CN1165601C - Process for hydrogenating residual oil and catalytically cracking heavy oil - Google Patents
Process for hydrogenating residual oil and catalytically cracking heavy oil Download PDFInfo
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- CN1165601C CN1165601C CNB011154969A CN01115496A CN1165601C CN 1165601 C CN1165601 C CN 1165601C CN B011154969 A CNB011154969 A CN B011154969A CN 01115496 A CN01115496 A CN 01115496A CN 1165601 C CN1165601 C CN 1165601C
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1077—Vacuum residues
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- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a process for hydrogenating residual oil and catalytically cracking heavy oil, which comprises the following steps: introducing the residual oil, a distilled product of oil slurry, catalytically cracked heavy cycle oil and optional distillate oil into a hydrotreater for a hydrogenation reaction under the presence of hydrogen and a hydrogenation catalyst; distilling oil produced by the reaction to obtain gasoline and diesel oil, and introducing hydrogenated residual oil and optional vacuum gas oil into a catalytic cracker for a cracking reaction under the presence of a cracking catalyst; introducing the heavy cycle oil produced by the reaction into a residual oil hydrotreater, distilling the oil slurry, and returning the distilled product back to the hydrotreater. The method can convert the slurry oil and the heavy cycle oil to light end products, which increases the yield of the gasoline and the diesel oil.
Description
The invention belongs to the method for handling hydrocarbon ils with other step of converting of a hydroprocessing technique process and, more particularly, is a kind of method that residual hydrocracking and two kinds of processing methodes of heavy oil fluid catalytic cracking are organically combined.
At present the world is being faced with crude oil and becomes and heavily become bad trend, and people gradually reduce the demand of heavy fuel oil (HFO), and the demand of lightweight oil is then significantly increased.Therefore oil refining enterprise is pursued the maximum conversion of residual oil one after another.
In the whole bag of tricks of residual oil lighting, residual oil hydrogenation-catalytic cracking combined technological is a kind of good technology.Residual oil has improved hydrogen richness after removing impurity such as metal, sulphur, nitrogen through hydrotreatment, can be used as fine heavy oil fluid catalytic cracking raw material.Residual hydrocracking heavy oil is because molecular structure relation is processed through heavy oil fluid catalytic cracking in addition, and gasoline octane rating is very high, C
3, C
4The productive rate of alkene is also very high, and the sulphur content in the product is very low simultaneously, can satisfy modern environmental protection requirement, therefore now the residual hydrogenation tail oil is directly obtained more and more general application as the technology of heavy oil fluid catalytic cracking raw material.
Conventional residual hydrocracking-heavy oil catalytic cracking process is that heavy cycle oil is circulated to further processing in the heavy oil catalytically cracking equipment.Because heavy cycle oil contains polycyclic aromatic hydrocarbons, thereby light oil yield is low, the green coke amount is big, has increased the revivifier load, has reduced the treatment capacity and the economic benefit of heavy oil catalytically cracking equipment.The sulphur content of heavy cycle oil is higher in addition, exceeds one times than hydrogenation tail oil approximately, and the heavy cycle oil circulation also makes the product sulphur content rise.
USP4,713,221 disclose on the residual hydrogenation of routine and catalytic cracking combined basis, the heavy cycle oil of catalytic cracking (comprising gas oil catalytic cracking and heavy oil fluid catalytic cracking) is circulated to residual hydrogenation equipment, with carry out hydrogenation after topped crude mixes, hydrogenated residue enters catalytic cracking unit.The change that this is little can make the benefit of one barrel of crude oil of the every processing in refinery have a net increase of 0.29 dollar.But catalytically cracked oil will make catalytic cracking regenerator green coke amount increase in the catalytic cracking unit internal recycling, influence unit capacity, if get rid of outward, the useful matter in the slurry oil is not used, and influences the benefit of device.
