CN1123625C - Process for treating and mixing residual oil - Google Patents
Process for treating and mixing residual oil Download PDFInfo
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- CN1123625C CN1123625C CN 00123132 CN00123132A CN1123625C CN 1123625 C CN1123625 C CN 1123625C CN 00123132 CN00123132 CN 00123132 CN 00123132 A CN00123132 A CN 00123132A CN 1123625 C CN1123625 C CN 1123625C
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Abstract
The present invention discloses technology for processing and combining residual oil, which organically combines the technology of residual oil hydrogenation, catalytic cracking, solvent deasphalting, etc. A hydrogenation device of the existing residual oil fixed bed flexibly treats raw oil, the treatment quantity of the raw oil is also increased, and/or the operational severity of the device is correspondingly decreased, and the service life of a hydrogenation catalyst is prolonged. At the same time, the treatment capacity of a catalytic cracking device and the total liquid recovery of the device are also improved, a coke yield and a cracking gas yield are decreased, and the high light aromatics of heavy raw materials and residual oil raw materials is realized. Main raw materials (or auxiliary materials) of bitumen with high quality are also obtained, and the reasonable use of petroleum resources is realized.
Description
The present invention relates to the processing treatment technology of weight, residual oil.In particular, relate to the refining and conversion of the heavy hydrocarbon of high bituminous matter, colloid, sulphur, nitrogen and metal.It comprises weight, Residue Hydrotreating Technology, catalytic cracking process, solvent deasphalting technology, be characterized in that this combination process not only can adapt to heaviness, the poor qualityization of stock oil, increase the processing power of residual oil, and can also effectively reduce the coking and deactivation speed of catalyzer in the hydrogenation technique device, the green coke amount of coker and the coking yield and the gas yield of catalytic cracking unit; The yield of light ends such as the gasoline of raising coking and catalytic cracking unit and diesel oil.
Along with crude oil becomes heavy day by day, becomes bad, more and more heavy, residual oil needs processing treatment.Processing treatment heavy, residual oil (＞500 ℃) will be not lower boiling product with its cracking still, as petroleum naphtha, intermediate oil and vacuum gas oil, but also will improve their hydrogen-carbon ratio, and this just need realize by the method for decarburization or hydrogenation.Wherein decarbonization process comprises coking, solvent deasphalting, heavy oil fluid catalytic cracking etc.; Hydrogenation comprises hydrocracking, hydrofining etc.At present, in the technology of process residual oils still based on decarbonization process, its principal feature is to be subjected to the influence of stock oil character bigger, especially be subjected to the influence of colloid in the stock oil, bituminous matter and aromaticity content obvious, and the yield of liquid product is not high, quality product is also poor, and coke output is also big, need carry out aftertreatment.Hydrogenation method can remedy the deficiency of decarbonization process, not only can hydrocracking residual oil, and improve the productive rate of liquid product, and can also remove heteroatoms wherein, quality product is not bad.But hydrogenation method can not be processed all weights, residual oil because of the tooling cost problem, and the result makes the refining of petroleum worker remove to develop the combination process of hydrogenation and decarburization very naturally.
A kind of method has been described among the CN1117071A, this method is that residual oil raw material carries out diasphaltene earlier, obtain pitch fractions and deasphalted oil, in the presence of hydrogen, deasphalted oil obtains the deasphalted oil of upgrading, the deasphalted oil behind the upgrading and one or more flash distillation fraction oil distillate fusion by the catalyst for demetalation bed, the blended oil that generates carries out hydrocracking again, to produce one or more fraction oil distillates.This method is because residual oil has at first adopted solvent deasphalting process, this process belongs to physical process, can only separate high boiling point components such as the bituminous matter in the residual oil raw material, colloid and macromole condensed-nuclei aromatics, can not make these high boiling components in the residual oil raw material carry out chemical conversion and become lower boiling ideal composition, when handling, can cause the yield of lower boiling purpose product cut oil such as last petroleum naphtha, intermediate oil and vacuum gas oil lower than the insufficient poor residuum raw material of low boiler cut.
