CN1393525A - Process for transforming high-sulfur high-metal residual oil - Google Patents
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Abstract
A process for transforming high-S and high-metal residual oil includes such steps as hydrogenation reaction of residual oil, oil slurry, solvent, asphalt-removed oil, circulating heavy oil and solvent refined oil in a hydrogenating reactor under the existance of hydrogen and hydrocatalyst, separating products to obtian gas, naphtha, hydrogenated diesel oil and hydrogenated tail oil, cracking the said hydrogenated tail oil, and separating the resultant. Its advantages are low cost and raised yield and quality of light oil.
Description
The invention belongs to a hydroprocessing technique process, one does not exist catalytic cracking step under the hydrogen situation and one not existing treating process under the hydrogen situation to handle the multistage processes of hydrocarbon ils, more particularly, be a kind of method that residual oil solvent deasphalting, hydrotreatment and three kinds of technological processs of catalytic cracking are organically combined.
World Oil Market constantly increases the demand of light-end products, therefore with residual oil to greatest extent lighting become the target that oil refining enterprise is pursued.At refinery, the light oil yield height of catalytic cracking (FCC) device, good in economic efficiency, thereby, enlarge the FCC raw material sources, improve the light oil yield of full factory, become the advantageous measure of each refinery.
The main raw material of FCC apparatus is vacuum gas oil normally, utilizes the FCC apparatus process residual oils, and common way is that residual oil is directly mixed in the vacuum gas oil together as the FCC raw material, or with after the residual hydrocracking as the FCC raw material.For directly mixing residual oil, because metal in the residual oil, sulphur, nitrogen, carbon residue equal size are very high, so incorporation is lower.For residual hydrocracking, because the working pressure of residual hydrogenation equipment very high (hydrogen dividing potential drop 〉=12.0MPa), the lower (LHSV≤0.25h of charging air speed
-1), catalyst life is short and can not regenerate (being generally work-ing life 11 months), makes that the residual hydrogenation equipment investment is huge, process cost is higher, thereby has limited the residual hydrogenation technology in industrial applying.
Asphaltene in vacuum residues (C
7Or C
5Insolubles) content is the greatest factor that influences the hydrogenation technique condition, particularly hydrogen dividing potential drop and volume space velocity.As everyone knows, can remove bituminous matter in the residual oil by solvent deasphalting technology, and the deasphalted oil of this " totally " can processed comparatively easily conversion very " totally ".Therefore many documents proposition employing solvent deasphaltings and other processing means such as hydrocracking or catalytic cracking make up process residual oils.
US4,752,376 propose to use at normal temperatures and pressures C
5, C
6Deng heavier normal paraffin solvent deasphalting, deasphalted oil is through two sections hydrogenation catalyst hydrofinings that employing is different, for following process is supplied raw materials.But solvent deasphalting is difficult to application and economic inadequately under the normal temperature and pressure in actual production.
US4,447,313 propose to use at normal temperatures the pentane solvent diasphaltene, and deasphalted oil is refining with the Pd-ZSM5 catalyst hydrogenation, for following process is supplied raw materials.But dissolved dose of diasphaltene and deasphalted oil are handled with the catalyst hydrogenation that contains precious metal, and is economical inadequately in actual production.
US6,117,306 propositions are residual oil elder generation hydrogenation, will carry out solvent deasphalting again through the vacuum residuum that distillation obtains and handle.Deasphalted oil is carried out catalytic cracking reaction at last after hydrotreatment.This side's product yield is higher, but long flow path and need high-pressure hydrogenation, and investment and all non-well-established law high value of process cost are high.
EP683218A2 adopts solvent deasphalting to handle residual oil, deasphalted oil after hydrodemetallation (HDM) and distillate mix laggard horizontal high voltage hydrocracking.Owing to be hydrogenation unit entirely, therefore investment is bigger.
The objective of the invention is to provide on the basis of existing technology a kind of process for transforming high-sulfur high-metal residual oil, to improve the yield and the quality of lightweight oil.
