CN101418222B - Composite process for treatment of inferior residual oil - Google Patents
Composite process for treatment of inferior residual oil Download PDFInfo
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- CN101418222B CN101418222B CN200710157792A CN200710157792A CN101418222B CN 101418222 B CN101418222 B CN 101418222B CN 200710157792 A CN200710157792 A CN 200710157792A CN 200710157792 A CN200710157792 A CN 200710157792A CN 101418222 B CN101418222 B CN 101418222B
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Abstract
The invention discloses a combined process method for treating inferior residual oil. The method comprises the following steps: a residual oil material enters a solvent deasphalting device to obtain DAO and deoil asphalt; the obtained DAO enters a hydrogenation device of a boiling bed and is treated to obtained a lightweight distillation fraction and hydrogenated tail oil; the hydrogenated tail oil enters a catalytic cracking device and is treated to obtain a lightweight distillation fraction and oil slurry; at least partial oil slurry and the deoil asphalt are mixed, enter a hydrogenation device of a suspension bed and are treated to obtain a lightweight distillation fraction and unconverted tail oil, wherein the unconverted tail oil circularly returns the solvent deasphalting device; and the lightweight distillation fraction and the DAO are mixed and enter the hydrogenation device of the boiling bed. The combined process course organically combines a decarbonization process and a hydrogenation process; and according to different properties of raw materials, a corresponding process and operation condition is adopted so as to maximize conversion of the residual oil material while minimizing equipment investment.
Description
Technical field
The present invention relates to a kind of method of producing light ends oil, particularly solvent deasphalting, boiling bed hydrogenation, catalytic cracking and floating bed hydrocracking technology are organically combined the combined method of producing light ends oil by poor residuum.
Background technology
Fast development along with global economy; The quick growth of lightweight, clean fuel oil demand and former oil quality are worse and worse; Heavy constituent content is increasingly high; How effectively to utilize non-renewable petroleum resources, realize residual oil lighting to greatest extent, production high value petroleum products is the current important topic that faces.
The residual oil processing technology comprises hydrogenation and two types of technological processs of decarburization, and wherein decarbonization process mainly comprises solvent deasphalting, coking, RFCC etc., and hydrogenation technique mainly comprises hydrotreatment, unifining etc.The decarbonization process facility investment is low, but liquid product yield is low, and character is poor.The hydrogenation technique quality product is better, and liquid yield is high, but owing to uses high pressure reactor to cause investment higher.The residual hydrogenation technology of comparative maturity is the fixed bed residual hydrogenation at present, but this technology receives the restriction of feedstock property, and to the metal of raw material, index requests such as carbon residue are relatively stricter.And the Residue Hydrotreating Technology adaptability to raw material of liquid bed and suspension bed is wide, more and more receives people's attention.Face quality residual oil raw material worse and worse, how decarbonization process and hydrogenation process are organically combined, realization residual oil maximum conversion and capital contribution are minimum to be the technology of being badly in need of at present.
CN1393525A proposes a kind of solvent deasphalting, fixed bed hydrogenation is handled and the method for the combined processing high-sulfur high-metal residual oil of catalytic cracking.Residual oil obtains deasphalted oil (DAO) and de-oiled asphalt through solvent extraction; Wherein deasphalted oil is sent into fixed bed hydrogenation treatment unit upgrading with optional heavy catalytic cycle oil; Hydrogenation tail oil is sent into the CCU cracking; All or part of heavy cycle oil is circulated to the fixed bed hydrogenation treatment unit in its product, and all or part of catalytic slurry loops back solvent deasphalting unit.There is following problem in this method; Contain the catalytic cracking catalyst powder in the first catalytic slurry, carry easily in the entering deasphalted oil, after DAO sends into the fixed bed hydrogenation device through solvent extraction; Catalyst fines is easy to be deposited on the beds, causes bed pressure drop to raise and obstruction; It two is that the pitch that solvent deasphalting unit removes is not used preferably, and this part component is difficult to become asphaltic products., can only cause the wasting of resources as mixing asphalt material or oil fuel.
