阅读说明：本技术 一种制备球形载体的成球装置和方法 (Balling device and method for preparing spherical carrier ) 是由 于宁 马爱增 王国成 王嘉欣 刘建良 臧高山 张玉红 王涛 于 2018-08-31 设计创作，主要内容包括：本发明涉及一种制备球形载体的成球装置和方法,本发明成球装置的成球容器在容器本体的相对侧壁上设置液体入口和液体出口,并使成球液通过成球液循环机构、液体入口和液体出口在容器本体中进行循环,提高球形载体的球形度和耐磨损性。(The invention relates to a balling device and a method for preparing a spherical carrier, wherein a balling container of the balling device is provided with a liquid inlet and a liquid outlet on the opposite side walls of a container body, and balling liquid is circulated in the container body through a balling liquid circulating mechanism, the liquid inlet and the liquid outlet, so that the sphericity and the wear resistance of the spherical carrier are improved.)

1. A balling device for preparing spherical carrier comprises a container body (1) for containing balling liquid and a balling liquid circulating mechanism positioned outside the container body (1), the container body (1) is divided into a balling area (31), a solidifying area (32) and a collecting area (33) from top to bottom, the top is provided with a top opening for dropping the slurry drops, the container body (1) is provided with a liquid inlet (11) and a liquid outlet (12) on the side walls of two opposite sides of the two upper areas, balling liquid enters the container body (1) from the liquid inlet (11) through a pipeline, is discharged out of the container body (1) from the liquid outlet (12), returns to the liquid inlet for circulation, is circulated through a first balling liquid circulating mechanism (2) in the balling area (31), and is circulated through a second balling liquid circulating mechanism (3) in the curing area (32) and the collecting area (33).

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 according to claim 1 or 2, in which the balling liquid circulation means comprises a pipeline (4) and a circulation pump, the liquid inlet (11) and the liquid outlet (12) are connected to the outlet and the inlet of the circulation pump, respectively, via the pipeline (4), and the axis of the pipeline (4) forms an angle α of 70-110 ° with the side wall of the container body (1) below the pipeline (4) in the vertical direction.

4. A balling device according to claim 1 or 2, in which the liquid inlet (11) provided in each zone is located on one side of the container body (1) and the liquid outlet (12) provided in each zone is located on the other side of the container body (1).

5. 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.

6. A balling apparatus as claimed in claim 1 or 2, in which the open area of each liquid inlet (11) is from 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).

7. Balling device according to claim 1, wherein the liquid inlets (11) and liquid outlets (12) of the balling zone (31) and the solidification zone (32) of the container body (1) are arranged in at least one row in the vertical direction.

8. The balling device as claimed in claim 7, wherein the liquid inlets (11) and the liquid outlets (12) of the solidification zone (32) of the container body (1) are arranged in 2 to 4 rows in the vertical direction.

9. The beading apparatus according to claim 7 or 8, wherein the liquid inlet timings and the liquid flow rates of the plurality of rows of the liquid inlets (11) are independently and controllably provided, and the liquid outlet timings and the liquid flow rates of the plurality of rows of the liquid outlets (12) are independently and controllably provided in the vertical direction of the vessel body (1).

10. Balling device according to claim 7 or 8, wherein the distance between the adjacent liquid inlet openings (11) in the vertical direction is 10-100cm and the distance between the adjacent liquid outlet openings (12) is 10-100 cm.

11. A balling apparatus according to claim 7 or 8, in which the horizontal spacing between the liquid inlets (11) in the same row is between 0.5 and 50cm and the horizontal spacing between the liquid outlets (12) in the same row is between 0.5 and 50 cm.

12. Balling device according to claim 1, in which the container body (1) is a cuboid having a length of 0.5 to 5m, a width of 0.5 to 2m and a height of 1 to 5 m.

13. A method of preparing a spherical support using the apparatus of claim 1, the method comprising: the carrier slurry is dripped into the top opening of the container body (1) in a slurry drop mode through a ball dripping device (100), and sequentially contacts with the balling liquid in a balling area (31), a curing area (32) and a collecting area (33) in the container body (1) and falls into balls, meanwhile, the balling liquid in the balling area (31) is introduced into the container body through a liquid inlet (11) by adopting a first balling liquid circulating mechanism (2) and is discharged through a liquid outlet (12) of the balling area to form a first circulation, the balling liquid in the curing area (32) and the collecting area (33) is introduced into the container body (1) through the liquid inlet (11) by adopting a second balling liquid circulating mechanism (3) and is discharged through liquid outlets (12) of the two areas to form a second circulation, and the wet balls obtained in the collecting area (33) are taken out, dried and roasted.