Method provided by the invention comprises:
Residual oil and low molecular hydrocarbon kind solvent obtain deasphalted oil (DAO) and de-oiled asphalt through the solvent deasphalting process extracting, wherein DAO and optional heavy catalytic cycle oil, the refining oil of extracting out of optional solvent enters hydrotreater together, reaction in the presence of hydrogen and hydrogenation catalyst, separated product obtains gas, petroleum naphtha, hydrogenated diesel oil and hydrogenation tail oil, wherein hydrogenation tail oil enters catalytic cracking (FCC) device, 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, wherein partly or entirely heavy cycle oil is circulated to hydrotreater, heavy cycle oil also can be in the catalytic cracking unit internal recycling, and partly or entirely slurry oil is circulated to solvent deasphalting unit.
Below solvent deasphalting, DAO hydrotreatment and three kinds of technological processs of catalytic cracking are described in detail respectively.
(1) residual oil solvent deasphalting
The used raw material of solvent deasphalting is the mixture of residual oil and catalytically cracked oil, and wherein residual oil is long residuum or/and the preferred vacuum residuum of vacuum residuum, and the sulphur content of residual oil is 1～5 heavy %, and metal Ni and V content are 50～700ppm; Catalytically cracked oil can be all from the heavy oil catalytically cracking equipment among the present invention, it also can be the mixture of the slurry oil that obtains of the slurry oil that obtains of the heavy oil catalytically cracking equipment among the present invention and non-wax catalysis cracking unit of the present invention, in the solvent deasphalting raw material, catalytically cracked oil accounts for 1～30 heavy %; The low molecular hydrocarbon kind solvent is to be selected from C
3～C
8A kind of or its mixture in alkane or alkene, condensate oil, light naphthar, the petroleum naphtha, preferred C
4～C
6A kind of or its mixture in alkane or the alkene.
Residual oil raw material and solvent can be respectively enter from the upper and lower of extraction tower, carry out counter current contact in extraction tower, also can separate by entering extraction tower after the pre-mixing more earlier.
The operational condition of solvent deasphalting is as follows: extraction temperature is 60～280 ℃ preferred 100～240 ℃, and pressure is the preferred 3.0～5.0MPa of 1.0～6.0MPa, and solvent ratio is the preferred 4.0～8.0v/v of 1.0～15.0v/v.
Solvent deasphalting both can carry out extracting under the undercritical conditions of solvent, also carry out extracting under the super critical condition of solvent.Under the undercritical conditions of solvent, carry out extracting, be meant that service temperature and pressure are lower than the critical temperature and the emergent pressure of solvent respectively.Under the super critical condition of solvent, carry out extracting, be meant that service temperature and pressure are higher than the critical temperature and the emergent pressure of solvent respectively.
Solvent deasphalting can adopt the single hop flow process, and promptly the liquid stream that comes out from the extraction tower top obtains DAO after solvent recuperation, and DAO is all as the raw material of hydrotreatment.Solvent in the DAO solution can reclaim by critical recovery, flash distillation and steam stripped method successively, also can reclaim by supercritical recovery, flash distillation and steam stripped method successively.Critical recovery is meant near the purpose that reaches DAO and separated from solvent the criticality of solvent, supercritical recovery is meant under the supercritical state of solvent DAO and separated from solvent, compare with independent flash distillation (also claiming evaporation) method, critical recovery or supercritical recovery solvent method can be saved energy consumption.Solvent in the bituminous solution can reclaim by flash distillation and steam stripped method successively.
Solvent deasphalting also can adopt two sections flow processs, promptly the liquid stream that comes out from the extraction tower top is separated into DAO solution and hydrosol through settling vessel, DAO solution and hydrosol obtain DAO and colloid respectively after solvent recuperation, the wherein colloid deasphalted oil of also weighing, both can be used as oil fuel, also can be used as the blend component of road bitumen, DAO is all as the raw material of hydrotreatment.Method for recovering solvents in the DAO solution is identical with the single hop flow process, and the solvent in hydrosol and the bituminous solution can reclaim by flash distillation and steam stripped method successively.