US7214308 proposes the method for a kind of solvent deasphalting and the combined process residual oils of boiling bed hydrogenation.Residual oil obtains deasphalted oil (DAO) and de-oiled asphalt through solvent extraction, in the boiling bed hydrogenation reactor drum, is handling deasphalted oil (DAO) and de-oiled asphalt under the different operation conditions optimization respectively then.Wherein process of the liquid bed processing condition mitigation of the ebullating bed reactor condition (especially working pressure) of deasphalted oil than the processing de-oiled asphalt.During this process using liquid bed processes de-oiled asphalt, owing to be rich in a large amount of macromole condensed-nuclei aromatics, colloid and bituminous matter in the de-oiled asphalt, viscosity is big; Mobile poor; Cause the liquid bed catalytic hydrogenation reaction mainly to occur in catalyst surface, macromolecular substance can not get into the duct of catalyzer and react, so the utilization ratio of catalyzer is low; Cause the catalyzer displacement frequent, cost is higher.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of combination process of handling residual oil raw material is provided, make it can process inferior raw material, maximum improves the yield and the quality of clean cargo, reduces cost of investment simultaneously.
The combination process of processing poor residuum of the present invention comprises the steps:
A, residual oil raw material get into solvent deasphalting unit, obtain deasphalted oil and de-oiled asphalt;
The deasphalted oil that obtains among b, the step a gets into the boiling bed hydrogenation treatment unit, in the presence of hydrogen and catalyzer, carries out hydro-upgrading, and separated product obtains light ends oil and hydrogenation tail oil;
The hydrogenation tail oil that obtains among c, the step b gets into CCU; Under the catalytic cracking catalyst effect, carry out cracking; Separated product obtains light ends, heavy cycle oil and slurry oil; Heavy cycle oil can also can partly or entirely be circulated to the boiling bed hydrogenation treatment unit in the cracking of CCU circulating inside;
At least a portion slurry oil that obtains among the de-oiled asphalt that obtains among d, the step a and the step c mixes the back and gets into the floating bed hydrogenation device; Under hydrogen and disperse type catalyzer effect, carry out the hydrocracking reaction, separated product obtains light ends (comprising light naphthar, diesel oil, wax oil) and unconverted tail oil.
The unconverted tail oil of at least a portion that obtains in e, the steps d is circulated to the solvent deasphalting unit of step a, and at least a portion light ends then is circulated to the boiling bed hydrogenation device of step b.
The residual oil raw material of addressing among the step a comprises that metal content is at least 120 μ g/g in the residual oil that crude distillation obtains, particularly raw material, and carbon residue is at least the residual oil of 10wt%.Solvent for use is selected from C
3～C
8In alkane or alkene, white oil, light naphthar, the petroleum naphtha one or more, preferred light naphthar.The light naphthar that when device goes into operation, can adopt other technological processs to produce under the normal operating condition, adopts steps d floating bed hydrogenation operating unit produces among the present invention light naphthar as supplementing solvent, is used for the solvent of replenish loss.
Residual oil raw material and solvent can carry out counter current contact respectively from the upper and lower entering of solvent deasphalting unit in extraction tower, also can get into extraction tower again through pre-mixing earlier and separate.
The operational condition of solvent deasphalting is among the present invention: temperature is 80～260 ℃, and pressure is 2.0～6.0MPa, and the solvent volume ratio is 1.0～10.0; Preferred temperature is 120～210 ℃, and pressure is 4.0～5.0MPa, and solvent volume is than 4.0～8.0.
Old process is adopted in the solvent deasphalting operation, can be that single hop also can be two sections.
The solvent deasphalting unit controlling index is that the content of heptane insolubles generally is lower than 1wt% in the deasphalted oil (DAO), is preferably to be lower than 0.1wt%, is preferably to be lower than 0.05wt%; And the DAO productive rate is generally 20～85wt%, is preferably 20～60wt%.Basically asphaltenes not among the DAO like this can carry out boiling bed hydrogenation under than the demulcent condition and transform with production high-quality FCC charging, and the pitch that removes also can satisfy the charging requirement of floating bed hydrogenation device.
