CN101760235B - Heavy crude oil hydrocracking method - Google Patents
Heavy crude oil hydrocracking method Download PDFInfo
- Publication number
- CN101760235B CN101760235B CN 200810246528 CN200810246528A CN101760235B CN 101760235 B CN101760235 B CN 101760235B CN 200810246528 CN200810246528 CN 200810246528 CN 200810246528 A CN200810246528 A CN 200810246528A CN 101760235 B CN101760235 B CN 101760235B
- Authority
- CN
- China
- Prior art keywords
- agent
- weight
- hydrogen
- hydrocracking
- carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a heavy crude oil hydrocracking method. In the method, heavy crude oil is sequentially subjected to the steps of a hydrogenation protective agent, a hydrodemetallization agent, a hydrodesulfurization agent I, a hydrocracking agent and a hydrodesulfurization II in the presence of hydrogen, wherein the filling weight percentage of the hydrogenation protective agent, the hydrodemetallization agent, the hydrodesulfurization agent I, the hydrocracking agent and the hydrodesulfurization agent II are respectively 2-20%, 10-78%, 10-78%, 5-50% and 5-50% by taking an integral catalyst as a reference. According to the method provided by the invention, the heavy crude oil with the API (American Petroleum Institute) degree smaller than 20 can be processed to obtain hydrogenated crude oil with enhanced API and reduced viscosity, and moreover, the operating period of a hydrogenation processing device is prolonged.
Description
Technical field
The invention belongs to a kind of in the situation that there is the method for the refining crude oil of hydrogen, more particularly belong to a kind of method of heavy crude oil hydrocracking.
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 commercially being accustomed to representing with the API degree crude oil, the relation of it and relative density is:
By formula as seen, less its corresponding API degree of relative density is larger, and heavier crude oil then its API degree is less.Heavy crude typically refers to density greater than 0.934g/cm
3, the API degree is less than 20 crude oil.
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 are 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 will reach peak value in from now on 15～20 years, then enter 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, the 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 remedy.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 all are 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 cleaning 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, therefore is difficult to carry and refining.Heavy oil transportation is to the processing of downstream refinery, often also uneconomical, therefore should consider viscous crude is 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 the oil field.Viscous crude adopts hydrogenation technique processing, and the synthetic crude yield can be greater than 100%.Adopting hydrogenation technique processing viscous crude near the oil field, is in fact that Sweet natural gas and the viscous crude that the oil field is abundant is converted into the tight product of low-density oil.
US4427535 has introduced a kind of method that realizes the heavy oil high conversion by hydrocracking.The method adopts the ebullated bed technology, can process asphaltenes 10%～28%, and the heavy crude inferior of carbon residue 12%～35% is such 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 0.25～5.0h
-1Condition under, can reach the high conversion of 65 volume %～80 volume %.But because the boiling bed process investment is higher and have more engineering technology problem, so the method is of limited application.
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 used hydrocracking catalyst 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 that is carried on the carrier, and this component is at least a element that is selected from periodictable the 6th, 8,9 and 10 family's 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 with 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 objective of the invention is to provide on the basis of existing technology a kind of method of heavy crude oil hydrocracking, technical problem to be solved is exactly difficult less than 20 heavy crude at fixed bed processing API degree, the problem that catalyst deactivation is fast.
Method provided by the present invention: heavy crude passes through the hydrogenation protecting agent successively in the presence of hydrogen, hydrodemetallation (HDM) agent, hydrogen desulfurization agent I, hydrocracking agent and hydrogen desulfurization agent II; 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 2%～20%; 10%～78%; 10%～78%, 5%～50%, 5%～50%.
Advantage of the present invention:
1, according to method provided by the invention, can utilize near the natural gas source that enriches in oil field as the hydrogen feedstock of cheapness.Heavy crude can increase substantially the API degree after hydrocracking, impurity reduction content promotes greatly crude oil and is worth.Heavy crude viscosity after hydrocracking can reduce greatly simultaneously, improves the defeated performance of its pipe.
