CN100363106C - Solid catalyst with particular form - Google Patents
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- CN100363106C CN100363106C CNB2004101028195A CN200410102819A CN100363106C CN 100363106 C CN100363106 C CN 100363106C CN B2004101028195 A CNB2004101028195 A CN B2004101028195A CN 200410102819 A CN200410102819 A CN 200410102819A CN 100363106 C CN100363106 C CN 100363106C
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- catalyst
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- 239000011949 solid catalyst Substances 0.000 title claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims description 63
- 239000008187 granular material Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 7
- 238000009792 diffusion process Methods 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000004517 catalytic hydrocracking Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 206010013786 Dry skin Diseases 0.000 description 4
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- -1 as tungstates Chemical compound 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004512 die casting Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000009760 electrical discharge machining Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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Abstract
The present invention relates to a solid catalyst with a special shape. The present invention is in a bar-shaped structure in a straight blade multi-blade shape, the cross section of the solid catalyst is composed of four equal blades, and adjacent blades are alternately connected in a concave circular arc mode and a direct cross mode or a tangential mode. The present invention has the advantages of high granule crushing resistance intensity and high porosity, and is suitable for being used for a catalysis process controlled by diffusion, particularly catalytic reaction processes of hydrofinishing, hydrocracking and hydrodemetalization.
Description
Technical field
The present invention relates to a kind of solid catalyst with special shape.
Background technology
As everyone knows, the hydrogenation reaction of petroleum distillate and residual oil all belongs to the reaction of DIFFUSION CONTROLLED as hydrofinishing, hydrocracking and HDM etc.Along with the raising of hydrogenation device for treatment amount, the design scale of hydrogenation reactor is increasing, and the reactor catalyst loadings that has has reached more than 100 tons.Therefore for the catalytic performance and the corresponding physical property of this type of catalyst, have higher requirement as the bed layer pressure degradation in diffusion, crushing strength and the use of catalyst.The shape of improving catalyst can be improved the above-mentioned performance of catalyst greatly.
Design has the catalyst of special shape, usually to consider the factor of following several respects: one, for short the evolving path being provided for reactant and product molecule, to guarantee that catalyst has advantages of high catalytic activity, need catalyst that bigger external surface area/volume ratio is arranged, or smaller volume/external surface area is arranged than (volume of catalyst/external surface area ratio is commonly referred to as granularity, down together); Two, fall in order to reduce the pressure of material by beds, increase the appearance dirt ability of beds simultaneously, need catalyst that higher bed voidage is arranged; Three, for reduce or avoid catalyst the transportation, sieve and the filling process in cause fragmentation, and the pressure drop increase that brings because of broken powder delivery under the operating condition of HTHP, reaction system block and even occur the situation of being forced to stop work, and needs catalyst to have certain crushing strength.
USP4328130 discloses a kind of quatrefoil catalyst, and the shape of this catalyst is to have opened four grooves on cylindrical outer surface evenly distributedly.This kind catalyst since width of rebate less than the blade face width, thereby avoided the closs packing 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 catalyst granules, in use easily cause the stress undue concentration and ftracture, or because of corner wearing and tearing powder delivery, so its crushing strength and tear strength are lower.
EP0220933 discloses a kind of quatrefoil catalyst that adopts circular arc to connect, though this catalyst has overcome US4 to a certain extent, 328,130 provide the shortcoming of catalyst, and its crushing strength is still relatively poor.
CN1081939A discloses a kind of butterfly catalyst, and this catalyst granules is the leafy shape structure of strip, and its cross section is made up of four circular blades, and wherein the radius of two adjacent leaves is R1, and the radius of two adjacent leaves is R2, R1＞R2 in addition.The catalyst granules crushing strength of this shape improves, but falls still bigger by the catalyst bed stressor layer of this catalyst filling.
Summary of the invention
The objective of the invention is the deficiency that exists at existing solid catalyst with special shape, a kind of new solid catalyst with special shape is provided.
Catalyst provided by the invention is the leafy shape structure of the straight leaf of strip, and its cross section is equal to blade by four and forms, and alternately is connected by spill circular arc and directly crossing or tangent mode between adjacent blades.
Compare with existing catalyst, the catalyst performance of levying with the crushing strength and the catalyst bed stressor layer petition of surrender provided by the invention obviously improves.
For example, the specific strength of the ratio definition catalyst granules that falls with crushing strength and pressure, the specific strength value that the invention provides catalyst granules is greater than 1.94N.Pa
-1, the specific strength value of Comparative Examples catalyst granules is then all less than 1.76N.Pa
-1
Description of drawings
Fig. 1 is the schematic cross-section of a kind of catalyst provided by the invention.
Fig. 2 is the enlarged diagram of the blade in formation catalyst shown in Figure 1 cross section.
Fig. 3 is the schematic cross-section of another kind of catalyst provided by the invention.
Fig. 4 is the enlarged diagram of the blade in formation catalyst shown in Figure 3 cross section.
The schematic cross-section of a kind of catalyst that Fig. 5 provides for CN1081939A.
The schematic cross-section of a kind of catalyst that Fig. 6 provides for EP0220933.