Boiling bed hydrogenation treatment technology described in the step b is conventional boiling bed residual oil hydrogen addition technology.But its operational condition is owing to the improvement of feedstock property, and more conventional boiling bed residual oil hydrogenation technique parameter relaxes manyly.Its processing parameter is generally: 350～450 ℃ of temperature of reaction, preferably 380～430 ℃; Reaction pressure is 5.0～18.0MPa, is preferably 7.0～15.0MPa; Hydrogen to oil volume ratio is 500～2000, is preferably 700～1500; Volume space velocity is 0.1～5.0h during liquid
-1, be preferably 0.2～3.0h
-1Boiling-bed catalyst is the conventional hydrotreating catalyst in this area, and wherein the activity of such catalysts metal can be in nickel, cobalt, molybdenum and the tungsten one or more.Can comprise by weight percentage like the catalyzer composition: nickel or cobalt are 0.5%～10% (calculating by its oxide compound); Molybdenum or tungsten are 1%～25% (calculating by its oxide compound), and carrier can be in aluminum oxide, silicon oxide, aluminium oxide-silicon oxide or the titanium oxide one or more.The shape of catalyzer is extrudate or sphere, and bulk density is 0.5～0.9g/cm
3, particle diameter (spherical diameter or bar shaped diameter) is 0.04～1.0mm, specific surface area is 80～300m
2/ g.Described boiling bed hydrogenation treatment unit comprises at least one ebullated bed reactor.
CCU described in the step c comprises a reactor drum, a revivifier and a separation column at least.The catalytic cracking reaction condition is: 470～570 ℃ of temperature of reaction, 1～5 second reaction times, agent weight of oil than 3～10,650～750 ℃ of regeneration temperatures.The catalytic cracking catalyst that is adopted comprises the catalyzer that is generally used for catalytic cracking; Like silica-alumina catalyst, silica-magnesia catalyst, acid-treated carclazyte and molecular sieve cracking catalyst; Molecular sieve cracking catalyst preferably, wherein molecular sieve is optional self-contained or do not contain Y or HY molecular sieve, the super-stable Y molecular sieves that contains or do not contain rare earth, ZSM-5 series molecular sieve, the high-silica zeolite with five-membered ring structure, beta-molecular sieve or its mixture of rare earth.Adopt molecular sieve cracking catalyst active high, green coke is few, and gasoline yield is high, transformation efficiency is high.The reactor drum of described CCU can be the catalyst cracker of various types, and preferably riser reactor or riser tube add the bed reactor drum.Technical process is generally: raw oil injects from the riser reactor bottom; Contact with high temperature catalyst from the fresh regenerated of revivifier; The oil gas that cracking reaction generates and the catalyst mixture of deposit coke move up along riser reactor, accomplish the catalytic cracking reaction of whole raw oil.
The boiling bed hydrogenation tail oil can be produced various light ends after catalytic cracking, wherein gasoline fraction is the desirable blending component of stop bracket gasoline; Diesel oil distillate can be used as the product blending component, or further hydro-upgrading; Heavy cycle oil can also can partly or entirely be circulated to boiling bed hydrogenation treatment unit hydro-upgrading in the cracking of CCU circulating inside; Partly or entirely slurry oil can be used as the charging of floating bed hydrogenation device, and the remainder slurry oil can get rid of in addition.Slurry oil is as the good solvent of green coke precursor in the floating bed hydrogenation process, and contained catalyst fines then can be used as the green coke carrier and carries the discharge process green coke, helps prolonging the production cycle of floating bed hydrogenation device.
The raw material that uses in the floating bed hydrogenation process of addressing in the steps d is the parallel feeding of de-oiled asphalt and catalytic slurry, and wherein the weight ratio of de-oiled asphalt and catalytic slurry is 0.1～10.0, is preferably 0.3～8.0; The disperse type catalyzer that the floating bed hydrogenation process is used can be a water-soluble catalyst, also can be oil-soluble catalyst.Water-soluble catalyst can be the heteropolyacid salt aqueous solution of two or more metals in periodic table of elements VIB, VIIB and the group VIII metal, like phospho-molybdic acid nickel, phospho-wolframic acid nickel etc.; Described oil-soluble catalyst can be the oil soluble organic cpds of two or more metals in periodic table of elements VIB, VIIB and the group VIII metal, like many carbonyl compound, naphthenate compound and the porphyrin class inner complex of molybdenum, nickel, cobalt.In weight metal, the content of above-mentioned disperse type catalyzer in raw material is 50～3000 μ g/g, is preferably 100～2000 μ g/g.