Bituminous matter is the main impurity that influences the residual hydrocracking operating severity, is the key factor that influences next step residual hydrocracking.Residual oil is behind the solvent deasphalting upgrading, and the bituminous matter among the DAO is removed substantially, and the N.heptane insolubles among the control DAO is lower than 1 heavy %, preferably is lower than 0.1 heavy %, is preferably lower than 0.05 heavy %.Be worth very low and more difficult because solvent deasphalting process is paid the gilsonite of product, refinery wishes that all its productive rate is the smaller the better, therefore, under the prerequisite that guarantees the DAO quality, reduce gilsonite output as much as possible, for FCC provides more raw materials, DAO is 70～95 heavy % with respect to the yield of residual oil raw material, preferred 80～90 heavy %.Gilsonite can be used as gasified raw material, circulating fluidized bed (CFB) raw material, boiler of power plant fuel, Pitch Water Slurry raw material, binding agent etc.
(2) DAO hydrotreatment
Because DAO is from vacuum residuum, therefore its hydrotreatment technical qualification are more complicated and harsh than vacuum gas oil (VGO) or coker gas oil, but, can provide the fine raw material for FCC fully by selecting performance hydrogenation catalyst combination preferably and appropriate processing condition.
Not only contain impurity such as S, N among the DAO, also have more metal, as Ni, V and Fe etc., its carbon residue is also than VGO height in addition, therefore will adopt the connect mode of compound filling of 2-3 kind hydrogenation catalyst usually, and the DAO of poor quality is carried out hydrotreatment.These catalyzer comprise protective material, hydrodemetallation (HDM) (HDM) catalyzer, hydrofining (HDS/HDN) catalyzer; its active metal component is nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum or cobalt-molybdenum; carrier is aluminum oxide, silicon-dioxide or amorphous aluminum silicide, and wherein aluminum oxide is the most frequently used carrier.Protective material mainly is the impurity such as Fe, Ca that remove in the raw material, prevents beds pressure drop rising; The HDM catalyzer mainly is the heavy metals such as Ni, V that remove in the raw material, and the Hydrobon catalyst that prevents the downstream is because of deposition heavy metal inactivation; The main effect of Hydrobon catalyst is S, the N impurity that removes in the raw material, and it is saturated to carry out suitable hydrogenation, to improve the catalytic cracking performance of raw material.Three kinds of catalyzer can be connected and are divided in the fixed-bed reactor, and also can connect is divided in two fixed-bed reactor.The percent by volume of protective material filling can be 2～10%, and the HDM catalyzer is 10～40%, and Hydrobon catalyst is 50～90%, and best compound filling ratio is according to deciding the performance of raw material oil properties, catalyzer and the running period of requirement etc.
The raw material of hydrotreatment is that DAO, optional heavy catalytic cycle oil, optional solvent are made with extra care the mixture of extracting oil out.The adding of oil is extracted in heavy catalytic cycle oil and solvent treatment out, helps the hydrotreatment of DAO.
The processing condition of DAO hydrotreatment mainly are hydrogen dividing potential drop and volume space velocity, decide according to the technological process of solvent deasphalting and the residual oil raw material source of DAO.Usually C3-DAO can operate under the VGO of routine hydroprocessing technique condition and there is no problem; Adopt conventional VGO hydroprocessing condition that certain difficulty is arranged for C4, C5-DAO, therefore need suitably to improve the hydrotreatment severity, adopt the operational condition that is similar to middle pressure hydrocracking usually, and each raw material is treated with a certain discrimination.No matter which kind of DAO raw material is carried out hydrotreatment, must be lower than 1 heavy % by the strict N.heptane insolubles of controlling among the DAO, preferably be lower than 0.1 heavy %, be preferably lower than 0.05 heavy %.If N.heptane insolubles surpasses this level, adopting hydrotreatment to carry out the DAO upgrading will be as hydrotreatment residual oil difficulty.Usually the operational condition of DAO hydrotreatment can be selected in following scope: hydrogen dividing potential drop 5.0～12.0MPa, volume space velocity 0.30～1.0h
-1, 350～410 ℃ of temperature of reaction and hydrogen-oil ratio 350～1000Nm
3/ m
3
(3) catalytic cracking
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 active ingredient of the employed catalytic cracking catalyst of catalytic cracking is selected from Y or HY zeolite, the ultrastable Y that contains or do not contain rare earth, ZSM-5 series zeolite, the supersiliceous zeolite with five-membered ring structure, β zeolite or its mixture that contains or do not contain rare earth.Processing condition are: the weight ratio (hereinafter to be referred as agent-oil ratio) 3～10 of 470～570 ℃ of temperature of reaction, 1～5 second reaction times, catalyzer and stock oil, and 650～750 ℃ of regeneration temperatures, the stock oil here is meant hydrogenation tail oil.
