CN101020843B - Hydrogenation process for producing catalytically cracked material - Google Patents
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Abstract
The hydrogenation process for producing catalytically cracked material includes the successive contacting and reaction of the mixture of material oil and hydrogen with hydrogenation protecting agent, residual oil hydrogenating and demetallizing agent and residual oil hydrogenating and desulfurizing agent, cooling the reaction resultants, and separating obtain hydrogen-rich liquid and gas products. The catalyst includes hydrogenation protecting agent in 2-10 vol%, residual oil hydrogenating and demetallizing agent in 5-70 vol%, and residual oil hydrogenating and desulfurizing agent 20-93 vol%. The present invention makes it possible to produce high quality catalytically cracked material via adding residual oil in 5-50 wt% into gas oil.
Description
Technical field
The invention belongs to a kind of method at the following refining hydrocarbon ils of the situation that has hydrogen, more particularly, is a kind of method of hydrotreating of producing catalytically cracked material.
Background technology
In recent years, along with rapid development of national economy, oil consumption presents the gesture of sharp increase, disparities between supply and demand are comparatively outstanding, and the heavy oil demand reduces day by day, and the light oil demand constantly increases, therefore in order sufficiently and reasonably to utilize petroleum resources, oil refining industry must develop to the deep processing direction.In order to improve the level of crude oil processing, increase yield of light oil, the heavy oil lighting just becomes oil refining industry at present and one of main task in the future.Catalytic cracking is one of most important crude oil secondary processing processing method, but at present along with the construction of more and more hydroeracking units, the contradiction that hydrocracking and catalytic cracking are contended over raw materials mutually occurred, causes the shortage of the main raw material vacuum gas oil of catalytic cracking.Meanwhile, along with the minimizing of oil fuel demand, residual oil is faced with the strong request of further processing.Therefore handle a part of residual oil with existing catalytic cracking unit, become one of effective ways that address the above problem.But owing to generally contain heavy metal and bituminous matters such as nickel, vanadium in the residual oil, can produce pollution and generate a large amount of coke cracking catalyst, so need carry out pre-treatment to residual oil raw material, to reduce in the raw material particularly sulphur, nitrogen, metal impurities content and to reduce carbon residue.
In addition, along with the strictness day by day of environmental regulation, more and more higher to the sulphur content requirement of gasoline products, China is lower than 150ppm in the Europe III emission standard of part city implementation with regard to the sulphur content that requires gasoline at present.Accounting at China's catalytically cracked gasoline about 80 weight % of gasoline total amount, also is the main source of sulfur in gasoline simultaneously.In order to produce doctor negative catalytically cracked gasoline, usually require the sulphur content in the catalytically cracked material to be lower than 0.30 heavy %, and the sulphur content of mixing the catalytically cracked material behind the residual oil weighs % usually above 2.0, after the sulfocompounds that therefore must will mix 80 weight % in the catalytically cracked material behind the residual oil remove, could satisfy this requirement.
US4534852 discloses a kind of hydrogenation pretreatment process of catalytically cracked material, this method can be handled residual oil and gas oil mixing raw material, wherein the ratio of residual oil is 5～60 volume %, mixing raw material carries out hydrogenation reaction successively with after two kinds of hydrogenation catalysts contact, and resultant of reaction obtains the catalytically cracked material of low-sulfur, low-metal content after separating.This method adopts two kinds of catalyst combination loading modes, and the catalyzer of top filling is compared with the catalyzer of bottom filling, and the active metallic content height, specific surface area is little, accumulation is big, phosphorus content is high.But the desulfurization degree of this method is lower, is 45～75 heavy %.
CN1100122C discloses a kind of method of gas oil inferior being carried out hydrotreatment production catalytic cracking charging; this method adopts the catalyst combination of a kind of hydrogenation protecting agent/hydrodemetallation (HDM) agent/Hydrobon catalyst; metal content, sulphur content, the nitrogen content of gas oil feedstocks inferior are reduced significantly, can satisfy the requirement of catalytic cracking unit charging.But the handled raw material of this method is the mixture of coker gas oil, deasphalted oil and vacuum gas oil, can not handle residual oil is mixed mixing raw material behind the gas oil.