2, the preferred hydrocracking catalyst activity of the present invention is high, can process the API degree lower, and the heavy crude that foreign matter content is higher can be converted into high-quality crude with crude oil more inferior, for bringing larger economic benefit in the refinery.
3, hydrogenation catalyst grading method provided by the present invention has farthest been brought into play the function of various catalyzer, and the foulant in can the effective elimination raw material reaches the purpose of protection Primary Catalysts, guarantees the hydrotreater long-time running.
Embodiment
Method implementation of the present invention is as follows: heavy crude passes through the hydrogenation protecting agent successively in the presence of hydrogen, hydrodemetallation (HDM) agent, hydrogen desulfurization agent I, hydrocracking agent and hydrogen desulfurization agent II; Under hydrogenation conditions, carry out the reactions such as hydrodemetallation (HDM), hydrogenating desulfurization, hydrodenitrification, removal of ccr by hydrotreating, hydrocracking, olefin saturated and aromatic saturation, its reaction effluent separates after cooling, obtains the hydrogenation crude oil of the increase of API degree, reduced viscosity after the separation.
According to method provided by the invention, the product of the hydrogenation reaction that obtains is separated into known in those skilled in the art, for example this separation comprise the advanced horizontal high voltage gas-oil separation of product of the hydrogenation reaction that will obtain, then carry out the low pressure gas-oil separation, then carry out fractionation.The operational condition of described high-pressure oil gas separation, low pressure gas-oil separation and fractionation also is known in those skilled in the art.
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, the liquefied coal coil.
The reaction conditions of described hydrogenation reaction is: hydrogen dividing potential drop 4.0～20.0MPa, 330～440 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000Nm
3/ m
3, volume space velocity 0.1～2.0h
-1The reaction conditions of preferred hydrogenation reaction is: hydrogen dividing potential drop 6.0～18.0MPa, 340～420 ℃ of temperature of reaction, hydrogen to oil volume ratio 400～1800Nm
3/ m
3, volume space velocity 0.15～1.5h
-1
Hydrogenator of the present invention is fixed-bed reactor, and quantity is at least 3.The hydrogenation protecting agent, the hydrodemetallation (HDM) agent, hydrogen desulfurization agent I, hydrocracking agent and hydrogen desulfurization agent II divide bed to be seated in the fixed-bed reactor successively.
Because under comparatively harsh hydroprocessing condition, the metallic impurity in the heavy crude, mechanical impurity, colloid and other particulate matter easily are 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 again bed pressure drop to rise, make full scale plant frequent shutdowns and catalyst changeout more, this will reduce the utilization ratio of full scale plant greatly, cause larger financial loss to enterprise.Therefore, the present invention at first loads relatively large, the active relatively minimum hydrogenation protecting agent of pore volume, and the foulant in the energy effective elimination raw material reaches the purpose of protecting Primary Catalysts, guarantees the hydrotreater long-time running.
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; take the gross weight of catalyzer as 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 contents such as nickel and vanadium are high in the heavy crude, therefore need a certain amount of hydrodemetallation (HDM) agent of filling.Described hydrodemetallation (HDM) agent can not only remove the metallic impurity such as nickel in the crude oil, vanadium; thereby effectively stop these heavy metal depositions to the catalyzer in downstream; hydrogenation activity and life cycle to downstream catalyst have all played 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 the molybdenum and/or the tungsten that load on this carrier, and nickel and/or cobalt, take the gross weight of catalyzer as benchmark, and in oxide compound, the content of molybdenum and/or tungsten is 0.5～18 % by weight, the content of nickel and/or cobalt is 0.3～8 % by weight, and this pore size distribution of 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 the same catalyzer, also can be the different catalysts with said function.Sulfocompound in hydrogen desulfurization agent I and the 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 the molybdenum and/or the tungsten that load on this carrier, and nickel and/or cobalt, take the gross weight of catalyzer as 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 this pore size distribution of carrier is that diameter is that the pore volume of 60～100 dusts accounts for 75%～98% of total pore volume.This hydrogen desulfurization agent has high desulphurizing activated, also has stronger demetalization, holds metal ability and the higher carbon residue performance of taking off.