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; The all or part of hydrotreater that is circulated to of heavy cycle oil further transforms, and heavy cycle oil also can not be circulated to hydrotreater, but only in the catalytic cracking unit internal recycling; The all or part of solvent deasphalting unit that is circulated to of slurry oil, the remaining slurry oil of part circulation time can get rid of in addition.
Compare with the solvent deasphalting-hydrotreatment-FCC combination process of routine, method of the present invention has been further strengthened the relation between solvent deasphalting, hydrotreatment, the FCC three, rather than the processing route that advances under going out on simple.Specifically, mix slurry oil in the raw material vacuum residuum of solvent deasphalting, thereby further improved the yield of DAO from FCC; The heavy cycle oil that mixes among the DAO from FCC carries out hydrotreatment again, can provide more fine raw materials for FCC, has improved FCC working ability and lightweight oil output relatively; The slurry oil of FCC mixes in the vacuum residuum raw material as solvent deasphalting, and the heavy cycle oil of FCC can mix among the DAO raw material as hydrotreatment.
Below in conjunction with accompanying drawing method provided by the present invention is further detailed.
Accompanying drawing is a process for transforming high-sulfur high-metal residual oil principle process synoptic diagram provided by the present invention.
Process for transforming high-sulfur high-metal residual oil flow process provided by the present invention is:
After the residual oil raw material after the preheating of pipeline 1 and the FCC slurry oil mixing from pipeline 25, enter solvent deasphalting unit 4 through pipeline 2, the low molecular hydrocarbons kind solvent enters solvent deasphalting unit 4 through pipeline 3, extracting obtains DAO and de-oiled asphalt, wherein de-oiled asphalt goes out device through pipeline 6, DAO draws through pipeline 5, with the heavy catalytic cycle oil from pipeline 24, after the mixing of the refining extraction oil of the optional solvents of pipeline 20, enter hydrotreater 7 through pipeline 21, hydrogen enters hydrotreater 7 through pipeline 22, in the presence of hydrogenation catalyst, react, separated product obtains gas, naphtha, hydrogenated diesel oil and hydrogenation tail oil, gas wherein, naphtha, hydrogenated diesel oil is respectively through pipeline 8,9,10 go out device, hydrogenation tail oil is successively through pipeline 11,12 enter FCC apparatus 13, 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, dry gas wherein, liquefied gas, gasoline, diesel oil is respectively through pipeline 14,15,16,17 go out device, heavy-cycle oil is successively through pipeline 18,24, the 21 all or part of hydrotreaters 7 that are circulated to, heavy-cycle oil also can be successively through pipeline 18,23,12 all are circulated to catalytic cracking unit 13, slurry oil is successively through pipeline 19,25, the 2 all or part of solvent deasphalting units 4 that are circulated to, slurry oil also can be successively through pipelines 19,26 parts are got rid of outward.
The invention has the advantages that:
1, removed the metal more than 75% and most asphalitine in the residual oil by solvent deasphalting, so the hydrotreatment of DAO can be in middle pressure (5.0～12.0MPa) and relatively high charging air speed (0.30～1.0h-1) under carry out. So the investment decrease of hydrogenation plant, processing charges is also lower, and hydrogenation tail oil is the FCC raw material of high-quality.