CN1382776A discloses the method for a kind of residual hydrocracking and catalytically cracking heavy oil, this method is carried out hydrogenation reaction with residual oil at hydrotreater, the hydrogenated residue of gained enters catalytic cracking unit with optional vacuum gas oil and carries out cracking reaction, the heavy cycle oil of catalytic cracking returns hydrotreater, and the thing that steams that the distillation slurry oil obtains returns hydrotreater.This method is organically joined together two devices, residual oil, heavy cycle oil and slurry oil can be converted into light-end products.But this method needs residual hydrogenation equipment, so investment cost and process cost height.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of method of hydrotreating of producing catalytically cracked material.
Method provided by the invention comprises: the raw material oil-hydrogen mixture carries out the hydrotreatment reaction under the effect of hydrogenation catalyst; its resultant of reaction obtains hydrogen-rich gas and product liquid after refrigerated separation; described stock oil is the mixture of gas oil and residual oil; hydrogenation catalyst is by the hydrogenation protecting agent; residuum hydrogenating and metal-eliminating agent and residuum hydrodesulfurization agent are formed; with the integer catalyzer volume is benchmark; wherein hydrogenation protecting agent; the admission space percentage ratio of residuum hydrogenating and metal-eliminating agent and residuum hydrodesulfurization agent is respectively 2～10 volume %; 5～70 volume %, 20～93 volume %.
Method provided by the present invention can be mixed the residual oil of refining 5～50 heavy % in gas oil, produce the fine catalytically cracked material, has not only widened the catalytically cracked material source, has also improved the working depth of residual oil.Flow process of the present invention is simple, and is easy to operate, and investment cost and process cost are low, raw material impurity decreasing ratio height, and the device run stability is good, and running period is long.
Embodiment
Method provided by the invention is so concrete enforcement:
Enter hydrogenator behind stock oil and the hydrogen mixture and contact with hydrogenation catalyst, at hydrogen dividing potential drop 4.0～12.0MPa, preferred 6.0～11.0MPa, 330～420 ℃ of temperature of reaction, preferred 340～410 ℃, volume space velocity 0.1～1.5h
-1, preferred 0.2～1.2h
-1, hydrogen to oil volume ratio 100～1200Nm
3/ m
3, preferred 200～1000Nm
3/ m
3Reaction conditions under, carry out hydrodemetallation (HDM), removal of ccr by hydrotreating, hydrogenating desulfurization, hydrodenitrification and aromatic hydrocarbons saturated reaction.Its resultant of reaction obtains hydrogen-rich gas and product liquid after refrigerated separation, the hydrogen-rich gas of gained recycles as recycle hydrogen, and the gained product liquid is the fine catalytically cracked material.Hydrogenation catalyst is made up of hydrogenation protecting agent, residuum hydrogenating and metal-eliminating agent and residuum hydrodesulfurization agent; with the integer catalyzer volume is benchmark; the admission space percentage ratio of wherein hydrogenation protecting agent, residuum hydrogenating and metal-eliminating agent and residuum hydrodesulfurization agent is respectively 2～10 volume %; 5～70 volume %, 20～93 volume %.Best filling ratio is decided according to the performance of raw material oil properties, catalyzer and the conditions such as runtime of requirement.
The used stock oil of the present invention is the mixture of gas oil and residual oil, is benchmark with the weight of whole stock oil, and the weight percent of residual oil is 5～50 heavy %.Concrete intermingled dregs ratio example is decided according to the performance of raw material oil properties, catalyzer and the conditions such as runtime of requirement.Described gas oil is one or more the mixture in atmospheric gas oil, vacuum gas oil, coker gas oil and the deasphalted oil; Described residual oil is one or more the mixture in long residuum and the vacuum residuum.
