a collecting area (33) from top to bottom, and the top of the container body is provided with a top opening for dropping slurry drops; the side walls of two opposite sides of the solidification area (32) of the container body (1) are alternately provided with a plurality of rows of liquid inlets (11) and liquid outlets (12) along the vertical direction, balling liquid enters the container body (1) from the liquid inlets (11) through pipelines, is discharged out of the container body (1) from the liquid outlets (12), returns to the liquid inlets (11) and is circulated through a balling liquid circulating mechanism (2).

2. Balling device according to claim 1, in which a row of liquid inlets (11) is provided on the side wall of the collecting zone (33) of the vessel body (1) and a row of liquid outlets (12) is provided opposite on the side wall of the other side.

3. A balling apparatus as claimed in claim 1 or 2, wherein the balling liquid circulation means comprises a line (4) and a circulation pump, the liquid inlet (11) is connected to the outlet of the circulation pump via the line (4), the liquid outlet (12) is connected to the inlet of the circulation pump via the line (4), and the axis of the line (4) forms an angle α of 70-110 ° with the side wall of the vessel body (1) below the line (4) in the vertical direction.

4. A balling apparatus according to claim 1 or 2, in which the number of liquid inlets (11) or liquid outlets (12) in the same row is 1 to 20.

5. The beading apparatus according to claim 1 or 2, wherein the liquid feeding timing and the liquid flow rate of each liquid inlet (11) are independently and controllably controlled, and the liquid feeding timing and the liquid flow rate of each liquid outlet (12) are independently and controllably controlled.

6. Balling device according to claim 1 or 2, wherein the distance between adjacent liquid inlet openings (11) is 10-100cm and the distance between adjacent liquid outlet openings (12) is 10-100cm in the vertical direction.

7. A balling apparatus as claimed in claim 1 or 2, in which the horizontal spacing between the liquid inlets (11) or liquid outlets (12) of the same row is in the range 0.5 to 50cm, and the open area of each liquid inlet (11) is in the range 0.5 to 20cm²The opening area of each liquid outlet (12) is 0.5-20cm²The opening area of the liquid inlet (11) is not larger than that of the liquid outlet (12).

8. A balling device according to claim 1 or 2, in which the liquid inlet (11) and the liquid outlet (12) are arranged alternately in the vertical direction on the side walls on opposite sides of the solidification zone (32).

9. A balling device according to claim 1 or 2, in which the liquid inlet (11) and the liquid outlet (12) are each circular, square, rectangular, oval or triangular in shape.

10. Balling device according to claim 1 or 2, wherein the container body (1) is a cuboid having a length of 0.5-5m, a width of 0.5-2m and a height of 1-5 m.

11. A method of preparing a spherical support using the apparatus of claim 1, the method comprising: and (2) dropping the carrier slurry into the top opening of the container body (1) in the form of slurry drops through a ball dropping device (100), contacting with the balling liquid in the container body (1) and dropping to form balls, meanwhile, introducing the balling liquid into the container body (1) through the liquid inlet (11) by adopting a balling liquid circulating mechanism (2), then discharging the container body (1) through the liquid outlet (12), taking out wet balls obtained in the collecting region (33), drying and roasting.

12. The method according to claim 11, wherein the balling liquid in the balling zone (31), the solidifying zone (32) and the collecting zone (33) is the same and is selected from hydrocarbon oil, and the hydrocarbon oil is at least one of gasoline, diesel oil, kerosene, medical lubricating oil, liquid paraffin oil and white oil.

13. The method according to claim 11, wherein the balling liquid in the balling zone (31), the solidifying zone (32) and the collecting zone (33) is different, the balling liquid in the balling zone (31) is selected from hydrocarbon oil, the hydrocarbon oil is at least one of gasoline, diesel oil, kerosene, medical lubricating oil, liquid paraffin oil and white oil, and the balling liquid in the solidifying zone (32) and the collecting zone (33) is ammonia water.