2, slurry oil is incorporated into together depitching in the residual oil, so that deasphalted oil can improve productive rate under the prerequisite that keeps mass conservation. Valuable constituent also is fully used in the slurry oil in addition, removes simultaneously the catalyst fines in the slurry oil, is conducive to follow-up catalytic reaction process, has improved the economic benefit of device.
3, carry out again catalytic cracking after the deasphalted oil hydrotreatment, removed the sulphur in the raw material and increased saturation degree, satisfied environmental requirement, improved light oil yield and quality, reduced coke yield, thereby improved the whole economic efficiency of device.
4, by adopting the method for partial material circulation, solvent deasphalting, hydrotreatment, FCC three are carried out whole organic assembling, can reduce by a relatively large margin investment and operating cost, improved yield and the quality of light oil
The following examples will give further instruction to method provided by the invention, but therefore not limit the present invention.
Comparative Examples 1
The explanation of this Comparative Examples is the situation that raw material carries out solvent deasphalting with single vacuum residuum.
Test is carried out on medium-sized solvent deasphalting unit, vacuum residuum feed and C
5Alkane solvent enters from the upper and lower of extraction tower respectively, carries out counter current contact in extraction tower, in 190 ℃ of temperature, pressure 4.0MPa, solvent ratio is to carry out one section extracting under the condition of 6.0v/v.The liquid stream that comes out from the extraction tower top obtains DAO successively behind critical solvent recovery, flash distillation, stripping, the de-oiled asphalt that bottoms obtains behind flash distillation, stripping recovery solvent successively is as the fuel of circular fluid bed.
Test conditions and the results are shown in Table 1, as can be seen from Table 1, the yield of DAO is 82.0 heavy %, and the N.heptane insolubles of DAO is 0.1 heavy %, and Ni and V are 17.7ppm.
The present embodiment explanation is the situation that raw material carries out solvent deasphalting with the mixture of vacuum residuum and FCC slurry oil.Test the identical of used solvent and condition and Comparative Examples 1, test conditions and the results are shown in Table 1, as can be seen from Table 1, the yield of DAO is 85.0 heavy %, and the N.heptane insolubles of DAO is 0, and the content of Ni and V is 12.2ppm.Compare with Comparative Examples 1, in vacuum residuum, mix 15 heavy %FCC slurry oils after, the yield of DAO increases by 3.0 percentage points, does not contain N.heptane insolubles among the DAO, the content of Ni and V reduces, DAO is a kind of fine residual hydrocracking raw material.
Comparative Examples 2
The situation that the explanation of this Comparative Examples is carried out hydrotreatment with the DAO in the Comparative Examples 1.
The catalyst combination that test is adopted is: RG-10A/RG-10B/RF-220/RF-1000=3/2/30/65 (v%); wherein RG-10A, RG-10B are the hydrogenation protecting agent; be by the catalyst plant production of Changling Refinery Chemical Industry Co., Ltd. of China Petrochemical Corp., RF-220, RF-1000 are respectively Hydrodemetalation catalyst, Hydrobon catalyst is produced by Dutch Aksu chemical company.
The processing condition of hydrotreatment are: hydrogen dividing potential drop 8.0MPa, volume space velocity 0.5h
-1, hydrogen-oil ratio 700Nm
3/ m
3, 390 ℃ of temperature of reaction.
Test-results sees Table 2, and the result of table 2 shows, the DAO of single vacuum residuum is carried out hydrotreatment, and the carbon residue of hydrogenation tail oil is 4.36 heavy %, and its sulphur content is 0.30 heavy %.
Present embodiment illustrates the situation of carrying out hydrotreatment with after DAO among the embodiment 1 and the mixing of FCC heavy cycle oil.
The catalyzer that test is adopted is all identical with Comparative Examples 2 with processing condition.
Test-results sees Table 2, and the result of table 2 shows, the DAO that mixes slurry oil in the diasphaltene raw material is carried out hydrotreatment, and the carbon residue of hydrogenation tail oil is 3.24 heavy %, and the content of its Ni and V is extremely low, and sulphur content is 0.20 heavy %, is a kind of fine FCC raw material.