14. The method according to claim 13, 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.

15. The method according to claim 13, 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.

16. The method according to claim 13, wherein the support slurry contains at least one selected from the group consisting of alumina, silica and a molecular sieve.

17. The method according to claim 13, 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 balling method for preparing 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 CN 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 method for preparing a spherical carrier.

In order to achieve the above purpose, the present invention provides a sphere forming device for preparing spherical carriers, which comprises a container body for containing sphere forming liquid and a sphere forming liquid circulating mechanism positioned outside the container body, wherein the container body is divided into a sphere forming area, a solidification area and a collection area from top to bottom, the top of the container body is provided with a top opening for dropping slurry droplets, the side walls of the two opposite sides of the upper two areas of the container body are respectively and oppositely provided with a liquid inlet and a liquid outlet, the sphere forming liquid enters the container body from the liquid inlet through a pipeline, is discharged out of the container body from the liquid outlet, and returns to the liquid inlet for circulation, the sphere forming liquid in the sphere forming area is circulated through a first sphere forming liquid circulating mechanism, and the sphere forming liquid in the solidification area and the collection area is circulated through a second sphere forming liquid circulating mechanism.

The invention also provides a method for preparing the spherical carrier by using the device provided by the invention, which comprises the following steps: and (2) dropping the carrier slurry into the top opening of the container body in the form of slurry droplets through a ball dropping device, sequentially contacting with the balling liquid in the balling area, the curing area and the collecting area of the container body, dropping the balling liquid into balls, simultaneously introducing the balling liquid in the balling area into the container body through a liquid inlet by adopting a first balling liquid circulating mechanism, discharging the balling liquid through a liquid outlet of the balling area to form a first circulation, introducing the balling liquid in the curing area and the collecting area into the container body through a liquid inlet by adopting a second balling liquid circulating mechanism, discharging the balling liquid through liquid outlets of the two areas to form a second circulation, and taking out, drying and roasting the wet balls obtained in the collecting area.

The balling container of the invention can give acting force to slurry drops falling in the balling container through the transverse flow of the balling liquid so as to rotate the slurry drops, thereby eliminating the trailing phenomenon generated by the slurry drops in the process of preparing the spherical carrier and improving the sphericity and the wear resistance of the prepared spherical carrier.

Drawings

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

Fig. 2 is a front view of the balling vessel of the apparatus of fig. 1.

Fig. 3 is a left side view of the balling vessel of the apparatus of fig. 1.

Fig. 4 is a right side view of the balling vessel of the apparatus of fig. 1.

Fig. 5 is a top view of the balling vessel of the apparatus of fig. 1.

Fig. 6 is a schematic structural diagram of another embodiment of the balling device provided by the invention.

FIG. 7 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 a first ball forming liquid circulating mechanism 3 a second ball forming liquid circulating mechanism

31 balling zone 32, curing zone 33, collecting zone

4 pipeline

100 dropping ball device

Detailed Description

As shown in FIG. 6, the balling device of the present invention is provided with a liquid inlet 11 and a liquid outlet 12 on the side walls of the container body 1 on the opposite sides of the balling zone 31 and the solidifying zone 32, and makes the balling liquid enter the container body 1 from the liquid inlet of each zone through the first balling liquid circulating mechanism 2 and the second balling liquid circulating mechanism 3, and discharges the container body 1 through the liquid outlet of each zone, thereby forming two balling liquid circulating systems, and the slurry drop in the container body 1 is rotated by the action force in the falling process of the balling zone 31, the solidifying zone 32 and the collecting zone 33, thereby eliminating the tailing phenomenon caused by the dropping of the slurry and improving the sphericity and the wear resistance of the spherical carrier.

Preferably, as shown in fig. 1, a row of liquid inlets 11 is also provided on the side wall of the collecting region 33 of the container body, see in particular fig. 4, and a row of liquid outlets 12 is provided opposite to the side wall on the other side, see in particular fig. 3.