CN1262306A discloses a kind of residual hydrocracking-catalytic cracking combination process, is that residual oil and clarified oil enter the residual hydrocracking device together, carries out hydrogenation reaction in the presence of hydrogen and hydrogenation catalyst; The hydrogenated residue of reaction gained enters catalytic cracking unit, carries out cracking reaction in the presence of cracking catalyst, and heavy cycle oil circulates in catalytic cracking unit inside; The slurry oil of reaction gained obtains clarified oil through the separator separation, is back to hydrogenation unit.Because the full cut of slurry oil enters the residual hydrocracking device, the easy green coke thing in the slurry oil will increase the carbon deposit of hydrogenation catalyst, has reduced the activity and the operational cycle of hydrogenation catalyst, and because of heavy cycle oil not hydrogenation cause catalytic cracking unit green coke amount to increase.
The objective of the invention is to provide on the basis of existing technology a kind of and the heavy oil of catalytic cracking by-product can be transformed to greatest extent the residual hydrogenation that improves the residual hydrogenation operation simultaneously and the method for catalytically cracking heavy oil.
Method provided by the invention may further comprise the steps:
The steam thing, heavy catalytic cycle oil, optional distillate of residual oil and catalytically cracked oil enter residual hydrogenation equipment together, carry out hydrogenation reaction in the presence of hydrogen and hydrogenation catalyst, reaction product isolated obtains gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenated residue;
Hydrogenated residue enters heavy oil catalytically cracking equipment separately or with vacuum gas oil, in the presence of cracking catalyst, carry out cracking reaction, reaction product isolated obtains dry gas, liquefied gas, gasoline, diesel oil, heavy cycle oil and slurry oil, and wherein heavy cycle oil is circulated to residual hydrogenation equipment;
Slurry oil is after fractionation by distillation goes out resistates, and the thing that steams of slurry oil is back to hydrogenation unit.
Described residual oil is vacuum residuum or long residuum.Typical Residue Hydrotreating Technology condition is: hydrogen dividing potential drop 5.0～22.0MPa, 330～450 ℃ of temperature of reaction, volume space velocity 0.1～3.0 hour
-1, hydrogen and stock oil volume ratio (hereinafter to be referred as hydrogen-oil ratio) 350～2000, the stock oil here is meant the mixture that steams thing, heavy cycle oil and optional distillate of residual oil, slurry oil, and wherein catalytically cracked oil steams 3～50 heavy % that thing and heavy catalytic cycle oil account for the residual hydrogenation equipment combined feed total feed.Optional distillate is to be selected from coker gas oil, deasphalted oil, inferior heavy vacuum gas oil and solvent treatment to extract one or more mixture among the oil out, and these distillates can be added in the residual oil, also can not add.Described catalyzer can be various hydrogenation catalysts, and its active metal component is nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum or cobalt-molybdenum, and carrier is aluminum oxide, silicon-dioxide or amorphous aluminum silicide, and wherein aluminum oxide is the most frequently used carrier.
The residual hydrogenation type of reactor can be fixed bed, moving-bed or ebullated bed, and residual hydrogenation equipment comprises a reactor and a separation column at least.
Gas in the hydrotreatment products can be used as hydrogen feedstock or sneaks in the refinery gas, hydrotreated naphtha can be used as the raw material of reformation or ethylene unit, hydrogenated diesel oil is an ideal diesel product blending component, the boiling spread of hydrogenated residue is＞350 ℃, can be all as the charging of heavy oil catalytically cracking equipment.
Catalytic cracking unit can be that every covering device should comprise a reactor, a revivifier and a separation column at least more than a cover or overlapped.The employed catalyzer of catalytic cracking is REY, REHY, ZSM-5 molecular sieve catalyst or mixture, processing condition are: the weight ratio (hereinafter to be referred as agent-oil ratio) 3～10 of 470～570 ℃ of temperature of reaction, 0.5～5 second reaction times, catalyzer and stock oil, 650～800 ℃ of regeneration temperatures, the stock oil here is meant hydrogenated residue and optional vacuum gas oil (being called for short VGO), wherein the boiling point of hydrogenated residue＞350 ℃.