Residual oil not only molecular weight is big, and its carbon residue, heavy metal, sulphur and nitrogen content are all far above vacuum gas oil, therefore these impurity can cause many adverse influences to catalytic cracking reaction, need carry out hydrotreatment to the catalytic cracking charging of mixing behind the slag, to reduce its foreign matter content.Carbon residue is represented the polycyclic aromatic hydrocarbon content in colloid and the bituminous matter of concentrating in the stock oil, and in catalytic cracking process, polycyclic aromatic hydrocarbons is attracted to catalyst surface, finally forms coke, makes the catalytic cracking catalyst inactivation.Heavy metal mainly refers to nickel and vanadium.Though nickel can not enter catalyzer inside, can not reduce activity of such catalysts, can promote dehydrogenation reaction and generate hydrogen that promote condensation reaction and generate polycyclic aromatic hydrocarbons and the final coke that generates, total effect reduces gasoline yield.Vanadium can enter catalyzer inside, and is oxidized to V
2O
5, V
2O
5Form eutectic with silicon, aluminium in the catalyzer, the latter is melted and saboteur's sieve structure under regeneration condition.Nitride can in and the acid site of catalytic cracking catalyst, cause catalyst deactivation.Sulfide influences quality product and generate SO in revivifier
X, contaminate environment.
At the above-mentioned characteristic of above-mentioned residual oil, the present invention has adopted comparatively rational catalyst filling grating scheme, has promptly adopted three kinds of catalyzer altogether, and filling is followed successively by hydrogenation protecting agent, residuum hydrogenating and metal-eliminating agent and residuum hydrodesulfurization agent in proper order.These three kinds of catalyzer heaps are followed successively by the residuum hydrodesulfurization agent than size〉the residuum hydrogenating and metal-eliminating agent〉the hydrogenation protecting agent; the pore volume size is followed successively by the hydrogenation protecting agent〉the residuum hydrogenating and metal-eliminating agent〉the residuum hydrodesulfurization agent, active size is followed successively by the residuum hydrodesulfurization agent〉the residuum hydrogenating and metal-eliminating agent〉the hydrogenation protecting agent.
Used hydrogenation protecting agent contains a kind of alumina supporter and the molybdenum and/or the tungsten that load on this alumina supporter among the present invention; and nickel and/or cobalt; gross weight with catalyzer is a benchmark; and in oxide compound; the content of molybdenum and/or tungsten is 1～10 heavy %, and the content of nickel and/or cobalt is 0.5～3 heavy %.Described aluminum oxide is a gama-alumina.Described alumina supporter has following pore distribution: bore dia be the pore volume of 100～200 dusts account for total pore volume 50～90%, bore dia be the pore volume of 200～1000 dusts account for total pore volume 5～30%, bore dia accounts for 5～40% of total pore volume greater than the pore volume of 1000 dusts, and all the other pore volumes are that diameter is occupied less than the hole of 100 dusts.The heap of this hydrogenation protecting agent is than 0.40～0.65g/cm
3, pore volume is not less than 0.50ml/g, preferably is not less than 0.60ml/g.This hydrogenation protecting agent has low coke content, low pore volume rate of descent, good activity stability and high intensity.Because metallic impurity, mechanical impurity, colloid and other particulate matter of mixing in the slag raw material are easy to be deposited between the outside surface and granules of catalyst of catalyzer, catalyst deactivation is caused in the blocking catalyst aperture on the one hand; On the other hand, cause bed pressure drop to rise again, make full scale plant frequent shutdowns and catalyst changeout more, this will reduce the utilization ratio of full scale plant greatly, cause bigger financial loss to enterprise.Therefore at the top loading of reactor big, the active very low hydrogenation protecting agent of pore volume, can remove the foulant in the raw material, reach the purpose of protection Primary Catalysts.
