CN101760235A - Heavy crude oil hydrocracking method - Google Patents
Heavy crude oil hydrocracking method Download PDFInfo
- Publication number
- CN101760235A CN101760235A CN 200810246528 CN200810246528A CN101760235A CN 101760235 A CN101760235 A CN 101760235A CN 200810246528 CN200810246528 CN 200810246528 CN 200810246528 A CN200810246528 A CN 200810246528A CN 101760235 A CN101760235 A CN 101760235A
- Authority
- CN
- China
- Prior art keywords
- agent
- weight
- carrier
- hydrocracking
- content
- 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.)
- Granted
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 ofly, more particularly belong to a kind of method of heavy crude hydrocracking in the method that has under the situation of hydrogen refining crude oil.
Background technology
The relative density size of crude oil, very big for the influence 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.International represent the weight of crude oil in commercial custom with the API degree, the relation of it and relative density is:
By formula as seen, more little its corresponding API degree of relative density is big more, and heavy more crude oil then its API degree is more little.Heavy crude typically refers to density greater than 0.934g/cm
3, the API degree is less than 20 crude oil.
Unconventional heavy crude resource such as viscous crude and tar sand is abundanter in the world.According to estimates, about 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 higher relatively.Estimate that conventional crude output will reach peak value in from now on 15～20 years, enter period of depletion then.But along with the development of world economy especially economics of underdevelopment, energy-output ratio presents increase by a relatively large margin.According to the prediction of USDOE information management office, in the period of nineteen ninety-five to 2015, 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 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 heavy crude such as viscous crude, deep processing, the cleaning petroleum products of the compliance with environmental protection requirements of production maximum.
Heavy crude particularly viscosity of thickened oil is very big, and contains a large amount of sulphur, nitrogen and metallic compound, therefore is difficult to carry and refining.Give downstream refinery processing with heavy oil transportation, 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%.Near the oil field, adopt hydrogenation technique processing viscous crude, come down to Sweet natural gas and viscous crude that the oil field is abundant and be converted into oils.
US4427535 has introduced a kind of method that realizes the heavy oil high conversion by hydrocracking.This method adopts ebullated bed technology, can process asphaltenes 10%～28%, and the heavy crude inferior of carbon residue 12%～35% is 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 ebullated bed technology investment is higher and have more engineering technology problem, so this method is of limited application.
CN1756831A has introduced a kind of method of catalytic hydrofinishing crude oil, this 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 the 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.This 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 hydrocracking, technical problem to be solved is exactly to handle the API degree less than 20 heavy crude difficulty, the problem that catalyst deactivation is fast on fixed bed.
Method provided by the present invention: heavy crude passes through the hydrogenation protecting agent successively in the presence of hydrogen, hydrodemetallation (HDM) agent, hydrogenating desulfurization agent I, hydrocracking agent and hydrogenating desulfurization agent II; With the integer catalyzer is benchmark, by volume, and the filling percentage ratio of described hydrogenation protecting agent, hydrodemetallation (HDM) agent, hydrogenating desulfurization agent I, hydrocracking agent and hydrogenating desulfurization agent II is respectively 2%～20%; 10%～78%; 10%～78%, 5%～50%, 5%～50%.
Advantage of the present invention:
1,, can utilize near the hydrogen feedstock of the natural gas source that enriches in oil field as cheapness according to method provided by the invention.Heavy crude can increase substantially the API degree after hydrocracking, reduce foreign matter content, promotes crude oil greatly and is worth.Heavy crude viscosity after hydrocracking can reduce greatly simultaneously, improves the defeated performance of its pipe.