Purpose of the present invention is exactly the deficiency at above-mentioned Technology, develop the method that a kind of material by high metal, high Conradson carbon residue, sulphur and nitrogen content obtains the lower boiling purpose product cut oil such as petroleum naphtha, intermediate oil and vacuum gas oil of low impurity content, not only can improve the yield of lower boiling purpose product cut oil, and can also prolong the work-ing life of hydrogenation catalyst in the hydrogenation unit.
Specific embodiments of the present invention comprises the steps:
(1) in a treatment zone that has hydrogen to exist, handles heavy, hydrocarbon raw material inferior, metal, Conradson carbon residue, sulphur and the nitrogen content of reaction liquid effluent are reduced.This processing section comprises at least one reactor or reaction bed;
(2) will deliver to atmospheric tower from the liquid phase effluent of the hydrotreatment of step (1), and be separated obtaining light ends and long residuum by this tower, described light ends mainly is meant cuts such as gasoline, diesel oil.
(3) will deliver to vacuum distillation tower in the part in the long residuum that step (2) obtain, reclaim vacuum gas oil and vacuum residuum by this tower;
(4) vacuum residuum that step (3) is obtained is sent into solvent deasphalting unit and is carried out diasphaltene, a kind of deasphalted oil and a kind of de-oiled asphalt.Can make the blend component of catalytic cracking charging and the raw material of production lubricant base according to the quality of deasphalted oil character, also can return hydrogenation reaction section of the present invention and carry out hydrotreatment.
(5) vacuum gas oil that step (3) is obtained obtains remaining long residuum with step (2) and mixes, and sends into catalytic cracking unit together and carries out lighting.Can access a kind of gas fraction, a kind of gasoline fraction, a kind of gas oil fraction and a kind of slurry oil in the catalytic cracking reaction section.Wherein gas fraction mainly comprises stable hydrocarbon and unsaturated hydrocarbons (methane, ethane, propane, the butane of C1-C4., ethene, propylene, butylene).
The described long residuum amount of delivering in the vacuum distillation tower of step (2) be according to the character of long residuum itself and the described catalytic cracking unit of step (5) to the index request decision of charging, the mixture of remainder should be able to satisfy the index request of the described catalytic cracking unit of step (5) to charging in the long residuum that vacuum gas oil that described step (3) obtains and step (2) obtain.
There is the condition of the material treatment step (1) that hydrogen exists as follows usually: in the hydrogenation reaction section, heavy, residual hydrocracking technology can be any technology of the present invention that is applicable to, as fixed bed weight, residual hydrogenation technology, suspension bed weight, residual hydrogenation technology, ebullated bed weight, residual hydrogenation technology, expanded bed weight, residual hydrogenation technology, heavy, the residual hydrogenation technology of moving-bed., residual hydrogenation technology heavy with at present industrial more ripe fixed bed is example, described reactor or reaction bed comprise a kind of hydrogenation catalyst at least, and the heavy residual oil hydrocatalyst of employing is meant the single catalyst or the combination catalyst of functions such as having weight, residuum hydrogenating and metal-eliminating, hydrogenating desulfurization, hydrodenitrification and hydrocracking.These catalyzer generally all are to be carrier with porous refractory inorganic oxides such as aluminum oxide, oxide compound or the sulfide of group vib and/or VIII family metal such as W, Mo, Co, Ni etc. are active ingredient, the catalyzer that optionally adds other various auxiliary agents such as P, Si, elements such as F, B, for example CEN, the FZC series of being produced by Fushun Petrochemical Research Institute pilot scale base weighs, residuum hydrogenating and metal-eliminating catalyst, and ZTN, the ZTS catalyst series produced by first fertilizer plant of Qilu Petrochemical company just belong to this class catalyzer.At present in fixed bed residual hydrogenation technology, it often is the supporting use of multiple catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst, hydrodenitrogenation catalyst are wherein arranged, the filling order generally is that stock oil is contacted with hydrodemetallation (HDM), hydrogenating desulfurization, hydrodenitrification, hydrocracking catalyst successively, sometimes also can be according to circumstances, adorn one or both catalyzer less, for example only load Hydrodemetalation catalyst and Hydrobon catalyst, and do not adorn hydrodenitrogenation catalyst and hydrocracking catalyst.Technology with these several catalyst mix fillings is also arranged certainly.Be 5-35MPa in absolute pressure normally, preferably 10-20Mpa, temperature are 300-500 ℃, preferably 350-450 ℃ of operation down.Volume space velocity and hydrogen dividing potential drop are to select according to the characteristic for the treatment of material and the transformation efficiency and the refining depth of requirement during liquid.Volume space velocity is in 0.1-5.0h during liquid
-1, 0.15-2h preferably
-1Scope in.Hydrogen to oil volume ratio is 100-5000, is preferably 500-3000.
