CN102161910B - Method for producing high-quality diesel by using heavy crude oil - Google Patents
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Abstract
The invention discloses a method for producing high-quality diesel by using heavy crude oil. A reaction part has two reaction regions, wherein the first reaction region is filled with a hydrogenation protector, a hydrogenation demetalizing agent, a hydrogenation desulfurizer I and a hydrogenation cracking agent in turn from top down; and the second reaction region is filled with a hydrogenation desulfurizer II. The product of the hydrogenation reaction is cooled, separated and distilled to form gases, a gasoline distillate, a diesel distillate and normal-pressure residual oil; and a minor part of the normal-pressure residual oil is pumped out of the device and a major part of the normal-pressure residual oil is circulated to the entrance of a hydrogenation reactor. According to the method provided by the invention, rich natural gas resources near oil fields can be used as cheap hydrogen production raw materials, heavy crude oil with an API (American Petroleum Institute) gravity of smaller than 20 can be converted into high-quality gasoline and diesel, infinite oil resource can be fully utilized, and high economic benefit can be creased.
Description
Technical field
The invention belongs to a kind of is the cleavage method that obtains lower boiling hydrocarbon ils in the situation that there is hydrogen, more particularly belongs to a kind of method that heavy crude oil hydrocracking is produced high-quality diesel.
Background technology
The relative density size of crude oil, very large for the impact of its exploitation, accumulating and tooling cost, directly have influence on economic benefit.On international petroleum market, crude oil is fixed the price according to the quality, and relative density is an important indicator of its quality of reflection.The international weight of being commercially accustomed to representing with API degree crude oil, the relation of it and relative density is:
From formula, less its corresponding API degree of relative density is larger, and heavier crude oil its API degree is less.Heavy crude typically refers to density and is greater than 0.934g/cm
3, the crude oil that API degree is less than 20.
The unconventional heavy crude resource such as viscous crude and tar sand is abundanter in the world.According to estimates, approximately 4,000 hundred million tons of global viscous crude and tar sand reserves, be 2.7 times of conventional crude workable reserve.And at present, most conventional crudes have dropped into exploitation, and recovery percent of reserves is relatively high.Estimate that conventional crude output, by reach peak value in from now on 15～20 years, then enters period of depletion.But along with the development of world economy especially economics of underdevelopment, energy-output ratio presents increase by a relatively large margin.According to USDOE Information Management Bureau prediction, between nineteen ninety-five to 2015 year, world energy consumption amount will increase by 54%.Wherein the developing country in Asia will increase by 129%.The huge breach of the energy will mainly rely on the unconventional heavy crude such as viscous crude to make up.To mid-term 21 century, unconventional heavy crude output will account for the over half of crude oil ultimate production.Also that's about the size of it for the domestic situation of China, and the Bohai Sea crude oil of recent development, Tahe Crude Oil are all unmanageable unconventional heavy crude.So the task that the processing of China heavy crude faces is how from the heavy crude such as viscous crude, deep processing, the clean petroleum products that meets environmental requirement of production maximum.
Heavy crude particularly viscosity of thickened oil is very large, and contains a large amount of sulphur, nitrogen and metallic compound, is therefore difficult to carry and refining.Heavy oil transportation is to the processing of downstream refinery, often also uneconomical, therefore should consider viscous crude to be processed into synthetic crude near oil field or well head.Viscous crude is processed near oil field or well head, can adopt hydrogenation technique, because there is abundant natural gas source to can be used as the raw material of hydrogen manufacturing near oil field.Viscous crude adopts hydrogenation technique processing, and synthetic crude yield can be greater than 100%.Near oil field, adopting hydrogenation technique processing viscous crude, is in fact that abundant Sweet natural gas and the viscous crude in oil field is converted into oils.
