CN103805241A - Gradation combination method of heavy oil hydrotreating catalyst - Google Patents
Gradation combination method of heavy oil hydrotreating catalyst Download PDFInfo
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- CN103805241A CN103805241A CN201210440571.8A CN201210440571A CN103805241A CN 103805241 A CN103805241 A CN 103805241A CN 201210440571 A CN201210440571 A CN 201210440571A CN 103805241 A CN103805241 A CN 103805241A
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Abstract
The invention discloses a gradation combination method of a heavy oil hydrotreating catalyst. A reactor is respectively filled with a hydrogenation protection/demetalization catalyst and a hydrodesulfurization catalyst from up to down; in the reaction material flow direction, the particle size of the catalyst decreases, the pore size decreases, the voidage decreases, and the activity increases from low to high; the active metal components of the hydrogenation protection/demetalization catalyst are in protein-type distribution; the active metal components of the desulphurization catalyst are distributed in a manner that fewer active metal components are at the outside and more active metal components are at the inside. The catalyst gradation combination of the invention gives full play of the function of each catalyst, makes effective use of the active center of the catalyst during inferior heavy oil processing, reduces the catalyst cost, and improves the demetalization, desulphurization and residual carbon removing activity and stability of the whole system.
Description
Technical field
The present invention relates to a kind of heavy oil hydrogenating treatment catalyst grading composition method, can be used for the higher residual hydrocracking process in FCC raw materials pretreatment field, particularly metals content impurity.
Background technology
Heavy-oil hydrogenation is processed in volume increase light-end products can meet stricter environmental regulation requirement, is to help refiner to tackle one of effective technology scheme of Vehicles Collected from Market demand.Due to particularly residual oil complicated component of heavy oil, contain a large amount of impurity, particularly metal Ni, V, Fe, Ca, Na etc. have poisoning effect to desulfurization catalyst and de-carbon residue catalyzer, and therefore, heavy-oil hydrogenation is processed general adopt " catalyst combination loading technology ".
USP4447314 has proposed a kind of dual catalyst system for residual hydrocracking process.The first catalyzer is macroporous catalyst, and the second catalyzer is small catalyst.Raw material is first by the first catalyzer, then order by the second catalyzer to realize demetalization and the desulfurization of residual oil.
But along with the aggravation of crude oil in poor quality, the deposition of metallic impurity in reactive system become the key of restriction heavy oil hydrogenation equipment long-term operation.In the time of the higher poor residuum of processing metal content, a large amount of metallic impurity are deposited in above-mentioned patent catalyzer duct, very easily cause aperture to block and cause catalyst activity decay very fast, inner active centre can not get effective utilization simultaneously, and catalyst center place active metal component is wasted.
CN101928592A discloses a kind of grading composition method of hydrogenation catalyst: reactor loads respectively hydrodemetallation (HDM) and Hydrobon catalyst from top to bottom; Feed stream from top to bottom, keeps along logistics direction, and catalyst activity increases gradually, and aperture reduces gradually, and granularity reduces gradually, and porosity reduces gradually; Catalyst for demetalation, Hydrobon catalyst are made up of one or more catalyzer; Active metal component and acidic assistant concentration distribute and are uneven distribution, from granules of catalyst surface to center, the active metal component of Hydrodemetalation catalyst and acidic assistant concentration step increase, the active metal component of Hydrobon catalyst and acidic assistant concentration gradient reduce; Cubage by weight, catalyst for demetalation accounts for 15～80%; Desulfurization catalyst accounts for 20～85%; For heavy distillate and residual hydrogenation catalysis, there is better demetalization, de-carbon residue, desulphurizing activated and stability, control the temperature rise of beds, slow down the deactivation rate of catalyzer.