The operational condition of floating bed hydrogenation process is: reaction pressure 8～25MPa, 400～490 ℃ of temperature of reaction, volume space velocity 0.1～2.0h during liquid
-1, hydrogen to oil volume ratio (under the standardpressure) 200～1200.Be preferably reaction pressure 1 5～20MPa, 420～470 ℃ of temperature of reaction, volume space velocity 0.5～1.5h during liquid
-1Hydrogen to oil volume ratio (under the standardpressure) 400～1000.
The fractionation of floating bed hydrogenation product obtains various light ends and comprises light naphthar, diesel oil, wax oil, and unconverted tail oil loops back the solvent extraction device.Control the catalyst inventory of floating bed hydrogenation reactive system through effluxing a certain amount of residue, the level of residue that wherein effluxes is 1～10wt%, is preferably 2～5wt%.Oil circulation time boiling bed hydrogenation reactor drum of light ends carries out refining reaction.
Adopt suspension bed to carry out the hydrocracking process of deasphalted oil and catalytic slurry; Owing to use the highly active catalyzer of decentralized; Catalyzer is dispersed in the residual oil raw material oil with molecular form, and catalyst precursor is activated on the spot, so compare with load catalyst system; This reaction process is real contact reacts, does not have alternate mass transfer.Catalyzer disperses all hydrocarbon molecules are all effectively transformed with molecular form, can not receive the restriction of hydrocarbon molecule size.Bituminous matter component in the residual oil and other hydrocarbon molecule transform on an equal basis.Basically can eliminate the formation and the unconverted bitum deposition of potential coke precursors.Thereby the thermodynamic stability that keeps the no conversion hydrocarbon molecule.The distillate that floating bed hydrocracking generates loops back the boiling bed hydrogenation device, can the part dispersed catalyst be taken in the ebullated bed reactor, helps the carrying out of hydrogenation reaction, specifically can be referring to patent US5868923.It is second-rate that the floating bed hydrocracking that at high temperature carries out simultaneously de-oiled asphalt and catalytic slurry reacts the benzoline that obtains; And behind boiling bed hydrogenation, can obviously improve quality product; The benzoline that floating bed hydrogenation obtains gets into the flowability that the boiling bed hydrogenation device also can improve deasphalted oil; Help the carrying out of loaded catalyst heterogeneous catalyst diffusing step, thereby help the generation of hydrogenation reaction.
Advantage of the present invention is:
1, solvent deasphalting, boiling bed hydrogenation, floating bed hydrogenation and catalytic cracking process is combined, hydrogenation technique and decarbonization process are organically combined, make technology have adaptability to raw material widely, can process various poor residuums.
2, this combination process process can realize the lighting to greatest extent of residual oil, and can produce high-quality light-end products.
3. this combination process has possessed the technological merit of decarburization and hydrogenation technique simultaneously, has not only guaranteed quality product but also can reduce overall cost of ownership.
4, this combination process carries out solvent deasphalting to residual oil raw material and handles and to obtain deasphalted oil and de-oiled asphalt; Adopt liquid bed processing deasphalted oil can adopt relative demulcent operational condition; De-oiled asphalt and catalytic slurry carry out floating bed hydrogenation under harsh operational condition; Can make feedstock property and operational condition carry out rational Match, thereby make process lowest optimization.
5, the light naphthar that floating bed hydrocracking is produced is as the supplementing solvent of solvent extraction device, can avoid the operation of solvent extraction device required and introduce a large amount of light paraffins, reduces the production operation cost;
6, in the floating bed hydrogenation process, adopt catalytically cracked oil as solvent, help the dissolving of green coke precursor in the pitch hydroconversion process, reaction mass is not produced be separated, suppress the green coke of floating bed hydrogenation process effectively; Utilize the catalytic cracking catalyst powder that contains in the catalytic slurry as floating bed hydrogenation process green coke carrier on the other hand, can avoid reactor plugs.
Description of drawings
Fig. 1 is the combination process schematic flow sheet that the present invention handles residual hydrogenation.
Embodiment
Below in conjunction with Fig. 1 method provided by the present invention is further specified.