In the atmospheric tower fractionation of step (2), the cut point that generally guarantees long residuum is 300-400 ℃, preferably about 340-380 ℃.Could guarantee like this gasoline fraction and diesel oil distillate that hydrogenation generates in the logistics are told, and be sent into corresponding oil product jar or downstream processing unit (plant) respectively.
The long residuum that treatment step in the vacuum distillation tower of step (3) (2) obtains will guarantee that the cut point of vacuum residuum is 450-600 ℃, preferably about 500-550 ℃ in the vacuum distillation tower operation.Could guarantee like this vacuum gas oil fraction in the long residuum is told, the long residuum that obtains with step (2) mixes.The amount of carrying out the long residuum of reduced pressure treatment is to decide according to the required index of the character of long residuum behind the hydrogenation and catalytic cracking unit charging, and the index required as present catalytic cracking unit charging is: (1) sulphur content is not higher than 0.35w%-0.6w%; (2) Conradson carbon residue is less than 5w%-10w%; (3) heavy metal nickel and vanadium total content are not higher than 20-45 μ g/g; (4) the total nitrogen content general requirement is less than 0.35w%, or basic n content is less than 0.15w%.If the index of catalytic cracking unit charging surpasses above-mentioned restriction, the then easy inactivation of catalytic cracking catalyst, and gas, coke yield increase in the product; Productive rate such as gasoline, diesel oil reduces.If the character of the normal slag of hydrogenation satisfies catalytic cracking charging index, then needn't tell the normal slag of part and carry out reduced pressure treatment; Carry out reduced pressure treatment otherwise then must tell the part long residuum, the vacuum gas oil that reduced pressure treatment is obtained mixes with remaining long residuum, makes to mix the index that oil properties satisfies the catalytic cracking unit charging.The long residuum amount of specifically carrying out reduced pressure treatment by hydrogenation after the character of long residuum and the index decision of catalytic cracking unit charging.Long residuum character restriction desired value good more, the catalytic cracking unit charging is big more behind the general hydrogenation, and the long residuum amount of carrying out reduced pressure treatment is just more little, otherwise then big more.The solvent extraction device that vacuum residuum is sent into step (4) carries out the diasphaltene processing.
Adopt the solvent extraction process of being familiar with those skilled in the art of the present technique to carry out diasphaltene in the step (4).This solvent deasphalting technology can be used rotating disk contact tower or tray column, and hydrocarbon oil feed enters from the top, and extraction solvent enters from the bottom.The extraction medium that is adopted normally contains the light hydrocarbon solvent of alkane compound.The alkane compound that commerce provides comprises C
3～C
8Alkane is as propane, butane, Trimethylmethane, pentane, iso-pentane, hexane or two or more mixture wherein.For purposes of the invention, C preferably
3～C
7Alkane, most preferably butane, pentane or its mixture.Operational condition is generally: total extraction solvent and hydrocarbon-type oil weight ratio are 1.5～8: 1, and pressure is 0.1～5.0Mpa, and temperature is 60～250 ℃.According to the quality of deasphalted oil character, can also can return hydrogenation reaction section of the present invention and carry out hydrotreatment with it as the blend component of catalytic cracking charging or produce the raw material of lubricant base, the present invention preferably with it as the catalytic cracking charging.And the de-oiled asphalt behind the hydrogenation significantly reduces because of undesirable components such as impurity such as its contained sulphur, heavy metal and bituminous matters, can remove to do the bituminous blend component, can be used as the mixing raw material of coker feed, also can go hydrogen manufacturing, and the hydrogen of gained can be used for hydrogenation reaction section of the present invention.
