CN103102938A - Fluidized bed hydrotreatment method - Google Patents
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Abstract
The invention relates to a fluidized bed hydrotreatment method. According to the invention, at least two tandem fluidized bed hydrotreatment reactors are used; a mixed catalyst of at least two catalysts is used in a second fluidized bed hydrotreatment reactor, the two catalysts include a catalyst C and a catalyst D, a mixing volume ratio of the catalyst C to the catalyst D is 1: 0.1 to 1: 5, acid content in the catalyst D is 0.05 to 0.1 mmol/g higher than acid content in the catalyst C, and the content of an active metal oxide in the D is 3% to 8% higher than the content of an active metal oxide in the catalyst C; preferably, a first fluidized bed hydrotreatment reactor uses a mixed hydrotreatment catalyst with proper properties. The method provided by the invention improves operation performance of a fluidized bed residuum hydrotreatment process and enhances the level of hydrogenation activity and flexibility of operation.
Description
Technical field
The present invention relates to a kind of boiling bed hydrogenation treatment process, be specially adapted to the higher inferior heavy oil ebullated bed serial hydrogenation treating processes of heavy metal content.
Background technology
In recent years, along with oil price rise, the aggravation of crude oil heaviness, in poor quality trend, the crude oil difficulty of processing increases, the light-end products demand is risen and the decline of heavy fuel oil (HFO) demand, heavy oil deep processing task is day by day heavy, and processing heavy oil particularly heavy crude and heavy oil residue has become the oil refining industry problem needing to overcome.Simultaneously, increasingly strict along with the oil fuel standard, the residual hydrogenation technology of economic environmental protection also more and more gets more and more people's extensive concerning.Residual hydrocracking technique mainly contains fixed bed, ebullated bed, suspension bed and moving-bed.Fixed bed is because of its technology maturation, and is simple to operate and be widely applied.But residue fixed-bed hydrogenation technique has strict restriction to metal in raw material and carbon residue content.The boiling bed residual oil hydrogenation technique is because catalyzer can add online and discharge, be conducive to keep higher catalyst activity and long-term operation, strong to adaptability to raw material, processing scheme is flexible, can the higher inferior raw material of processing metal foreign matter content, as vacuum residuum etc.This technology not only can be used for hydrotreatment, can be used for simultaneously residual hydrocracking, and application prospect is very wide.
Difference according to process raw material oil and purpose product, the ebullated bed reactor part can be divided into single reactor or several parallel series, each series comprises several tandem reactors (tandem reactor refers to that reaction mass is successively by each reactor), the identical catalyzer of can packing in different reactor also can load different catalyzer.At present, the residual oil boiling bed hydrogenation cracking unit flow processs that adopt two reactors in series (H-Oil) and three reactors in series (LC-Fining) more, the reason of doing like this also helps the raising impurity removal percentage except unit scale.The First reactor of H-Oil device is mainly used in hydrocracking and demetalization, and second reactor is mainly used in hydrocracking, desulfurization and takes off carbon residue.The First reactor of LC-Fining device is mainly used in hydrocracking and demetalization, and second reactor is mainly used in hydrocracking, desulfurization and takes off carbon residue, and the 3rd reactor is mainly used in deep desulfuration.The reactor of boiling bed residual oil hydrogenation technique increases to two or more from one, and loads different catalysts in different reactor, and this has improved the operational situation of device.
To adopt the catalyzer of Different Pore Structures and performance due to different reactions.Different types of catalyzer and rational gradation composition scheme thereof that exploitation is applicable to the ebullated bed tandem process are very important.In the boiling bed hydrogenation technique process, stock oil and hydrogen upwards flow through beds, bed expansion, and granules of catalyst is in the irregular movement state in reactor, i.e. " boiling " state.So require catalyzer not only to have higher hydrogenation and activity of conversion, also will have higher crushing strength and wear resisting property.
In the boiling bed hydrogenation technology, in reactor, material is in strong back-mixing state, therefore can't realize as the different catalysts grating technology in the fixed bed hydrogenation technology, therefore generally can only use a kind of boiling bed hydrogenation catalyst in single reactor.Can reduce the efficient of reactor simultaneously, this can utilize two ebullated bed reactor series connection to be overcome.