14. The method according to claim 11, wherein the support slurry contains at least one selected from the group consisting of alumina, silica and a molecular sieve.

15. The method according to claim 11, wherein the flow linear velocity of the sphering liquid in the liquid outlet (12) and the liquid inlet (11) is 0.5 to 10 m/s.

Technical Field

The invention relates to the field of spherical carrier preparation, in particular to a balling device and a preparation method of a spherical carrier.

Background

The dropping ball is an important method for preparing spherical particles, and the method is widely applied to the preparation of catalyst spherical particles, such as oil ammonia column dropping balls of alumina.

The technological process of the currently advanced spherical oxide molding apparatus is described in detail in CN 205095741U and patent 205095740U. The balling columns in both patents are simple vertical containers, the upper layer in the balling column is an oil phase, and the lower layer is a curing liquid.

In the process of dropping balls by adopting the existing ball dropping method, the ball is in a trailing phenomenon in the vertical falling process of a ball forming column, so that the sphericity is reduced, and finally, the ball is excessively worn in the using process.

Disclosure of Invention

The invention aims to provide a balling device and a preparation method for a spherical carrier.

In order to achieve the purpose, the invention provides a balling device for spherical carriers, which comprises a container body for containing balling liquid and a balling liquid circulating mechanism positioned outside the container body, wherein the container body is divided into a balling area, a solidification area and a collection area from top to bottom, and the top of the container body is provided with a top opening for dropping slurry drops; the side walls of the two opposite sides of the container body solidification area are alternately provided with a plurality of rows of liquid inlets and liquid outlets along the vertical direction, the balling liquid enters the container body from the liquid inlets through pipelines, is discharged out of the container body from the liquid outlets, returns to the liquid inlets and is circulated through a balling liquid circulating mechanism.

The invention also provides a method for preparing the spherical carrier by adopting the device provided by the invention, which comprises the following steps: and dripping the carrier slurry into the top opening of the container body in a slurry drop mode through a ball dripping device, contacting with the balling liquid in the container body and dropping into balls, meanwhile, introducing the balling liquid into the container body through the liquid inlet by adopting a balling liquid circulating mechanism, discharging the container body through the liquid outlet, taking out the wet balls obtained in the collecting region, drying and roasting.

The balling container can provide transverse acting force in opposite directions to the slurry drops falling in the balling container, so that the slurry drops rotate, and the horizontal movement of the slurry drops is reduced, thereby eliminating the trailing phenomenon caused by the slurry drops in the vertical falling process of the slurry drops, and improving the sphericity and the wear resistance of the prepared spherical carrier.

Drawings

Fig. 1 is a schematic structural diagram of a first embodiment of a balling device provided by the invention.

Fig. 2 is a schematic structural diagram of a second embodiment of the balling device provided by the invention.

Fig. 3 is a schematic structural diagram of a third embodiment of the balling device provided by the invention.

Fig. 4 is a front view of the balling container body of the apparatus of fig. 3.

Fig. 5 is a left side view of the balling vessel body of the apparatus shown in fig. 3.

Fig. 6 is a right side view of the balling vessel body of the apparatus of fig. 3.

Fig. 7 is a top view of the balling container body of the apparatus shown in fig. 3.

FIG. 8 is a schematic representation of the angle α between the sidewall of the container body and the line of the present invention.

Description of the reference numerals

1 liquid inlet 12 and liquid outlet of vessel body 11

2 balling liquid circulation mechanism

31 balling zone 32, curing zone 33, collecting zone

4 pipeline

100 dropping ball device

Detailed Description

As shown in figures 1 and 2, the balling container of the invention is provided with a balling area, a curing area and a collecting area, a plurality of rows of liquid inlets 11 and liquid outlets 12 are alternately arranged on the side walls of two opposite sides of the curing area 32 of a container body 1 along the vertical direction, balling liquid enters the container body 1 from the liquid inlets 11 through a balling liquid circulating mechanism 2, is discharged out of the container body 1 through the liquid outlets 12, and forms circulation, so that slurry drops in the container body 1 are rotated by transverse acting force in opposite directions in the falling process, the horizontal movement of the slurry drops can be reduced, the tailing phenomenon caused by the dropping of the slurry drops is eliminated in the vertical falling process of the slurry drops, and the sphericity and the wear resistance of spherical carriers are improved.