As shown in figures 1 and 6, the balling liquid circulating mechanism can comprise a pipeline 4 and a circulating pump, a liquid inlet 11 and a liquid outlet 12 can be respectively connected with an outlet and an inlet of the circulating pump through the pipeline 4, a lateral line can be arranged on the pipeline so as to supplement 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 the left side view, fig. 3 and the right side view, fig. 4 of the container body of the balling apparatus shown in fig. 1, the liquid inlet 11 provided in each of the balling region 31, the solidifying region 32 and the collecting region 33 is located on one side of the container body 1, and the liquid outlet 12 provided in each of the balling region 31, the solidifying region 32 and the collecting region 33 is located on the other side of the container body 1.

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 the present invention, the areas of the liquid inlets and the liquid outlets may be set as required, the opening area of the liquid inlets may be small and the number of the liquid inlets may be large, and the opening area of the liquid outlets may be large and the number of the liquid outlets may be small, specifically, the opening area of each liquid inlet 11 may be 0.5 to 20cm²The open area of each liquid outlet 12 may be 0.5-20cm²The opening area of the liquid inlet 11 is preferably not larger than the opening area of the liquid outlet 12.

In one embodiment, as shown in fig. 3-4, the liquid inlets 11 and the liquid outlets 12 of the balling region 31 and the solidifying region 32 of the container body 1 are arranged in at least one vertical row, preferably, the liquid inlets 11 and the liquid outlets 12 of the solidifying region 32 of the container body 1 are arranged in 2-4 vertical rows, each liquid inlet may comprise 1-100, preferably 3-20 liquid inlets, and each liquid outlet may comprise 1-100, preferably 3-20 liquid inlets. The distance between the adjacent drain inlets and the liquid outlets may be set according to requirements, for example, the distance between the adjacent drain inlets 11 in the vertical direction may be 10-100cm, the distance between the adjacent drain outlets 12 may be 10-100cm, the horizontal distance between the same drain inlets 11 is 0.5-50cm, preferably 2-10cm, and the horizontal distance between the liquid outlets 12 of the same row is 0.5-50cm, preferably 2-10 cm.

In the present invention, the liquid inlet timing and the liquid flow rate of the liquid inlets 11 arranged in a plurality of rows in the vertical direction of the container body 1 may be independent and controllable, and the liquid outlet timing and the liquid flow rate of the liquid outlets 12 arranged in a plurality of rows may be independent and controllable, for example, the flow rate of the liquid circulation mechanism for forming balls may be adjustable, and the liquid inlet timing and the flow rate of the liquid may be controlled by a valve.

In the present invention, the container body may have various shapes such as a cylinder, a rectangular parallelepiped, etc., and each size of the container body may be within 20 meters, and may be set to a specific size as required.

In one embodiment, as shown in fig. 1 to 5, 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 on the side walls of the container body at opposite sides in the length direction to prevent the slurry from being applied with force and touching the container body.

As shown in fig. 1 and 6, the present invention also provides a method for preparing a spherical carrier using the apparatus provided by the present invention, the method comprising: the carrier slurry is dripped into the top opening of the container body 1 in the form of slurry drops through a dripper 100, and sequentially contacts with the balling liquid in the balling area 31, the curing area 32 and the collecting area 33 in the container body 1 and drops to form balls, meanwhile, the balling liquid in the balling area 31 is introduced into the container body through a liquid inlet 11 by using a first balling liquid circulating mechanism 2 and is discharged through a liquid outlet 12 of the balling area to form a first circulation, the balling liquid in the curing area 32 and the collecting area 33 is introduced into the container body 1 through the liquid inlet 11 by using a second balling liquid circulating mechanism 3 and is discharged through liquid outlets 12 of the balling area and the collecting area 33 to form a second circulation, and the wet balls obtained in the collecting area 33 are taken out, dried and roasted.

In the present invention, the dropping ball device is preferably installed near the liquid inlet side in the horizontal direction so that the slurry drop has a sufficient translational distance.

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

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 vessel at the liquid inlet should be such as to avoid disturbing the interface between the different liquids, and the liquid may be introduced into the spheronization zone away from the liquid interface, for example in the middle of the spheronization 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 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 2m, 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 1.