Gasoline in the catalytic cracking production is ideal high octane gasoline products blending component; If diesel-fuel cetane number is enough high, can directly mixes in the diesel product, otherwise need through hydrotreatment to improve its cetane value; Heavy cycle oil is circulated to residual hydrogenation equipment and further processes; Slurry oil is after fractionation by distillation obtains steaming thing and resistates, wherein the thing boiling spread that steams of slurry oil is 400～500 ℃, steam thing and account for 15～80 heavy % of the full cut of slurry oil, enter residual hydrogenation equipment with optional distillate, the resistates boiling point of slurry oil is decided on steaming the thing yield, generally greater than 480 ℃, resistates accounts for 85～20 heavy % of the full cut of slurry oil, can be used as the blend component of oil fuel or road bitumen.
Residual hydrocracking is the reaction of a diffusion control, demetalization section especially in front.Therefore viscosity and reactant molecule size are the key factors that influences the particularly full-bodied vacuum residuum hydrotreatment reaction of residual oil.The adding that steams thing and heavy cycle oil of slurry oil has reduced the viscosity of residual hydrocracking raw material, slurry oil steam thing and heavy cycle oil has very high aromaticity, help bituminous matter to dissociate into littler structure.These have all increased the speed that the residual oil molecular diffusion enters the catalyzer micropore, thereby can improve the metal impurities decreasing ratio, improve residual hydrocracking device air speed and treatment capacity.The raising of diffusion simultaneously also can improve the distribution of metal in the catalyzer micropore, makes catalyzer can hold more metal, has delayed the inactivation of catalyzer.
The adding that steams thing and heavy cycle oil of slurry oil also can improve the flow state of logistics in reactor.Excessive stock oil viscosity will cause pulsation in reactor.The adding that steams thing and heavy cycle oil of slurry oil will make stock oil viscosity reduce, and improve the flow state of logistics in reactor, overcome the operational difficulty and the hidden danger that cause because of pulsation.
Opposite with fraction oil hydrogenation unit is that the general rear portion of residual hydrocracking device bed carbon deposit is serious, and many more near the reactor outlet carbon deposit more.This mainly is because colloid and oil content hydrogenation saturating speed are fast, and bituminous matter hydrogenation saturating speed is slow, and side chain easily breaks, the virtue nuclear that only surplus aromaticity is high, thereby solubleness is more and more littler in the more and more higher environment solvent of saturation ratio, is very easy at last be deposited on form carbon deposit on the catalyzer.If add high aromaticity slurry oil steam thing and heavy cycle oil, can improve the aromaticity of solvent on every side, increase bitum peptizing power, reduce its deposition on the catalyzer of rear portion.The partial hydrogenation product that steams polycyclic aromatic hydrocarbons in thing and the heavy cycle oil of slurry oil is very strong hydrogen supply agent in addition, can reduce the condensation of residual oil hot radical, suppresses the generation of coking precursor.The carbon deposit that these all can significantly reduce catalyzer has reduced deactivation rate, has prolonged the operational cycle.
Below in conjunction with accompanying drawing method provided by the present invention is given further instruction, but the present invention is not limited thereto.
Accompanying drawing is the schematic flow sheet of residual hydrocracking provided by the present invention and catalytically cracking heavy oil method.
Residual oil and hydrogen from pipeline 1 and 2 enters residual hydrocracking device 3 respectively, in the presence of hydrogenation catalyst, react, the product of separating residual hydrogenation, obtain gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenated residue, gas wherein, hydrotreated naphtha and hydrogenated diesel oil are respectively through pipeline 4,5,6 ejectors, hydrogenated residue then enters heavy oil catalytically cracking equipment 10 with the optional vacuum gas oil (VGO) from pipeline 8 through pipeline 9 through pipeline 7, in the presence of Cracking catalyst, react, the product of heavy oil separation catalytic cracking, obtain dry gas, liquefied gas, gasoline, diesel oil, heavy-cycle oil and slurry oil, dry gas wherein, liquefied gas, gasoline and diesel oil are respectively through pipeline 11,12,13,14 ejectors, heavy-cycle oil is successively through pipeline 15,21 are circulated to residual hydrocracking device 3, slurry oil enters distilling apparatus 17 through pipeline 16, isolated residue goes out device through pipeline 18, slurry oil steam thing successively through pipeline 19,21 enter residual hydrocracking device 3, and optional distillate is successively through pipeline 20,21 enter residual hydrocracking device 3.