In one embodiment, as shown in fig. 3, in addition to three liquid inlets 11 and three liquid outlets 12 alternately arranged in the vertical direction on the side walls of the opposite sides of the curing zone, a row of liquid inlets 11 is arranged on the side wall of the collecting zone 33 of the container body 1, and a row of liquid outlets 12 is arranged on the side wall of the opposite side of the collecting zone, as shown in fig. 5 and 6. The liquids in the curing zone and the collection zone may be the same or both of similar properties.

As shown in figures 1, 2 and 3, the balling liquid circulating mechanism can comprise a pipeline 4 and a circulating pump, a liquid inlet 11 can be connected with an outlet of the circulating pump through the pipeline 4, a liquid outlet 12 can be connected with an inlet of the circulating pump through the pipeline 4, a lateral line can be arranged on the pipeline 4 so as to replenish new balling liquid and extract old balling liquid, the pipeline 4 can extend outwards from the liquid inlet 11 or the liquid outlet 12, an included angle α formed by the axis of the pipeline 4 and the side wall of the container body 1 below the pipeline 4 along the vertical direction can be 70-110 degrees, preferably 80-100 degrees, the cross section shape of the pipeline can be the same as that of the liquid inlet or the liquid outlet so as to facilitate the pipeline to be inserted into the liquid inlet or the liquid outlet, and the pipeline can be deeply inserted into the container body or flush with the inner side wall of the container body.

In one embodiment, as shown in fig. 3, which is a left side view, fig. 5 and a right side view, fig. 6 of the container body of the balling apparatus, the number of the liquid inlets 11 or the liquid outlets 12 in the same row may be set as required, for example, 1 to 20.

In the present invention, the liquid inlet timing and the liquid flow rate of each liquid inlet 11 can be independent and controllable, and the liquid outlet timing and the liquid flow rate of each liquid outlet 12 can be independent and controllable, for example, the flow rate of the ball forming liquid circulation mechanism can be adjusted, and the liquid inlet timing and the flow rate of the pipeline can be controlled by a valve.

In the present invention, the distance between the adjacent drain inlets and the liquid outlets may be set as required, for example, in the vertical direction, the distance between the adjacent drain inlets 11 is 10-100cm, and the distance between the adjacent drain outlets 12 is 10-100 cm. The horizontal spacing between the liquid inlets 11 or liquid outlets 12 of the same row may be 0.5-50cm, preferably 2-10 cm. The areas of the liquid inlets and the liquid outlets can be set according to the needs, the opening area of the liquid inlets can be small, the number of the liquid inlets is large, the opening area of the liquid outlets can be large, the number of the liquid outlets is small, and specifically, the opening area of each liquid inlet 11 can be 0.5-20cm²Preferably 0.5-10cm²The open area of each liquid outlet 12 may be 0.5-20cm²Preferably 0.5-10cm²The opening area of the liquid inlet 11 is preferably not larger than the opening area of the liquid outlet 12.

In one embodiment, the liquid inlet 11 and the liquid outlet 12 are alternately arranged 2-4 in the vertical direction on the side wall of the opposite sides of the curing zone 32.

In the present invention, the liquid inlet and the liquid outlet may have various shapes, for example, the shapes of the liquid inlet 11 and the liquid outlet 12 may be circular, square, rectangular, oval or triangular, preferably circular or rectangular, respectively.

In one embodiment, as shown in fig. 1 to 7, the container body 1 is a rectangular parallelepiped having a length of 0.5 to 5m, a width of 0.5 to 2m and a height of 1 to 5m, and it is preferable that a liquid inlet and a liquid outlet are provided at the side walls of the container body on opposite sides in the length direction, so as to prevent the slurry droplets from being forced to touch the container body.