In the step (5), the catalytic cracking technology that uses those skilled in the art of the present technique to be familiar with carries out hydrocarbon raw material catalytic cracking.The gas that the generates body recovery system of can degassing, gasoline fraction is preferably all delivered to the oil product jar.Gas oil often is sent to the further hydrotreatment of downstream hydrofining section at least in part, and slurry oil is preferably delivered to hydrogenation reaction system of the present invention and mixed with hydrogenating materials and carry out hydrogenation jointly then after separated the going out of suspension fine particle that it contains.Reason is to contain a large amount of arenes in the slurry oil of catalytic cracking, condensed-nuclei aromaticss such as bituminous matter in residual oil raw material and the hydrogenated products had solvability preferably, in hydrogenation process, the condensed-nuclei aromaticss such as bituminous matter that can reduce or eliminate in residual oil raw material and the hydrogenated products take place to assemble and the probability of coking, make residual hydrogenation equipment handle the worse residual oil of more character, and can also reduce sedimentation of coke amount on the hydrogenation catalyst, prolong the work-ing life of catalyzer, residual hydrogenation equipment can be turned round under higher transformation efficiency.The operational condition of catalytic cracking unit is generally: temperature is 450～600 ℃, preferably 460～550 ℃; The agent weight of oil is than 2～30, and preferably 2～20; With 0.1～15 second duration of contact of catalyzer, best 0.5～5 second; Pressure 0.1～0.5Mpa.The catalytic cracking catalyst that is adopted comprises the catalyzer that is generally used for catalytic cracking, as silica-alumina catalyst, silica-magnesia catalyst, acid-treated carclazyte and X type, Y type, ZSM-5, M type, layer post equimolecular sieve cracking catalyst, molecular sieve cracking catalyst preferably, this is because the active height of molecular sieve cracking catalyst, green coke is few, gasoline yield height, transformation efficiency height.The reactor of described catalytic cracking unit can be the catalyst cracker of various types, and preferably riser reactor or riser tube add the bed reactor.Technical process is generally: stock 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, finish the catalytic cracking reaction of whole stock oil.
The present invention is applicable to normal slag and the hydrocracking that subtracts slag, is particularly useful for the poor residuum hydrocracking of high metal, high carbon residue, high condensed ring material, high nitrogen-containing.
Compared with prior art, the present invention is owing to adopted residual hydrogenation, catalytic cracking, organic associating of technologies such as solvent deasphalting, not only make present residue fixed-bed hydrogenation device for treatment stock oil flexible, but also stock oil treatment capacity and/or the corresponding device operating severity that reduced have been increased, prolonged the work-ing life of hydrogenation catalyst, the processing power of catalytic cracking unit and the total liquid yield of device have also been improved simultaneously, coke and reacted gas productive rate have been reduced, realize heavy, the high lighting of residual oil raw material, and obtain the main raw material (or auxiliary material) of high quality asphalt, realized the reasonable utilization of petroleum resources.
Below in conjunction with embodiment the present invention is described in further details.Fig. 1 is the simple and easy schematic flow sheet of the embodiment of the invention, and Fig. 2 is a comparative example schematic flow sheet of the present invention.