US4427535 has introduced a kind of method that realizes heavy oil high conversion by hydrocracking.The method adopts ebullated bed technology, can process asphaltenes 10%～28%, and the heavy crude inferior of carbon residue 12%～35%, as Canadian cold air lake crude oil and Lloydminster crude oil.At 404 ℃～446 ℃ of temperature of reaction, reaction pressure 14.2MPa～21.1MPa, volume space velocity 0.25h
-1～5.0h
-1condition under, can reach the high conversion of 65 volume %～80 volume %.
CN1756831A has introduced a kind of method of catalytic hydrofinishing crude oil, the method is carried out catalytic hydrofinishing to untreated crude oil or topped crude, comprise hydrodemetallation (HDM), hydrocracking and hydrogenating desulfurization, it is characterized in that hydrocracking catalyst used comprises a kind of carrier, this carrier is by comprising zeolite and making at ultra-fine titanium family metal oxide particle and the matrix material of zeolite gap internal surface, this catalyzer also comprises a kind of catalytic active component being carried on carrier, and this component is at least one element that is selected from periodictable the 6th, 8,9 He10 family metals.The method is at hydrogen dividing potential drop 13.2MPa, hydrogen-oil ratio 550Nm
3/ m
3, 380 ℃ of metal remover temperature of reaction, 400 ℃ of cracking agent temperature of reaction, 360 ℃ of reactive desulfurizing agent temperature, liquid hourly space velocity 0.408h
-1condition under, can be by the density of Arabic heavy crude by 0.892g/cm
3(API degree 27.1) is reduced to 0.808g/cm
3(API degree 43.6).
Summary of the invention
The object of the invention is to provide on the basis of existing technology a kind of heavy crude oil hydrocracking to produce the method for high-quality diesel.
Method provided by the invention comprises: in reactive moieties, two reaction zones are set; the first reaction zone is loaded hydrogenation protecting agent, hydrodemetallation (HDM) agent, hydrogen desulfurization agent I and hydrocracking agent from top to bottom successively; second reaction zone filling hydrogen desulfurization agent II; the temperature of reaction of the first reaction zone than the temperature of reaction of second reaction zone high 15 ℃～40 ℃; that hydrogenation reaction resultant carries out is cooling, separation and fractionation; obtain gas, gasoline fraction, diesel oil distillate and long residuum; described long residuum part withdrawing device, remainder loops back hydrogenator entrance.In mass, the amount of described long residuum withdrawing device is 3%～20%.
The API degree of heavy crude of the present invention is less than or equal to 20.Described heavy crude can be one or more in viscous crude, super viscous crude, special viscous crude, shale oil, asphalt oil sand, liquefied coal coil.
High-sulfur heavy crude enters hydrogenator after mixing with long residuum from the bottom of atmospheric tower together with hydrogen in the present invention, carries out hydrogenation reaction successively through the first reaction zone and second reaction zone.Each reaction zone can be that a bed can be also an independent reactor.The reaction conditions of described hydrogenation reaction is: hydrogen dividing potential drop 4.0MPa～22.0MPa, 330 ℃～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300Nm
3/ m
3～2000Nm
3/ m
3, volume space velocity 0.1h
-1～2.0h
-1.The reaction conditions of preferred hydrogenation reaction is: hydrogen dividing potential drop 6.0MPa～19.0MPa, 340 ℃～440 ℃ of temperature of reaction, hydrogen to oil volume ratio 400Nm
3/ m
3～1800Nm
3/ m
3, volume space velocity 0.15h
-1～1.5h
-1.Hydrogenation reaction resultant enters high-pressure separator and carries out gas-liquid separation after cooling, obtains hydrogen-rich gas and product liquid, and hydrogen-rich gas loops back hydrogenator, and product liquid enters atmospheric tower distillation and obtains gas, gasoline fraction, diesel oil distillate and long residuum.Gasoline fraction and diesel oil distillate be as the finished product take-off equipment, long residuum small part take-off equipment, and major part loops back after hydrogenator entrance mixes with crude oil and enters hydrogenator.