USP6270654 discloses a kind of shortening process that adopts the multistage boiling bed reactor.It is 5-20wt% that this technique is used for the active metallic content that the catalyzer of the first step and second stage reactor contains, and the catalyzer pore volume is 0.4-1.2mL/g, and surface-area is 100-400m
2/ g, mean pore size is 8-25nm.Reactive metal is Mo-Co or the Mo-Ni(second stage).The every one-level of this multistage boiling bed reactor is only used a kind of boiling bed hydrogenation catalyst, concerning the same catalyzer, generally is not easy to adjust easily the distribution of macropore and aperture.Hydrogenation active metals component in macropore and aperture more can't be optimized and revised in addition, therefore can not be suitable for optimizing flexibly for the needed Hydrogenation of different pore size.
CN02109674.0 discloses a kind of Cascade boiling bed residual oil method of hydrotreating and equipment, uses microspheroidal hydrodemetallation (HDM), desulfurization, denitrification catalyst combination to carry out the residual hydrogenation reaction in a tandem ebullated bed reactor more than two sections.The tandem ebullated bed reactor has a plurality of conversion zones with independent catalyzer interpolation and relief outlet, every section is provided with the feed distributing plate of float valve structure and the three phase separation parts that are made of air guide, baffle member, gas-liquid division board and demister, in reactor, material can effectively carry out three-phase fluidization reaction and three phase separation, and can carry out catalyzer and replace online.Although this ebullated bed reactor and method have realized using multiple boiling-bed catalyst in a reactor, but use a large amount of inner members in reactor, cause on the one hand complex structure, equipment cost high, cause on the other hand the deficiencies such as the reactor volume utilization ratio is low, the increase of reactor scale, fluctuation of service.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of ebullated bed serial hydrogenation treatment process process, further improved the processing property of boiling bed residual oil hydroprocessing technique, improved hydrogenation activity level and flexibility of operation.
Boiling bed hydrogenation treatment process of the present invention comprises following content: use at least two boiling bed hydrogenation treatment reactor series connection, heavy raw oil and hydrogen enter first reactor from the bottom, react under the heavy raw oil hydroprocessing condition, reacting rear material is discharged first reactor from the top, mix with hydrogen and enter second reactor from the bottom, react under the heavy raw oil hydroprocessing condition, reacting rear material is discharged reactor from the top.Second interior mixed catalyst that uses at least two kinds of catalyzer of boiling bed hydrogenation treatment reactor, described two kinds of catalyzer are catalyzer C and catalyzer D, described catalyzer C and catalyzer D mixed volume are than being 1:(0.1～5), be preferably 1:(0.5～3), the mixed volume ratio that is catalyzer C and catalyzer D is 1:0.1 ~ 1:5, is preferably 1:0.5 ~ 1:3.
High 0.05 ~ the 0.1mmol/g of acid amount of the acid molar ratio catalyzer C of catalyzer D.The active metal oxide content of catalyzer D is higher than catalyzer C3～8 percentage point.
Use the mixed catalyst of a kind of catalyzer or two kinds of catalyzer in first boiling bed hydrogenation treatment reactor, the preferred mixed catalyst that uses at least two kinds of catalyzer, described two kinds of catalyzer are catalyst A and catalyst B, described catalyst A and catalyst B mixed volume are than being 1:(0.1～10), be preferably 1:(0.5～5), the mixed volume ratio that is catalyst A and catalyst B is 1:0.1 ~ 1:10, is preferably 1:0.5 ~ 1:5.Wherein the average pore volume of catalyst A is than the large 4～15nm of mean pore size of catalyst B.
Described catalyzer is boiling bed hydrogenation treatment catalyst.
Wherein the character of catalyst A is: catalyst specific surface is 80～200m
2/ g, bore dia〉pore volume in hole of 20nm accounts for 40% of total pore volume at least, is generally 40%～65%, and the average pore diameter of catalyzer is more than 20nm, to be preferably 22 ~ 40nm; By weight, catalyzer contains VI B family metal oxide (as MoO
3) 1.0%～10.0%, be preferably 1.5%～8.5%, contain group VIII metal oxide compound (as NiO or CoO) 0.1%～8.0%, preferably 0.5%～5.0%.