As shown in Figure 1, the charging 1 that stock oil and hydrogen are formed enters residue fixed-bed hydrotreater 2, the resultant of reaction 3 of gained enters resultant separator 4, the hydrogen-rich gas 5 that obtains can return hydrogenation unit and recycle after purifying, the product liquid 6 that obtains enters atmospheric fractional tower 7, the gas 8 that fractionation obtains, gasoline 10 and diesel oil distillate 9 go out device, long residuum is divided into two-way at the bottom of the tower, and one road long residuum 12 enters vacuum fractionation tower 20, gets vacuum gas oil 14 and vacuum residuum 13.Wherein vacuum residuum 13 enters solvent extraction device 21 and carries out solvent deasphalting and handle, deasphalted oil 19 and de-oiled asphalt 23.De-oiled asphalt 23 goes out device, and deasphalted oil 19 is mixed into catalytic cracking unit 15 with vacuum gas oil 14, long residuum 11 and carries out cracking, gas 16, gasoline 17, diesel oil 18 and catalytically cracked oil 22 that catalytic cracking reaction generates go out device, catalytically cracked oil 22 in the present embodiment is for once passing through, do not return hydrogenation unit, calculate by unconverted oil during material balance.
As shown in Figure 2, the charging 1 that stock oil and hydrogen are formed enters residue fixed-bed hydrotreater 2, the resultant of reaction 3 of gained enters resultant separator 4, the hydrogen-rich gas 5 that obtains, can return hydrogenation unit after purifying recycles, the product liquid 6 that obtains enters atmospheric fractional tower 7, the gas 8 that fractionation obtains, gasoline 10 and diesel oil distillate 9 go out device, long residuum 11 directly enters catalytic cracking unit 15 and carries out cracking at the bottom of the tower, the gas 16 that catalytic cracking reaction generates, gasoline 17, diesel oil 18 and catalytically cracked oil 22 go out device, catalytically cracked oil 22 does not carry out other conversions again, calculates by unconverted oil during material balance.
Embodiment
On small-sized lifting tubular type catalytic cracking unit, mix pilot scale residual hydrocracking device and small-sized solvent extraction device is tested.The residue fixed-bed hydrogenation catalyst that uses in following test is heavy, the residuum hydrogenating and metal-eliminating catalyst of being produced by Fushun Petrochemical Research Institute pilot scale base of CEN, FZC series, by ZTN, ZTS series weight, residual hydrogenation denitrogenation, the desulfurization catalyst of first fertilizer plant of Qilu Petrochemical company production.The order of catalyst loading is hydrodemetallation (HDM), hydrogenating desulfurization, hydrodenitrogenation catalyst.The Hydrodemetalation catalyst that uses in this test is CEN-5, CEN-6; Protective material is CEN-2, CEN-4, FZC-16 (over current protection agent); Hydrobon catalyst ZTS-01, ZTS-02, ZTS-03; Hydrodenitrogenation catalyst ZTN-01.Filling ratio between each catalyzer is:
CEN-2∶FZC-16∶CEN-4∶CEN-5∶CEN-6∶ZTS-01∶ZTS-02∶ZTS-03∶ZTN-01＝1∶1.25∶1.5∶2.62∶7.8∶6.63∶0.69∶0.87∶11(V/V)。
The solvent that the solvent extraction device uses is the mixture of butane and pentane, and both volume ratios are 1: 1.
The employed catalyzer of catalytic cracking unit is RHZ200 (Qilu Petrochemical company of China Petrochemical Corporation catalyst plant is produced).
The stock oil that this test is used is isolated island vacuum residuum, and character sees Table 1.