Take integer catalyzer as benchmark, and by volume, the filling percentage ratio of described hydrogenation protecting agent, hydrodemetallation (HDM) agent, hydrogen desulfurization agent I, hydrocracking agent and hydrogen desulfurization agent II is respectively 5%～20%; 20%～65%; 20%～65%, 5%～40%, 5%～40%.
Under the hydroprocessing condition comparatively harsh, the metallic impurity in heavy crude, mechanical impurity, colloid and other particulate matter are easily deposited between the outside surface and granules of catalyst of catalyzer, and blocking catalyst aperture, causes catalyst deactivation on the one hand; On the other hand, cause again bed pressure drop to rise, make full scale plant frequent shutdowns and catalyst changeout more, this causes larger financial loss by the utilization ratio ，Gei enterprise that greatly reduces full scale plant.Therefore, first the present invention loads relatively large, the active relatively minimum hydrogenation protecting agent of pore volume, and the foulant in energy effective elimination raw material, reaches the object of protecting Primary Catalysts, guarantees hydrotreater long-time running.
Described hydrogenation protecting agent contains a kind of alumina supporter and loads on molybdenum and/or the tungsten on this alumina supporter; and nickel and/or cobalt; the gross weight of catalyzer of take is benchmark; and in oxide compound; the content of molybdenum and/or tungsten is 1 % by weight～10 % by weight, and the content of nickel and/or cobalt is 0.5 % by weight～3 % by weight.This hydrogenation protecting agent has low coke content, good activity stability and high intensity.
Because the metal content such as nickel and vanadium in heavy crude is high, therefore need to load a certain amount of hydrodemetallation (HDM) agent.Described hydrodemetallation (HDM) agent can not only remove the metallic impurity such as nickel in crude oil, vanadium; thereby effectively stop these heavy metal depositions to the catalyzer in downstream; the hydrogenation activity of downstream catalyst and life cycle have all been played to provide protection; and can also as much as possiblely hold these impurity, thereby delay the lift velocity of beds pressure drop and underspeeding of autocatalysis agent activity.
Described hydrodemetallation (HDM) agent contains a kind of alumina supporter and loads on molybdenum and/or the tungsten on this carrier, and nickel and/or cobalt, the gross weight of catalyzer of take is benchmark, and in oxide compound, the content of molybdenum and/or tungsten is 0.5 % by weight～18 % by weight, the content of nickel and/or cobalt is 0.3 % by weight～8 % by weight, and the pore distribution of this carrier is that bore dia is that the pore volume of 100～200 dusts accounts for 70% to 98% of total pore volume.
Hydrogen desulfurization agent I of the present invention and hydrogen desulfurization agent II can be same catalyzer, can be also the different catalysts with said function.Sulfocompound in hydrogen desulfurization agent I and hydrogen desulfurization agent II energy effective elimination stock oil, and part nitrogenous compound.Described hydrogen desulfurization agent I and hydrogen desulfurization agent II contain a kind of carrier and load on molybdenum and/or the tungsten on this carrier, and nickel and/or cobalt, the gross weight of catalyzer of take is benchmark, and in oxide compound, the content of molybdenum and/or tungsten is 8 % by weight～20 % by weight, the content of nickel and/or cobalt is 0.3 % by weight～8 % by weight, and carrier is aluminum oxide and optional silicon oxide, and 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 present invention has adopted has the more hydrocracking catalyst of high desulfurization activity and de-carbon residue activity.Described hydrocracking catalyst is to contain carrier and load on hydrogenation activity component on this carrier and the IVB family metal component in the periodic table of elements, described catalyzer, wherein, the total amount of catalyzer of take is benchmark, the content of described carrier is 5 % by weight～90 % by weight, in oxide compound, the content of described hydrogenation activity component is 5 % by weight～60 % by weight, and the content of described IVB family metal component is 0.5 % by weight～40 % by weight.
The carrier of described hydrocracking catalyst has pore structure, the aperture, most probable hole of this pore structure is in 6～14 nanometers, preferred 6～10 nanometers, aperture concentration degree is more than 7, preferably 7～9, described aperture concentration degree refers at specific pore volume and amasss the differential in aperture in the distribution curve with aperture, the ratio of peak height and halfwidth.