Wherein the character of catalyst B is: catalyst specific surface is 80～300m
2/ g, bore dia〉pore volume in hole of 20nm accounts for 20% of total pore volume at least, is generally 20%～45%, and the average pore diameter of catalyzer is more than 12nm, to be preferably 12 ~ 30nm; By weight, catalyzer contains VI B family metal oxide (as MoO
3) 1.0%～15.0%, be preferably 1.5%～13%, contain group VIII metal oxide compound (as NiO or CoO) 0.1%～8.0%, preferably 1.0%～5.0%.Can contain auxiliary agent, be selected from following several element: B, Ca, F, Mg, P, Si, Ti etc., auxiliary agent content is 0%～5.0%, the auxiliary element weighing scale.
Wherein the character of catalyzer C is: catalyst specific surface is 180～300m
2/ g, bore dia〉pore volume in 20nm hole accounts for 10% of total pore volume at least, is generally 10%～30%, and the average pore diameter of catalyzer is more than 9nm, to be preferably 9 ~ 15nm.Catalyzer contains VI B family metal oxide (as MoO
3) 3.0%～20.0%, be preferably 6.0%～18.0%, contain VIII family metal oxide (as NiO or CoO) 0.3%～8.0%, preferably 0.5%～5.0%.Contain at least a auxiliary agent, be selected from following several element: B, Ca, F, Mg, P, Si, Ti etc., auxiliary agent content is 0.5%～5.0%, auxiliary agent is in element wt.The acid amount of catalyzer C is 0.300 ~ 0.350mmol/g.
Wherein the character of catalyzer D is: catalyst specific surface is 100～250m
2/ g, bore dia〉pore volume in 20nm hole accounts for 10% of total pore volume at least, is generally 10%～20%, and the average pore diameter of catalyzer is more than 8nm, to be preferably 9 ~ 13nm.Catalyzer contains VI B family metal oxide (as MoO
3) 3.0%～25.0%, be preferably 8.0%～25.0%, contain VIII family metal oxide (as NiO or CoO) 1.0%～10.0%, preferably 1.0%～8.0%.Contain at least a auxiliary agent, be selected from following several element: B, Ca, F, Mg, P, Ti etc., auxiliary agent content is 0%～5.0%, the auxiliary element weighing scale.
Catalyst A, B, C, D are spherical, and diameter is 0.1～0.8mm, is preferably 0.1～0.6mm; Abrasion index≤2.0wt%.The carrier of catalyst A, B, C is Al
2O
3, the carrier of catalyzer D is Al
2O
3-SiO
2In catalyzer D, SiO
2Weight content is generally 10% ~ 50%, and preferably 10% ~ 30%.
In heavy raw material boiling bed hydrogenation treatment method of the present invention, heavy raw oil can be heavy oil, residual oil raw material arbitrarily, the general heavy hydrocarbon feedstocks that adopts boiling range＞500 ℃, contain sulphur, nitrogen, bituminous matter and a large amount of metal (as V, Fe, Ni, Ca, Na etc.) compound, metal content＞150 μ g/g.
In the inventive method, the volume of two ebullated bed reactors is preferably identical, the reaction effect that operational condition can reach according to character and the requirement of raw material is determined, reaction pressure is generally 8 ~ 25MPa, hydrogen to oil volume ratio is generally 100:1 ~ 1000:1, total liquid volume air speed (LHSV, the ratio of liquid phase feeding volume and the volume of total catalyst) is generally 0.1～5.0h
-1, the temperature of reaction of first ebullated bed reactor is generally 380～450 ℃, and the temperature of reaction of second reactor is generally 380～450 ℃.
In heavy raw material boiling bed hydrogenation treatment method of the present invention, ebullated bed reactor can adopt conventional ebullated bed reactor of the prior art, boiling bed hydrogenation reactor as described in CN02109404.7.
The present invention adopts catalyst A, the B of different physico-chemical properties to mix and catalyzer C, D mix the series connection use, the deficiency in the time of can making up independent the use.Restriction due to catalyst preparation technology, can not form the hydrogenation catalyst that satisfies different pore distributions and different activities Metal Distribution in the same catalyzer, the inventive method utilizes boiling-bed catalyst to be the characteristics of microsphere particle, catalyst mix of different nature is used, form the boiling bed hydrogenation processing reaction system of different pore distributions and different activities Metal Distribution on macroscopic view, improved the reaction effect of boiling bed hydrogenation processing reaction system.While is constant to keep hydrogenation activity because ebullated bed adds row's catalyzer online, can adjust as required the usage ratio of two kinds of catalyzer of each reactor, adapts to the variation of catalyst activity and the variation that processes raw material, and flexibility of operation improves greatly.The hydrogenation active metals of preferred catalyst A and catalyst B is used in conjunction with, make the combined reaction performance of reaction system improve, have higher metal removal activity and suitable asphaltenes conversion performance, preferred catalyzer C and catalyzer D are used in conjunction with, and have higher desulphurizing activated and bottoms conversion.