Table 1 stock oil main character
| Density (20 ℃), g/cm 3 | 0.998 | Fe，μg/g | 13.8 |
| Elementary composition | Ca，μg/g | 33.8 | |
| S，w％ | 2.52 | Saturated part, w% | 14.5 |
| N，w％ | 0.8 | Fragrance part, w% | 34.8 |
| Carbon residue, w% | 15.6 | Colloid, w% | 47.2 |
| Ni，μg/g | 48.0 | Bituminous matter, w% | 3.5 |
| V，μg/g | 2.2 |
Stock oil at first carries out fixed bed hydrogenation to be handled, and operational condition is as follows:
Temperature: 393 ℃ of pressure: the 15.4Mpa hydrogen-oil ratio, (V/V): 758
Air speed: 0.30h
-1Recycle hydrogen purity: 95V%
The liquid efflunent of reactor enters atmospheric tower and carries out the normal pressure fractionation, and the character of long residuum sees Table 2,30% long residuum and enters vacuum distillation tower and carry out underpressure distillation, and the character of vacuum gas oil, vacuum residuum sees Table 2, and the productive rate of hydrogenated products sees Table 2.
Table 2 residual hydrocracking result
| Sequence number | Data |
| Residue fixed-bed hydrogenated products productive rate, % | |
| H 2S+NH 3+ loss | 2.59 |
| C 1～C 4/ petroleum naphtha/diesel oil | 1.32/1.34/9.86 |
| The hydrogenation long residuum | 86.51 |
| The hydrogenation long residuum | |
| S/N，μg/g | 0.30/0.29 |
| Carbon residue/Ni+V, w%/μ g/g | 5.05/9.75 |
| The hydrogenation vacuum gas oil | |
| Yield, w% (accounting for long residuum) | 31.9 |
| Density (20 ℃), kg/m 3 | 906.0 |
| S/N，μg/g | 118/1054 |
| Carbon residue/Ni+V, w%/μ g/g | 0.16/0.22 |
| Saturated part, w% | 84.46 |
| Mononuclear aromatics, w% | 3.90 |
| Double ring arene, w% | 5.38 |
| Polycyclic aromatic hydrocarbons, w% | 6.26 |
| Hydrogenation vacuum residuum | |
| Yield, w% (accounting for long residuum) | 68.1 |
| Density (20 ℃), kg/m 3 | 935.0 |
| S/N/CCR，w％ | 0.42/0.36/7.2 |
| Ni+V，μg/g | 13.5 |
Vacuum residuum carries out solvent extraction, and the condition of solvent extraction is:
Temperature: 200 ℃ of pressure: 1.0Mpa agent-oil ratio: 5: 1 (V/V)
The result of vacuum residuum solvent extraction is:
Deasphalted oil yield: 78.5w%, de-oiled asphalt: 21.5w%
The mixing oil of long residuum+vacuum gas oil+deasphalted oil carries out the catalytic cracking lighting, mixes oil properties and sees Table 3, and de-oiled asphalt does not carry out lighting, when carrying out overall material balance, when the bituminous blend component is handled.The operational condition of catalytic cracking unit is:
Temperature: 502 ℃ of pressure: the 0.14Mpa agent-oil ratio, (W): 5.5
Finish duration of contact: 1 second
The reaction result of catalytic cracking sees Table 4.
Table 3 mixing oil character
| S/N/CCR，w％ | 0.24/0.24/4.18 |
| Ni+V，μg/g | 8.28 |
| Saturated part/fragrance part, w% | 57.06/28.02 |
| Colloid/bituminous matter, w% | 13.4/1.52 |
Table 4 catalytic cracking reaction result
The product of processes residual oil of the present invention distributes and sees Table 5.