The present invention has adopted to has more high desulfurization activity and takes off the hydrocracking catalyst of 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, take the total amount of catalyzer as benchmark, the content of described carrier is 5～90 % by weight, in oxide compound, the content of described hydrogenation activity component is 5～60 % by weight, and the content of described IVB family metal component is 0.5～40 % 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, the aperture concentration degree is more than 7, preferred 7～9, described aperture concentration degree refers in the long-pending distribution curve of differential with the aperture to the aperture of specific pore volume, the ratio of peak height and halfwidth.
Aperture, described most probable hole refers to: the pore structure that adopts BET method or platen press measure sample, can obtain the long-pending differential (dV/dr) to the aperture of specific pore volume with the distribution curve in aperture, the long-pending differential (dV/dr) to the aperture of the corresponding specific pore volume in certain aperture is illustrated near the corresponding pore volume in hole this aperture, 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 has been as well known to those skilled in the art, for example can adopt " commercial catalysts analytical test sign " (Sinopec press, nineteen ninety first version, the volumes such as Liu Xiyao, the structure determination of chapter 2 catalyst pores) the middle method of putting down in writing.
The aperture concentration degree refers in the long-pending distribution curve of differential with the aperture to the aperture of specific pore volume, 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 IVB 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 the hydrogenation activity component of routine, 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 as the preparation hydrocracking catalyst.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 of the carrier of hydrocracking catalyst provided by the invention less (aperture, most probable hole is little) and distribute concentrated (the aperture concentration degree is high), the hydrogenating desulfurization of catalyzer and hydrogenation take off the carbon residue performance and have obtained significant raising.
The following examples will be further described the present invention, but therefore not limit the present invention.
The hydrogenation protecting agent A that adopts among the embodiment, hydrodemetallation (HDM) agent B, hydrogen desulfurization agent C, hydrocracking agent D, it forms and physico-chemical property is listed in table 2.
Used stock oil E and the essential property of stock oil F are listed in table 1 among the embodiment, as can be seen from Table 1, and the API degree 19.7 of stock oil E, viscosity (80 ℃) 58.99mm
2/ s, sulphur content is 1.7 % by weight, 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 F, viscosity (80 ℃) 75.03mm
2/ s, sulphur content is 2.80 % by weight, and heavy metal (Ni+V) is 59.3 μ g/g, and carbon residue is 10.71%, is typical heavy inferior crude oil.
Embodiment 1
Stock oil E with enter successively four hydrogenators after hydrogen mixes and carry out hydrogenation reaction; wherein the first reactor (is called for short one anti-; below analogize) filling hydrogenation protecting agent A and hydrodemetallation (HDM) agent B; two anti-filling hydrogen desulfurization agent C; three anti-filling hydrocracking agent D, four anti-filling hydrogen desulfurization agent C.The hydrogenation reaction resultant enters high-pressure separator and carries out gas-liquid separation after cooling, obtain hydrogen-rich gas and product liquid, and hydrogen-rich gas loops back hydrogenator, and product liquid is the crude oil after the hydrocracking.Each catalyst loading ratio and the hydrogenation conditions of the present embodiment see Table 3; Above-mentioned flow process is moved 500 hours continuously, and the character of gained hydrogenation crude oil sees Table 4.
As can be seen from Table 4, after the hydrocracking, the API degree of heavy crude E has improved 15 more than the unit, reached more than 35, can be used as light crude and sell, sulfur content in crude oil, carbon residue and heavy metal decrease, the value of crude oil has obtained great lifting.Crude oil viscosity after hydrocracking can reduce greatly simultaneously, has improved the defeated performance of pipe of crude oil.