Embodiment
In boiling bed hydrogenation treatment process of the present invention, catalyst A, catalyst B and catalyzer C can adopt existing method preparation according to performance need, prepare as prior aries such as reference US7074740, US5047142, US4549957, US4328127, CN200710010377.5.Catalyzer D adopts the preparation method of CN200810010259.9.
The preparation process of boiling bed hydrogenation treatment catalyst is at first to prepare micro-spherical catalyst carrier, the hydrogenation active metals component that then adopts the pickling process load to need.The preparation process of support of the catalyst is as follows: the support of the catalyst feed product that humidity is suitable is made the particle of suitable size, and then with this particle spheroidizing, spherical carrier of catalyst is made in coccoid is dry, roasting.
The drying of support of the catalyst and roasting can be adopted condition well known to those skilled in the art, can adopt seasoning or dry under 80～150 ℃ as drying, and roasting is 600～1000 ℃ of roastings 1～6 hour.Pickling process supported active hydrogenation metal component can adopt method well known to those skilled in the art to carry out, and as the active metal salt wiring solution-forming with needs, with the solution impregnated catalyst carrier that contains active metal salt, then dry, roasting obtains final catalyzer.The drying process of catalyzer adopts seasoning or is dry under 60～150 ℃, and the roasting process of catalyzer was 400～600 ℃ of roastings 1～6 hour.
The raw material of boiling bed hydrogenation treatment catalyst microspheroidal carrier of the present invention can be determined according to requirements, for heavy, catalyst for hydrotreatment of residual oil carrier, suitable raw material is various aluminum oxide precursor, can add suitable additive to improve every character of carrier, additive commonly used such as carbon black, sesbania powder, starch, Mierocrystalline cellulose, polyvalent alcohol etc. in support material.Also can add as required hydrogenation active metals component and auxiliary agent, as one or more in tungsten, molybdenum, nickel, cobalt etc., auxiliary agent commonly used such as silicon, phosphorus, boron, fluorine, titanium, zirconium etc.The add-on of support of the catalyst auxiliary agent, additive, metal component is determined according to the service requirements of catalyzer.Catalyzer makes reactive metal and metal promoter change sulphided state into vulcanizing for before the heavy feed stock hydrogenation reaction, and sulfuration can be adopted vulcanization process known by the technical staff.
Further explain technical characterictic of the present invention and reaction effect below by embodiment, but be not limited to embodiment, percentage composition wherein by weight percentage.Specific surface area of catalyst, pore volume, can adopt N by several bore dias
2Determination of adsorption method.The catalyst acid amount adopts chemisorption (pyridine) and infrared spectroscopic determination, and instrument is the U.S. FIR-550 of Nicolet company type infrared spectrometer.
Embodiment 1
The catalyzer preparation
1. the preparation of catalyst A
The preparation spherical carrier of catalyst, mean pore size is 22nm, and the spherical catalyst particle is 0.3-0.4mm, and other catalyst preparation process is carried out with reference to US4328127 and CN200710010377.5.
Prepare according to a conventional method Mo-Ni solution, MoO in solution
3Content is that 6.00%, NiO content is 1.50%.Obtain final catalyst A with this solution by the above-mentioned carrier of incipient impregnation method dipping, its character is as shown in table 1.
2. the preparation of catalyst B
The preparation spherical carrier of catalyst, mean pore size is 15nm, and the spherical catalyst particle is 0.3-0.4mm, and other catalyst preparation process is carried out with reference to US7074740 and CN200710010377.5 method.
Prepare according to a conventional method Mo-Ni-P solution, MoO in solution
3Content is that 10.50%, NiO content is that 2.50%, P content is 1.00%.Obtain final catalyst B with this solution by the above-mentioned carrier of incipient impregnation method dipping, its character is as shown in table 1.
3. the preparation of catalyzer C
The preparation spherical carrier of catalyst, mean pore size is 11nm, and the spherical catalyst particle is 0.3-0.4mm, and other catalyst preparation process is carried out with reference to US7074740 and CN200710010377.5 method.