2, the preferred hydrocracking catalyst of the present invention is active high, and it is lower to process the API degree, and the heavy crude that foreign matter content is higher can be converted into high-quality crude with crude oil more inferior, for bringing bigger 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
The concrete enforcement of method of the present invention is as follows: heavy crude passes through the hydrogenation protecting agent successively in the presence of hydrogen, hydrodemetallation (HDM) agent, hydrogenating desulfurization agent I, hydrocracking agent and hydrogenating desulfurization agent II; Under hydrogenation conditions, carry out hydrodemetallation (HDM), hydrogenating desulfurization, hydrodenitrification, removal of ccr by hydrotreating, hydrocracking, reaction such as alkene is saturated and aromatic hydrocarbons is saturated, its reaction effluent separates after cooling, obtains the hydrogenation crude oil that the API degree increases, viscosity reduces 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, carry out fractionation then.Described high-pressure oil gas separation, low pressure gas-oil separation and fractionated operational condition also are 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, hydrogenating desulfurization agent I, hydrocracking agent and hydrogenating 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 are deposited between the outside surface and granules of catalyst of catalyzer easily, 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, the present invention at first loads relatively large, the active minimum relatively 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; gross weight with catalyzer is a benchmark; and in oxide compound; the content of molybdenum and/or tungsten is 1 weight %～10 weight %, and the content of nickel and/or cobalt is 0.5 weight %～3 weight %.This hydrogenation protecting agent has low coke content, good activity stability and high intensity.
Because therefore metal content height such as nickel and vanadium in the heavy crude need a certain amount of hydrodemetallation (HDM) agent of filling.Described hydrodemetallation (HDM) agent can not only remove 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 the autocatalysis agent is active underspeeds.
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, gross weight with catalyzer is a benchmark, and in oxide compound, the content of molybdenum and/or tungsten is 0.5～18 weight %, the content of nickel and/or cobalt is 0.3～8 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.
Hydrogenating desulfurization agent I of the present invention and hydrogenating desulfurization agent II can be with a kind of catalyzer, also can be the different catalysts with said function.Sulfocompound and part nitrogenous compound in hydrogenating desulfurization agent I and the hydrogenating desulfurization agent II energy effective elimination stock oil.Described hydrogenating desulfurization agent I and hydrogenating 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, gross weight with catalyzer is a benchmark, and in oxide compound, the content of molybdenum and/or tungsten is 8 weight %～20 weight %, the content of nickel and/or cobalt is 0.3 weight %～8 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.This hydrogenating 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 active hydrocracking catalyst of carbon residue.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, total amount with catalyzer is a benchmark, the content of described carrier is 5～90 weight %, in oxide compound, described hydrogenation activity components contents is 5～60 weight %, and the content of described IVB family metal component is 0.5～40 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 is meant 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 is meant: the pore structure that adopts BET method or mercury penetration method measure sample, can obtain the distribution curve of the long-pending differential (dV/dr) to the aperture of specific pore volume with the aperture, the long-pending differential (dV/dr) to the aperture of the pairing specific pore volume in certain aperture is illustrated near the pairing pore volume in hole this aperture, and wherein aperture, the pairing hole of Zui Da 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, 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 is meant 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 big more, shows that the intensity in aperture is high more.
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 (aperture concentration degree height), the hydrogenating desulfurization of catalyzer and hydrogenation take off the carbon residue performance and have obtained significant raising.
The following examples will give further instruction to the present invention, but therefore not limit the present invention.