Comparative Examples 3
The hydrogenation tail oil of Comparative Examples 2 is carried out the FCC test on the small-sized riser catalytic cracking testing apparatus of a cover.This device adopts DCS operating system, has riser reactor, can carry out circulating reaction-reproduction operation pattern, and maximum throughput is 1kg/h.
FCC tests catalyst system therefor MLC-500 is produced by Qilu Petrochemical company of Sinopec Group catalyst plant.Operational condition is: 500 ℃ of temperature of reaction, agent-oil ratio 6.0,2.7 seconds reaction times.The FCC operational condition listed by table 3 and product distributes.
The data of table 3 show that total light hydrocarbon yield is 80.8 heavy %, and light oil yield is 68.5 heavy %, and coking yield is 7.8 heavy %.
The hydrogenation tail oil of embodiment 2 is carried out FCC on the identical small-sized riser catalytic cracking testing apparatus of a cover and Comparative Examples 3 test.Operational condition is identical with Comparative Examples 3.The FCC operational condition listed by table 3 and product distributes, and table 4 is FCC gasoline and diesel oil character.
The data of table 3 show: total light hydrocarbon yield is 83.3 heavy %, has increased by 2.5 percentage points than Comparative Examples 3; Light oil yield is 70.5 heavy %, has increased by 2.0 percentage points than Comparative Examples 3; Coking yield is 7.3 heavy %, has descended 0.5 percentage point than Comparative Examples 3.As can be seen from Table 4, catalytic gasoline is a fine motor spirit component, and the sulphur content of catalytic diesel oil is also lower.
Table 1
| Numbering | Comparative Examples 1 | |
| Raw material is formed, heavy % | ||
| Vacuum residuum | ????100 | ????85 |
| The FCC slurry oil | ????0 | ????15 |
| Solvent | Skellysolve A | Skellysolve A |
| The solvent deasphalting condition | ||
| Temperature, ℃ | ????190 | ????190 |
| Pressure, MPa | ????4.0 | ????4.0 |
| Solvent ratio, v/v | ????6.0 | ????6.0 |
| The DAO yield, heavy % | ????82.0 | ????85.0 |
| DAO character | ||
| Density (20 ℃), g/cm 3 | ????0.9794 | ????0.9829 |
| Viscosity (100 ℃), mm 2/s | ????150 | ????82.06 |
| Conradson carbon residue, heavy % | ????11.4 | ????9.55 |
| S, heavy % | ????3.49 | ????3.15 |
| N, heavy % | ????0.22 | ????0.23 |
| ????Ni，ppm | ????3.6 | ????3.3 |
| ????V，ppm | ????14.1 | ????8.9 |
| N.heptane insolubles, heavy % | ????0.1 | ????0 |
| The de-oiled asphalt softening temperature, ℃ | ????160 | ????155 |
Table 2
| Numbering | Comparative Examples 2 | |
| Test conditions | ||
| The hydrogen dividing potential drop, MPa | ????8.0 | ????8.0 |
| Temperature of reaction, ℃ | ????390 | ????390 |
| Volume space velocity, h -1 | ????0.5 | ????0.5 |
| Hydrogen-oil ratio, Nm 3/m 3 | ????700 | ????700 |
| Product distributes, heavy % | ||
| Gas | ????3.8 | ????3.5 |
| Petroleum naphtha | ????0.8 | ????1.0 |
| Diesel oil | ????9.4 | ????9.5 |
| Hydrogenation tail oil | ????87.0 | ????87.1 |
| Hydrogenation tail oil character | ||
| Density (20 ℃), g/cm 3 | ????0.9389 | ????0.9449 |
| Conradson carbon residue, heavy % | ????4.36 | ????3.24 |
| Ni content, ppm | ????＜0.1 | ????＜0.1 |
| V content, ppm | ????0.1 | ????＜0.1 |
| Sulphur content, heavy % | ????0.30 | ????0.20 |
| Desulfurization degree, % | ????91.4 | ????93.7 |
Table 3
| Numbering | Comparative Examples 3 | |
| Operational condition | ||
| Temperature of reaction, ℃ | ????500 | ????500 |
| Reaction times, second | ????2.7 | ????2.7 |
| Agent-oil ratio, | ????6.0 | ????6.0 |
| Product distributes, heavy % | ||
| Dry gas | ????4.1 | ????3.9 |
| Liquefied gas | ????12.3 | ????12.8 |