The method leading portion catalyst for demetalation is from granules of catalyst surface to center, and active metal component concentration step increase, can weaken the deposition of metallic impurity in catalyzer aperture, has improved the stability of system.But for charging inferior, metallic impurity are still difficult to enter into depths, duct, thereby being not fully utilized, inner active centre causes the active metal component waste of catalyst center place, catalyzer cost is high.And for the desulfurization catalyst reducing for the active metal component concentration gradient of smaller aperture due, catalyzer aperture is easily blocked, catalyst activity decay is very fast.
The grading composition of the hydrogenation catalyst that CN101928593A relates to is on the basis of above-mentioned patent, has loaded denitrification catalyst after metal remover and desulfurization catalyst.Wherein the active metal component of metal remover and denitrification catalyst and acidic assistant concentration distribute and are uneven distribution, from granules of catalyst surface to center, the active metal component of Hydrodemetalation catalyst and acidic assistant concentration step increase, the active metal component of hydrodenitrogenation catalyst and acidic assistant concentration gradient reduce; The active metal component of desulfurization catalyst and acidic assistant concentration distribute and are evenly distributed.Cubage by weight, catalyst for demetalation accounts for 5～55%; Desulfurization catalyst accounts for 5～55%; Denitrification catalyst accounts for 5～55%.This combined method is by introducing denitrification catalyst, can process the charging that nitrogen content and carbon residue content are higher, but CN101928592A is the same with patent, metallic impurity are still difficult to enter into the depths, duct of macrobead catalyst for demetalation, thereby inner active centre is still not fully utilized and causes the active metal component waste of catalyst center place, and catalyzer cost is high.And for the equally distributed desulfurization catalyst of active metal of smaller aperture due, catalyzer aperture is easily blocked, catalyst activity decay is very fast.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of grading composition method of heavy oil hydrogenating treatment catalyst.Catalyzer grading composition of the present invention can be given full play to the effect of every class catalyzer, and before particularly effectively utilizing, the active centre of segment protect/catalyst for demetalation, when reducing catalyzer cost, improves the stability of whole system.
A kind of grading composition method that the invention provides heavy oil hydrogenating treatment catalyst, comprises following content:
Along the mobile direction of reaction mass, in hydroconversion reaction zone, load successively protection/catalyst for demetalation and Hydrobon catalyst; Wherein the active metal component of protection/catalyst for demetalation is uneven distribution, from granules of catalyst surface to center, described protection/catalyst for demetalation active metal component is " protein type " and distributes, the skin (" eggshell ") that is catalyzer does not contain or contains a small amount of metal, higher active metal is contained in the middle layer (" albumen ") of catalyzer, and the inside (" yolk ") of catalyzer does not contain or contain a small amount of metal component; From granules of catalyst surface to center, the active metal component of described desulfurization catalyst is distribute in outer lacking more.
In the inventive method, along the mobile direction of reaction mass, in described catalyst grade part system, catalyzer aperture is descending, and voidage is descending, and activity is transition from low to high.
Owing to containing in residual oil, the dirts such as a large amount of metallic impurity and Fe, Ca, Na are dirty, can be deposited on catalyst particles intergranular and cause the quick rising of bed pressure drop and cause stopping work in hydrogenation process.Therefore, conventionally at the protection/catalyst for demetalation that needs foremost to load one or more macrobeads (particle diameter is between 1.0mm ~ 10mm) of reactor, with maximum to hold dirt dirty, alleviate the generation of pressure drop.Because reaction molecular in residual oil is large, sterically hindered height, reaction is affected significantly by diffusion control, and reactant is difficult to diffuse into the inside of these large granular catalysts, causes the waste in inner active centre.
In the inventive method; the active metal of described large particle diameter protection/catalyst for demetalation is distributed as " protein type " and distributes; autocatalysis agent particle outside surface is generally divided into three layers to center, i.e. " albumen " in outer field " eggshell ", middle layer and inner " yolk ".Skin (" eggshell ") wherein does not contain or containing a small amount of metal, can effectively solve aperture and easily be blocked by metallic impurity the problem that causes permanent deactivation; Higher active metallic content is contained in the middle layer (" albumen ") of catalyzer; And the inside of catalyzer (" yolk ") does not contain or contains a small amount of metal component.Design is the metallic impurity of seldom measuring according to industrial application rear catalyst inside deposition like this.Reason is that this catalyst particle size causes greatly reaction molecular the evolving path long, the raw material reaction thing molecule maximum simultaneously touching, and the inside " yolk " that is difficult to diffuse into catalyzer is located.