Embodiment 2
Stock oil F with enter successively four hydrogenators after hydrogen mixes and carry out hydrogenation reaction; wherein the first reactor (is anti-) loads hydrogenation protecting agent A and hydrodemetallation (HDM) agent B; two anti-filling hydrogen desulfurization agent C, three anti-filling hydrocracking agent D, four anti-filling hydrogen desulfurization agent C.The hydrogenation reaction resultant enters high-pressure separator and carries out gas-liquid separation after cooling, obtain hydrogen-rich gas and product liquid, and hydrogen-rich gas loops back hydrogenator, and product liquid is the crude oil after the hydrocracking.Each catalyst loading ratio and the reaction conditions of the present embodiment see Table 3, and above-mentioned flow process is moved 500 hours continuously, and the character of gained hydrogenation crude oil sees Table 4.
As can be seen from Table 4, after the hydrocracking, the API degree of heavy crude F has improved 15 more than the unit, has reached 27.8, and can be used as middle matter crude oil and sell, sulfur content in crude oil, carbon residue and heavy metal decrease, the value of crude oil has obtained great lifting.Crude oil viscosity after hydrocracking can reduce greatly simultaneously, has improved the defeated performance of pipe of crude oil.
Table 1
| Stock oil | Stock oil E | Stock oil F |
| 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 | Hydrogenation protecting agent A | Hydrodemetallation (HDM) agent B | Hydrogen desulfurization agent C | Hydrocracking agent D |
| Chemical constitution, % by weight | ||||
| Nickel oxide | 1.5 | 1.7 | / | 7.0 |
| Cobalt oxide | / | / | 4.7 | / |
| Molybdenum oxide | 6.2 | 8.1 | 13.5 | 15.0 |
| Titanium oxide | / | / | / | 8.0 |
| Physical properties: | ||||
| Specific surface area, m 2/g | 200 | 150 | 260 | 240 |
| Pore volume, ml/g | 0.68 | 0.60 | 0.55 | 0.57 |
| Crushing strength, N/mm | The 25N/ grain | 16 | 14 | 15 |
| External diameter, mm | 4.6 | 1.1 | 1.1 | 1.1 |
| Shape | Raschig ring | The butterfly type | The butterfly type | The butterfly type |
Table 3
| Numbering | Embodiment 1 | Embodiment 2 |
| The catalyst loading volume, % | ||
| Hydrogenation protecting agent A | 3 | 5 |
| Hydrodemetallation (HDM) agent B | 20 | 25 |
| Hydrogen desulfurization agent C | 30 | 25 |
| Hydrocracking agent D | 32 | 30 |
| Hydrogen desulfurization agent C | 15 | 15 |
| Reaction conditions | ||
| The hydrogen dividing potential drop, MPa | 15.0 | 16.0 |
| One anti-temperature of reaction, ℃ | 380 | 385 |
| Two anti-temperature of reaction, ℃ | 380 | 385 |
| Three anti-temperature of reaction, ℃ | 390 | 395 |
| Four anti-temperature of reaction, ℃ | 360 | 365 |
| Average reaction temperature, ℃ | 380 | 385 |
| Volume space velocity, h -1 | 0.8 | 0.5 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 1000 | 1200 |
Table 4
| Product property | Embodiment 1 | Embodiment 2 |
| Density (15.6 ℃), g/cm 3 | 0.849 | 0.888 |
| The API degree | 35.2 | 27.8 |
| Viscosity (80 ℃), mm 2/s | 19.01 | 27.03 |
| Carbon residue, % by weight | 2.53 | 4.97 |
| Sulphur content, % by weight | 0.25 | 0.49 |
| Nitrogen content, % by weight | 0.21 | 0.33 |
| Metal content, μ g/g | ||
| Nickel | 3.4 | 9.6 |
| Vanadium | 0.3 | 2.0 |
| Nickel+vanadium | 3.7 | 11.6 |
| Desulfurization degree, % | 85.2 | 82.3 |
| Denitrification percent, % | 35.3 | 32.8 |
| Take off carbon yield, % | 52.5 | 50.1 |
| Demetallization per, % | 82.3 | 80.4 |
Claims (8)
1. the method for a heavy crude oil hydrocracking is characterized in that, heavy crude passes through the hydrogenation protecting agent successively in the presence of hydrogen, hydrodemetallation (HDM) agent, hydrogen desulfurization agent I, hydrocracking agent and hydrogen desulfurization agent II; 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 2%～20%, and 10%～78%, 10%～78%, 5%～50%, 5%～50%;
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, take the total amount of hydrocracking agent as benchmark, the content of described carrier is 5～90 % by weight, in oxide compound, the content of described hydrogenation activity component is 5～60 % by weight, and the content of described IVB family metal component is 0.5～40 % by weight; The carrier of described hydrocracking agent has pore structure, the aperture, most probable hole of this pore structure is in 6～14 nanometers, the aperture concentration degree is more than 7, and described aperture concentration degree refers in the long-pending distribution curve of differential with the aperture to the aperture of specific pore volume, the ratio of peak height and halfwidth.