| Gasoline | ????44.0 | ????45.0 |
| Diesel oil | ????24.5 | ????25.5 |
| Heavy oil (heavy cycle oil+slurry oil) | ????6.8 | ????5.0 |
| Coke | ????7.8 | ????7.3 |
| Loss | ????0.5 | ????0.5 |
| Amount to | ????100 | ????100 |
| Transformation efficiency, heavy % | ????68.7 | ????69.5 |
| Total light hydrocarbon yield, heavy % | ????80.8 | ????83.3 |
| Light oil yield, heavy % | ????68.5 | ????70.5 |
Table 4
| Catalytic gasoline character | |
| Density (20 ℃), g/cm 3 | ????0.7498 |
| Sulphur, ppm | ????150 |
| Alkene, heavy % | ????25 |
| ??RON | ????90.1 |
| ??MON | ????79.8 |
| Catalytic diesel oil: | |
| Density (20 ℃), g/cm 3 | ????0.9452 |
| Sulphur, heavy % | ????0.20 |
| Condensation point, ℃ | ????-39 |
| Cetane value | ????20 |
Claims (10)
1, a kind of process for transforming high-sulfur high-metal residual oil, it is characterized in that residual oil, catalytically cracked oil and low molecular hydrocarbon kind solvent obtain deasphalted oil and de-oiled asphalt through the solvent deasphalting process extracting, wherein deasphalted oil and optional heavy catalytic cycle oil, the refining oil of extracting out of optional solvent enters hydrotreater together, reaction in the presence of hydrogen and hydrogenation catalyst, separated product obtains gas, petroleum naphtha, hydrogenated diesel oil and hydrogenation tail oil, wherein hydrogenation tail oil enters catalytic cracking unit, 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, wherein partly or entirely heavy cycle oil is circulated to hydrotreater, heavy cycle oil also can be in the catalytic cracking unit internal recycling, and partly or entirely slurry oil is circulated to solvent deasphalting unit.
2, according to the method for claim 1, it is characterized in that described residual oil is long residuum or/and vacuum residuum, the sulphur content of residual oil is 1～5 heavy %, metal Ni and V content are 50～700ppm.
3, according to the method for claim 1, it is characterized in that described catalytically cracked oil can be all from the heavy oil catalytically cracking equipment among the present invention, it also can be the mixture of the slurry oil that obtains of the slurry oil that obtains of the heavy oil catalytically cracking equipment among the present invention and non-wax catalysis cracking unit of the present invention, in the solvent deasphalting raw material, catalytically cracked oil accounts for 1～30 heavy %.
4,, it is characterized in that described low molecular hydrocarbon kind solvent is to be selected from C according to the method for claim 1
3～C
8A kind of or its mixture in alkane or alkene, condensate oil, light naphthar, the petroleum naphtha.
5,, it is characterized in that described low molecular hydrocarbon kind solvent is to be selected from C according to the method for claim 1 or 4
4～C
6A kind of or its mixture in alkane or the alkene.
6,, it is characterized in that the operational condition of solvent deasphalting is according to the method for claim 1: 60～280 ℃ of extraction temperatures, pressure 1.0～6.0MPa, solvent ratio is 1.0～15.0v/v.
7,, it is characterized in that the operational condition of hydrotreatment is: hydrogen dividing potential drop 5.0～12.0MPa, volume space velocity 0.30～1.0h according to the method for claim 1
-1, 350～410 ℃ of temperature of reaction, hydrogen-oil ratio 350～1000Nm
3/ m
3
8, according to the method for claim 1, the active metal component that it is characterized in that hydrogenation catalyst is nickel-tungsten, nickel-tungsten-cobalt, nickel-molybdenum or cobalt-molybdenum, and carrier is aluminum oxide, silicon-dioxide or amorphous aluminum silicide.