The invention has the advantages that:
What 1, add slurry oil in residual oil especially decompression residuum steams thing and heavy-cycle oil, but decrease charging viscosity improves diffusivity and the removing impurities qualitative response speed of reactant, has reduced the sulphur, nickel, the content of vanadium that generate in the oil. Or guaranteeing to increase substantially the raw material air speed under the constant prerequisite of hydrogenated oil character.
2, the adding that steams thing and heavy-cycle oil of slurry oil can suppress the carbon deposit of hydrogenation reactor rear portion bed, and it is active to improve residual oil hydrocatalyst, prolongs the residual hydrogenation equipment operation cycle.
3, slurry oil steam thing and heavy-cycle oil can reduce sulfur content behind hydrogenation, thereby can reduce the sulfur content in RFCC vapour, the diesel oil; Slurry oil steam thing and heavy-cycle oil hydrogenation after can increase its saturation degree and hydrogen content, improve the yield (the yield sum that refers to liquefied gas, gasoline and diesel oil) of light oil, the yield that shows as hydrogenated diesel oil and catalytic cracking light oil improves; Reduce simultaneously the green coke amount, improve the treating capacity of heavy oil catalytically cracking equipment.
4, adopt method provided by the invention can make residual hydrogenation and catalytic cracking unit can process separately decompression residuum inferior, and with quality preferably VGO with hydrocracking unit fecund intermediate oil.
The following examples will give further instruction to method provided by the invention, but not thereby limiting the invention.Employed stock oil is vacuum residuum in embodiment and the Comparative Examples, and its character is listed in table 1.The residual hydrogenation test is carried out in two-tube reactor, dress hydrogenation protecting agent and Hydrodemetalation catalyst in first reactor (be called for short anti-), dress Hydrobon catalyst in second reactor (be called for short two anti-), three's ratio is 5: 45: 50, the trade names of wherein hydrogenation protecting agent, Hydrodemetalation catalyst, Hydrobon catalyst are respectively RG-10A, RDM-1, RMS-1, produce by Changling Refinery Chemical Industry Co., Ltd. of China Petrochemical Industry catalyst plant; Embodiment is identical with employed cracking catalyst in the Comparative Examples, is the catalyst plant production of Lanzhou branch office of group of CNPC, and trade names are LV-23.Processing condition and test-results are listed in table 2 and table 3, and in FCC tests, light oil wherein refers to liquefied gas, gasoline and diesel oil, and heavy oil refers to slurry oil and heavy cycle oil.
Embodiment 1
Stock oil A is the mixture that steams thing, heavy catalytic cycle oil of vacuum residuum, catalytically cracked oil, three's mass ratio was followed successively by 90: 4: 6, wherein the thing boiling spread that steams of catalytically cracked oil is 400～500 ℃, steams the 45 heavy % (down together) that thing accounts for the full cut of slurry oil.Test conditions is: hydrogen dividing potential drop 14.2MPa, 400 ℃ of anti-temperature, 405 ℃ of two anti-temperature, hydrogen-oil ratio 1000Nm
3/ m
3, air speed is 0.278h
-1, generate the distribution of oil nature and product and see Table 2.
In hydrogenated residue (＞363 ℃), mix VGO (accounting for 68.1 heavy % of vacuum residuum in the hydrogenating materials) again, together as catalytically cracked material.FCC tests is to carry out on fixed fluidized bed device, and test conditions is: 520 ℃ of temperature of reaction, agent-oil ratio 6: 1, air speed 10h
-1Product yield sees Table 2.
As can be seen from Table 1, in vacuum residuum, add catalytically cracked oil steam thing, heavy catalytic cycle oil after, its viscosity is from 1482mm
2/ s drops to 627mm
2/ s.As can be seen from Table 2, the sulphur content of hydrogenated oil is 0.50 heavy %, the content of Ni+V is 15.6ppm, the yield of hydrogenated diesel oil is 15.5 heavy % (accounting for vacuum residuum), the yield of catalytic cracking light oil is 77.7 heavy % (accounting for catalytically cracked material), and the green coke amount is 10.6 heavy % (accounting for catalytically cracked material).