Prepare according to a conventional method Mo-Co-P solution, MoO in solution
3Content is that 13.00%, CoO content is that 2.50%, P content is 1.00%.Obtain final catalyzer C with this solution by the above-mentioned carrier of incipient impregnation method dipping, its character is as shown in table 1.
4. the preparation of catalyzer D
The preparation spherical carrier of catalyst, mean pore size is 10nm, and the spherical catalyst particle is 0.3-0.4mm, and catalyst preparation process adopts the preparation method of CN200810010259.9.
Prepare according to a conventional method Mo-Co-P solution, MoO in solution
3Content is that 16.00%, CoO content is that 2.60%, P content is 1.00%.Obtain final catalyzer D with this solution by the above-mentioned carrier of incipient impregnation method dipping, its character is as shown in table 1.
Embodiment 2
During in selection embodiment 1, the 1L autoclave is packed in by volume 1:1 ratio mixing of catalyst A and B into, under the existence of hydrogen, carry out vacuum residuum hydrotreatment test.Testing selected Vacuum Residue Properties is: 520 ℃ of boiling ranges
+, sulphur content is 2.8wt%, and metal (Ni+V+Fe) content is 357 μ g/g, and asphalt content is 6.8%.Test conditions is: 410 ℃ of temperature of reaction, and reaction pressure 13MPa, the reaction times is 0.5h, finish volume ratio 15 repeats above-mentioned condition and does several times more, removes by filter catalyzer and obtains generating oil.The generation oil that obtains several times and certain stock oil are mixed for the stock oil of catalyzer C and catalyzer D mixing evaluation.
During in selection embodiment 1, the 1L autoclave is packed in by volume 1:2 ratio mixing of catalyzer C and D into, under the existence of hydrogen, carry out the hydrotreatment test.Test adopts mixing oil character to be: sulphur content is 1.50wt%, and metal (Ni+V+Fe) content is 78 μ g/g, and asphalt content is 2.8%.Test conditions is: 420 ℃ of temperature of reaction, and reaction pressure 13MPa, the reaction times is 0.5h, finish volume ratio 15, evaluation result sees Table 2.
Embodiment 3
In embodiment 2, select catalyst A and by volume 1:8 ratio mixing of B in embodiment 1, other test conditions is constant, and evaluation result sees Table 2.
Embodiment 4
In embodiment 2, select catalyzer C and by volume 1:5 ratio mixing of D in embodiment 1, other test conditions is constant, and evaluation result sees Table 2.
Embodiment 5
In embodiment 2, in selection embodiment 1, catalyst A and B mix in the 1:2 ratio, and the change trial condition is: 420 ℃ of temperature of reaction, and reaction pressure 15MPa, the reaction times is 0.5h, the volume ratio of finish volume ratio 15(stock oil and catalyzer); Catalyzer C and D mix in the 1:0.5 ratio, and the change trial condition is: 435 ℃ of temperature of reaction, and reaction pressure 15MPa, the reaction times is 1h, finish volume ratio 15, evaluation result sees Table 2.
Comparative example
Select to adopt respectively single catalyst A and catalyzer C to carry out evaluation test in embodiment 1, other test conditions is with embodiment 2, and evaluation result sees Table 2.
The main physico-chemical property of table 1 embodiment catalyzer.
| Project | Catalyst A | Catalyst B | Catalyzer C | Catalyzer D |
| MoO 3, quality % | 5.98 | 10.15 | 13.15 | 15.86 |
| NiO(CoO), quality % | 1.45 | 2.36 | 2.17 | 2.42 |
| P, quality % | - | 1.01 | 0.98 | 0.92 |
| Wear index, quality % | ＜2.0 | ＜2.0 | ＜2.0 | ＜2.0 |
| Pore volume, mL/g | 0.68 | 0.68 | 0.67 | 0.35 |
| Specific surface, m 2/g | 123 | 180 | 239 | 134 |
| The appearance in 20nm hole accounts for total pore volume % | 53.22 | 29.81 | 13.51 | 20.38 |
| Mean pore size, nm | 22 | 15 | 11 | 10 |
| The catalyst acid amount, mmol/g | 0.213 | 0.289 | 0.321 | 0.441 |
Table 2 catalyst performance evaluation result.