9, according to the method for claim 1, it is characterized in that catalytic cracking condition is: 470～570 ℃ of temperature of reaction, 1～5 second reaction times, the weight ratio 3～10 of catalyzer and hydrogenation tail oil, 650～750 ℃ of catalyst regeneration temperature.
10,, it is characterized in that the active ingredient of catalytic cracking catalyst is selected from Y or HY zeolite, the ultrastable Y that contains or do not contain rare earth, ZSM-5 series zeolite, the supersiliceous zeolite with five-membered ring structure, β zeolite or its mixture that contains or do not contain rare earth according to the method for claim 1.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100340643C (en) * | 2004-10-29 | 2007-10-03 | 中国石油化工股份有限公司 | Treatment method for inferior heavy oil and residual oil |
| CN101045884B (en) * | 2006-03-31 | 2010-05-12 | 中国石油化工股份有限公司 | Process of producing clean diesel oil and low carbon olefin with residual oil and heavy fraction oil |
| CN102311799A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Residual oil treatment combined process method |
| CN101418222B (en) * | 2007-10-26 | 2012-09-12 | 中国石油化工股份有限公司 | Composite process for treatment of inferior residual oil |
| CN103102944A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Combined process of hydrotreatment and light fraction-conversion for residual oil |
| CN103254936A (en) * | 2012-02-16 | 2013-08-21 | 中国石油天然气股份有限公司 | Combined process of hydrotreatment-catalytic cracking for residuum |
| CN105400543A (en) * | 2015-12-18 | 2016-03-16 | 广东石油化工学院 | Blend oil product and preparation method thereof |
| CN106147835A (en) * | 2015-03-30 | 2016-11-23 | 中国石油大学(北京) | A kind of combined method separating catalytic cracked oil pulp and preparing oil system needle coke |
| CN106147834A (en) * | 2015-03-30 | 2016-11-23 | 中国石油大学(北京) | A kind of combined method separating catalytic cracked oil pulp and preparing mesophase pitch |
-
2001
- 2001-06-29 CN CNB011198087A patent/CN1171978C/en not_active Expired - Lifetime
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100340643C (en) * | 2004-10-29 | 2007-10-03 | 中国石油化工股份有限公司 | Treatment method for inferior heavy oil and residual oil |
| CN101045884B (en) * | 2006-03-31 | 2010-05-12 | 中国石油化工股份有限公司 | Process of producing clean diesel oil and low carbon olefin with residual oil and heavy fraction oil |
| CN101418222B (en) * | 2007-10-26 | 2012-09-12 | 中国石油化工股份有限公司 | Composite process for treatment of inferior residual oil |
| CN102311799A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Residual oil treatment combined process method |
| CN103102944A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Combined process of hydrotreatment and light fraction-conversion for residual oil |
| CN103102944B (en) * | 2011-11-10 | 2015-04-01 | 中国石油化工股份有限公司 | Combined process of hydrotreatment and light fraction-conversion for residual oil |
| CN103254936A (en) * | 2012-02-16 | 2013-08-21 | 中国石油天然气股份有限公司 | Combined process of hydrotreatment-catalytic cracking for residuum |
| CN106147835A (en) * | 2015-03-30 | 2016-11-23 | 中国石油大学(北京) | A kind of combined method separating catalytic cracked oil pulp and preparing oil system needle coke |
| CN106147834A (en) * | 2015-03-30 | 2016-11-23 | 中国石油大学(北京) | A kind of combined method separating catalytic cracked oil pulp and preparing mesophase pitch |
| CN106147835B (en) * | 2015-03-30 | 2018-07-27 | 中国石油大学(北京) | A kind of separation catalytic cracked oil pulp simultaneously prepares the combined method that oil is needle coke |
| CN105400543A (en) * | 2015-12-18 | 2016-03-16 | 广东石油化工学院 | Blend oil product and preparation method thereof |
| CN105400543B (en) * | 2015-12-18 | 2017-02-01 | 广东石油化工学院 | Blend oil product and preparation method thereof |
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