A crude alcohol hydrogenation catalyst and its production method

Abstract

The present invention relates to a crude alcohol hydrogenation catalyst and a production method thereof. The crude alcohol hydrogenation catalyst includes a catalyst body and a strengthening layer. The surface of the catalyst body is provided with a plurality of grooves in an array, and there is a spacing between every two adjacent grooves. A strengthening layer is provided in each groove, and the outer surface of the strengthening layer and the outer surface of the catalyst body are on the same spherical surface. The strengthening layer and the catalyst body together form a sphere. The strengthening layer is spiral. The present invention provides a crude alcohol hydrogenation catalyst with high mechanical strength and abrasion resistance and a production method thereof. Moreover, the crude alcohol hydrogenation catalyst of the present invention has unexpected technical effects such as increasing the packing height, reducing the packing process, reducing the pressure drop, facilitating the gas flow distribution, being able to increase the space velocity, improving the reaction efficiency, quickly removing the reaction heat after increasing the space velocity, reducing the amount of cold hydrogen used, and having a low requirement for the control of the reaction temperature, and is suitable for use in the production of crude alcohol hydrogenation.

Description

Technical Field

[0001] The present invention relates to the technical field of hydrogenation catalysts, and particularly relates to a crude alcohol hydrogenation catalyst and a production method thereof. Background Art

[0002] After filtration and fractionation of MTO by-products, a mixture containing various substances such as water, methanol, acetaldehyde, acetone, butyraldehyde, and butanone is obtained, which is usually referred to as "crude alcohol" in industrial production. Since the components in crude alcohol are prone to form azeotropes and are difficult to separate and reuse, the by-products are usually dehydrated and used as fuel oil for heating the reaction kettle, resulting in a large amount of resource waste.

[0003] The aldehydes and ketones contained in the difficult-to-separate crude alcohol can be easily separated after catalytic hydrogenation to form various alcohols, and different products can be obtained after separation, which has strong economic benefits. However, it is found in production that in order to have sufficient catalytic ability, the existing catalyst usually has a very large specific surface area and a very large number of pores, which results in low mechanical strength of the catalyst and is easy to crush. Especially when the catalyst needs to be regenerated, the catalyst needs to be unloaded from the reactor, regenerated, and then reinstalled into the reactor. The repeated processes of unloading, handling, and reinstalling can cause the catalyst to be crushed and lost by up to 8%-12%. Moreover, when reinstalling, if the catalyst is crushed inside the reactor, the fine particles of the catalyst are prone to form a piled state, blocking the channels between the catalysts, which will lead to uneven gas flow in the reactor, and is easy to form problems such as channeling, local overheating, or coking. Therefore, there is an urgent need for a catalyst with high mechanical strength and abrasion resistance. Summary of the Invention

[0004] To solve the above technical problems, the present invention provides a crude alcohol hydrogenation catalyst and a production method thereof, aiming to provide a crude alcohol hydrogenation catalyst with high mechanical strength and abrasion resistance.

[0005] To achieve the above object, the technical solution of the present invention is:

[0006] A crude alcohol hydrogenation catalyst includes a catalyst body and a strengthening layer. The surface of the catalyst body is provided with a plurality of grooves in an array, there is a spacing between every two adjacent grooves, and a strengthening layer is provided in each groove. The outer surface of the strengthening layer is on the same spherical surface as the outer surface of the catalyst body, and the strengthening layer and the catalyst body together form a sphere.

[0007] Further, the strengthening layer is a low-temperature ceramic layer.

[0008] Further, the diameter of the sphere formed by the catalyst body and the strengthening layer is 10 mm to 15 mm, and the thickness of the strengthening layer is 1 mm to 2 mm.

[0009] Further, the sum of the outer surface areas of the multiple reinforcing layers is equal to the outer surface area of the catalyst body outside the grooves.

[0010] Further, each of the grooves is spiral.

[0011] The above method for producing a crude alcohol hydrogenation catalyst includes the following steps:

[0012] S1: Heat the catalyst support to 600 °C in a muffle furnace and calcine for 4 hours;

[0013] S2: Add the catalyst support to a mixed solution containing copper nitrate, nickel nitrate, and zinc nitrate, and stir and soak at 20 °C - 60 °C for 1 hour;

[0014] S3: Add a precipitant to the mother liquor, continue to stir the catalyst support in the mother liquor for 2 hours, then filter, wash with water, and add a graphite binder to form a viscous slurry;

[0015] S4: Add water to the low-temperature ceramic raw material to form a viscous slurry;

[0016] S5: Add the two viscous slurry materials prepared in steps S3 and S4 to a catalyst body extruder and a reinforcing layer extruder respectively, co-extrude through a T-shaped die head, and perform twisting and cutting operations while extruding. The two materials are co-extruded to form a cylindrical shape with a spiral low-temperature ceramic blank layer;

[0017] S6: After the cylindrical material cut in S5 is rounded by a rounding machine, it is dried at 150 °C for 1 hour, then subjected to biscuit firing at 750 °C for 1 hour, held at 640 °C for 2 hours, and then slowly cooled to below 100 °C to obtain the crude alcohol hydrogenation catalyst.

[0018] Further, the catalyst support is alumina particles or silica particles, and the particle size of the catalyst support is 60 - 80 mesh.

[0019] Further, the T-shaped head includes a housing, a diverter, a rotating head, and a driving motor. A material storage cavity is provided inside the housing, and a diverter is provided inside the material storage cavity. The two ends of the diverter are respectively aligned with the two ends of the housing. There is a gap between the middle of the outer wall of the diverter and the middle of the inner wall of the material storage cavity. The space between the middle of the outer wall of the diverter and the middle of the inner wall of the material storage cavity is the reinforcement layer channel. The inner hole of the diverter is the catalyst body channel. A plurality of diversion channels communicating with the reinforcement layer channel are provided on the outer wall at the left end of the diverter. The outer wall of the left end of the diverter outside the diversion channels is fixedly connected to the inner wall at the left end of the material storage cavity. The outer wall at the right end of the diverter closes the right end of the reinforcement layer channel. A connecting seat communicating with the reinforcement layer channel is provided on the inner wall of the housing. The rotating head is rotatably connected to the left end of the housing. A discharge channel coaxial with the opening at the left end of the material storage cavity is provided on the rotating head. A driving motor is fixedly connected to the outer wall of the housing, and the driving motor drives the rotating head to rotate.

[0020] Further, the diameter of the discharge channel is the same as the diameter of the opening at the left end of the material storage cavity. A plurality of guiding ribs along the length direction of the discharge channel are provided on the inner wall at the left part of the discharge channel. The inner wall of the discharge channel on the right side of the guiding ribs is a smooth inner wall.

[0021] Further, the guiding ribs are wedge-shaped ribs with the pointed part facing the central axis of the discharge channel, and the height of the guiding ribs is 0.5 mm.

[0022] Through the above technical solutions, the beneficial effects of the present invention are as follows:

[0023] For the crude alcohol hydrogenation catalyst of the present invention, a reinforcement layer is provided outside the catalyst body, and the reinforcement layer is a ceramic layer, which reduces the wear of the catalyst body.

[0024] The reinforcement layer on the crude alcohol hydrogenation catalyst of the present invention is spiral, which further increases the contact opportunity between the reinforcement layers of adjacent two crude alcohol hydrogenation catalysts and reduces the wear of the catalyst body.

[0025] The reinforcement layer of the present invention itself has a microporous structure and will not significantly weaken the catalytic performance of the catalyst. However, using the crude alcohol hydrogenation catalyst of the present invention can increase the filling height, reduce the filling process, reduce the pressure drop, facilitate the gas flow distribution, increase the space velocity, improve the reaction efficiency. After increasing the space velocity, the reaction heat can be quickly removed, and the amount of cold hydrogen used is also reduced.

[0026] The production method of the crude alcohol hydrogenation catalyst of the present invention uses special co-extrusion equipment, co-extrudes in a cylindrical shape, and twists after co-extrusion to form a spiral structure of the reinforcement layer. It is cut into sections, rolled into a round shape, and then dried and subjected to biscuit firing to form the finished product of the crude alcohol hydrogenation catalyst with a ceramic reinforcement layer. The production speed is fast, the product is regular, and the strength is high. The produced crude alcohol hydrogenation catalyst has a unique effect. Description of the Drawings

[0027] Figure 1 It is a schematic structural view of the crude alcohol hydrogenation catalyst of the present invention;

[0028] Figure 2 It is a top view of the cross-section of the crude alcohol hydrogenation catalyst of the present invention;

[0029] Figure 3 It is a schematic structural view of the T-shaped head of the extruder of the present invention;

[0030] Figure 4 Schematic structural view of the diverter of the present invention.

[0031] The reference numerals in the drawings are: 1, catalyst body; 2, reinforcing layer; 3, groove; 4, casing; 5, diverter; 6, rotating head; 7, drive motor; 8, diversion channel; 9, reinforcing layer channel; 10, catalyst body channel; 11, connecting seat; 12, discharge channel; 13, tooth; 14, gear; 15, guiding rib. Specific Embodiments

[0032] The present invention will be further described below in conjunction with the drawings and specific embodiments:

[0033] It should be noted that the directional terms such as "front", "rear", "left", "right", "upper", "lower", "bottom surface" and "top surface" used in the following description refer to the directions in the drawings, and the terms "inner" and "outer" respectively refer to the directions towards or away from the geometric center of a specific component.

[0034] As Figures 1 to 2 shown, a crude alcohol hydrogenation catalyst includes a catalyst body 1 and a reinforcing layer 2. A plurality of grooves 3 are arranged in an array on the surface of the catalyst body 1, and there is a spacing between every two adjacent grooves 3. A reinforcing layer 2 is arranged in each groove 3. The outer surface of the reinforcing layer 2 and the outer surface of the catalyst body 1 are on the same spherical surface, and the reinforcing layer 2 and the catalyst body 1 together form a sphere.

[0035] The reinforcing layer 2 is a low-temperature ceramic layer, which can provide sufficient strength for the catalyst body 1, including support strength and wear strength, so that the crude alcohol hydrogenation catalyst is not easily crushed and is wear-resistant when in contact with each other. The pores of the low-temperature ceramic itself can also allow hydrogen and gaseous crude alcohol to pass through. Even if the reinforcing layer 2 covers a certain outer surface area of the catalyst body 1, the catalytic effect will not be significantly reduced due to covering the surface of the catalyst body 1, and a certain catalytic effect can still be maintained.

[0036] The diameter of the sphere formed by the catalyst body 1 and the strengthening layer 2 is 10 mm - 15 mm, and the thickness of the strengthening layer 2 is 1 mm - 2 mm. In the crude alcohol hydrogenation catalyst of the present invention, the catalyst body 1 plays a catalytic role, and the strengthening layer 2 plays a role in improving the surface strength and slowing down the wear effect. The diameter of the traditional catalyst is 0.8 mm - 3 mm. When in use, porcelain ball cushions need to be laid both above and below the catalyst in the hydrogenation reactor, and the porcelain ball cushions have sequentially changing diameters. Usually, the bottom layer is porcelain balls with a diameter of 12 mm, the upper layer is porcelain balls with a diameter of 6 mm, then upwards are porcelain balls with a diameter of 3 mm, and then the catalyst. Above the catalyst is a porcelain ball covering layer with sequentially increasing diameters. The role of the porcelain balls covering the catalyst can, on the one hand, prevent gas or liquid from directly blowing onto the catalyst, and on the other hand, redistribute the materials from the distributor. However, the crude alcohol hydrogenation catalyst of the present invention with a diameter of 10 mm - 15 mm will not be blown by gas itself and can achieve the redistribution of materials. Therefore, when using the crude alcohol hydrogenation catalyst of the present invention, the porcelain ball support and covering can be cancelled, and only the crude alcohol hydrogenation catalyst of the present invention is needed. This can not only reduce the process flow, but also the larger gaps formed between the large-diameter crude alcohol hydrogenation catalysts are beneficial to reducing the pressure drop and facilitating the gas flow distribution. And after cancelling the porcelain balls, the filling height of the crude alcohol hydrogenation catalyst can be increased, increasing the contact opportunity between the gas-phase materials and the catalyst body 1, which is sufficient to make up for the reduced catalytic effect due to the setting of the strengthening layer 2. Even if the space velocity is increased, a sufficient conversion rate can be achieved. That is, the catalytic effect of the crude alcohol hydrogenation catalyst of the present invention is only slightly weakened due to the setting of the strengthening layer 2, but it is compensated by the increased filling height. Using the crude alcohol hydrogenation catalyst of the present invention can reduce the filling process (no longer filling porcelain balls, not requiring screening after unloading, etc.), reduce the pressure drop, facilitate the gas flow distribution, be able to increase the space velocity, and improve the reaction efficiency, which are all not achievable by the existing catalysts. Catalytic hydrogenation is an exothermic reaction. After increasing the space velocity, the reaction heat can be quickly removed, and the amount of cold hydrogen used is also reduced, and the control requirement for the reaction temperature is low.

[0037] The sum of the outer surface areas of multiple said strengthening layers 2 is equal to the outer surface area of the catalyst body 1 outside the groove 3, striving to make the strengthening layer 2 and the catalyst body 1 evenly distributed on the spherical surface and having similar widths. This can reduce wear while not affecting the catalytic efficiency.

[0038] Each said groove 3 is spiral. The spiral coiling of the groove 3 and the strengthening layer 2 can increase the contact opportunity between the strengthening layers even when there is relative rolling between adjacent two crude alcohol hydrogenation catalysts during the processes of filling, unloading, and leveling the crude alcohol hydrogenation catalysts, reducing wear.

[0039] The production method of the above-mentioned crude alcohol hydrogenation catalyst includes the following steps:

[0040] S1: Heat the catalyst support to 600 °C in a muffle furnace and calcine for 4 hours;

[0041] S2: Add the catalyst support to a mixed solution containing copper nitrate, nickel nitrate, and zinc nitrate, and stir and soak at 20 °C - 60 °C for 1 hour;

[0042] S3: Add a precipitant to the mother liquor, continue to stir the catalyst support in the mother liquor for 2 hours, then filter, wash with water, and add a graphite binder to form a viscous slurry;

[0043] S4: Add water to the low-temperature ceramic raw material to form a viscous slurry;

[0044] S5: Add the two viscous slurry materials prepared in steps S3 and S4 to the catalyst body extruder and the reinforcing layer extruder respectively, co-extrude through a T-shaped die head, and perform twisting and cutting operations while extruding. The two materials are co-extruded to form a cylindrical shape with a spiral low-temperature ceramic blank layer;

[0045] S6: The cylindrical material cut in S5 is rounded by a rounding machine. The rounding machine can be a umbrellatype rounding machine or a conveyor belt type rounding machine. After rounding, the reinforcing layer 2 of the crude alcohol hydrogenation catalyst forms a state with narrow ends and wide middle. Dry at 150 °C for 1 hour, then perform a preliminary firing at 750 °C for 1 hour, keep the temperature at 640 °C for 2 hours, and then slowly cool down to below 100 °C to obtain the crude alcohol hydrogenation catalyst.

[0046] The catalyst support is alumina particles or silica particles, and the particle size of the catalyst support is 60 - 80 mesh.

[0047] Such as Figures 3 to 4As shown, the T-shaped head includes a casing 4, a diverter 5, a rotating head 6 and a driving motor 7. A storage cavity is provided in the casing 4. The diameter of the storage cavity is large in the middle and small at both ends. The two ends of the storage cavity pass through the two ends of the casing 4 respectively. A diverter 5 is provided in the storage cavity. The diverter 5 is cylindrical. The two ends of the diverter 5 are aligned with the two ends of the casing 4 respectively. There is a gap between the middle of the outer wall of the diverter 5 and the middle of the inner wall of the storage cavity. The space between the middle of the outer wall of the diverter 5 and the middle of the inner wall of the storage cavity is a reinforcement layer channel 9. The inner hole of the diverter 5 is a catalyst body channel 10. A plurality of diverter channels 8 connected to the reinforcement layer channel 9 are provided on the outer wall of the left end of the diverter 5. The diverter channel 8 is a trough body formed by the peripheral wall of the diverter 5 being concave toward the central axis of the diverter 5. The outer wall of the left end of the diverter 5 outside the diverter channel 8 is fixedly connected to the inner wall of the left end of the storage chamber, and the outer wall of the right end of the diverter 5 closes the right end of the reinforcement layer channel 9. The right end of the casing 4 is connected to the catalyst body extruder, and the screw of the catalyst body extruder extends into the right part of the diverter 5. A connecting seat 11 communicating with the reinforcement layer channel 9 is provided on the inner wall of the casing 4, and the connecting seat 11 is connected to the reinforcement layer extruder. The rotating head 6 is rotatably connected to the left end of the casing 4, and a discharge channel 12 coaxially opposite to the opening at the left end of the storage chamber is provided on the rotating head 6. The outer circumferential array of the rotating head 6 is provided with teeth 13. A drive motor 7 is fixedly connected to the outer wall of the casing 4, and a gear 14 meshing with the teeth 13 is connected to the output shaft of the drive motor 7. The drive motor 7 drives the rotating head 6 to rotate.

[0048] The diameter of the discharge channel 12 is consistent with the diameter of the left end opening of the storage cavity. A plurality of guide ribs 15 are provided on the left inner wall of the discharge channel 12 along the length direction of the discharge channel 12. The inner wall of the discharge channel 12 on the right side of the guide rib 15 is a smooth inner wall. When the guide rib 15 contacts the co-extruded material extruded from the left end of the casing 4, the co-extruded material forms a small groove inward. The guide rib 15 rotates with the co-extruded material as the rotating head 6 rotates. The left end opening of the diverter 5 does not rotate. Therefore, the co-extruded material located at the smooth inner wall of the discharge channel 12 will form a twisted state, and while twisting, it moves to the left under the push of the subsequent material extruded by the diverter 5. When the co-extruded material is discharged from the discharge channel 12 and cut into sections, a cylindrical shape with a spiral ceramic green layer is formed.

[0049] The guide ribs 15 are wedge-shaped ribs with their tips facing the central axis of the discharge channel 12. The height of the guide ribs 15 is 0.5 mm, which can both drive the co-extruded material to rotate and not cut off the reinforcing layer 2. The small grooves formed by the guide ribs 15 can be restored when the crude alcohol hydrogenation catalyst is rolled into a ball by the rounding machine.

[0050] The abrasion rate of the catalytic cracking catalyst is determined by the catalyst abrasion method specified in Q / SH 3360 209-2006. The abrasion amount of the catalyst of the present invention is 2%-5%, which is reduced by 40%-75% compared with the abrasion rate (8%-12%) of the existing catalyst.

[0051] The preferred embodiments of the present invention have been described in detail above in conjunction with the accompanying drawings. However, the present invention is not limited to the above embodiments, and various modifications can be made to the technical solutions of the present invention without departing from the spirit of the present invention, that is, within the scope of disclosure.

Claims

1. A crude alcohol hydrogenation catalyst, characterized in that, It includes a catalyst body (1) and a strengthening layer (2). A plurality of grooves (3) are arranged in an array on the surface of the catalyst body (1). There is a spacing between every two adjacent grooves (3). A strengthening layer (2) is arranged in each groove (3). The outer surface of the strengthening layer (2) and the outer surface of the catalyst body (1) are on the same spherical surface. The strengthening layer (2) and the catalyst body (1) together form a sphere; The strengthening layer (2) is a low-temperature ceramic layer; The sphere formed by the catalyst body (1) and the strengthening layer (2) has a diameter of 10 mm - 15 mm, and the thickness of the strengthening layer (2) is 1 mm - 2 mm; The production method of the crude alcohol hydrogenation catalyst includes the following steps: S1: Heat the catalyst carrier to 600 °C in a muffle furnace and calcine for 4 hours; S2: Add the catalyst carrier into a mixed solution containing copper nitrate, nickel nitrate, and zinc nitrate, and stir and soak at 20 °C - 60 °C for 1 hour; S3: Add a precipitant to the mother liquor, continue to stir the catalyst carrier in the mother liquor for 2 hours, then filter, wash with water, and add a graphite binder to form a viscous slurry; S4: Add water to the low-temperature ceramic raw material to form a viscous slurry; S5: Add the two viscous slurry materials prepared in steps S3 and S4 into the catalyst body extruder and the strengthening layer extruder respectively, co-extrude through a T-shaped die head, and perform twisting and cutting operations while extruding. The two materials are co-extruded to form a cylindrical shape with a spiral low-temperature ceramic blank layer; S6: After the cylindrical material cut in S5 is rounded by a rounding machine, dry it at 150 °C for 1 hour, then perform a biscuit firing at 750 °C for 1 hour, keep it at 640 °C for 2 hours, and then slowly cool it to below 100 °C to obtain the crude alcohol hydrogenation catalyst.

2. The crude alcohol hydrogenation catalyst according to claim 1, characterized in that, The sum of the outer surface areas of the plurality of strengthening layers (2) is equal to the outer surface area of the catalyst body (1) outside the grooves (3).

3. The crude alcohol hydrogenation catalyst according to claim 1, characterized in that, Each of the grooves (3) is spiral.

4. A production method of a crude alcohol hydrogenation catalyst for producing a crude alcohol hydrogenation catalyst as described in claim 1, characterized in that, It includes the following steps: S1: Heat the catalyst carrier to 600 °C in a muffle furnace and calcine for 4 hours; S2: Add the catalyst carrier into a mixed solution containing copper nitrate, nickel nitrate, and zinc nitrate, and stir and soak at 20 °C - 60 °C for 1 hour; S3: Add a precipitant to the mother liquor, continue to stir the catalyst carrier in the mother liquor for 2 hours, then filter, wash with water, and add a graphite binder to form a viscous slurry; S4: Add water to the low-temperature ceramic raw material to form a viscous slurry; S5: Add the two viscous slurry materials prepared in steps S3 and S4 into the catalyst body extruder and the strengthening layer extruder respectively, co-extrude through a T-shaped die head, and perform twisting and cutting operations while extruding. The two materials are co-extruded to form a cylindrical shape with a spiral low-temperature ceramic blank layer; S6: After the cylindrical material cut in S5 is rounded by a rounding machine, dry it at 150 °C for 1 hour, then perform a biscuit firing at 750 °C for 1 hour, keep it at 640 °C for 2 hours, and then slowly cool it to below 100 °C to obtain the crude alcohol hydrogenation catalyst.

5. The production method of a crude alcohol hydrogenation catalyst according to claim 4, characterized in that, The catalyst carrier is alumina particles or silica particles, and the particle size of the catalyst carrier is 60 - 80 mesh.

6. The production method of a crude alcohol hydrogenation catalyst according to claim 4, characterized in that, The T-shaped head includes a casing (4), a diverter (5), a rotating head (6) and a driving motor (7). A material storage cavity is provided inside the casing (4), and a diverter (5) is arranged in the material storage cavity. The two ends of the diverter (5) are respectively aligned with the two ends of the casing (4). There is a gap between the middle part of the outer wall of the diverter (5) and the middle part of the inner wall of the material storage cavity. The space between the middle part of the outer wall of the diverter (5) and the middle part of the inner wall of the material storage cavity is a reinforcing layer channel (9). The inner hole of the diverter (5) is a catalyst body channel (10). A plurality of diversion channels (8) communicating with the reinforcing layer channel (9) are provided on the outer wall at the left end of the diverter (5). The outer wall at the left end of the diverter (5) outside the diversion channels (8) is fixedly connected to the inner wall at the left end of the material storage cavity. The outer wall at the right end of the diverter (5) closes the right end of the reinforcing layer channel (9). A connecting seat (11) communicating with the reinforcing layer channel (9) is provided on the inner wall of the casing (4). The rotating head (6) is rotatably connected to the left end of the casing (4). A discharge channel (12) coaxial with the opening at the left end of the material storage cavity is provided on the rotating head (6). A driving motor (7) is fixedly connected to the outer wall of the casing (4), and the driving motor (7) drives the rotating head (6) to rotate.

7. A production method of a crude alcohol hydrogenation catalyst according to claim 6, characterized in that, The diameter of the discharge channel (12) is the same as the diameter of the opening at the left end of the material storage cavity. A plurality of guiding ribs (15) along the length direction of the discharge channel (12) are provided on the inner wall at the left part of the discharge channel (12). The inner wall of the discharge channel (12) on the right side of the guiding ribs (15) is a smooth inner wall.

8. A production method of a crude alcohol hydrogenation catalyst according to claim 7, characterized in that, The guiding ribs (15) are wedge-shaped ribs with the pointed parts facing the central axis of the discharge channel (12), and the height of the guiding ribs (15) is 0.5 mm.

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