Used residuum hydrogenating and metal-eliminating agent contains a kind of alumina supporter and the molybdenum and/or the tungsten that load on this carrier among the present invention, and nickel and/or cobalt, gross weight with catalyzer is a benchmark, and in oxide compound, the content of molybdenum and/or tungsten is 0.5～18 heavy %, the content of nickel and/or cobalt is 0.3～8 heavy %, and the pore distribution of this carrier is that bore dia is that the pore volume of 100-200 dust accounts for 70% to 98% of total pore volume.The heap of this residuum hydrogenating and metal-eliminating agent is than 0.45～0.70g/cm
3, pore volume is not less than 0.45ml/g, preferably is not less than 0.55ml/g.This residuum hydrogenating and metal-eliminating agent can remove heavy metal such as nickel, vanadium in the raw material, owing to stoped these heavy metal depositions to the residuum hydrodesulfurization agent in downstream effectively, thus guarantee the hydrogenation activity of residuum hydrodesulfurization agent and prolong its life cycle.Loaded big, the active lower residuum hydrogenating and metal-eliminating agent of pore volume at protectant rear portion; it can not only remove the metallic impurity in the charging; and can also as much as possiblely hold these impurity, thereby delay the lift velocity of beds pressure drop and the autocatalysis agent is active underspeeds.
Used residuum hydrodesulfurization agent contains a kind of carrier and the molybdenum and/or the tungsten that load on this carrier among the present invention, and nickel and/or cobalt, gross weight with catalyzer is a benchmark, and in oxide compound, the content of molybdenum and/or tungsten is 8～20 heavy %, the content of nickel and/or cobalt is 0.3～8 heavy %, and carrier is aluminum oxide and optional silicon oxide.The pore distribution of this carrier is that diameter is that the pore volume of 60～100 dusts accounts for 75～98% of total pore volume.The heap of this residuum hydrodesulfurization agent is than 0.50～0.75g/cm
3, pore volume is not less than 0.40ml/g, preferably is not less than 0.50ml/g.Loaded less, the active higher residuum hydrodesulfurization agent of this pore volume in the back of residuum hydrogenating and metal-eliminating agent, it can remove sulfur-bearing, nitrogen compound, colloid and bituminous matter in the residual oil effectively, sulfur-bearing, nitrogen compound in also can effective elimination gas oil.This residuum hydrodesulfurization agent promptly has high desulphurizing activated, also has stronger demetalization, holds metal ability and the higher carbon residue performance of taking off.
Catalytically cracked material is carried out the hydrogenation pre-treatment have following advantage: by aromatic hydrocarbons and the alkene that contains in the saturated raw material of hydrofining energy, improve the hydrogen richness of catalytically cracked material, thereby reduce the growing amount of coke in the catalytic cracking process effectively, improve the cracking performance of catalytic cracking charging, reduce the Hydrocarbon Content by Catalytic Cracking Operation severity, improve the product distribution and improve the purpose product selectivity.By hydrofining the sulphur content of catalytically cracked material is descended, thereby the sulphur content of catalytic cracking product is descended, become the clean fuel that reaches the low sulfur content standard-required.In addition, again because the sulphur and the nitrogen content of catalytically cracked material are lower,, produce the contained SO of flue gas in the catalyst regeneration process so generate the sulphur and the nitrogen content of coke on the cracking catalyst surface also lower
xAnd NO
xCan significantly descend, reduce pollution environment.
Advantage of the present invention is:
1, the present invention can make existing catalytic cracking unit mix the residual oil of refining 5～50 heavy %, has widened the catalytically cracked material source, has alleviated the contradiction that hydrocracking and catalytic cracking are contended over raw materials, and has improved the working depth of residual oil simultaneously.
2, flow process of the present invention is simple, and is easy to operate, be applicable to newly-built, at the wax oil medium-pressure hydrocracking treatment unit of building or having built, for the device of having built, as long as can realize by simple transformation.Method provided by the invention is compared with existing residual hydrocracking technology, and pressure is low, volume space velocity is high, and cost of investment and running cost are low
3, raw material impurity decreasing ratio height of the present invention, the device run stability is good, and running period is long, can be up to 2 years.Because the present invention adopts catalyzer and the rational catalyst grating mode that is fit to handle residual oil raw material, can give full play to catalyzer activity separately, can avoid catalyzer heavy metal poisoning, bed coking again, and the speed that rises of delayed response device pressure drop, thereby quality product height, device are long running period.