Aperture, described most probable hole refers to: the pore structure that adopts BET method or mercury penetration method measure sample, can obtain specific pore volume and amass to the differential in aperture (dV/dr) distribution curve with aperture, the corresponding specific pore volume in certain aperture is long-pending is illustrated near the corresponding pore volume in hole in this aperture to the differential in aperture (dV/dr), and wherein maximum aperture, the corresponding hole of dV/dr is called aperture, most probable hole.Wherein, the long-pending measuring method of BET method, mercury penetration method and specific pore volume is known to the skilled person, for example can adopt < < commercial catalysts analytical test to characterize > > (Sinopec press, nineteen ninety first version, the volumes such as Liu Xiyao, the structure determination of chapter 2 catalyst pores) the middle method of recording.
Aperture concentration degree refers at specific pore volume and amasss the differential in aperture in the distribution curve with aperture, the ratio of peak height and halfwidth.The ratio of peak height and halfwidth is larger, shows that the intensity in aperture is higher.
Described IVB family metal component is preferably titanium and/or zirconium, more preferably titanium and zirconium, and in oxide compound, the weight ratio of titanium and zirconium can be 1: 0.1-10, is preferably 1: 0.2-5.When DangIVB family metal component is titanium and zirconium, can further improve the hydrogenation activity of catalyzer.The existence form of described IVB family metal component is preferably the oxide compound of IVB family metal.
Described hydrogenation activity component can be conventional hydrogenation activity component, for example, can comprise the oxide compound of VIII family metal and the oxide compound of group vib metal.The oxide compound of described VIII family metal is preferably the oxide compound of nickel, and the oxide compound of described group vib metal is preferably the oxide compound of molybdenum and the oxide compound of tungsten, and the weight ratio of the oxide compound of the oxide compound of nickel, the oxide compound of molybdenum and tungsten can be 1: 0.1-10: 1-50.
Described carrier can be the conventional carrier of preparing hydrocracking catalyst that is used as.Described carrier can comprise heat-resistant inorganic oxide.Described carrier can also comprise molecular sieve, and the weight ratio of heat-resistant inorganic oxide and molecular sieve can be 1: 0.1-5.
Compare with existing hydrocracking catalyst, the aperture less (aperture, most probable hole is little) of the carrier of hydrocracking catalyst provided by the invention and distribute concentrated (aperture concentration degree is high), the de-carbon residue performance of the hydrogenating desulfurization of catalyzer and hydrogenation has obtained significant raising.
Advantage of the present invention:
1, the present invention utilizes near the abundant natural gas source in oil field as cheap hydrogen feedstock, heavy crude is converted into gasoline and the diesel oil of high-quality, takes full advantage of limited petroleum resources, can be that refinery creates higher economic benefit.
2, the preferred hydrocracking agent of the present invention activity is high, can process API degree lower, the heavy crude that foreign matter content is higher.
3, hydrogenation catalyst grading method provided by the present invention, has farthest brought into play the function of various catalyzer, and the foulant in can effective elimination raw material reaches the object of protection Primary Catalysts, guarantees hydrogenation unit long-time running.
Accompanying drawing explanation
Accompanying drawing is the method flow schematic diagram that a kind of heavy crude oil hydrocracking provided by the invention is produced high-quality diesel.