Comparative Examples 1
Compare with embodiment 1, the raw material of residual hydrogenation equipment only is a vacuum residuum in this Comparative Examples.Test conditions is: hydrogen dividing potential drop 14.2MPa, 400 ℃ of anti-temperature, 405 ℃ of two anti-temperature, hydrogen-oil ratio 1000Nm
3/ m
3, air speed is 0.278h
-1, generate the distribution of oil nature and product and see Table 2.
In hydrogenated residue (＞363 ℃), mix VGO (accounting for 68.1 heavy % of vacuum residuum in the hydrogenating materials), with embodiment 1 in identical slurry oil steam thing and heavy cycle oil, together as catalytically cracked material.FCC tests is to carry out on fixed fluidized bed device, and test conditions is: 520 ℃ of temperature of reaction, agent-oil ratio 6: 1, air speed 10h
-1Product yield sees Table 2.
As can be seen from Table 2, the yield of hydrogenated diesel oil is 10.4 heavy % (accounting for the hydrogenation charging), lacks 4.1 percentage points than the yield of embodiment 1 hydrogenated diesel oil; The yield of catalytic cracking light oil is 74.2 heavy % (accounting for catalytically cracked material), lacks 3.5 percentage points than the yield of embodiment 1 catalytically cracked gasoline; The green coke amount is 12.1 heavy % (accounting for catalytically cracked material), increases by 1.5 percentage points than embodiment 1 green coke amount.
Comparative Examples 2
Compare with embodiment 1, the raw material of residual hydrogenation equipment is the mixture (mass ratio of the former with the latter is 94: 6) of vacuum residuum and heavy catalytic cycle oil in this Comparative Examples.Test conditions is: hydrogen dividing potential drop 14.2MPa, 400 ℃ of anti-temperature, 405 ℃ of two anti-temperature, hydrogen-oil ratio 1000Nm
3/ m
3, air speed is 0.266h
-1, generate the distribution of oil nature and product and see Table 2.
In hydrogenated residue (＞363 ℃), mix VGO (accounting for 68.1 heavy % of vacuum residuum in the hydrogenating materials) again, together as catalytically cracked material.FCC tests is to carry out on fixed fluidized bed device, and test conditions is: 520 ℃ of temperature of reaction, agent-oil ratio 6: 1, air speed 10h
-1Product yield sees Table 2.
As can be seen from Table 2, though the yield of catalytic cracking light oil, green coke amount be more approaching with embodiment 1 respectively, but the sulphur content of hydrogenated oil is 0.61 heavy %, the content of Ni+V is 17.5ppm, exceed 1.9ppm than embodiment 1, the yield of hydrogenated diesel oil is 14.7 heavy % (accounting for the hydrogenation charging), lacks 0.8 percentage point than the yield of embodiment 1 hydrogenated diesel oil.In addition since slurry oil to steam thing not processed, this part material also can't be converted into light-end products.
Embodiment 2
The residual hydrogenation test is carried out in two-tube reactor; dress hydrogenation protecting agent and Hydrodemetalation catalyst in first reactor; adorn Hydrobon catalyst in second reactor; three's ratio is 5: 45: 50; stock oil B is the mixture that steams thing, heavy catalytic cycle oil of vacuum residuum, catalytically cracked oil, and three's mass ratio was followed successively by 80: 7: 13.Test conditions is: hydrogen dividing potential drop 14.2MPa, 400 ℃ of anti-temperature, 405 ℃ of two anti-temperature, hydrogen-oil ratio 1000Nm
3/ m
3, air speed is 0.313h
-1, generate the distribution of oil nature and product and see Table 3.
In hydrogenated residue (＞363 ℃), mix VGO (accounting for 76.6 heavy % of vacuum residuum in the hydrogenating materials) again, together as catalytically cracked material.FCC tests is to carry out on fixed fluidized bed device, and test conditions is: 520 ℃ of temperature of reaction, agent-oil ratio 6: 1, air speed 10h
-1Product yield sees Table 3.