| Project | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Comparative example |
| Ebullated bed one anti-/ two anti-processing condition | ? | ? | ? | ? | ? |
| Temperature/℃ | 405/415 | 405/415 | 405/415 | 420/430 | 410/420 |
| Pressure/MPa | 13 | 13 | 13 | 15 | 13 |
| Reaction times/h | 0.5/0.5 | 0.5/0.5 | 0.5/0.5 | 0.5/1.0 | 0.5/0.5 |
| The finish volume ratio | 15 | 15 | 15 | 15 | 15 |
| Relative hydrogenation activity * | ? | ? | ? | ? | ? |
| Desulfurization degree | 105 | 119 | 108 | 125 | 100 |
| Demetallization per * * | 104 | 102 | 105 | 141 | 100 |
| The asphaltenes conversion rate | 102 | 99 | 112 | 132 | 100 |
| 500 ℃+transformation efficiency | 110 | 115 | 126 | 158 | 100 |
* hydrogenation activity 100 calculating take the comparative example reactivity worth as benchmark.The * metal is (Ni+V+Fe).
As can be seen from the table: hydrogenation catalyst A, B with different physico-chemical properties mix and catalyzer C, D mixing series connection use, its hydrogenation activity uses than the series connection of single catalyst and all is improved at hydrogenating desulfurization, residual oil conversion aspect, has made up the deficiency when the single catalyst series connection is used.
Claims (10)
1. boiling bed hydrogenation treatment process, use at least two boiling bed hydrogenation treatment reactor series connection, heavy raw oil and hydrogen enter first reactor from the bottom, react under the heavy raw oil hydroprocessing condition, reacting rear material is discharged first reactor from the top, mix entering second reactor from the bottom with hydrogen, react under the heavy raw oil hydroprocessing condition, reacting rear material is discharged reactor from the top; It is characterized in that: second interior mixed catalyst that uses at least two kinds of catalyzer of boiling bed hydrogenation treatment reactor, second described two kinds of catalyzer of boiling bed hydrogenation treatment reactor is catalyzer C and catalyzer D, described catalyzer C and catalyzer D mixed volume are than being 1:0.1 ~ 1:5, high 0.05 ~ 0.1 mmol/g of acid amount of the acid molar ratio catalyzer C of catalyzer D, the active metal oxide content of catalyzer D is higher than catalyzer C3～8 percentage point; Described catalyzer is boiling bed hydrogenation treatment catalyst.
2. in accordance with the method for claim 1, it is characterized in that: the mixed catalyst that uses at least two kinds of catalyzer in first boiling bed hydrogenation treatment reactor, described two kinds of catalyzer are catalyst A and catalyst B, described catalyst A and catalyst B mixed volume are than being 1:0.1 ~ 1:10, and the mean pore size of catalyst A is than the large 4～15nm of mean pore size of catalyst B.
3. it is characterized in that in accordance with the method for claim 2: catalyst A and catalyst B mixed volume are than being 1:0.5 ~ 1:5; Catalyzer C and catalyzer D mixed volume are than being 1:0.5 ~ 1:3.
4. it is characterized in that in accordance with the method for claim 2: wherein the character of catalyst A is: catalyst specific surface is 80～200m
2/ g, bore dia〉pore volume in hole of 20nm accounts for 40% of total pore volume at least, and the average pore diameter of catalyzer is more than 20nm; By weight, catalyzer contains VI B family metal oxide 1.0%～10.0%, contains group VIII metal oxide compound 0.1%～8.0%; The character of catalyst B is: catalyst specific surface is 80～300m
2/ g, bore dia〉pore volume in hole of 20nm accounts for 20% of total pore volume at least, and the average pore diameter of catalyzer is more than 12nm; By weight, catalyzer contains VI B family metal oxide 1.0%～15.0%, contains group VIII metal oxide compound 0.1%～8.0%.
5. in accordance with the method for claim 2, it is characterized in that: the catalyst A bore dia pore volume in the hole of 20nm accounts for 40%～65% of total pore volume, the average pore diameter of catalyst A is 22 ~ 40nm; By weight, it is 1.5%～8.5% that catalyst A contains VI B family metal oxide, and containing the group VIII metal oxide compound is 0.5%～5.0%; The catalyst B bore dia〉pore volume in hole of 20nm accounts for 20%～45% of total pore volume, and the average pore diameter of catalyst B is 12 ~ 30nm; By weight, catalyst B contains VI B family metal oxide 1.5%～13%, and containing the group VIII metal oxide compound is 1.0%～5.0%.