Embodiment
Below by accompanying drawing, method of the present invention is further described, but not thereby limiting the invention.As shown in the figure: after heavy crude and the long residuum mixing from pipeline 17 from pipeline 1; with together with hydrogen from pipeline 2 through process furnace 3 heating; and enter hydrogenator 5 by pipeline 4; successively through having loaded hydrogenation protecting agent; hydrodemetallation (HDM) agent; the hydroconversion reaction zone I of hydrogen desulfurization agent I and hydrocracking agent, and the hydroconversion reaction zone II that has loaded hydrogen desulfurization agent II reacts.Hydrogenation reaction resultant enters high-pressure separator 7 through pipeline 6 and carries out gas-liquid separation, obtain hydrogen-rich gas and product liquid, gained hydrogen-rich gas is mixed with the new hydrogen from pipeline 12 after circulating hydrogen compressor 10 pressurizations by pipeline 9, a mixed hydrogen part is mixed with raw material through pipeline 11 and pipeline 2, and another part is squeezed into hydroconversion reaction zone II through pipeline 18 as cold hydrogen.The product liquid of high-pressure separator 7 gained enters atmospheric tower distillation 13 through pipeline 8 and carries out fractionation, obtains gasoline fraction, diesel oil distillate and long residuum.Gasoline fraction and diesel oil distillate respectively through pipeline 14 and pipeline 15 as the finished product take-off equipment, long residuum part is through pipeline 16 take-off equipments, most ofly through pipeline 17, loops back after hydrogenator entrance mixes with crude oil and enters hydrogenator.
The following examples will be further described the present invention, but therefore not limit the present invention.
In embodiment, stock oil A used and the essential property of stock oil B are listed in table 1, as can be seen from Table 1, and the API degree 19.7 of stock oil A, viscosity (80 ℃) 58.99mm
2/ s, sulphur content is 1.7%, and heavy metal (Ni+V) is 21.1 μ g/g, and carbon residue is 5.34%; The API degree 12.6 of stock oil B, viscosity (80 ℃) 75.03mm
2/ s, sulphur content is 2.80%, and heavy metal (Ni+V) is 59.3 μ g/g, and carbon residue is 10.71%, is typical heavy inferior crude oil.
The hydrogenation protecting agent adopting in embodiment and the trade names of hydrodemetallation (HDM) agent are respectively RG-10B and RDM-2.Hydrogen desulfurization agent I and hydrogen desulfurization agent II are same catalyzer, and its trade names are RMS-1, and above several catalyzer are Sinopec catalyzer branch office Chang Ling catalyst plant and produce.Hydrocracking agent is laboratory preparation, and it forms and physico-chemical property is listed in table 2.
Stock oil A enters after mixing with hydrogen and enters successively the first reaction zone and hydrogenation reaction is carried out in second reaction zone, and the first reaction zone is loaded hydrogenation protecting agent, hydrodemetallation (HDM) agent, hydrogen desulfurization agent I and hydrocracking agent from top to bottom successively.Second reaction zone filling hydrogen desulfurization agent II.Hydrogenation reaction resultant enters high-pressure separator and carries out gas-liquid separation after cooling, obtain hydrogen-rich gas and product liquid, hydrogen-rich gas loops back hydrogenator, and product liquid obtains gas, gasoline fraction, diesel oil distillate and long residuum after entering atmospheric tower distillation.Gasoline fraction and diesel oil distillate be as the finished product take-off equipment, long residuum take-off equipment 4%, and all the other loop back after hydrogenator entrance mixes with crude oil and enter hydrogenator.The catalyst loading of the present embodiment and reaction conditions are in Table 3, and the character of gained gasoline fraction and diesel oil distillate is in Table 4.
As can be seen from Table 4, the sulphur of gasoline fraction, nitrogen content are all lower, can be used as gasoline blend component or reformed pre-hydrogenated charging.Diesel oil distillate character is good, sulphur content, nitrogen content be all less than 100 μ g/g, condensation point for-18 ℃, cetane index has reached 51, is good low-sulfur diesel-oil blend component.