Residual oil raw material 1 can be pre-mixed with solvent 16; Also can send into static mixer 2 by pipeline respectively mixes; Mixture is sent into solvent deasphalting unit 3, and the solvent deasphalting operation can be that one-part form can be a two-part also, obtains DAO 4 and de-oiled asphalt 8; Mix with hydrogen 9 after deasphalted oil 4 preheatings and send into boiling bed hydrogenation treatment unit 5, under conventional boiling bed hydrogenation catalyst and processing condition, carry out heteroatoms and carbon residues such as hydrogenation and removing sulphur, nitrogen, product obtains light ends 10 and hydrogenation tail oil 11 through separation; Hydrogenation tail oil 11 gets into heavy oil catalytically cracking equipment 6, and cracking under catalytic cracking catalyst and reaction conditions obtains light-end products 14, heavy cycle oil 17 and catalytic slurry 15; Heavy cycle oil 17 can partly or entirely be circulated to boiling bed hydrogenation treatment unit 5; Also can partly or entirely loop back CCU 6; Partly or entirely catalytic slurry 15 is sent into floating bed hydrocracking device 7 after mixing from the de-oiled asphalt 8 of solvent extraction device and hydrogen 9; Under the disperse type catalyzer effect; De-oiled asphalt and catalytic slurry hydrocracking obtain 12 (comprising light naphthar, diesel oil and wax oil) of light ends oil; Part light naphthar wherein can be used as the supplementing solvent of solvent deasphalting unit, and 12 of the light ends oil of remainder mix the back with deasphalted oil 4 and get into boiling bed hydrogenation treatment unit 5, and unconverted tail oil 13 all or on a small quantity effluxes the back together with disperse type catalyzer and sends solvent deasphalting unit 3 back to by pipeline.
For further specifying all main points of the present invention, adopt the flow process of Fig. 1, enumerate following examples, but therefore do not limit the present invention.
Typical poor residuum is used in test, and its feedstock property is seen table 1.Can know that by table 1 subtracting slag in the sand has metal content height, carbon residue height and the high characteristics of sulphur content; Wherein only the content of nickel, vanadium and iron promptly reaches 190 μ g/g; Asphalt content surpasses 8wt%; Carbon residue content surpasses 18wt%, is that conventional fixed bed Residue Hydrotreating Technology is difficult to the directly poor residuum of processing.
Embodiment 1
Present embodiment carries out the reaction process of residual hydrogenation for adopting solvent deasphalting, liquid bed, suspension bed and catalytic cracking combined technique.At first residual oil raw material with by butane and pentane and on a small quantity by the floating bed hydrogenation generation＜145 ℃ of mixed solvent uniform mixing in static mixer that naphtha fraction is formed; Get into two sections solvent deasphalting units then; Obtain DAO and de-oiled asphalt; Mix with hydrogen after the DAO preheating and send into the boiling bed hydrogenation treatment unit; Under conventional boiling bed hydrogenation catalyst and processing condition, carry out hydrogenation reaction, remove heteroatoms and carbon residues such as sulphur in the raw material, nitrogen, hydrogenation products obtains gasoline, diesel oil and hydrogenation tail oil through separation; The boiling bed hydrogenation tail oil gets into heavy oil catalytically cracking equipment and reacts, and cracking obtains light-end products, heavy cycle oil and catalytic slurry under catalytic cracking catalyst and reaction conditions; Heavy cycle oil all is circulated to the boiling bed hydrogenation treatment unit; Catalytic slurry is sent into the floating bed hydrocracking device after mixing from the de-oiled asphalt of solvent extraction device and hydrogen; In the presence of disperse type catalyzer, carry out hydrocracking reaction; After distillation, obtain light ends oil (comprising light naphthar, diesel oil and wax oil) and floating bed hydrogenation tail oil; Wherein＜145 ℃ of petroleum naphthas are as the supplementing solvent of solvent deasphalting unit, and it is further refining that the light ends oil of remainder gets into the boiling bed hydrogenation treatment unit, sends the unconverted floating bed hydrogenation tail oil of the overwhelming majority back to solvent deasphalting unit together with disperse type catalyzer by pipeline.The reaction conditions of solvent deasphalting wherein, boiling bed hydrogenation, floating bed hydrocracking and CCU is seen table 2 respectively, and test-results is seen table 3.