Active metal component is protection/catalyst for demetalation design that " protein type " distributes; can avoid causing the waste in inner active centre because impurity cannot be diffused into granules of catalyst inside; can reduce metallic impurity when catalyst pores is salty long-pending; effectively reduce the content of catalyst activity metal component, thereby reduce catalyzer cost.
Desulfurization catalyst in the inventive method adopts the Catalyst Design of larger aperture; raw material is after one or more protection/catalyst for demetalation of leading portion; reactant molecule is effectively destroyed, and molecular dimension diminishes, and can effectively be diffused into the granule interior of desulfurization catalyst.Therefore active metal component be designed to outer few in distribute more, can weaken metallic impurity when catalyst pores is salty long-pending like this, more effectively utilize the inner active centre of catalyzer, improve activity and the stability of system.
In heavy oil hydrogenating treatment catalyst grading composition method of the present invention, catalyzer grading distribution scheme is take the weight of whole catalyzer as benchmark, and protection/catalyst for demetalation is 20% ~ 75%, and preferably 30% ~ 65%; Desulfurization catalyst is 25% ~ 80%, preferably 35% ~ 70%.The filling of hydrogenation catalyst grating system generally adopts cloth bag type filling or dense phase loading, and the filling technology of catalyzer is the routine operation in this area.
Catalyzer of the present invention select porous oxide as aluminum oxide be carrier, active metal component is generally group VIB metal and/or group VIII metal, group VIB metal is generally selected from least one in Mo and W, and group VIII metal is generally selected from least one in Co and Ni.Can also select to add one or more in P, B, Si, F, Ti and Zr for auxiliary agent.
Above-mentioned two kinds of catalyzer can adopt ordinary method of the prior art to be prepared.As protection/catalyst for demetalation can first adopt method preparation as described in CN101927169A, then the method for embathing with deionized water preparation.Desulfurization catalyst can be by the method preparation according to described in patent EP0204314 and CN101462080.
Catalyst grade of the present invention is joined combined system and can under the hydroprocessing condition of any applicable this area, be used.Conventionally processing condition are: 330 ℃ ~ 450 ℃ of average reaction temperature, are preferably 350 ℃ ~ 430 ℃, preferably 360 ℃ ~ 420 ℃; Reactive hydrogen dividing potential drop 8.0MPa ~ 20.0 MPa, is preferably 10.0MPa ~ 18.0 MPa, preferably 12.0MPa ~ 18.0 MPa; When liquid, volume space velocity is 0.15h
-1~ 3.0h
-1, be preferably 0.2h
-1~ 2.0h
-1, preferably 0.2h
-1~ 1.2h
-1; Hydrogen to oil volume ratio 300 ~ 1500, is preferably 400 ~ 1300, and preferably 500 ~ 1000.
Compare with the grading method of heavy oil hydrogenating treatment catalyst in prior art, catalyzer grading composition of the present invention can be given full play to the effect of every class catalyzer, in the time of processing poor residuum, can effectively utilize catalyst active center, when reducing catalyzer cost, improve activity and the stability of whole system demetalization, desulfurization and de-carbon residue.
Accompanying drawing explanation
Fig. 1 is active metal " protein type " distribution schematic diagram in protection/catalyst for demetalation cross section.
Fig. 2 is protection/catalyst for demetalation active metal component radial distribution situation.
Fig. 3 is the active metal distribution schematic diagram in desulfurization catalyst cross section.
Fig. 4 is desulfurization catalyst active metal component radial distribution situation.