Stock oil B enters after mixing with hydrogen and enters successively the first reaction zone and hydrogenation reaction is carried out in second reaction zone, and the first reaction zone is loaded hydrogenation protecting agent, hydrodemetallation (HDM) agent, hydrogen desulfurization agent I and hydrocracking agent from top to bottom successively.Second reaction zone filling hydrogen desulfurization agent II.Hydrogenation reaction resultant enters high-pressure separator and carries out gas-liquid separation after cooling, obtain hydrogen-rich gas and product liquid, hydrogen-rich gas loops back hydrogenator, and product liquid obtains gas, gasoline fraction, diesel oil distillate and long residuum after entering atmospheric tower distillation.Gasoline fraction and diesel oil distillate be as the finished product take-off equipment, long residuum take-off equipment 7%, and all the other loop back after hydrogenator entrance mixes with crude oil and enter hydrogenator.The catalyst loading of the present embodiment and reaction conditions are in Table 3, and the character of gained gasoline fraction and diesel oil distillate is in Table 4.
As can be seen from Table 4, the sulphur of gasoline fraction, nitrogen content are all lower, can be used as gasoline blend component or reformed pre-hydrogenated charging.Diesel oil distillate character is better, sulphur content, nitrogen content be all less than 150 μ g/g, condensation point for-17 ℃, cetane index has reached 50, is good low-sulfur diesel-oil blend component.
Table 1
| Stock oil | Stock oil A | Stock oil B |
| Density (15.6 ℃), g/cm 3 | 0.935 | 0.982 |
| API | 19.7 | 12.6 |
| Viscosity (80 ℃), mm 2/s | 58.99 | 75.03 |
| Carbon residue, % by weight | 5.34 | 10.71 |
| Sulphur content, % by weight | 1.70 | 2.80 |
| Nitrogen content, % by weight | 0.38 | 0.49 |
| Metal content, μ g/g | ||
| Nickel | 19.1 | 50.5 |
| Vanadium | 2.0 | 9.8 |
| Nickel+vanadium | 21.1 | 59.3 |
Table 2
| Catalyzer | Hydrocracking catalyst |
| Chemical constitution, % by weight | |
| Nickel oxide | 7.0 |
| Molybdenum oxide | 15.0 |
| Titanium oxide | 8.0 |
| Physical properties: | |
| Specific surface area, m 2/g | 240 |
| Pore volume, ml/g | 0.57 |
| Crushing strength, N/ |
15 |
| External diameter, mm | 1.1 |
| Shape | Butterfly type |
Table 3
| | Embodiment | 1 | |
| Catalyst loading ratio, volume % | |||
| Hydrogenation protecting agent | 5 | 8 | |
| Hydrodemetallation (HDM) agent | 25 | 30 | |
| Hydrogen desulfurization agent I | 25 | 24 | |
| Hydrocracking agent | 30 | 23 | |
| Hydrogen desulfurization agent II | 15 | 15 | |
| Reaction conditions | |||
| Hydrogen dividing potential drop, MPa | 15.0 | 16.0 | |
| The first reaction zone temperature of reaction, ℃ | 385 | 400 | |
| Second reaction zone temperature of reaction, ℃ | 365 | 365 | |
| Volume space velocity, h -1 | 0.7 | 0.4 | |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 1100 | 1300 |
Table 4
Claims (11)
1. a method of being produced high-quality diesel by heavy crude, it is characterized in that, in reactive moieties, two reaction zones are set, the first reaction zone is loaded hydrogenation protecting agent from top to bottom successively, hydrodemetallation (HDM) agent, hydrogen desulfurization agent I and hydrocracking agent, second reaction zone filling hydrogen desulfurization agent II, the temperature of reaction of the first reaction zone than the temperature of reaction of second reaction zone high 15 ℃～40 ℃, hydrogenation reaction resultant carries out cooling, separation and fractionation, obtain gas, gasoline fraction, diesel oil distillate and long residuum, described long residuum part withdrawing device, remainder loops back hydrogenator entrance.
2. in accordance with the method for claim 1, it is characterized in that, in mass, the amount of the long residuum of described withdrawing device is 3%～20%.
3. in accordance with the method for claim 1, it is characterized in that, the API degree of described heavy crude is less than or equal to 20.
4. in accordance with the method for claim 1; it is characterized in that; take integer catalyzer as benchmark; by volume; the filling percentage ratio of described hydrogenation protecting agent, hydrodemetallation (HDM) agent, hydrogen desulfurization agent I, hydrocracking agent and hydrogen desulfurization agent II is respectively 5%～20%, and 20%～65%, 20%～65%; 5%～40%, 5%～40%.