6. it is characterized in that in accordance with the method for claim 1: the character of catalyzer C is: catalyst specific surface is 180～300m
2/ g, bore dia〉pore volume in 20nm hole accounts for 10% of total pore volume at least, and the average pore diameter of catalyzer is more than 9nm, and in catalyst weight, catalyzer contains VI B family metal oxide 3.0%～20.0%, contains VIII family metal oxide 0.3%～8.0%; The character of catalyzer D is: catalyst specific surface is 100～250m
2/ g, bore dia〉pore volume in 20nm hole accounts for 10% of total pore volume at least, and the average pore diameter of catalyzer is more than 8nm, and in catalyst weight, catalyzer contains VI B family metal oxide 3.0%～25.0%, contains VIII family metal oxide 1.0%～10.0%.
7. in accordance with the method for claim 1, it is characterized in that: catalyzer C bore dia the pore volume in 20nm hole accounts for 10%～30% of total pore volume, the average pore diameter of catalyzer C is 9 ~ 15nm, in catalyst weight, catalyzer C contains VI B family metal oxide 6.0%～18.0%, contains VIII family metal oxide 0.5%～5.0%; Catalyzer D bore dia〉pore volume in 20nm hole accounts for 10%～20% of total pore volume, and the average pore diameter of catalyzer D is 9 ~ 13nm, and in catalyst weight, catalyzer D contains VI B family metal oxide 8.0%～25.0%, contains VIII family metal oxide 1.0%～8.0%.
8. in accordance with the method for claim 3, it is characterized in that: catalyst A, catalyst B, catalyzer C and catalyzer D are spherical, and diameter is 0.1～0.8mm, and the carrier of catalyst A, catalyst B, catalyzer C is Al
2O
3, the carrier of catalyzer D is Al
2O
3-SiO
2
9. in accordance with the method for claim 8, it is characterized in that: in catalyzer D, by weight, SiO
2Content be 10% ~ 50%, preferably 10% ~ 30%.
10. in accordance with the method for claim 1, it is characterized in that: heavy raw oil hydrotreatment reaction pressure is 8 ~ 25MPa, and hydrogen to oil volume ratio is 100:1 ~ 1000:1, and total liquid volume air speed is 0.1～5.0h
-1, the temperature of reaction of first ebullated bed reactor is 380～450 ℃, the temperature of reaction of second reactor is 380～450 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104293389A (en) * | 2013-07-18 | 2015-01-21 | 中国石油化工股份有限公司 | Residual oil hydrogenation treatment method |
| CN104560138A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Fluidized bed heavy oil hydrotreating method |
| CN106947523A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of boiling bed residual oil hydrocracking process |
| CN107286988A (en) * | 2016-04-13 | 2017-10-24 | 中国石油化工股份有限公司 | A kind of process for handling poor ignition quality fuel |
| CN107286987A (en) * | 2016-04-13 | 2017-10-24 | 中国石油化工股份有限公司 | A kind of group technology for handling poor ignition quality fuel |
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| CN104293389A (en) * | 2013-07-18 | 2015-01-21 | 中国石油化工股份有限公司 | Residual oil hydrogenation treatment method |
| CN104293389B (en) * | 2013-07-18 | 2016-01-13 | 中国石油化工股份有限公司 | A kind of process for hydrogenating residual oil |
| CN104560138A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Fluidized bed heavy oil hydrotreating method |
| CN104560138B (en) * | 2013-10-22 | 2016-10-26 | 中国石油化工股份有限公司 | A kind of boiling bed heavy oil hydrogenation treatment method |
| CN106947523A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of boiling bed residual oil hydrocracking process |
| CN106947523B (en) * | 2016-01-07 | 2018-10-12 | 中国石油化工股份有限公司 | A kind of boiling bed residual oil hydrocracking process |
| CN107286988A (en) * | 2016-04-13 | 2017-10-24 | 中国石油化工股份有限公司 | A kind of process for handling poor ignition quality fuel |
| CN107286987A (en) * | 2016-04-13 | 2017-10-24 | 中国石油化工股份有限公司 | A kind of group technology for handling poor ignition quality fuel |
| CN107286988B (en) * | 2016-04-13 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of process handling poor ignition quality fuel |
| CN107286987B (en) * | 2016-04-13 | 2019-03-19 | 中国石油化工股份有限公司 | A kind of group technology handling poor ignition quality fuel |
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