The invention also provides a method for preparing the spherical carrier by using the device, which comprises the following steps: and (2) dropping the carrier slurry into the top opening of the container body 1 in the form of slurry drops through a ball dropping device 100, contacting with the balling liquid in the container body 1 and dropping to form balls, meanwhile, introducing the balling liquid into the container body 1 through the liquid inlet 11 by adopting a balling liquid circulating mechanism 2, discharging the container body 1 through the liquid outlet 12, taking out the wet balls obtained in the collecting region 33, drying and roasting.

The device of the invention can be applied to oil ammonia column molding or hot oil column molding spherical carriers, and the balling liquid can comprise hydrocarbon oil, including or not including ammonia water.

In one embodiment, the balling liquid in the balling zone 31, the solidifying zone 32 and the collecting zone 33 is the same and is selected from hydrocarbon oil, and the hydrocarbon oil is at least one of gasoline, diesel oil, kerosene, medical lubricating oil, liquid paraffin oil and white oil.

In another embodiment, the balling liquid in the balling zone 31, the solidifying zone 32 and the collecting zone 33 is different, the balling liquid in the balling zone 31 is selected from hydrocarbon oil, the hydrocarbon oil is at least one of gasoline, diesel oil, kerosene, medical lubricating oil, liquid paraffin oil and white oil, and the balling liquid in the solidifying zone 32 and the collecting zone 33 is ammonia water. In this embodiment, the liquid introduced into the body of the container at the liquid inlet should be kept as small as possible to avoid disturbing the interface between the different liquids, and the liquid may be introduced in the solidification zone away from the liquid interface, for example in the middle of the solidification zone.

In the present invention, the carrier slurry may contain at least one selected from the group consisting of alumina, silica and a molecular sieve, and may contain components such as urea and a gelling agent.

In the present invention, a reasonable liquid flow rate is selected according to parameters such as the size of the balling container, for example, the flow linear velocities of the balling liquid in the liquid outlet 12 and the liquid inlet 11 may be 0.5 to 10m/s, respectively.

The following examples further illustrate the process provided by the present invention, but are not intended to limit the invention thereto.

Comparative example 1

The conventional cylindrical oil ammonia column with no hole on the side wall is adopted for balling, the height of the oil ammonia column is 2m, and the diameter is 30 cm. The oil phase of the upper balling zone is diesel oil, the viscosity is 0.41cP, and the height of the oil layer is 15 cm. The lower layer solidification region and the collection region are ammonia water phase with concentration of 8 mass%, the height of the solidification region is 170cm, and the height of the collection region is 10 cm. The distance between the bottom of the ball dropping device and the oil surface is 3cm, and the ball dropping speed is 30 drops/min.

Mixing aluminum hydroxide (the content of aluminum oxide is 68 mass percent), deionized water, nitric acid and urea according to the mass ratio of 76: 140: 3: 20 to prepare slurry, dripping the slurry out of a dropper of a dropping ball device, entering an oil phase of an oil ammonia column to form balls, smoothly passing through an oil-ammonia water interface, entering an ammonia water phase and gelling into solid pellets. Aging the gelled pellets in ammonia water in a collecting region for 10h, taking out wet pellets, drying at 60 ℃ for 10h, drying at 120 ℃ for 3h, and roasting at 550 ℃ for 3h to obtain the aluminum oxide pellets. The sphericity of the pellets as determined by laser granulometry was 0.953.

Comparative example 2

The pelletization was carried out as in comparative example 1, except that the oil-ammonia column was replaced with a hot oil column using liquid paraffin as the oil phase (supplied by Beijing Co., Ltd., chemical reagent of national drug group), the oil bath temperature was 95 ℃ and the oil phase thickness was 195cm, and the height of the pelletization zone, the solidification zone and the collection zone was the same as that of the oil-ammonia column. The sphericity of the pellet obtained after dropping ball forming, washing, drying and roasting is 0.950.

Example 1

A cuboid-shaped oil ammonia column (container body) is adopted for balling, the length of the oil ammonia column is 1.5m, the width is 55cm, the height is 2m, except the structure of the oil ammonia column, an oil phase and an ammonia water phase are used, and the heights of a balling area, a curing area and a collecting area are the same as those of a comparative example 1. The schematic structure of the balling device is shown in figure 1.

The method comprises the steps of arranging a row of liquid outlets at a position 60cm away from the bottom of an oil ammonia column on the side wall of one side in the length direction of the oil ammonia column, arranging a row of liquid inlets at a position 150cm away from the bottom of the oil ammonia column, arranging a row of liquid inlets at a position 90cm away from the bottom of the oil ammonia column on the side wall of the other side in the length direction of the oil ammonia column, and arranging a row of liquid outlets at a position 120cm away from the bottom of the oil ammonia column, wherein each liquid inlet comprises 10 liquid inlets, each liquid inlet is a circular hole with a hole diameter of 1cm, the distance between the centers of adjacent circular holes is 5 cm., a circulating pump and four pipelines are adopted to carry out liquid circulation on the two rows of liquid inlets and the two rows of liquid outlets, so that liquid flows from the liquid inlets to the liquid outlets in the oil ammonia column, the liquid flowing speed in each pipeline is 1m/s, the α formed by each pipeline and the side wall of the oil ammonia column below the pipeline along the vertical direction is 80 degrees, and the sphericity of small balls obtained after the small balls are formed, dried and roasted is 0..

Example 2

A rectangular hot oil column (container body) was used for the pelletization, the hot oil column had a length of 1.5m, a width of 55cm and a height of 2m, and an oil phase was used in addition to the structure of the hot oil column, and the height of the pelletization zone, the solidification zone and the collection zone were the same as in comparative example 2. The schematic structure of the balling device is shown in figure 1.

The method comprises the steps of arranging a row of liquid outlets at the position, 90cm away from the bottom of a hot oil column, of the side wall of one side in the length direction of the hot oil column, arranging a row of liquid inlets at the position, 150cm away from the bottom of the hot oil column, of the side wall of the other side in the length direction of the hot oil column, arranging a row of liquid inlets at the position, 90cm away from the bottom of the hot oil column, and arranging a row of liquid outlets at the position, 150cm away from the bottom of the hot oil column, wherein each liquid inlet comprises 10 liquid inlets, each liquid inlet is a circular hole with the diameter of 1cm, the distance between the circle centers of adjacent circular holes is 5 cm., a circulating pump and four pipelines are adopted to carry out liquid circulation on the two rows of liquid inlets and the two rows of liquid outlets, so that liquid flows from the liquid inlets to the liquid outlets in the hot oil column, the flowing speed of the pipelines is 1m/s, the included angle α formed by the pipelines and the side wall of the hot oil column below the pipelines in the vertical direction is 85 degrees, and the sphericity of small spheres obtained.

Example 3

A rectangular oil-ammonia column is adopted for balling, the length of the oil-ammonia column is 1.5m, the width is 55cm, the height is 2m, except the structure of the oil-ammonia column, an oil phase and an ammonia water phase are used, and the heights of a balling area, a curing area and a collecting area are the same as those of the comparative example 1. The schematic structure of the balling device is shown in figure 2.

The method comprises the steps of arranging a row of liquid outlets at a position 60cm away from the bottom of an oil ammonia column on the side wall of one side of the oil ammonia column in the length direction, arranging a row of liquid inlets at a position 140cm away from the bottom of the oil ammonia column, arranging a row of liquid inlets at a position 80cm away from the side wall of the other side of the oil ammonia column in the length direction, arranging a row of liquid outlets at positions 120cm and 40cm away from the bottom of the oil ammonia column, wherein each liquid inlet comprises 10 liquid inlets, each liquid inlet is a circular hole with the diameter of 1cm, the distance between the centers of adjacent circular holes is 5 cm., and a circulating pump and five pipelines are adopted to carry out liquid circulation on the two rows of liquid inlets and three liquid outlets, so that liquid flows from the liquid inlets to the liquid outlets in the oil ammonia column, the liquid flowing speed in each pipeline is 1.2m/s, the included angle of α degrees formed by the pipeline and the side wall of the oil ammonia column below the pipeline along the vertical direction is 85 degrees, and the spherical shape of a small ball obtained after drying and roasting is 972.

Example 4

A rectangular oil-ammonia column is adopted for balling, the length of the oil-ammonia column is 2m, the width is 55cm, the height is 2m, except the structure of the oil-ammonia column, an oil phase and an ammonia phase are used, and the heights of a balling area, a curing area and a collecting area are the same as those of comparative example 1. The schematic structure of the balling device is shown in figure 3.

The side wall of one side of the oil ammonia column in the length direction is 5cm and 90cm away from the bottom of the oil ammonia column, a row of liquid outlets are respectively arranged at the height of 55cm and 125cm, a row of liquid inlets are respectively arranged at the height of 55cm and 125cm away from the bottom of the oil ammonia column, a row of liquid outlets are respectively arranged at the height of 5cm and 90cm, each liquid outlet comprises 10 liquid inlets, each liquid inlet is a circular hole with the diameter of 1cm, the distance between the centers of circles of adjacent circular holes is 5cm, each liquid outlet comprises 10 liquid outlets, each liquid outlet is a circular hole with the diameter of 1cm, the distance between the centers of adjacent circular holes is 5 cm., a circulating pump and eight pipelines are adopted to carry out liquid circulation on the four liquid inlets and the four liquid outlets, so that liquid flows from the liquid inlets to the liquid outlets in the oil ammonia column, the liquid flowing speed in each pipeline is 1m/s, the included angle α formed by the side wall of the oil ammonia column below each pipeline and the side wall of the oil ammonia column in the vertical direction is 85 degrees, and the spherical shape of a small ball after drying ball is obtained by roasting, and the ball shape is 0.972.

Example 5

A rectangular oil ammonia column is adopted for balling, the length of the oil ammonia column is 1m, the width of the oil ammonia column is 55cm, the height of the oil ammonia column is 2m, except for the structure of the oil ammonia column, an oil phase and an ammonia water phase are used, and the heights of a balling area, a curing area and a collecting area are the same as those of a comparative example 1.

The method comprises the steps of respectively arranging a row of liquid outlets at the positions, 30cm and 110cm from the bottom of an oil ammonia column, of the side wall of one side of the oil ammonia column in the length direction, respectively arranging a row of liquid inlets at the positions, 70cm and 170cm from the bottom of the oil ammonia column, respectively arranging a row of liquid inlets at the positions, 130cm and 50cm from the side wall of the other side of the oil ammonia column in the length direction, respectively arranging a row of liquid outlets at the positions, 150cm and 90cm from the bottom of the oil ammonia column, respectively, wherein each liquid inlet comprises 10 liquid inlets, each liquid inlet is a circular hole with the diameter of 1cm, the distance between the centers of adjacent circular holes is 5cm, liquid circulation is carried out on the four liquid inlets and the four liquid outlets by adopting a circulating pump and eight pipelines at the distance of 5 cm., so that liquid flows from the liquid inlets to the liquid outlets in the oil ammonia column, the liquid flow speed in each pipeline is 1m/s, and the included angle α formed by the side wall of the oil ammonia column in the vertical direction is 85 degrees, and the spherical shape of a small roasted ball is obtained after the ball is baked at a degree of 979.

As can be seen from the sphericity of the pellets prepared in examples 1 to 5 and comparative examples 1 and 2, the spherical carrier prepared using the balling vessel of the present invention has a better sphericity.