The hydrogenation protecting agent A that is adopted among the embodiment, hydrodemetallation (HDM) agent B, hydrogenating desulfurization agent C, hydrocracking agent D, it is formed 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 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 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 four hydrogenators successively after hydrogen mixes and carry out hydrogenation reaction; wherein first reactor (is called for short one anti-; below analogize) filling hydrogenation protecting agent A and hydrodemetallation (HDM) agent B; two anti-filling hydrogenating desulfurization agent C; three anti-filling hydrocracking agent D, four anti-filling hydrogenating 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 the catalyst loading ratio and the hydrogenation conditions of 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 reduce significantly, and 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 four hydrogenators successively after hydrogen mixes and carry out hydrogenation reaction; wherein first reactor (is anti-) loads hydrogenation protecting agent A and hydrodemetallation (HDM) agent B; two anti-filling hydrogenating desulfurization agent C, three anti-filling hydrocracking agent D, four anti-filling hydrogenating 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 the catalyst loading ratio and the reaction conditions of 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 matter crude oil is sold in can be used as, and sulfur content in crude oil, carbon residue and heavy metal reduce significantly, and 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, weight % | ??5.34 | ??10.71 |
| Sulphur content, weight % | ??1.70 | ??2.80 |
| Nitrogen content, 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 | Hydrogenating desulfurization agent C | Hydrocracking agent D |
| Chemical constitution, weight % | ||||
| Nickel oxide | ??1.5 | ??1.7 | ??/ | ??7.0 |
| Cobalt oxide | ??/ | ??/ | ??4.7 | ??/ |
| Catalyzer | Hydrogenation protecting agent A | Hydrodemetallation (HDM) agent B | Hydrogenating desulfurization agent C | Hydrocracking agent D |
| 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 |
| Hydrogenating desulfurization agent C | ??30 | ??25 |
| Hydrocracking agent D | ??32 | ??30 |
| Hydrogenating desulfurization agent C | ??15 | ??15 |
| Reaction conditions | ||
| The hydrogen dividing potential drop, MPa | ??15.0 | ??16.0 |
| One anti-temperature of reaction, ℃ | ??380 | ??385 |
| Numbering | Embodiment 1 | Embodiment 2 |
| 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, weight % | ??2.53 | ??4.97 |
| Sulphur content, weight % | ??0.25 | ??0.49 |
| Nitrogen content, 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 |
| Product property | Embodiment 1 | Embodiment 2 |
| Denitrification percent, % | ??35.3 | ??32.8 |
| Take off carbon yield, % | ??52.5 | ??50.1 |
| Demetallization per, % | ??82.3 | ??80.4 |
Claims (10)
1. the method for a heavy crude hydrocracking is characterized in that, heavy crude passes through the hydrogenation protecting agent successively in the presence of hydrogen, hydrodemetallation (HDM) agent, hydrogenating desulfurization agent I, hydrocracking agent and hydrogenating desulfurization agent II; With the integer catalyzer is benchmark, by volume, and the filling percentage ratio of described hydrogenation protecting agent, hydrodemetallation (HDM) agent, hydrogenating desulfurization agent I, hydrocracking agent and hydrogenating desulfurization agent II is respectively 2%～20%; 10%～78%; 10%～78%, 5%～50%, 5%～50%.
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; gross weight with catalyzer is a benchmark; and in oxide compound, the content of molybdenum and/or tungsten is 1 weight %～10 weight %, and the content of nickel and/or cobalt is 0.5 weight %～3 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, gross weight with catalyzer is a benchmark, and in oxide compound, the content of molybdenum and/or tungsten is 0.5～18 weight %, the content of nickel and/or cobalt is 0.3～8 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.
5. in accordance with the method for claim 1, it is characterized in that, described hydrogenating desulfurization agent I and hydrogenating 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, gross weight with catalyzer is a benchmark, and in oxide compound, the content of molybdenum and/or tungsten is 8 weight %～20 weight %, the content of nickel and/or cobalt is 0.3 weight %～8 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.
6. in accordance with the method for claim 1, it is characterized in that, 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, is a benchmark with the total amount of catalyzer, the content of described carrier is 5～90 weight %, in oxide compound, described hydrogenation activity components contents is 5～60 weight %, and the content of described IVB family metal component is 0.5～40 weight %.
7. in accordance with the method for claim 6, it is characterized in that, the carrier of described hydrocracking catalyst 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, described aperture concentration degree is meant 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.
8. in accordance with the method for claim 6, it is characterized in that the hydrogenation activity component of described hydrocracking catalyst comprises VIII family metal and group vib metal, described IVB family metal component is titanium and/or zirconium.