2. 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.
3. 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; take the gross weight of catalyzer as 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.
4. in accordance with the method for claim 1, it is characterized in that, described hydrodemetallation (HDM) agent contains a kind of alumina supporter and the molybdenum and/or the tungsten that load on this carrier, and nickel and/or cobalt, take the gross weight of catalyzer as benchmark, and in oxide compound, the content of molybdenum and/or tungsten is 0.5～18 % by weight, the content of nickel and/or cobalt is 0.3～8 % by weight, and this pore size distribution of carrier is that bore dia is that the pore volume of 100～200 dusts accounts for 70% to 98% of total pore volume.
5. 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 the molybdenum and/or the tungsten that load on this carrier, and nickel and/or cobalt, take the gross weight of catalyzer as 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 this pore size distribution of carrier is that diameter is that the pore volume of 60～100 dusts accounts for 75%～98% of total pore volume.
6. in accordance with the method for claim 1, 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.
7. 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 4.0～20.0MPa, 330～440 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000Nm
3/ m
3, volume space velocity 0.1～2.0h
-1
8. in accordance with the method for claim 7, it is characterized in that, the reaction conditions of described hydrogenation reaction is: hydrogen dividing potential drop 6.0～18.0MPa, 340～420 ℃ of temperature of reaction, hydrogen to oil volume ratio 400～1800Nm
3/ m
3, volume space velocity 0.15～1.5h
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810246528 CN101760235B (en) | 2008-12-25 | 2008-12-25 | Heavy crude oil hydrocracking method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810246528 CN101760235B (en) | 2008-12-25 | 2008-12-25 | Heavy crude oil hydrocracking method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101760235A CN101760235A (en) | 2010-06-30 |
| CN101760235B true CN101760235B (en) | 2013-03-06 |
Family
ID=42491618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200810246528 Active CN101760235B (en) | 2008-12-25 | 2008-12-25 | Heavy crude oil hydrocracking method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101760235B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103028443B (en) * | 2011-09-30 | 2015-06-17 | 中国石油化工股份有限公司 | Porous support, preparation method and application thereof, catalyst, and hydrocracking method |
| CN103028448B (en) * | 2011-09-30 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst and preparation method and application thereof, and hydrocracking method |
| CN103028445B (en) * | 2011-09-30 | 2015-06-17 | 中国石油化工股份有限公司 | Porous carrier as well as preparation method and application thereof |
| CN103028444B (en) * | 2011-09-30 | 2015-06-17 | 中国石油化工股份有限公司 | Porous carrier, preparation method and application thereof as well as catalyst and hydrocracking method |
| CN103045302B (en) * | 2011-10-17 | 2015-02-18 | 中国石油化工股份有限公司 | Method for grading catalysts for hydrotreatment |
| CN103059933B (en) * | 2011-10-24 | 2015-02-25 | 中国石油化工股份有限公司 | Hydrotreating method of high-acid high-calcium heavy crude oil |
| 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 |
| FR3000097B1 (en) * | 2012-12-20 | 2014-12-26 | Ifp Energies Now | INTEGRATED PROCESS FOR THE TREATMENT OF PETROLEUM LOADS FOR THE PRODUCTION OF LOW SULFUR CONTENT FIELDS |
| CN107570152A (en) * | 2017-08-17 | 2018-01-12 | 孟庆桓 | A kind of catalyst and hydrotreating method for high calcium content heavy crude oil hydrocracking |