| Product distributes | |
| Dry gas, w% | 2.83 |
| Liquefied gas, w% | 9.64 |
| Gasoline, w% | 40.29 |
| Diesel oil, w% | 37.30 |
| Slurry oil, w% | 5.19 |
| Coke, w% | 4.62 |
| Loss, w% | 0.13 |
Table 5 residual oil product processed of the present invention distributes
Comparative example
| Raw material, w% | |
| Residual oil | 100 |
| Hydrogen | 1.62 |
| Product, w% | |
| H 2S+NH 3+ loss | 2.70 |
| Dry gas | 2.66 |
| Liquefied gas | 8.97 |
| Gasoline | 34.66 |
| Diesel oil | 40.71 |
| Total lightweight oil | 75.37 |
| Catalytically cracked oil | 4.29 |
| Coke | 3.82 |
| De-oiled asphalt | 3.80 |
Stock oil at first carries out hydrotreatment, the same embodiment of hydrogenation catalyst of fixed bed hydrogenation device filling.Operational condition is as follows:
Temperature: 393 ℃ of pressure: the 15.4Mpa hydrogen-oil ratio, (V/V): 758
Air speed: 0.30h
-1Recycle hydrogen purity: 95V%
The liquid efflunent of reactor carries out the normal pressure fractionation, and the character of hydrogenation long residuum sees Table 6, and the productive rate of hydrogenated products sees Table 6.
Table 6 residual hydrocracking result
| Sequence number | Data |
| Residue fixed-bed hydrogenated products productive rate, % | |
| H 2S+NH 3+ loss | 2.59 |
| C 1～C 4/ petroleum naphtha/diesel oil | 1.32/1.34/9.86 |
| The hydrogenation long residuum | 86.51 |
| The normal slag of hydrogenation | |
| S/N，μg/g | 0.30/0.29 |
| Carbon residue/Ni+V, w%/μ g/g | 5.05/9.75 |
| Saturated part/fragrance part, w% | 53.31/28.87 |
| Colloid/bituminous matter, w% | 15.88/1.94 |
The hydrogenation long residuum carries out the catalytic cracking lighting, the same embodiment of catalyzer that catalytic cracking unit is used, and the device operational condition is:
Temperature: 502 ℃ of pressure: the 0.14Mpa agent-oil ratio, (W): 5.5
Finish duration of contact: 1 second
The reaction result of catalytic cracking sees Table 7.
Table 7 catalytic cracking reaction result
| Product distributes | |
| Dry gas, w% | 3.31 |
| Liquefied gas, w% | 10.71 |
| Gasoline, w% | 38.98 |
| Diesel oil, w% | 28.40 |
| Slurry oil, w% | 9.89 |
| Coke, w% | 8.54 |
| Loss, w% | 0.17 |
This comparative example residual oil product processed of table 8 distributes
| Raw material, w% | |
| Residual oil | 100 |
| Hydrogen | 1.62 |
| Product, w% | |
| H 2S+NH 3+ loss | 2.74 |
| Dry gas | 3.86 |
| Liquefied gas | 10.26 |
| Gasoline | 35.01 |
| Diesel oil | 33.81 |
| Total lightweight oil | 68.82 |
| Catalytically cracked oil | 8.55 |
| The catalytic cracking coke | 7.39 |
By table 6 and table 8 as can be seen the light oil yield of combination process of the present invention exceed 6.55% than the light oil yield of the existing technology in the comparative example, and the yield of slurry oil and coke is low respectively by 4.26% and 3.57%, and unconverted oil (comprising de-oiled asphalt) also hangs down 4.03%.If present embodiment adopts catalytically cracked oil of the present invention to return the further hydrocracking scheme of hydrogenation system, the yield of light oil among the embodiment will be higher, and the yield of coke also can be lower.