9. 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
10. in accordance with the method for claim 9, 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 true CN101760235A (en) | 2010-06-30 |
| CN101760235B 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) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103028443A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Porous support, preparation method and application thereof, catalyst, and hydrocracking method |
| CN103028448A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Catalyst and preparation method and application thereof, and hydrocracking method |
| CN103028445A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Porous carrier as well as preparation method and application thereof |
| CN103028444A (en) * | 2011-09-30 | 2013-04-10 | 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 |
| CN103045302A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Method for grading catalysts for hydrotreatment |
| CN103059933A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Hydrotreating method of high-acid high-calcium heavy crude oil |
| CN103374392A (en) * | 2012-04-13 | 2013-10-30 | 中国石油化工股份有限公司 | Hydro-upgrading method of catalytic cracking raw oil |
| 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 |
| RU2657898C2 (en) * | 2012-12-20 | 2018-06-18 | Ифп Энержи Нувелль | Complex method for processing oil raw material for liquid fuel production with low sulfur content |
| 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 |
| CN113930254A (en) * | 2020-06-29 | 2022-01-14 | 中国石油化工股份有限公司 | Method for producing chemical raw material by hydrocracking crude oil |
| CN113930256A (en) * | 2020-06-29 | 2022-01-14 | 中国石油化工股份有限公司 | Hydrocracking method for producing chemical raw materials from high-nitrogen crude oil |
| CN113930255A (en) * | 2020-06-29 | 2022-01-14 | 中国石油化工股份有限公司 | Hydrogenation method for producing chemical raw materials from crude oil |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HUP0101008A3 (en) * | 1998-03-14 | 2002-10-28 | Chevron U S A Inc San Ramon Sa | Hydrocarbon conversion process and catalysts used therein |
| JP2004263117A (en) * | 2003-03-04 | 2004-09-24 | Idemitsu Kosan Co Ltd | Catalytic hydrogenation method for crude oil |
| CN101191077B (en) * | 2006-11-22 | 2011-09-14 | 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
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103028448A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Catalyst and preparation method and application thereof, and hydrocracking method |
| CN103028445A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Porous carrier as well as preparation method and application thereof |
| CN103028444A (en) * | 2011-09-30 | 2013-04-10 | 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 |
| CN103028443A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Porous support, preparation method and application thereof, catalyst, and hydrocracking method |
| 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 |
| 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 |
| 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 |
| CN103045302A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Method for grading catalysts for hydrotreatment |
| 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 |
| CN103059933A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Hydrotreating method of high-acid high-calcium heavy crude oil |
| 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 |
| CN103374392A (en) * | 2012-04-13 | 2013-10-30 | 中国石油化工股份有限公司 | Hydro-upgrading method of catalytic cracking raw 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 |
| RU2657898C2 (en) * | 2012-12-20 | 2018-06-18 | Ифп Энержи Нувелль | Complex method for processing oil raw material for liquid fuel production with low sulfur content |
| 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 |
| CN113930254A (en) * | 2020-06-29 | 2022-01-14 | 中国石油化工股份有限公司 | Method for producing chemical raw material by hydrocracking crude oil |
| CN113930256A (en) * | 2020-06-29 | 2022-01-14 | 中国石油化工股份有限公司 | Hydrocracking method for producing chemical raw materials from high-nitrogen crude oil |
| CN113930255A (en) * | 2020-06-29 | 2022-01-14 | 中国石油化工股份有限公司 | Hydrogenation method for producing chemical raw materials from crude oil |
| 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 |
| 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101760235B (en) | 2013-03-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101760235B (en) | Heavy crude oil hydrocracking method | |
| CN102453530B (en) | Hydrogenation method for processing heavy oil | |
| CN101591565B (en) | Hydrogenation and refining method of gasoline with poor quality | |
| CN103540350B (en) | Inferior heavy oil and hydrotreatment combined process | |
| CN103059928B (en) | Hydrotreating device and application thereof as well as residual oil hydrotreating method | |
| CN102899081B (en) | Wax oil hydrotreating method | |
| CN100587038C (en) | Hydrogenation method for producing good quality catalytic cracking material | |
| CN107875979B (en) | Grading filling method and application of fixed bed hydrogenation catalyst | |
| CN101191077B (en) | Hydrogenation deacidification method for acid-containing crude oil | |
| CN101343566A (en) | Method for improving running period of hydrogenation plant for poor petroleum naphtha | |
| CN102876364B (en) | Hydrotreatment method | |
| CN101020843B (en) | Hydrogenation process for producing catalytically cracked material | |
| CN101684414A (en) | Hydrotreating method of high-acid and high-calcium crude 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 | |
| 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 | |
| CN102453529A (en) | Method for processing heavy material by using up-flow reactor system | |
| 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 | |
| CN103102945B (en) | A kind of inferior heavy oil working method | |
| 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 |