With the tungsten-nickel catalyzator of aluminum oxide as carrier, wherein tungstenic is that 12wt% (presses WO to the loaded catalyst that the boiling bed hydrogenation process is used in the catalyzer as spheric
3Calculate), nickeliferous is 5wt% (pressing NiO calculates), the bulk density of catalyzer is 0.78g/cm
3, surface-area is 290m
2/ g, pore volume are 0.54ml/g, and the granules of catalyst diameter is 0.15mm.
Floating bed hydrogenation test catalyst system therefor is water-soluble disperse type catalyzer, i.e. the phospho-molybdic acid nickel heteropolyacid salt aqueous solution, and catalyzer consists of: Mo 6.0wt%, Ni 0.7wt%, P 0.26 wt%.
FCC tests is carried out on riser fluid catalytic cracking, adopts circulating reaction-reproduction operation pattern.The CHV-1 catalyzer that catalytic cracking catalyst is produced for Changling Refinery Chemical Industry Co., Ltd.'s catalyst plant.
Table 1 feedstock property
| Project | Subtract slag in the sand |
| Density (20 ℃), kg.m -3 | 1024.8 |
| Carbon residue, wt% | 20.7 |
| Metallic element | |
| Ni，μg.g -1 | 43.4 |
| V，μg.g -1 | 143.6 |
| Four proximate analyses, wt% | |
| Stable hydrocarbon | 9.9 |
| Aromatic hydrocarbon | 52.2 |
| Colloid | 29.5 |
| Bituminous matter | 8.4 |
| Boiling range, % | |
| 350～520℃ | 10 |
| ＞520℃ | 90 |
Table 2 combination process test conditions
| Project | Data |
| The solvent deasphalting condition | |
| Temperature, ℃ | 160 |
| Pressure, MPa | 4.0 |
| Solvent ratio, v/v | 7 |
| The boiling bed hydrogenation reaction conditions | |
| The hydrogen dividing potential drop, MPa | 10 |
| Temperature of reaction, ℃ | 400 |
| Volume space velocity, h -1 | 4 |
| Hydrogen to oil volume ratio, v/v | 800 |
| The floating bed hydrogenation reaction conditions | |
| The reaction stagnation pressure, MPa | 18 |
| Volume space velocity, h -1 | 1.2 |
| Temperature of reaction, ℃ | 450 |
| The catalyzer add-on, μ g.g -1 | 500 |
| Hydrogen-oil ratio, v/v | 800 |
| The catalytic cracking reaction condition | |
| Temperature of reaction, ℃ | 500 |
| Reaction times, second | 2.5 |
| Agent weight of oil ratio | 6.0 |
Table 3 test-results
| Project | Data |
| Product distributes (is benchmark with the fresh feed), wt% | |
| Dry gas | 7.2 |
| Liquefied gas | 11.2 |
| Gasoline | 41.0 |
| Diesel oil | 34.8 |
| Coke | 3.2 |
| Externally extracting oil | 2.6 |
| Gasoline property: | |
| Sulphur, μ g.g -1 | 120 |
| Nitrogen, μ g.g -1 | 15 |
| Octane value (RON) | 89 |
| Diesel oil character: | |
| Sulphur, μ g.g -1 | 230 |
| Nitrogen, μ g.g -1 | 45 |
| Cetane value | 43 |
Comparative example 1
Comparative example 1 adopts the technological process of solvent deasphalting and liquid bed combination.At first residual oil raw material and C
4/ C
5Mixed solvent mixes through static mixer, gets into solvent deasphalting unit then and obtains deasphalted oil (DAO) and de-oiled asphalt.Wherein two placed in-line ebullated bed reactors of de-oiled asphalt entering carry out hydrocracking reaction; Deasphalted oil entering pressure comparatively demulcent boiling bed hydrogenation device carries out unifining and cracking reaction; Use therein catalyzer is with embodiment 1; Solvent deasphalting and ebullating bed reactor condition are seen table 4, and reaction result is seen table 5.