The following examples will give further instruction to the present invention, but therefore not limit the present invention.
Used raw material is the mixing oil of gas oil and residual oil among the embodiment, wherein gas oil 1 is decompression three-way distillate (hereinafter to be referred as subtracting three), gas oil 2 is two kinds and subtracts three mixture, residual oil is vacuum residuum, the main character of gas oil and residual oil is as shown in table 1, and the main character of mixing oil is as shown in table 2.
The trade names of the hydrogenation protecting agent of being adopted among the embodiment, residuum hydrogenating and metal-eliminating agent and residuum hydrodesulfurization agent are respectively RG-10B, RDM-2 and RMS-1, and its composition and physico-chemical property are as shown in table 3.More than several catalyzer be the catalyst plant production of Sinopec catalyst Co. Chang Ling.
Embodiment 1
The used stock oil A of present embodiment is the mixing raw material of gas oil 1 and residual oil, and wherein residual oil accounts for 15 heavy % of raw material gross weight, and the main character of stock oil A is as shown in table 2.Stock oil A with enter hydrogenator after hydrogen mixes, contact hydrogenation protecting agent, residual oil catalyst for demetalation and slag oil desulfurization catalyzer successively and react, its resultant of reaction obtains hydrogen-rich gas and product liquid after refrigerated separation.With the integer catalyzer volume is benchmark, and the admission space percentage ratio of wherein hydrogenation protecting agent, residuum hydrogenating and metal-eliminating agent and residuum hydrodesulfurization agent is respectively 5 volume %, 20 volume % and 75 volume %.The reaction conditions of present embodiment and product liquid character are as shown in table 4.
As can be seen from Table 4, the sulphur content of product liquid is 0.29 heavy %, and carbon residue is 1.65 heavy %, and nickel content is 1.2ppm, and content of vanadium is 1.5ppm, illustrates that this product liquid is the high quality raw material of catalytic cracking.
Embodiment 2
The used stock oil B of present embodiment is the mixing raw material of gas oil 2 and residual oil, and wherein residual oil accounts for 10 heavy % of raw material gross weight, and the main character of stock oil B is as shown in table 2.Stock oil B with enter hydrogenator after hydrogen mixes, contact hydrogenation protecting agent, residual oil catalyst for demetalation and slag oil desulfurization catalyzer successively and react, its resultant of reaction obtains hydrogen-rich gas and product liquid after refrigerated separation.With the integer catalyzer volume is benchmark, and the admission space percentage ratio of wherein hydrogenation protecting agent, residuum hydrogenating and metal-eliminating agent and residuum hydrodesulfurization agent is respectively 5 volume %, 45 volume % and 50 volume %.The reaction conditions of present embodiment and product liquid character are as shown in table 4.
As can be seen from Table 4, the sulphur content of product liquid is 0.29 heavy %, and carbon residue is 0.8 heavy %, and nickel content is 0.7ppm, and content of vanadium is 0.8ppm, illustrates that this product liquid is the high quality raw material of catalytic cracking.