| CN111116292A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Method and device for preparing low-carbon olefin from petroleum hydrocarbon |
| CN113930256B (en) * | 2020-06-29 | 2023-06-09 | 中国石油化工股份有限公司 | Hydrocracking method for producing chemical raw material from high-nitrogen crude oil |
| CN113930254B (en) * | 2020-06-29 | 2023-06-23 | 中国石油化工股份有限公司 | Method for producing chemical raw materials by hydrocracking crude oil |
| CN113930255B (en) * | 2020-06-29 | 2023-06-09 | 中国石油化工股份有限公司 | Hydrogenation method for producing chemical raw materials from crude oil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999047625A1 (en) * | 1998-03-14 | 1999-09-23 | Chevron U.S.A. Inc. | Hydrocarbon conversion process and catalysts used therein |
| CN1756831A (en) * | 2003-03-04 | 2006-04-05 | 出光兴产株式会社 | Catalytic hydrofining method for crude oil |
| CN101191077A (en) * | 2006-11-22 | 2008-06-04 | 中国石油化工股份有限公司 | Hydrogenation deacidification method for acid-containing crude oil |
-
2008
- 2008-12-25 CN CN 200810246528 patent/CN101760235B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999047625A1 (en) * | 1998-03-14 | 1999-09-23 | Chevron U.S.A. Inc. | Hydrocarbon conversion process and catalysts used therein |
| CN1756831A (en) * | 2003-03-04 | 2006-04-05 | 出光兴产株式会社 | Catalytic hydrofining method for crude oil |
| CN101191077A (en) * | 2006-11-22 | 2008-06-04 | 中国石油化工股份有限公司 | Hydrogenation deacidification method for acid-containing crude oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101760235A (en) | 2010-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101760235B (en) | Heavy crude oil hydrocracking method | |
| CN102453530A (en) | Hydrogenation method for processing heavy oil | |
| CN103059928B (en) | Hydrotreating device and application thereof as well as residual oil hydrotreating method | |
| US6531054B1 (en) | Process for effecting deep HDS of hydrocarbon feedstocks | |
| CN103540350B (en) | A kind of inferior heavy oil, hydrotreatment combination process | |
| CN101591565A (en) | A kind of hydrofinishing process of inferior patrol | |
| CN101191077B (en) | Hydrogenation deacidification method for acid-containing crude oil | |
| CN102899081B (en) | Wax oil hydrotreating method | |
| CN107875979A (en) | A kind of grading loading methods and applications of fixed bed hydrogenation catalyst | |
| CN102876364B (en) | Hydrotreatment method | |
| CN101684414B (en) | Hydrotreating method of high-acid and high-calcium crude oil | |
| CN101020843B (en) | Hydrogenation process for producing catalytically cracked material | |
| CN101343566A (en) | Method for improving running period of hydrogenation plant for poor petroleum naphtha | |
| CN103102940A (en) | Combined process for hydrotreatment of heavy oil | |
| CN102465009B (en) | Multistage boiling bed heavy oil hydrogenation treatment method | |
| CN111100700A (en) | Hydrocracking pretreatment method for high-nitrogen high-dry-point raw material | |
| CN1990830B (en) | hydrorefining method for coker gasoline | |
| CN108018084B (en) | Heavy oil hydrotreating method for improving catalyst utilization rate | |
| EP2441817B1 (en) | Ebullated bed hydrotreating process of heavy crude oil | |
| CN103059983A (en) | Hydrofining catalyst combined filling method | |
| CN111100698A (en) | Hydrocracking method for high-dry-point high-nitrogen raw oil | |
| CN102161910B (en) | Method for producing high-quality diesel by using heavy crude oil | |
| CN102108307B (en) | Method for lowering contents of impurities and polycyclic aromatic hydrocarbons in catalytic-cracking heavy oil | |
| CN103102953B (en) | Pretreatment method for crude lube stock | |
| CN107875978B (en) | Grading filling method and application of hydrogenation catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |