CN1045400C - Solid catalyst with special shape - Google Patents
Solid catalyst with special shape Download PDFInfo
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- CN1045400C CN1045400C CN 92109335 CN92109335A CN1045400C CN 1045400 C CN1045400 C CN 1045400C CN 92109335 CN92109335 CN 92109335 CN 92109335 A CN92109335 A CN 92109335A CN 1045400 C CN1045400 C CN 1045400C
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Abstract
The present invention discloses a solid catalyst in a special shape (a butterfly shape). The particle of the catalyst is in the shape of strip-shaped straight leaves and have multiple leaves, the cross section of the particle is composed of four circular leaves, wherein the radius of two adjacent leaves is R1, the radius of other two adjacent leaves is R2, and R1 is more than R2. According to the difference of the connecting modes of the four circular leaves, the shape of the catalyst can also be divided into a butterfly shape A and a butterfly shape B. Compared with the prior art, the present invention has the advantages of small granularity of the particle of the catalyst, high strength and low pressure drop of the bed of the catalyst in use, and is suitable for diffusion controlled catalytic reaction processes and is especially suitable for the catalytic reaction processes of hydrogenation treatment, hydrogenation refinement, hydrogenation demetallization, etc.
Description
The invention belongs to solid catalyst, especially for the solid catalyst of the hydrotreatment process of petroleum cuts oil and residual oil with special shape.
As everyone knows, the hydrogenation reaction of petroleum cuts and residual oil all belongs to reaction by diffusion control as hydrofining, hydrocracking and hydrodemetallation (HDM) etc.Along with the raising of hydrogenation device for treatment amount, the design scale of hydrogenator is increasing, and the loadings of the reactor catalyst that has is up to more than 100 tons.Therefore for the catalytic performance and the corresponding physicals of this type of catalyzer, have higher requirement as the bed layer pressure degradation in diffusion, crushing strength and the use of catalyzer.The shape of improving catalyzer often can be improved the above-mentioned performance of catalyzer greatly.
Design has the catalyzer of special shape, usually need consider the factor of three aspects simultaneously: one, for short the evolving path being provided for reactant and product molecule, to guarantee that catalyzer has advantages of high catalytic activity, thereby need catalyst system therefor that big outer surface area/volume ratio is arranged, or smaller volume/surface area ratio (the so-called granularity of the volume/surface area ratio of catalyzer, down with) arranged; Two, in order to make catalyzer that higher filling voidage be arranged, fall with the pressure of reduction streams by beds, need to reduce the symmetrical degree in granules of catalyst cross section or adopt additive method, with the close-packed of avoiding the groove leaf phase embedding between the granules of catalyst in use to form; Three, for reduce or avoid transport catalyst, sieve and the filling process in the loss that causes because of fragmentation and the pressure drop increase that under the operational condition of High Temperature High Pressure, brings, the reactive system situation stopping up and even be forced to stop work because of broken powder delivery, need catalyzer to have good crushing strength.
USP4391740, USP4489173, USP4394303 and RD168-002 disclose class symmetry quatrefoil respectively or have had the asymmetric leafy shape catalyzer of two symmetry axis.Because the catalyzer of this type of shape symmetry degree is higher, thereby in catalyst loading, easily forms the close packed array (see figure 4), it is excessive to cause the catalyst bed stressor layer to fall thus, brings disadvantageous effect to catalyzed reaction.
USP4328130 discloses a kind of quatrefoil catalyzer, and the shape of this catalyzer is to open four grooves on cylindrical outside surface evenly distributedly.This kind catalyzer since width of rebate less than the blade face width, thereby avoided the close-packed that the embedding of groove leaf phase causes between particle, but owing to all adopt sharp-pointed corner to connect between the leaf groove of this type of granules of catalyst, in use easily cause stress excessively to concentrate and break, or because of corner wearing and tearing powder delivery, so its crushing strength and tear strength are all lower.EP220933 has invented a kind of quatrefoil catalyzer that adopts circular arc to connect, because its leaf groove makes that more deeply its crushing strength is relatively poor.
USP4673664 discloses a kind of spiral quatrefoil catalyzer, avoided producible close-packed phenomenon in the catalyzer application fully, having reduced bed layer pressure widely falls, but because this twisted phenomena, destroyed the rib-shaped structure of the leafy shape granules of catalyst of straight leaf, make that its crushing strength is lower, the preparation method of the used orifice plate of shaping of catalyst is also comparatively complicated simultaneously.
The objective of the invention is to overcome the shortcoming of prior art, a kind of butterfly quatrefoil catalyzer with small grain size, high strength and low-symmetry is provided.
Technical characterictic of the present invention is that this granules of catalyst is the leafy shape structure of the straight leaf of strip, its cross section is made up of four circular leaves, wherein the radius of two adjacent leaves in four circular leaves is R1, the radius of two adjacent leaves is R2 in addition, connection between the R1＞R2, four roundleaves can be in the following way:
(1) two radius is between the roundleaf of R1, and by the circular arc connection of spill, camber line and roundleaf are tangent or crossing; All adopt between other roundleaves and directly intersect or tangent mode connects (butterfly-A shape);
Between (2) four roundleaves all the garden arc by spill connect camber line and roundleaf tangent or crossing (butterfly-B shape).
Fig. 1 is the schematic cross-section of butterfly of the present invention-A shape catalyzer.
Fig. 2 is the schematic cross-section of butterfly of the present invention-B shape catalyzer.
Fig. 3 is a catalyzer close-packed synoptic diagram of the present invention.
Fig. 4 is the described asymmetric quatrefoil catalyzer close-packed synoptic diagram with two symmetry axis of RD-168-002.
Further describe technical characterstic of the present invention below in conjunction with accompanying drawing.
As shown in Figure 1, in butterfly of the present invention-A shape catalyst, the radius that is used for connecting two radiuses the concave circular arcs of the roundleaf that is R1 is R3, wherein, and R3＜R2, preferably R3≤0.5R2. By " trapezoidal " that four roundleaf circle center line connectings form, the angle α of its long base and hypotenuse is 50～90 °, is preferably 75～85 °. The external diameter of a circle in catalyst granules cross section is 0.5～8.0mm.
As shown in Figure 2, in butterfly of the present invention-B shape catalyst, be used for connecting two radiuses is R1, radius and is the radius that R2 and radius are respectively the concave circular arcs between the adjacent roundleaf of two couple of R1 and R2, be respectively R3, R4 and R5, wherein R3, R4 and R5 are 0.1～0.95R2, are preferably 0.5～0.7R2. By " trapezoidal " that four roundleaf centers of circle form, the angle of long base and hypotenuse is 50～90 °, is preferably 75～85 °. The external garden in catalyst granules cross section typically has a diameter from 0.5～8.0mm.
The size of butterfly A of the present invention and butterfly Type B catalyst granules, the leaf groove size of particle and the ratio between them can change according to actual needs. React for the hydrogenation catalyst by DIFFUSION CONTROLLED, in order to reduce the diffusion distance of material, often need catalyst to have the little particle size of trying one's best.
The comparatively typical sizes of butterfly A of the present invention and butterfly Type B granules of catalyst is:
Butterfly type A:
R1=0.35mm X =1.29mm
R2=0.30mm Y =1.50mm
R3=0.11mm α=80 ° butterfly type B:
R1=0.30mm R5=0.10mm
R2=0.25mm X =1.25mm
R3=0.21mm Y =1.50mm
R4=0.14mm α=80°
Adopt above-mentionedly when big and the adjacent in twos structure of leaflet, can reduce the particulate symmetry, make it in the reality filling, be difficult for forming the close-packed (see figure 3); Adopting four roundleaf circle center line connectings is the structure of ladder type, can improve the ability that particulate bears external force, thereby increases its crushing strength; Adopt part or all of circular arc to connect between leaf, can disperse external force equably, can increase the particulate total surface area again.
Can find out by Fig. 3 and Fig. 4, butterfly particle shape symmetry degree low (the symmetrical number of axle is 1) of the present invention is difficult for during filling forming neat close packed array (Fig. 3), so the bed voidage height, fluid is little by the resistance to flow of bed, and the pressure that shows as beds reduces.And symmetrical trilobal and asymmetric quatrefoil particle shape are highly symmetric (the symmetrical number of axle are respectively 3 and 2), easily form close packed array as shown in Figure 4 during filling.Because a particulate leaf embeds in the ditch mortise of adjacent particle, has therefore reduced bed voidage, has increased resistance to flow.With the leafy shape particle of garden cylindricality and other straight leaves relatively, particle of the present invention hour still has lower bed layer pressure to fall in granularity, can satisfy the requirement of in the industrial production bed layer pressure being fallen.This point is of practical significance to the Industrial Catalysis process, because little granules of catalyst can provide excellent contact, minimizing extends influence, thereby has improved the service efficiency of catalyzer.
The bar shaped particle of catalyzer of the present invention or support of the catalyst normally will prepare the material of catalyzer or support of the catalyst, by having the orifice plate in special shape hole as mentioned above, with conventional method extrusion molding.Because catalyst shape of the present invention still belongs to the leafy shape of straight leaf, so the making of orifice plate still can adopt the drilling method of conventional straight leaf profile hole, as punching press, electric spark-erosion perforation and use the die casting etc. of thermosetting resin or metal material.
Above-mentioned with conventional extrusion process, the granules of catalyst for preparing described shape, typically refer to the process that adopts conventional kneading method to prepare catalyzer, being about to active metal component, extrusion aid, inorganic oxygen compound carrier and water mixes, put into the extrusion equipment moulding, and then oven dry, roasting, make the process of catalyst prod.
Above-mentioned with conventional extrusion process, the catalyst carrier particle for preparing described shape, typically refer to the process that adopts ordinary method to prepare support of the catalyst, being about to inorganic oxygen compound carrier, extrusion aid and water mixes, put into the extrusion equipment moulding, and then oven dry, roasting, make the process of support of the catalyst.
Above-mentioned active metal component generally is meant metallic element and compound thereof, particularly molybdenum, tungsten and/or the cobalt of VI B family and/or VIII family, the compound of nickel, as tungstate, molybdate, cobalt salt and nickel salt; Above-mentioned inorganic oxygen compound carrier, normally aluminum oxide, silicon oxide and zeolite etc.; Above-mentioned extrusion aid generally comprises mineral acid, as nitric acid, hydrochloric acid, and organic acid, as oxalic acid, and expanding agent etc.
The present invention is applicable to the fixed bed catalyst process, is specially adapted to the catalytic reaction process of petroleum fractions and residual hydrocracking.
The present invention compared with prior art has following advantage.
1. the present invention has been owing to adopted the very low quatrefoil shape of symmetrical degree (the symmetrical number of axle is 1), thereby when catalyst loading, is difficult for forming close packed array, so the bed voidage height, and fluid is little by the resistance to flow of bed, and the catalyst bed stressor layer falls little.
2. the present invention makes it have good crushing strength owing to adopted the circular straight leaf quatrefoil structure of circle center line connecting formation " trapezoidal ".At first, the present invention has four straight leaves (promptly have four support elements and each element and be the line support), the outer force rate two that average each leaf is born under certain external force effect is leaf little with the trilobal particle, littler than only having the leafy shape particle of point-supported spiral, thereby crushing strength is than latter height; Secondly, the present invention has four straight leaves of circle, adopts circular arc to connect between roundleaf again, and this garden domes help disperseing external force, have avoided the stress undue concentration, and its trapezoidal cross-sectional shape can be born higher external force, thereby crushing strength is also than latter height.
3. the present invention makes it have less granularity owing to adopted the catalyzer of special shape.
4. the present invention makes it than the leafy shape coating of particles of spiral owing to adopted the particle shape of circular straight leaf, the processing of being more convenient for.
The technical characterstic that the invention is further illustrated by the following examples.
Example 1
This case introduction the moulding process of alumina supporter.
Get 300 gram aluminium hydrate powder (German imported products, trade names SB) mixes with 9.0 gram field mountain valley with clumps of trees and bamboo powder (Shanghai local products company product), add 9.0 gram citric acids (Beijing Chemical Plant's product), 2.8 being nitric acid and 200 ml deionized water of 66 heavy %, ml concn mixes, put into the banded extruder extrusion molding that installs orifice plate, promptly obtain difform strip particle; With resulting through 120 ℃ of oven dry, the following 600 ℃ of roastings of air 4 hours can obtain alumina supporter.
Example 2
This case introduction the strength test process of alumina supporter.
The particulate crushing strength shows on the electronic intensity measuring device in numeral to be measured, select 22 particles that length is 3mm during measurement, put into determinator, make each leaf of particle simultaneously stressed, after removing the big and minimum value of 22 amounts in the data, get the arithmetical mean of all the other 20 data, just can obtain the crushing strength data.The results are shown in Table 1.
Example 3
This case introduction after the granules of catalyst filling, the test process that pressure falls.
The downflow reactor measurement that the employing internal diameter is 19.2mm falls in the bed layer pressure of carrier granule, and bed height is 346mm.The reactor entry and exit are respectively fitted with pressure warning unit.With the air is flow media, measures 25 ℃ of temperature, normal pressure, air velocity 393g/h.cm
2Measuring result sees Table 1.
Table 1
[notes]
| Support shapes | Trilobal | Quatrefoil | Butterfly-A shape | Butterfly-B shape |
| Particle length, mm | 3.0 | 3.0 | 3.0 | 3.0 |
| Maximum outside diameter, mm | 1.6 | 1.6 | 1.6 | 1.3 |
| Granularity (V/S), mm | 0.252 | 0.206 | 0.207 | 0.203 |
| Crushing strength, N/m | 23.1 | 25.3 | 35.5 | 37.8 |
| Relative crushing strength | 100 | 110 | 154 | 164 |
| KPa/m falls in pressure | 15.20 | 13.14 | 12.16 | 11.77 |
| Relative pressure falls | 100 | 86 | 80 | 77 |
| Bulk density, g/ml | 0.718 | 0.666 | 0.655 | 0.561 |
Used quatrefoil catalyzer in the table is the disclosed shape of RD168-002
Claims (4)
1, a kind of solid catalyst with special shape, it is characterized in that this granules of catalyst is the leafy shape structure of the straight leaf of strip, its cross section is made up of four circular leaves, the radius of two adjacent leaves wherein is R1, the radius of two adjacent leaves is R2 in addition, connection between the R1＞R2, four roundleaves can be in the following way:
(1) two radius is between the roundleaf of R1, and by the circular arc connection of spill, camber line and roundleaf are tangent or crossing; All adopt between other roundleaves and directly intersect or tangent mode connects (butterfly-A type);
Between (2) four roundleaves all the garden arc by spill connect camber line and roundleaf tangent or crossing (butterfly-Type B).
2, according to the described catalyzer of claim 1, the radius that it is characterized in that being used to connect two radiuses in butterfly-A type catalyzer the spill circular arc of the roundleaf that is R1 is R3, wherein, and R3＜R2.
3, according to the described catalyzer of claim 1, it is characterized in that being used in butterfly-Type B catalyzer connecting two radiuses is R1, radius and is the radius that R2 and radius are respectively the spill circular arc between the adjacent roundleaf of two couple of R1 and R2, be respectively R3, R4 and R5, wherein, R3, R4 and R5 are all less than R2.
4,, it is characterized in that " trapezoidal " that form by four roundleaf circle center line connectings that the angle of long base and hypotenuse is 50～90 ° according to the described catalyzer of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92109335 CN1045400C (en) | 1992-08-14 | 1992-08-14 | Solid catalyst with special shape |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92109335 CN1045400C (en) | 1992-08-14 | 1992-08-14 | Solid catalyst with special shape |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1081939A CN1081939A (en) | 1994-02-16 |
| CN1045400C true CN1045400C (en) | 1999-10-06 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92109335 Expired - Lifetime CN1045400C (en) | 1992-08-14 | 1992-08-14 | Solid catalyst with special shape |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2886194A1 (en) | 2013-12-19 | 2015-06-24 | IFP Energies nouvelles | Helical extrusion of asymmetric multilobe catalyst supports |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100363106C (en) * | 2004-12-28 | 2008-01-23 | 中国石油化工股份有限公司 | Solid catalyst with particular form |
-
1992
- 1992-08-14 CN CN 92109335 patent/CN1045400C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2886194A1 (en) | 2013-12-19 | 2015-06-24 | IFP Energies nouvelles | Helical extrusion of asymmetric multilobe catalyst supports |
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| Publication number | Publication date |
|---|---|
| CN1081939A (en) | 1994-02-16 |
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