Embodiment
Adopt catalyzer grading composition method, load respectively hydrogenation protecting/catalyst for demetalation and Hydrobon catalyst in reactor from top to bottom, protection/catalyst for demetalation and Hydrobon catalyst all can be made up of one or more.The grading composition principle of catalyzer is: along logistics direction, the particle diameter of catalyzer is descending, and aperture is descending, and voidage is descending, and activity is transition from low to high.Wherein protection/catalyst for demetalation active metal component is " protein type " distribution, and the skin of catalyzer and centre portions do not contain or containing a small amount of metal, higher active metal is contained in the middle layer of catalyzer; Desulfurization catalyst active metal component is distribute in outer lacking more.
embodiment 1
This example provides the preparation process that a kind of catalyst grade part is, loads respectively protection/catalyst for demetalation and desulfurization catalyst in reactor from top to bottom, and quality filling ratio is 55%:45%.
Protection/catalyst for demetalation preparation method is as follows:
First according to method preparation described in CN101927169A.Take 150g water-intake rate 1.10mL/g, the tooth ball-type Al of circumcircle diameter 2.8mm
2o
3carrier, sprays 30mL concentration and is 10% ammonia soln, spraying in process, at the uniform velocity splashes into 60mL containing 6.5g ammonium molybdate (MoO
3content is 82%) and the ammonia soln of 4.5g nickelous nitrate (NiO content 25%) in dipping solution and stir, after having sprayed, and then spray again 30mL containing 5g ammonium molybdate (MoO
3content is 82%) and the ammonia soln of 3g nickelous nitrate (NiO content 25%), spray after 20mL, at the uniform velocity splash into 45mL containing 7.5g ammonium molybdate (MoO
3content is 82%) and the ammonia soln of 8g nickelous nitrate (NiO content 25%) in dipping solution and stir, soak while dripping.Rear homogenizing 20 minutes are sprayed.
Sample after homogenizing is immersed in deionized water 3 ~ 5 seconds, take out at latter 120 ℃ dry 10 hours, then roasting 3 hours in 500 ℃ of air, make catalyzer.Wherein MoO
3content is that 7.88%, NiO content is 2.0%.Mean pore size 20.8nm.
Desulfurization catalyst preparation method is as follows:
The distribution that provides according to patent EP0204314, the method for dipping repeatedly, preparation active ingredient is the catalyzer of Mo, Co and Ni.Get 200g Al
2o
3carrier, at room temperature, impregnated in Co and Ni content and is respectively 4h in 5%, 4% 250mL Co-Ni hydrochloric acid soln, soaks 30 minutes after taking-up in deionized water.Then at 120 ℃ dry 3 hours, then roasting 2 hours in 500 ℃ of air.The catalyzer making immerses containing 1h in the ammonia soln of the ammonium molybdate of 5g Neutral ammonium fluoride (Mo content is 10%) again.After taking out, with deionized water wash, at 120 ℃ dry 3 hours, then roasting 2 hours in 500 ℃ of air, make catalyzer.Wherein MoO
3content is that 12.2%, NiO content is that 3.5%, CoO content is 2.0%.Mean pore size 11.6nm.
embodiment 2
This example provides the preparation process that a kind of catalyst grade part is, loads respectively protection/catalyst for demetalation and desulfurization catalyst in reactor from top to bottom, and quality filling ratio is 50%:50%.
Protection/catalyst for demetalation preparation method is with embodiment 1.
Desulfurization catalyst preparation method:
Prepare according to patent CN101462080 supplying method.Take 200g Al
2o
3carrier, by the order of tartrate, ammonium paramolybdate, nickelous nitrate, above-mentioned substance is added in deionized water successively, the ratio of tartaric mole number and ammonium paramolybdate, nickelous nitrate mole number sum is 0.2, and wherein nickelous nitrate (NiO content 25%) is 18.1g, ammonium molybdate (MoO
3content is 82%) be 30.2g, add 209mL deionized water, stir to dissolving completely, obtain dipping solution.Mix that rear to survey steeping fluid pH matter with pH meter be that 1.5. immerses carrier in steeping fluid, after 120 minutes at 80 ℃ dry 6 hours, then roasting 3 hours in 500 ℃ of air, make catalyzer.Wherein MoO
3content is that 12.5%, NiO content is 2.5%.Mean pore size 11.0nm.
embodiment 3
This example provides the preparation process that a kind of catalyst grade part is, loads respectively protection/catalyst for demetalation and desulfurization catalyst in reactor from top to bottom, and quality filling ratio is 60%:40%.
Protection/catalyst for demetalation preparation method is with embodiment 1.
Desulfurization catalyst is selected containing 2%TiO
2al
2o
3carrier, preparation method is with embodiment 1.
embodiment 4
This example provides the preparation process that a kind of catalyst grade part is, loads respectively protection/catalyst for demetalation and desulfurization catalyst in reactor from top to bottom, and quality filling ratio is 60%:40%.
Protection/catalyst for demetalation is by two kinds of catalyzer gradation compositions, and a kind of circumcircle diameter of selecting is the gear type Al of 4.0mm
2o
3carrier, it is the tooth ball-type Al of 2.8mm that another kind is selected circumcircle diameter
2o
3carrier.Both mass ratios are 1:1.Two kinds of protection/catalyst for demetalation preparation methods are with embodiment 1.
Desulfurization catalyst is selected containing 2%ZrO
2al
2o
3carrier, preparation method is with embodiment 1.
embodiment 5
This example provides the preparation process that a kind of catalyst grade part is, loads respectively protection/catalyst for demetalation and desulfurization catalyst in reactor from top to bottom, and quality filling ratio is 40%:60%.
Protection/catalyst for demetalation preparation method is with embodiment 1.
Desulfurization catalyst is selected containing 2%TiO
2al
2o
3carrier, preparation method is with embodiment 2.
embodiment 6
This example provides the preparation process that a kind of catalyst grade part is, loads respectively protection/catalyst for demetalation and desulfurization catalyst in reactor from top to bottom, and quality filling ratio is 40%:60%.
Protection/catalyst for demetalation preparation method is with embodiment 1.
Desulfurization catalyst is by two kinds of catalyzer gradation compositions.Two kinds of method for preparing catalyst are respectively with embodiment 1 and embodiment 2.Both mass ratios are 1:1.
embodiment 7
This example provides the preparation process that a kind of catalyst grade part is, loads respectively protection/catalyst for demetalation and desulfurization catalyst in reactor from top to bottom, and quality filling ratio is 40%:60%.
Protection/catalyst for demetalation preparation method is with embodiment 1.
Desulfurization catalyst is by two kinds of catalyzer gradation compositions.Two kinds of method for preparing catalyst are respectively with embodiment 1 and embodiment 2.Both mass ratios are 1:1.
comparative example 1
In reactor, load respectively protection/catalyst for demetalation and desulfurization catalyst from top to bottom, quality filling ratio is 50%:50%.Protection/catalyst for demetalation and desulfurization catalyst adopt the equally distributed preparation method of conventional catalyst active metal.
Protection/catalyst for demetalation is prepared as follows:
With Al
2o
3for carrier, adopt saturated method supported active metal component Mo, the Ni of spraying.Take the carrier of 150g water-intake rate 1.08mL/g, spray containing 18.6g ammonium molybdate (MoO
3content is 82%) and the ammonia soln 162mL of 17.1g nickelous nitrate (NiO content 25%).After homogenizing 10 minutes, at 120 ℃ dry 3 hours, then roasting 3 hours in 500 ℃ of air, make catalyzer.Wherein MoO
3content is that 8.58%, NiO content is 2.7%.
Desulfurization catalyst is prepared as follows:
With Al
2o
3for carrier, adopt saturated method supported active metal component Mo, the Ni of spraying.Take the carrier of 150g water-intake rate 1.0mL/g, spray containing 30.0g ammonium molybdate (MoO
3content is 82%) and the ammonia soln 150mL of 27.0g nickelous nitrate (NiO content 25%).After homogenizing 10 minutes, at 120 ℃ dry 3 hours, then roasting 3 hours in 500 ℃ of air, make catalyzer.Wherein MoO
3content is that 13.4%, NiO content is 3.6%.
comparative example 2
This comparative example is the catalyst combination method that patent CN101928592A provides, and loads respectively catalyst for demetalation and desulfurization catalyst in reactor from top to bottom, and quality filling ratio is 45%:55%.Wherein the active metal component of metal remover and desulfurization catalyst is uneven distribution, from granules of catalyst surface to center, and the active metal component step increase of Hydrodemetalation catalyst, the active metal component gradient of Hydrobon catalyst reduces.Method for preparing catalyst is with patent CN101928592A.
Catalyst for demetalation is prepared as follows:
With Al
2o
3make carrier, the distribution that provides according to patent EP0204314, the method for dipping repeatedly, preparation active ingredient is the catalyzer of Mo, Co and Ni.Get 500g Al
2o
3carrier, at room temperature, impregnated in Co and Ni content and is respectively 4h in 4.0%, 3.0% 750mLCo-Ni hydrochloric acid soln, soaks 30 minutes after taking-up in deionized water.Then at 120 ℃ dry 3 hours, then roasting 2 hours in 500 ℃ of air.The catalyzer making immerses containing 1h in the ammonia soln of the ammonium molybdate of 5g Neutral ammonium fluoride (Mo content is 8.0%) again.After taking out, with deionized water wash, at 120 ℃ dry 3 hours, then roasting 2 hours in 500 ℃ of air, make catalyzer.Wherein MoO
3content is that 8.7%, NiO content is that 1.15%, CoO content is 1.85%.Mean pore size 19.6nm.
Desulfurization catalyst is prepared as follows:
Take the Al of 150g water-intake rate 1.10mL/g
2o
3carrier, passes into water vapor 1h, then contains 10.9g ammonium molybdate (MoO at 330mL
3content is 82%) and the immersion 1h of 9.5g nickelous nitrate (NiO content 25%) and 2g85% phosphoric acid, then at 120 ℃ dry 3 hours, then roasting 5 hours in 500 ℃ of air; Taking-up passes into water vapor 3h, then contains 20.5g ammonium molybdate (MoO at 330mL
3content is 82%) and the immersion 1h of 17.0g nickelous nitrate (NiO content 25%) and 6g85% phosphoric acid, then at 120 ℃ dry 3 hours, then roasting 3 hours in 500 ℃ of air; Take out and pass into water vapor 4h, then contain 28.2g ammonium molybdate (MoO at 330mL
3content is 82%) and the immersion 1h of 27.5g nickelous nitrate (NiO content 25%) and 10g85% phosphoric acid, then at 120 ℃ dry 3 hours, then roasting makes catalyzer for 3 hours in 500 ℃ of air.Wherein MoO
3content is that 13.25%, NiO content is 3.7%.Mean pore size 11.2nm.
embodiment 8
The present embodiment is embodiment 1,2,3 and comparative example 1, activity and the stability simultaneous test of comparative example 2 catalyst combination systems on 100mL fixed bed small hydrogenation device.Evaluate stock oil character as table 1.Appreciation condition is in table 2.
Table 1 is evaluated stock oil.
| Stock oil character | Normal slag in sand |
| Density (20 ℃)/kgm -3 | 983.5 |
| Ni+ V/μg·g -1 | 108.8 |
| S,% | 3.3 |
| CCR，% | 14.5 |
Table 2 appreciation condition.
| Temperature/℃ | 390 |
| Pressure/MPa, | 15.7 |
| Volume space velocity/h -1 | 0.3 |
| Gas-oil ratio | 758 |
The total metal contents in soil of embodiment 1, embodiment 2, embodiment 3 and comparative example catalyst combination system is in table 3.
The total metal contents in soil contrast of table 3 catalyst combination system.
| Numbering | Metal remover metal content M1, % | Sweetening agent metal content M2, % | Metal remover weight fraction m1, % | Sweetening agent weight fraction m2, % | The total metal M of combined system, % |
| Embodiment 1 | 9.88 | 15.7 | 55 | 45 | 12.49 |
| Embodiment 2 | 9.82 | 15.0 | 50 | 50 | 12.41 |
| Embodiment 3 | 9.80 | 15.2 | 60 | 40 | 11.96 |
| Comparative example 1 | 11.28 | 17.0 | 50 | 50 | 14.14 |
| Comparative example 2 | 11.7 | 16.95 | 45 | 55 | 14.59 |
The calculating formula of combined system total metal contents in soil is: M=M1* m1+ M2* m2.
In embodiment of the present invention 1-3, catalyst activity metal component is uneven distribution, and therefore the total metal contents in soil of its combined system will be lower than comparative example 1 and comparative example 2.
The catalyst combination system running activity rating of 400 hours the results are shown in table 4.
Table 4 catalyst combination system activity rating result.
| Impurity removal percentage, % | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 |
| Demetallization per | 92.5 | 91.5 | 92.9 | 90.2 | 91.0 |
| Desulfurization degree | 83.2 | 83.8 | 83.1 | 82.9 | 82.7 |
| De-carbon yield | 58.5 | 57.9 | 57.6 | 57.0 | 57.1 |
As can be seen from Table 4, at system total metal contents in soil, lower than comparative example in the situation that, demetallization per, desulfurization degree and the de-carbon yield of embodiment 1, embodiment 2, embodiment 3 is all higher than comparative example 1 and comparative example 2 catalyst combination.Catalyst combination system stability evaluation result is listed in table 5.
Table 5 catalyst combination system stability evaluation result.
| Runtime | 400h | 400h | 1200h | 1200h | 3000h | 3000h |
| Numbering | Embodiment 2 | Comparative example 2 | Embodiment 2 | Comparative example 2 | Embodiment 2 | Comparative example 2 |
| Demetallization per relatively, % | 1.0 | 0.994 | 0.966 | 0.958 | 0.919 | 0.909 |
| Desulfurization degree relatively, % | 1.0 | 0.987 | 0.975 | 0.960 | 0.922 | 0.907 |
| Relatively de-carbon yield, % | 1.0 | 0.986 | 0.962 | 0.946 | 0.918 | 0.902 |
As can be seen from Table 5, along with the prolongation of runtime, at system total metal contents in soil, lower than comparative example 2 in the situation that, demetallization per, desulfurization degree and the de-carbon yield of embodiment 2 all combine higher than comparative catalyst; And the attenuation degree of decreasing ratio is all less than comparative catalyst's combination.Illustrate that catalyst combination method of the present invention can, in reducing catalyzer cost, improve activity and the stability of whole system.
Claims (10)
1. a grading composition method for heavy oil hydrogenating treatment catalyst, comprises following content:
Along the mobile direction of reaction mass, in hydroconversion reaction zone, load successively protection/catalyst for demetalation and Hydrobon catalyst; Wherein the active metal component of protection/catalyst for demetalation is uneven distribution, from granules of catalyst surface to center, the skin that is catalyzer does not contain or contains a small amount of metal, and higher active metallic content is contained in the middle layer of catalyzer, and the inside of catalyzer does not contain or contain a small amount of metal component; From granules of catalyst surface to center, the active metal component of described desulfurization catalyst is distribute in outer lacking more.
2. in accordance with the method for claim 1, it is characterized in that, along the mobile direction of reaction mass, the catalyzer aperture in described hydroconversion reaction zone is descending, and voidage is descending, and activity is transition from low to high.