As can be seen from Table 1, in vacuum residuum, add catalytically cracked oil steam thing, heavy catalytic cycle oil after, its viscosity is from 1482mm
2/ s drops to 320mm
2/ s.As can be seen from Table 3, the sulphur content of hydrogenated oil is 0.51 heavy %, the content of Ni+V is 13.8ppm, the yield of hydrogenated diesel oil is 18.0 heavy % (accounting for the hydrogenation charging), the yield of catalytic cracking light oil is 77.3 heavy % (accounting for catalytically cracked material), and the green coke amount is 10.2 heavy % (accounting for catalytically cracked material).
Comparative Examples 3
Compare with embodiment 2, the raw material of residual hydrogenation equipment only is a vacuum residuum in this Comparative Examples.Test conditions is: hydrogen dividing potential drop 14.2MPa, 400 ℃ of anti-temperature, 405 ℃ of two anti-temperature, hydrogen-oil ratio 1000Nm
3/ m
3, air speed is 0.25h
-1, generate the distribution of oil nature and product and see Table 3.
In hydrogenated residue (＞363 ℃), mix VGO (accounting for 76.6 heavy % of vacuum residuum in the hydrogenating materials) again, together as catalytically cracked material.FCC tests is to carry out on fixed fluidized bed device, and test conditions is: 520 ℃ of temperature of reaction, agent-oil ratio 6: 1, air speed 10h
-1Product yield sees Table 3.
As can be seen from Table 3, the yield of hydrogenated diesel oil is 10.4 heavy % (accounting for the hydrogenation charging), lacks 7.6 percentage points than the yield of embodiment 2 hydrogenated diesel oils; The yield of catalytically cracked gasoline is 72.2 heavy % (accounting for catalytically cracked material), lacks 4.9 percentage points than the yield of embodiment 2 catalytic cracking light oil; The green coke amount is 11.8 heavy % (accounting for catalytically cracked material), has more 1.6 percentage points than the green coke amount of embodiment 2.
Embodiment 3
The residual hydrogenation test is carried out in two-tube reactor; dress hydrogenation protecting agent and Hydrodemetalation catalyst in first reactor; adorn Hydrobon catalyst in second reactor; three's ratio is 5: 45: 50; stock oil C is the mixture that steams thing, heavy catalytic cycle oil, coker gas oil of vacuum residuum, catalytically cracked oil, and four mass ratio was followed successively by 75: 4: 11: 10.Test conditions is: hydrogen dividing potential drop 14.2MPa, 400 ℃ of anti-temperature, 405 ℃ of two anti-temperature, hydrogen-oil ratio 1000Nm
3/ m
3, air speed is 0.333h
-1, generate the distribution of oil nature and product and see Table 3.
FCC tests is to carry out on fixed fluidized bed device, and as catalytically cracked material, test conditions is with hydrogenated residue (＞363 ℃): 520 ℃ of temperature of reaction, agent-oil ratio 6: 1, air speed 10 h
-1Product yield sees Table 3.
As can be seen from Table 1, in vacuum residuum, add catalytically cracked oil steam thing, heavy catalytic cycle oil, coker gas oil after, its viscosity is from 1482mm
2/ s drops to 211mm
2/ s.As can be seen from Table 3, the sulphur content of hydrogenated oil is 0.49 heavy %, the content of Ni+V is 13.6ppm, the yield of hydrogenated diesel oil is 19.2 heavy % (accounting for the hydrogenation charging), the yield of catalytic cracking light oil is 71.2 heavy % (accounting for catalytically cracked material), and the green coke amount is 12.3 heavy % (accounting for catalytically cracked material).