The specific embodiment
According to the present invention, a kind of cross section of preferred catalyst as shown in Figure 1, wherein said blade as shown in Figure 2, this blade is that the semi arch of R1 is along two parallel tangent line extension L1 by radius, and with two radiuses tangent forming of quadrant arc that be R2, excessive between the interim quadrant arc by straight line L2, the radius that is used to connect the spill circular arc of two blades is R3, R1 〉=R2, R1＞R3, L1=0-3R1, be preferably L1=0.5R1-2.5R1, L2=0-R1, be preferably L2=0-0.3R1.
According to the present invention, the cross section of another kind of preferred catalyst as shown in Figure 3, wherein said blade as shown in Figure 4, this blade is that the circle of R1 is along two parallel tangent lines by radius, on one side with straight line extension L1, the circular arc that with the radius is R4 is on one side justified tangent and crossing forming with this extension respectively, the one side of extending with straight line between the blade connects by the spill circular arc, the radius that wherein is used to connect the spill circular arc of two blades is R3, R3+2R1 〉=R4, R1＞R3, is preferably L1=0.5R1-2.5R1 at L1=0-3R1.
The leaf groove size of the size of catalyst granules of the present invention, particle and the ratio between them can change according to actual needs.For for the reaction of DIFFUSION CONTROLLED,, often need catalyst to have the little particle size of trying one's best in order to reduce the diffusion distance of material.Maximum outside diameter with the catalyst cross section is a benchmark, and the comparatively typical sizes of catalyst granules of the present invention is: the 1-4 millimeter.
Catalyst of the present invention can be the material with the preparation catalyst, by having the orifice plate in special shape hole as mentioned above, adopts conventional method extrusion modling to obtain.Also can be at first with the material of preparation catalyst carrier by having the orifice plate in special shape hole as mentioned above, adopt conventional method extrusion modling, activation, afterwards this carrier contact with the solution that contains active metal component, dry also the activation obtain.
Wherein said orifice plate can adopt the drilling method of conventional straight leaf irregularly-shaped hole, as punching press, electric spark-erosion perforation, also can use the die casting of thermosetting resin or metal material to make.
Described active metal component generally is meant metallic element and compound thereof, particularly molybdenum, tungsten and/or the cobalt of VIB and/or VIII family, the compound of nickel, as tungstates, molybdate, cobalt salt and nickel salt; Above-mentioned inorganic oxide carrier, normally aluminium oxide, silica and zeolite etc.; Above-mentioned extrusion aid generally comprises inorganic acid, as nitric acid, hydrochloric acid, and organic acid, as oxalic acid, and expanding agent etc.
The invention provides catalyst and be suitable for catalytic reaction process, be specially adapted to the hydrotreatment course of reaction of fraction oil of petroleum, residual oil by DIFFUSION CONTROLLED.
Further specify the present invention below by embodiment.
Embodiment 1
The preparation method who the invention provides catalyst carrier and this carrier is described
Get 400 gram aluminium hydrate powder (Chang Ling oil plant catalyst plant product, the trade mark is CD) extruded mouldings, the hole shape of orifice plate as shown in Figure 1, R1=0.214 wherein, R2=0.200, R3=0.183.L1=0.232.The orifice plate maximum outside diameter is 1.6, and in 120 ℃ of dryings 4 hours, roasting was 4 hours under 600 ℃ of blowing air conditions, obtains carrier Z1 with the wet bar of gained.
The preparation method who the invention provides catalyst carrier and this carrier is described
Get 400 gram aluminium hydrate powder (with example 1) extruded mouldings, the hole shape of orifice plate as shown in Figure 2, R1=0.214 wherein, R4=0.611, R3=0.183.The orifice plate maximum outside diameter is 1.6, and in 120 ℃ of dryings 4 hours, roasting was 4 hours under 600 ℃ of blowing air conditions, obtains carrier Z2 with the wet bar of gained.
Comparative Examples 1
Illustrate that existing method provides the preparation method of catalyst carrier and this carrier
Get 400 gram aluminium hydrate powder (with example 1) extruded mouldings, shown in Figure 5 among the hole shape of orifice plate such as the CN1081939A, R1=0.35 wherein, R2=0.31, R3=0.11, α=100 °.The orifice plate maximum outside diameter is 1.6, and in 120 ℃ of dryings 4 hours, roasting was 4 hours under 600 ℃ of blowing air conditions, obtains carrier D1 with the wet bar of gained.
Comparative Examples 2
Illustrate that existing method provides the preparation method of catalyst carrier and this carrier
Get 400 gram aluminium hydrate powder (with example 1) extruded mouldings, shown in Figure 6 among the hole shape of orifice plate such as the EP0220933, R1=0.239 wherein, R2=0.159, R3=0.210.The orifice plate maximum outside diameter is 1.6, and in 120 ℃ of dryings 4 hours, roasting was 4 hours under 600 ℃ of blowing air conditions, obtains carrier D2 with the wet bar of gained.