3. in accordance with the method for claim 1, it is characterized in that, take the weight of whole catalyzer as benchmark, protection/catalyst for demetalation content is 20% ~ 75%, and desulfurization catalyst content is 25% ~ 80%.
4. in accordance with the method for claim 3, it is characterized in that, take the weight of whole catalyzer as benchmark, protection/catalyst for demetalation content is 30% ~ 65%, and desulfurization catalyst content is 35% ~ 70%.
5. in accordance with the method for claim 1, it is characterized in that, described protection/catalyst for demetalation and Hydrobon catalyst are take porous oxide as carrier, and active metal component is group VIB metal and/or group VIII metal.
6. in accordance with the method for claim 5, it is characterized in that, one or more that also contain in described protection/catalyst for demetalation and Hydrobon catalyst in P, B, Si, F, Ti and Zr are auxiliary agent.
7. in accordance with the method for claim 1, it is characterized in that, the processing condition of described hydroconversion reaction zone are: 330 ℃ ~ 450 ℃ of average reaction temperature, and reactive hydrogen dividing potential drop 8.0MPa ~ 20.0 MPa, when liquid, volume space velocity is 0.15h
-1~ 3.0h
-1, hydrogen to oil volume ratio 300 ~ 1500.
8. in accordance with the method for claim 5, it is characterized in that, described group VIB metal is selected from least one in Mo and W, and group VIII metal is selected from least one in Co and Ni.
9. in accordance with the method for claim 7, it is characterized in that, the processing condition of described hydroconversion reaction zone are: 350 ℃ ~ 430 ℃ of average reaction temperature, and reactive hydrogen dividing potential drop 10.0MPa ~ 18.0 MPa, when liquid, volume space velocity is 0.2h
-1~ 2.0h
-1, hydrogen to oil volume ratio 400 ~ 1300.
10. in accordance with the method for claim 9, it is characterized in that, the processing condition of described hydroconversion reaction zone are: 360 ℃ ~ 420 ℃ of average reaction temperature, reactive hydrogen dividing potential drop 12.0MPa ~ 18.0 MPa, volume space velocity 0.2h when liquid
-1~ 1.2h
-1, hydrogen to oil volume ratio 500 ~ 1000.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107880932A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst grading method and heavy oil hydrogenation treatment method |
| CN107875979A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of grading loading methods and applications of fixed bed hydrogenation catalyst |
| CN111315849A (en) * | 2017-09-30 | 2020-06-19 | 环球油品有限责任公司 | Method and apparatus for hydroprocessing hydrocarbon streams |
| CN114713239A (en) * | 2020-12-22 | 2022-07-08 | 中国石油化工股份有限公司 | Catalyst grading method for oil product hydrogenation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107880932A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst grading method and heavy oil hydrogenation treatment method |
| CN107875979A (en) * | 2016-09-29 | 2018-04-06 | 中国石油化工股份有限公司 | A kind of grading loading methods and applications of fixed bed hydrogenation catalyst |
| CN107880932B (en) * | 2016-09-29 | 2019-09-24 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst grading method and heavy oil hydrogenation treatment method |
| CN107875979B (en) * | 2016-09-29 | 2021-02-09 | 中国石油化工股份有限公司 | Grading filling method and application of fixed bed hydrogenation catalyst |
| CN111315849A (en) * | 2017-09-30 | 2020-06-19 | 环球油品有限责任公司 | Method and apparatus for hydroprocessing hydrocarbon streams |
| CN111315849B (en) * | 2017-09-30 | 2022-11-15 | 环球油品有限责任公司 | For treating hydrocarbon streams carrying out hydrogenation method and device for machining |
| CN114713239A (en) * | 2020-12-22 | 2022-07-08 | 中国石油化工股份有限公司 | Catalyst grading method for oil product hydrogenation |
| CN114713239B (en) * | 2020-12-22 | 2024-05-31 | 中国石油化工股份有限公司 | Catalyst grading method for oil hydrogenation |
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