Table 1
| The stock oil title | Vacuum residuum | A | B | C |
| Raw material is formed, heavy % | ||||
| Vacuum residuum | 100 | 90 | 80 | 75 |
| Slurry oil steam thing | 0 | 4 | 6 | 4 |
| Heavy cycle oil | 0 | 6 | 14 | 11 |
| Coker gas oil | 0 | 0 | 0 | 10 |
| Density (20 ℃), g/cm 3 | 1.0238 | 1.0217 | 1.0221 | 1.0113 |
| Viscosity (100 ℃), mm 2/s | 1476 | 627 | 320 | 211 |
| Carbon residue, heavy % | 20.5 | 18.5 | 16.6 | 15.8 |
| Sulphur, heavy % | 5.1 | 4.72 | 4.33 | 4.28 |
| Nickel, ppm | 36.7 | 33.0 | 29.4 | 27.5 |
| Vanadium, ppm | 112 | 101 | 89.6 | 84 |
| Stable hydrocarbon, heavy % | 11.6 | 12.9 | 14.8 | 18.1 |
| Aromatic hydrocarbons, heavy % | 54.4 | 55.3 | 56.3 | 54.1 |
| Colloid, heavy % | 27.4 | 25.5 | 23.5 | 22.7 |
| Bituminous matter (C 7Insolubles), heavy % | 6.6 | 5.9 | 5.3 | 5.0 |
Table 2
| Embodiment 1 | Comparative Examples 1 | Comparative Examples 2 | |
| Residual hydrocracking | |||
| Raw material is formed, heavy % | |||
| Vacuum residuum | 90 | 100 | 94 |
| Slurry oil steam thing | 4 | 0 | 0 |
| Heavy cycle oil | 6 | 0 | 6 |
| Processing condition | |||
| The hydrogen dividing potential drop, MPa | 14.2 | 14.2 | 14.2 |
| Temperature of reaction, ℃ | |||
| First reactor | 400 | 400 | 400 |
| Second reactor | 405 | 405 | 405 |
| Volume space velocity, hour -1 | 0.278 | 0.25 | 0.266 |
| Hydrogen-oil ratio | 1000 | 1000 | 1000 |
| Generate oil nature | |||
| Sulphur, heavy % | 0.50 | 0.80 | 0.61 |
| Nickel, ppm | 6.9 | 9.0 | 8.1 |
| Vanadium, ppm | 8.7 | 10 | 9.4 |
| Product distributes, heavy % | |||
| Gas+H 2The S+ hydrotreated naphtha | 10.0 | 11.0 | 10.4 |
| Hydrogenated diesel oil | 15.5 | 10.4 | 14.5 |
| Hydrogenated residue | 74.5 | 78.6 | 75.1 |
| Heavy oil fluid catalytic cracking | |||
| Processing condition | |||
| Temperature of reaction, ℃ | 520 | 520 | 520 |
| Agent-oil ratio | 6 | 6 | 6 |
| Air speed, h -1 | 10 | 10 | 10 |
| Product distributes, heavy % | |||
| Dry gas | 3.2 | 3.2 | 3.2 |
| Liquefied gas | 20.3 | 19.8 | 20.0 |
| Gasoline | 46.5 | 43.5 | 46.3 |
| Diesel oil | 10.9 | 10.9 | 11.0 |
| Heavy oil | 8.5 | 10.5 | 8.7 |
| Coke | 10.6 | 12.1 | 10.8 |
Table 3
| Embodiment 2 | Comparative Examples 3 | Embodiment 3 | |
| Residual hydrocracking | |||
| Raw material is formed, heavy % | |||
| Vacuum residuum | 80 | 100 | 75 |
| Slurry oil steam thing | 7 | 0 | 4 |
| Heavy cycle oil | 13 | 0 | 11 |
| Coker gas oil | 0 | 0 | 10 |
| Processing condition | |||
| The hydrogen dividing potential drop, MPa | 14.2 | 14.2 | 14.2 |
| Temperature of reaction, ℃ | |||
| First reactor | 400 | 400 | 400 |
| Second reactor | 405 | 405 | 405 |
| Volume space velocity, hour -1 | 0.278 | 0.25 | 0.333 |
| Hydrogen-oil ratio | 1000 | 1000 | 1000 |
| Generate oil nature | |||
| Sulphur, heavy % | 0.51 | 0.80 | 0.49 |
| Nickel, ppm | 7 | 9 | 6.4 |
| Vanadium, ppm | 6.8 | 10 | 7.2 |
| Product distributes, heavy % | |||
| Gas+H 2The S+ hydrotreated naphtha | 8.8 | 11.0 | 8.7 |
| Hydrogenated diesel oil | 18.0 | 10.4 | 19.2 |
| Hydrogenated residue | 73.2 | 78.6 | 72.1 |
| Heavy oil fluid catalytic cracking | |||
| Processing condition | |||
| Temperature of reaction, ℃ | 520 | 520 | 520 |
| Agent-oil ratio | 6 | 6 | 6 |
| Air speed, h -1 | 10 | 10 | 10 |
| Product distributes, heavy % | |||
| Dry gas | 3.3 | 3.1 | 3.9 |
| Liquefied gas | 20.2 | 16.9 | 17.8 |
| Gasoline | 46.4 | 43.6 | 42.5 |
| Diesel oil | 10.6 | 11.6 | 10.9 |
| Heavy oil | 9.3 | 12.9 | 12.6 |
| Coke | 10.2 | 11.8 | 12.3 |
Claims (4)
1, the method for residual hydrocracking and catalytically cracking heavy oil comprises:
The steam thing, heavy catalytic cycle oil, optional distillate of residual oil and catalytically cracked oil enter residual hydrogenation equipment together, carry out hydrogenation reaction in the presence of hydrogen and hydrogenation catalyst, hydrogenation conditions is: hydrogen dividing potential drop 5.0～22.0MPa, 330～450 ℃ of temperature of reaction, volume space velocity 0.1～3.0 hour
-1, hydrogen-oil ratio 350～2000Nm
3/ m
3Reaction product isolated obtains gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenated residue, the thing boiling spread that steams of described catalytically cracked oil is 400～500 ℃, steam thing and account for 15～80 heavy % of the full cut of slurry oil, described distillate is to be selected from coker gas oil, deasphalted oil, inferior heavy vacuum gas oil and solvent treatment to extract one or more mixture among the oil out;
Hydrogenated residue enters heavy oil catalytically cracking equipment separately or with vacuum gas oil, in the presence of cracking catalyst, carry out cracking reaction, processing condition are: the weight ratio 3～10 of 470～570 ℃ of temperature of reaction, 0.5～5 second reaction times, catalyzer and stock oil, 650～800 ℃ of regenerated cracking catalyst temperature, reaction product isolated obtains dry gas, liquefied gas, gasoline, diesel oil, heavy cycle oil and slurry oil, and wherein heavy cycle oil is circulated to residual hydrogenation equipment;
Slurry oil is after fractionation by distillation goes out resistates, and the thing that steams of slurry oil is circulated to hydrogenation unit.
2,, it is characterized in that described residual oil is vacuum residuum or long residuum according to the method for claim 1.
3, according to the method for claim 1, it is characterized in that described activity of hydrocatalyst metal component is selected from nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum or cobalt-molybdenum, carrier is selected from aluminum oxide, silicon-dioxide or amorphous aluminum silicide.
4, according to the method for claim 1, the stock oil that it is characterized in that residual hydrogenation equipment is the mixture that steams thing, heavy catalytic cycle oil and optional distillate of residual oil, catalytically cracked oil, and wherein catalytically cracked oil steams 3～50 heavy % that thing and heavy catalytic cycle oil account for the hydrogenation unit combined feed total feed.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011154969A CN1165601C (en) | 2001-04-28 | 2001-04-28 | Process for hydrogenating residual oil and catalytically cracking heavy oil |
| KR1020020022946A KR100644987B1 (en) | 2001-04-28 | 2002-04-26 | Process and Apparatus for Processing Residue |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011154969A CN1165601C (en) | 2001-04-28 | 2001-04-28 | Process for hydrogenating residual oil and catalytically cracking heavy oil |
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| Publication Number | Publication Date |
|---|---|
| CN1382776A CN1382776A (en) | 2002-12-04 |
| CN1165601C true CN1165601C (en) | 2004-09-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011154969A Expired - Lifetime CN1165601C (en) | 2001-04-28 | 2001-04-28 | Process for hydrogenating residual oil and catalytically cracking heavy oil |
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| KR (1) | KR100644987B1 (en) |
| CN (1) | CN1165601C (en) |
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-
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Also Published As
| Publication number | Publication date |
|---|---|
| CN1382776A (en) | 2002-12-04 |
| KR20020084408A (en) | 2002-11-07 |
| KR100644987B1 (en) | 2006-11-13 |
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