Table 1
| The stock oil title | Gas oil 1 | Gas oil 2 | Residual oil |
| Density (20 ℃), g/cm 3 | 0.9320 | 0.9334 | 1.0108 |
| The stock oil title | Gas oil 1 | Gas oil 2 | Residual oil |
| Viscosity (100 ℃), mm 2/s | 10.54 | 12.30 | 638.0 |
| Carbon residue, heavy % | 0.66 | 0.52 | 19.2 |
| Sulphur, heavy % | 3.1 | 3.1 | 4.3 |
| Nitrogen, heavy % | 0.12 | 0.13 | 0.26 |
| Carbon, heavy % | 85.49 | 85.15 | 84.85 |
| Hydrogen, heavy % | 11.97 | 11.86 | 10.48 |
| Metal content, ppm | |||
| Nickel | 0 | 0 | 22.9 |
| Vanadium | 0 | 0 | 75.6 |
| Four components, heavy % | |||
| Stable hydrocarbon | 56.4 | 56.6 | 15.7 |
| Aromatic hydrocarbons | 39.4 | 40.2 | 53.5 |
| Colloid | 4.1 | 3.2 | 24.7 |
| Bituminous matter (C 7Insolubles) | 0.1 | 0 | 6.1 |
Table 2
| The mixing oil title | A | B |
| The gas oil ratio, heavy % | 85 (gas oils 1) | 90 (gas oils 2) |
| The residual oil ratio, heavy % | 15 | 10 |
| Density (20 ℃), g/cm 3 | 0.9438 | 0.9566 |
| Viscosity (100 ℃), mm 2/s | 16.48 | 15.8 |
| Carbon residue, heavy % | 3.4 | 2.3 |
| Sulphur, heavy % | 2.7 | 3.2 |
| Nitrogen, heavy % | 0.14 | 0.14 |
| Carbon, heavy % | 85.39 | 85.12 |
| Hydrogen, heavy % | 11.75 | 11.72 |
| Metal content, ppm | ||
| Nickel | 3.4 | 2.4 |
| Vanadium | 11.3 | 8.0 |
| Four components, heavy % | ||
| Stable hydrocarbon | 50.3 | 52.5 |
| Aromatic hydrocarbons | 41.5 | 41.5 |
| Colloid | 7.2 | 5.3 |
| Bituminous matter (C 7Insolubles) | 1.0 | 0.6 |
Table 3
| The catalyzer trade name | RG-10B | RDM-2 | RMS-1 |
| Chemical constitution, heavy % | |||
| Nickel oxide | 1.5 | 1.7 | - |
| Cobalt oxide | - | - | 4.5 |
| Molybdenum oxide | 6.2 | 8.1 | 13.5 |
| Physical properties: | |||
| Specific surface area, m 2/g | 150 | 140 | 260 |
| Pore volume, ml/g | 0.68 | 0.60 | 0.55 |
| The catalyzer trade name | RG-10B | RDM-2 | RMS-1 |
| Crushing strength, N/mm | The 25N/ grain | 16 | 12 |
| External diameter, mm | 4.6 | 1.1 | 1.1 |
| Shape | Raschig ring | The butterfly type | The butterfly type |
| The heap specific density, g/cm 3 | 0.50 | 0.55 | 0.65 |
Table 4
| Numbering | Embodiment 1 | Embodiment 2 |
| Reaction conditions | ||
| The hydrogen dividing potential drop, MPa | 10.0 | 8.0 |
| Temperature of reaction, ℃ | 382 | 385 |
| Volume space velocity, h -1 | 0.5 | 0.5 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 700 | 700 |
| Product liquid character: | ||
| Density (20 ℃), g/cm3 | 0.8964 | 0.9061 |
| Carbon residue, heavy % | 1.65 | 0.80 |
| Sulphur, heavy % | 0.29 | 0.29 |
| Nitrogen, heavy % | 0.08 | 0.11 |
| Hydrogen, heavy % | 12.74 | 12.50 |
| Metal content, ppm | ||
| Nickel | 1.2 | 0.7 |
| Vanadium | 1.5 | 0.8 |
Claims (7)
1. method of hydrotreating of producing catalytically cracked material, the raw material oil-hydrogen mixture carries out the hydrotreatment reaction under the effect of hydrogenation catalyst, its resultant of reaction obtains hydrogen-rich gas and product liquid after refrigerated separation, it is characterized in that described stock oil is the mixture of gas oil and residual oil, hydrogenation catalyst is by the hydrogenation protecting agent, residuum hydrogenating and metal-eliminating agent and residuum hydrodesulfurization agent are formed, with the integer catalyzer volume is benchmark, wherein hydrogenation protecting agent, the admission space percentage ratio of residuum hydrogenating and metal-eliminating agent and residuum hydrodesulfurization agent is respectively 2～10 volume %, 5～70 volume %, 20～93 volume %; The reaction conditions of described hydrotreatment is: hydrogen dividing potential drop 4.0～12.0MPa, 330～420 ℃ of temperature of reaction, hydrogen to oil volume ratio 100～1200Nm
3/ m
3, volume space velocity 0.1～1.5h
-1
2. in accordance with the method for claim 1, it is characterized in that described gas oil is one or more the mixture in atmospheric gas oil, vacuum gas oil, coker gas oil and the deasphalted oil; Described residual oil is one or more the mixture in long residuum and the vacuum residuum.