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 loads on molybdenum and/or the tungsten on this alumina supporter; and nickel and/or cobalt; the gross weight of catalyzer of take is benchmark; and in oxide compound, the content of molybdenum and/or tungsten is 1 % by weight～10 % by weight, the content of nickel and/or cobalt is 0.5 % by weight～3 % by weight.
6. in accordance with the method for claim 1, it is characterized in that, described hydrodemetallation (HDM) agent contains a kind of alumina supporter and loads on molybdenum and/or the tungsten on this carrier, and nickel and/or cobalt, the gross weight of catalyzer of take is benchmark, and in oxide compound, the content of molybdenum and/or tungsten is 0.5 % by weight～18 % by weight, the content of nickel and/or cobalt is 0.3 % by weight～8 % by weight, and the pore distribution of this carrier is that bore dia is that the pore volume of 100～200 dusts accounts for 70% to 98% of total pore volume.
7. in accordance with the method for claim 1, it is characterized in that, described hydrogen desulfurization agent I and hydrogen desulfurization agent II contain a kind of carrier and load on molybdenum and/or the tungsten on this carrier, and nickel and/or cobalt, the gross weight of catalyzer of take is benchmark, and in oxide compound, the content of molybdenum and/or tungsten is 8 % by weight～20 % by weight, the content of nickel and/or cobalt is 0.3 % by weight～8 % by weight, carrier is aluminum oxide and optional silicon oxide, and 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.
8. in accordance with the method for claim 1, it is characterized in that, described hydrocracking agent is to contain carrier and load on hydrogenation activity component on this carrier and the IVB family metal component in the periodic table of elements, described hydrocracking agent, wherein, the total amount of hydrocracking agent of take is benchmark, the content of described carrier is 5 % by weight～90 % by weight, in oxide compound, the content of described hydrogenation activity component is 5 % by weight～60 % by weight, and the content of described IVB family metal component is 0.5 % by weight～40 % by weight.
9. in accordance with the method for claim 8, it is characterized in that, the carrier of described hydrocracking agent has pore structure, its aperture, most probable hole is in 6～14 nanometers, aperture concentration degree is more than 7, described aperture concentration degree refers at specific pore volume and amasss the differential in aperture in the distribution curve with aperture, the ratio of peak height and halfwidth..
10. in accordance with the method for claim 8, it is characterized in that, the hydrogenation activity component of described hydrocracking agent comprises VIII family metal and group vib metal, and described IVB family metal component is titanium and/or zirconium.
11. in accordance with the method for claim 1, it is characterized in that, the reaction conditions of described hydrogenation reaction is: hydrogen dividing potential drop 4.0MPa～22.0MPa, 330 ℃～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000Nm
3/ m
3, volume space velocity 0.1h
-1～2.0h
-1.
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| CN1335370A (en) * | 2000-07-24 | 2002-02-13 | 中国石油化工股份有限公司 | Heavy oil residual oil processing method |
| CN101177621A (en) * | 2007-03-26 | 2008-05-14 | 中科合成油技术有限公司 | Hydrogenation processing method for full-range f-t synthetic oil |
| CN101220287A (en) * | 2007-12-13 | 2008-07-16 | 神华集团有限责任公司 | Coal and stone oil joint processing method for producing high quality engine fuel |
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|---|---|---|---|---|
| CN1335370A (en) * | 2000-07-24 | 2002-02-13 | 中国石油化工股份有限公司 | Heavy oil residual oil processing method |
| CN101177621A (en) * | 2007-03-26 | 2008-05-14 | 中科合成油技术有限公司 | Hydrogenation processing method for full-range f-t synthetic oil |
| CN101220287A (en) * | 2007-12-13 | 2008-07-16 | 神华集团有限责任公司 | Coal and stone oil joint processing method for producing high quality engine fuel |
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