The side walls on two sides of the oil ammonia column in the length direction are respectively arranged as a liquid inlet side and a liquid outlet side (namely, the distance between the liquid inlet side and the liquid outlet side is 2m), five liquid drainage inlets are respectively arranged at the positions of the liquid inlet side and the bottom of the oil ammonia column, each liquid drainage inlet comprises 10 liquid inlets, each liquid inlet is a circular hole with the hole diameter of 1cm, the distance between the circle centers of adjacent circular holes is 5cm, the height between the liquid outlet side and the bottom of the oil ammonia column is 5cm, 100cm, 130cm, 150cm and 190cm, each liquid drainage outlet comprises 10 liquid outlets, each liquid outlet is a circular hole with the hole diameter of 1cm, the distance between the circle centers of adjacent circular holes is 5cm, a circulating pump and two pipelines are adopted in a balling area to circulate liquid between a row of liquid inlets and a row of liquid outlets, a circulating pump and eight pipelines are adopted in a solidifying area to circulate liquid between the four liquid inlets and the liquid outlets, so that liquid flows from the liquid inlets to the liquid outlets in the oil ammonia column, the liquid outlet side walls and the liquid outlet side walls of the liquid column flow along the direction, the direction of 3590 degrees of the liquid inlet and the liquid outlet, and the lateral walls of the liquid outlet side walls of the liquid, and the liquid outlet side walls of the liquid are formed by a small angle of 3590.83, and the straight line formed after the straight line, and the straight ammonia column.

Example 2

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

The hot oil column is characterized in that a liquid inlet side and a liquid outlet side are respectively arranged on two sides in the length direction of the hot oil column (namely the liquid inlet side and the liquid outlet side are separated by 2m), five liquid drainage inlets are respectively arranged at the height positions of 5cm, 100cm, 130cm, 150cm and 190cm of the liquid inlet side, each liquid drainage inlet comprises 10 liquid inlets, each liquid inlet is a circular hole with the hole diameter of 1cm, the distance between the circle centers of the adjacent circular holes is 5cm, five liquid drainage outlets are respectively arranged at the height positions of 5cm, 100cm, 130cm, 150cm and 190cm of the liquid outlet side, each liquid drainage outlet comprises 10 liquid outlets, each liquid outlet is a circular hole with the hole diameter of 1cm, the distance between the circle centers of the adjacent circular holes is 5cm, a circulating pump and two pipelines are adopted in a balling area to circulate liquid between a row of liquid inlets and a row of liquid outlets, one circulating pump and eight pipelines are adopted in a solidification area and a collection area to circulate liquid between the four liquid drainage inlets and the liquid outlets, so that the balling liquid flows from the liquid inlets to the liquid outlets in the hot oil column, the liquid inlet area and the liquid outlet, the liquid outlet area, the ball washing pipeline and the ball washing pipeline form an included angle of 358, which is formed by the hot oil column is 85.85 degrees and the vertical drying pipeline, and the hot oil column wall is formed by the.

Example 3

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 fig. 6.

The two sides of the oil ammonia column in the length direction are respectively provided with a liquid inlet side and a liquid outlet side (namely the liquid inlet side and the liquid outlet side are separated by 2m), four liquid drainage inlets are respectively arranged at the positions of the heights of 100cm, 130cm, 150cm and 190cm of the liquid inlet side, each group of liquid inlets comprises 10 liquid inlets, each liquid inlet is a circular hole with the hole diameter of 1cm, the distance between the circle centers of the adjacent circular holes is 5cm, four liquid drainage outlets are respectively arranged at the positions of 100cm, 130cm, 150cm and 190cm of the liquid outlet side, each group of liquid outlets comprises 10 liquid outlets, each liquid outlet is a circular hole with the hole diameter of 2cm, the distance between the circle centers of the adjacent circular holes is 5cm, a circulating pump and two pipelines are adopted in a balling area to circulate liquid between a row of liquid inlets and a row of liquid outlets, a circulating pump and six pipelines are adopted in a solidification area to circulate liquid between the three liquid drainage inlets and the liquid outlets, so that the balling liquid flows from the liquid inlets to the liquid outlets in the oil ammonia column, the liquid inlet side of the liquid inlet side is 0.8m/s, and the angle formed by the lateral wall of a vertical ammonia column is 3585 degrees after the ammonia column is dried, and the lateral wall of the ammonia column is formed by the ammonia column, and the ammonia column, the included angle of 3585 degrees, which is 356 degrees.

From the sphericity of the pellets prepared in examples 1, 2 and 3 and comparative examples 1 and 2, it can be seen that the spherical carrier prepared using the balling apparatus of the present invention has a better sphericity.