3. in accordance with the method for claim 1, it is characterized in that in the described stock oil, is benchmark with the weight of whole stock oil, and the weight percent of residual oil is 5～50 heavy %.
4. in accordance with the method for claim 1, it is characterized in that the reaction conditions of described hydrotreatment is: hydrogen dividing potential drop 6.0～11.0MPa, 340～410 ℃ of temperature of reaction, hydrogen to oil volume ratio 200～1000Nm
3/ m
3, volume space velocity 0.2～1.2h
-1
5. in accordance with the method for claim 1; it is characterized in that described hydrogenation protecting agent contains a kind of alumina supporter and the molybdenum and/or the tungsten that load on this alumina supporter; and nickel and/or cobalt; gross weight with catalyzer is a benchmark; and in oxide compound; the content of molybdenum and/or tungsten is 1～10 heavy %, and the content of nickel and/or cobalt is 0.5～3 heavy %.
6. in accordance with the method for claim 1, it is characterized in that described residuum hydrogenating and metal-eliminating agent contains a kind of alumina supporter and the molybdenum and/or the tungsten that load on this carrier, and nickel and/or cobalt, gross weight with catalyzer is a benchmark, and in oxide compound, the content of molybdenum and/or tungsten is 0.5～18 heavy %, and the content of nickel and/or cobalt is 0.3～8 heavy %, and the pore distribution of this carrier is that bore dia is that the pore volume of 100-200 dust accounts for 70% to 98% of total pore volume.
7. in accordance with the method for claim 1, it is characterized in that described residuum hydrodesulfurization agent contains a kind of carrier and the molybdenum and/or the tungsten that load on this carrier, and nickel and/or cobalt, gross weight with catalyzer is a benchmark, and in oxide compound, the content of molybdenum and/or tungsten is 8～20 heavy %, and the content of nickel and/or cobalt is 0.3～8 heavy %, and carrier is aluminum oxide and optional silicon oxide.
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| CN101928601B (en) * | 2009-06-25 | 2014-04-30 | 中国石油化工股份有限公司 | Processing method for catalytic cracking heavy oil |
| CN102311793A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Catalytic cracking material pretreatment method |
| CN103374392B (en) * | 2012-04-13 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of hydrogenation modification method of catalytically cracked stock |
| CN103374402B (en) * | 2012-04-13 | 2015-05-20 | 中国石油化工股份有限公司 | Hydro-upgrading method of catalytic cracking raw oil |
| CN107345158B (en) * | 2016-05-05 | 2019-07-23 | 中国石油化工股份有限公司 | A kind of heavy oil hydrogenation treatment method |
| CN107794086B (en) * | 2016-09-07 | 2019-09-24 | 中国石油化工股份有限公司 | A kind of hydrocarbons hydrogenation deferrization system and method |
| US10954457B2 (en) * | 2019-02-13 | 2021-03-23 | Saudi Arabian Oil Company | Methods including direct hydroprocessing and high-severity fluidized catalytic cracking for processing crude oil |
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| CN1313379A (en) * | 2000-03-10 | 2001-09-19 | 中国石油化工集团公司 | Process for hydrogenating poor-quality raw material for catalytic cracking |
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| CN1313379A (en) * | 2000-03-10 | 2001-09-19 | 中国石油化工集团公司 | Process for hydrogenating poor-quality raw material for catalytic cracking |
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