Embodiment 3-4
The performance that the invention provides catalyst granules is described
Show the crushing strength of measuring carrier granular on the electronic intensity measuring device in numeral.Concrete grammar is: get 12 length respectively and be 5 millimeters Z1, Z2, measure the crushing strength of each particle, remove a maximum and a minimum of a value, count the crushing strength of particle with its arithmetic mean of instantaneous value.
At internal diameter is that the bed layer pressure of measuring carrier granular in 19.2 millimeters the downflow reactor is fallen, and bed height is 346 millimeters.The reactor entry and exit are equipped with pressure gauge respectively.With the air is flow media, measures 25 ℃ of temperature, normal pressure, air velocity 393g/h.cm
2
The specific strength of the ratio definition catalyst granules that falls with crushing strength and pressure, the results are shown in Table 1.
Comparative Examples 3-4
Measure the specific strength of D1, D2 respectively according to the method for example 3, the results are shown in Table 1.
Table 1
| Example | 3 | 4 | Comparative Examples 3 | Comparative Examples 4 |
| Carrier | Z1 | Z2 | D1 | D2 |
| Specific strength/N.Pa -1 | 1.99 | 1.94 | 1.76 | 1.47 |
In the result that table 1 provides, the specific strength value that the invention provides catalyst granules is greater than 1.94N.Pa
-1, the specific strength value of Comparative Examples catalyst granules is then less than 1.76N.Pa
-1Explanation is fallen the catalyst performance provided by the invention that is associated with crushing strength and catalyst bed stressor layer and is obviously improved.
Claims (5)
1. solid catalyst with special shape, this catalyst is the leafy shape structure of the straight leaf of strip, its cross section is equal to blade by four and forms, and alternately is connected by spill circular arc and directly crossing or tangent mode between adjacent blades.
2. according to the described catalyst of claim 1, it is characterized in that, described blade is that the semi arch of R1 is along two parallel tangent line extension L1 by radius, and with two radiuses tangent forming of quadrant arc that be R2, wherein excessive by straight line L2 between the quadrant arc, the radius that is used to connect the spill circular arc of two blades is R3, R1 〉=R2, R1＞R3, L1=0-3R1, L2=0-R1.
3. according to the described catalyst of claim 1, it is characterized in that, described blade is that the circle of R1 is along two parallel tangent lines by radius, on one side with straight line extension L1, on one side with the radius be R4 circular arc respectively with tangent and crossing the forming of this extensions circle, pass through the connection of spill circular arc with one side of straight line extension between the blade, the radius that wherein is used to connect the spill circular arc of two blades is R3, R3+2R1 〉=R4, R1＞R3, L1=0-3R1.
4. according to claim 2 or 3 described catalyst, it is characterized in that described L1=0.5R1-2.5R1.
5. according to the described catalyst of claim 2, it is characterized in that described L2=0-0.3R1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004101028195A CN100363106C (en) | 2004-12-28 | 2004-12-28 | Solid catalyst with particular form |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004101028195A CN100363106C (en) | 2004-12-28 | 2004-12-28 | Solid catalyst with particular form |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1795989A CN1795989A (en) | 2006-07-05 |
| CN100363106C true CN100363106C (en) | 2008-01-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004101028195A Active CN100363106C (en) | 2004-12-28 | 2004-12-28 | Solid catalyst with particular form |
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| Country | Link |
|---|---|
| CN (1) | CN100363106C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010084112A1 (en) * | 2009-01-20 | 2010-07-29 | Shell Internationale Research Maatschappij B.V. | Process for the hydro-demetallization of hydrocarbon feedstocks |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024124889A1 (en) * | 2022-12-16 | 2024-06-20 | 中国石油化工股份有限公司 | Catalyst molded body |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0220933A1 (en) * | 1985-10-25 | 1987-05-06 | Mobil Oil Corporation | Quadrulobe-type shaped catalytic extrudates |
| CN1081939A (en) * | 1992-08-14 | 1994-02-16 | 中国石油化工总公司 | Solid catalyst with special shape |
| CN2389717Y (en) * | 1999-09-29 | 2000-08-02 | 中国石油化工集团公司 | Homoheterostyly catalyst |
| CN2645761Y (en) * | 2003-09-15 | 2004-10-06 | 中国石油化工股份有限公司 | Asymmetric isocylindrical granule |
-
2004
- 2004-12-28 CN CNB2004101028195A patent/CN100363106C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0220933A1 (en) * | 1985-10-25 | 1987-05-06 | Mobil Oil Corporation | Quadrulobe-type shaped catalytic extrudates |
| CN1081939A (en) * | 1992-08-14 | 1994-02-16 | 中国石油化工总公司 | Solid catalyst with special shape |
| CN2389717Y (en) * | 1999-09-29 | 2000-08-02 | 中国石油化工集团公司 | Homoheterostyly catalyst |
| CN2645761Y (en) * | 2003-09-15 | 2004-10-06 | 中国石油化工股份有限公司 | Asymmetric isocylindrical granule |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010084112A1 (en) * | 2009-01-20 | 2010-07-29 | Shell Internationale Research Maatschappij B.V. | Process for the hydro-demetallization of hydrocarbon feedstocks |
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| Publication number | Publication date |
|---|---|
| CN1795989A (en) | 2006-07-05 |
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