The reaction conditions of table 4 simultaneous test
| Project | Data |
| The solvent deasphalting condition | |
| Temperature, ℃ | 160 |
| Pressure, MPa | 4.0 |
| Solvent ratio, v/v | 7 |
| Handle the boiling bed hydrogenation reaction conditions of DAO | |
| The hydrogen dividing potential drop, MPa | 10 |
| Temperature of reaction, ℃ | 415 |
| Volume space velocity, h -1 | 1 |
| Hydrogen to oil volume ratio, v/v | 800 |
| Handle the boiling bed hydrogenation reaction conditions of de-oiled asphalt | |
| The reaction stagnation pressure, MPa | 20 |
| Volume space velocity, h -1 | 0.5 |
| Temperature of reaction, ℃ | 430 |
| Hydrogen-oil ratio, v/v | 800 |
Table 5 test-results
| Project | Data |
| Product distributes (is benchmark with the fresh feed), wt% | |
| Gas | 4.5 |
| Gasoline | 17.5 |
| Diesel oil | 31.7 |
| Wax oil | 27.4 |
| Residual oil | 18.9 |
| Gasoline property: | |
| Sulphur, μ g.g -1 | 110 |
| Nitrogen, μ g.g -1 | 12 |
| Octane value (RON) | 83 |
| Diesel oil character: | |
| Sulphur, μ g.g -1 | 250 |
| Nitrogen, μ g.g -1 | 48 |
| Cetane value | 46 |
Warp can be known with the comparative example contrast, adopts technology of the present invention can improve yield of light oil, realize the lighting of heavy residual oil to greatest extent, and the vapour that obtains, diesel oil sulphur and nitrogen content is very low, can be used as good petrol and diesel oil blend component.
Claims (7)
1. a combination process of handling poor residuum comprises the steps:
A, residual oil raw material get into solvent deasphalting unit, obtain deasphalted oil and de-oiled asphalt; The operational condition of said solvent deasphalting unit is: temperature is 80～260 ℃, and pressure is 2.0～6.0MPa, and the solvent volume ratio is 1.0～10.0;
The deasphalted oil that b, step a obtain gets into the boiling bed hydrogenation treatment unit, in the presence of hydrogen and catalyzer, carries out hydro-upgrading, and separated product obtains light ends oil and hydrogenation tail oil; The operational condition of said boiling bed hydrogenation treatment unit is: temperature of reaction is 350～450 ℃, and reaction pressure is 5.0～18.0MPa, and hydrogen to oil volume ratio is 500～2000, and volume space velocity is 0.1～5.0h during liquid
-1
The hydrogenation tail oil that c, step b obtain gets into CCU, under the catalytic cracking catalyst effect, carries out cracking, and separated product obtains light ends, heavy cycle oil and slurry oil; The operational condition of said CCU is: temperature of reaction is 470～570 ℃, and the reaction times is 1～5 second, and agent weight of oil ratio is 3～10, regeneration temperature is 650～750 ℃;
At least a portion slurry oil that obtains among the de-oiled asphalt that obtains among d, the step a and the step c mixes the back and gets into the floating bed hydrogenation device, under hydrogen and disperse type catalyzer effect, carries out hydrocracking and reacts, and separated product obtains light ends and unconverted tail oil; The operational condition of said floating bed hydrogenation device is: reaction pressure is 8～25MPa, and temperature of reaction is 400～490 ℃, volume space velocity 0.1～2.0h during liquid
-1, hydrogen to oil volume ratio 200～1200;
The unconverted tail oil of at least a portion that obtains in e, the steps d is circulated to the solvent deasphalting unit of step a, and at least a portion light ends is circulated to the boiling bed hydrogenation device of step b.
2. combination process according to claim 1 is characterized in that, metal content is at least 120 μ g/g in the residual oil raw material described in the step a, and carbon residue content is at least 10wt%.
3. combination process according to claim 1 is characterized in that, uses light naphthar as solvent residual oil raw material to be separated among the step a.
4. combination process according to claim 1 is characterized in that, the operational condition of solvent deasphalting unit described in the step a is: temperature is 120～210 ℃, and pressure is 4.0～5.0MPa, and the solvent volume ratio is 4.0～8.0.
5. combination process according to claim 1 is characterized in that, single hop or two-stage process are adopted in the solvent deasphalting operation described in the step a.
6. combination process according to claim 1 is characterized in that, the heavy cycle oil CCU circulating inside cracking that obtains among the step c perhaps partly or entirely is circulated to the boiling bed hydrogenation treatment unit.
7. combination process according to claim 1 is characterized in that, the weight ratio of de-oiled asphalt and catalytic slurry is 0.1～10.0 in the steps d.
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