Claims (15)
1, a kind of process for treating and mixing residual oil comprises:
(1) at one treatment of heavy hydrocarbon class raw material in the treatment zone that hydrogen exists is arranged, metal, Conradson carbon residue, sulphur and the nitrogen content of reaction liquid effluent are reduced, this processing section comprises at least one reactor or reaction bed;
(2) will deliver to atmospheric tower from the liquid phase effluent of the hydrotreatment of step (1), separate obtaining light ends and long residuum by this tower;
(3) will deliver to vacuum distillation tower in the part in the long residuum that step (2) obtain, reclaim vacuum gas oil and vacuum residuum by this tower;
(4) vacuum residuum that step (3) is obtained is sent into solvent deasphalting unit and is carried out diasphaltene, obtains deasphalted oil and de-oiled asphalt;
(5) vacuum gas oil that step (3) is obtained obtains remaining long residuum with step (2) and mixes, and sends into catalytic cracking unit together and carries out lighting;
The described long residuum amount of delivering in the vacuum distillation tower of step (2) be according to the character of long residuum itself and the described catalytic cracking unit of step (5) to the index request decision of charging, the mixture of remainder should be able to satisfy the index request of the described catalytic cracking unit of step (5) to charging in the long residuum that vacuum gas oil that described step (3) obtains and step (2) obtain; Step (1) has in the treatment zone of hydrogen existence, and the heavy hydrocarbon hydrogenation conditions is: reaction pressure is 5-35MPa, and temperature of reaction is 300-500 ℃, and volume space velocity is 0.1-5.0h during liquid
-1, hydrogen to oil volume ratio is 100-5000.
2, process for treating and mixing residual oil according to claim 1 is characterized in that described reactor of step (1) or reaction bed are fixed bed hydrogenation reactor or reaction bed, wherein loads at least a fixed bed hydrogenation and handles catalyzer.
3, process for treating and mixing residual oil according to claim 1, it is characterized in that described reactor of step (1) or reaction bed are fixed bed hydrogenation reactor or reaction bed, wherein load at least a fixed bed hydrogenation demetalization catalyzer, at least a fixed bed hydrogenation desulfurization catalyst, stock oil at first contacts with Hydrodemetalation catalyst, contacts with Hydrobon catalyst again.
4, process for treating and mixing residual oil according to claim 1, it is characterized in that described heavy hydrocarbon hydrogenation conditions is: reaction pressure is 10-20Mpa, and temperature of reaction is 350-450 ℃, and volume space velocity is 0.15-2h during liquid
-1, hydrogen to oil volume ratio is 500-3000.
5, process for treating and mixing residual oil according to claim 1 is characterized in that in the atmospheric tower fractionation of described step (2), the cut point of long residuum is 300-400 ℃.
6, process for treating and mixing residual oil according to claim 1 is characterized in that in the atmospheric tower fractionation of described step (2), the cut point of long residuum is 340-380 ℃.
7, process for treating and mixing residual oil according to claim 1 is characterized in that in the vacuum distillation tower of described step (3) that the cut point of vacuum residuum is 450-600 ℃.
8, process for treating and mixing residual oil according to claim 1 is characterized in that in the vacuum distillation tower of described step (3) that the cut point of vacuum residuum is 500-550 ℃.
9, process for treating and mixing residual oil according to claim 1, it is characterized in that solvent deasphalting technology is used rotating disk contact tower or tray column in the described step (4), hydrocarbon oil feed enters from the top, and extraction solvent enters from the bottom, the extraction medium that is adopted is the light hydrocarbon solvent that contains alkane compound, operational condition is: total extraction solvent and hydrocarbon-type oil weight ratio are 1.5～8: 1, and pressure is 0.1～5.0Mpa, and temperature is 60～250 ℃.
10, process for treating and mixing residual oil according to claim 1 is characterized in that the employed solvent of solvent deasphalting technology is selected from C in the described step (4)
3～C
7In the alkane one or more.
11, process for treating and mixing residual oil according to claim 1 is characterized in that the employed solvent of solvent deasphalting technology is butane, pentane or their mixture in the described step (4).
12, process for treating and mixing residual oil according to claim 1 is characterized in that the middle solvent deasphalting technology gained deasphalted oil of described step (4) enters the described catalytic cracking unit of step (5) and further handles.
13, process for treating and mixing residual oil according to claim 1, the operational condition that it is characterized in that catalytic cracking unit in described (5) step is: temperature is 450～600 ℃, pressure 0.1～0.5Mpa, agent weight of oil be than 2～30, reaction raw materials and 0.1～15 second duration of contact of catalyzer.
14, process for treating and mixing residual oil according to claim 1, the operational condition that it is characterized in that catalytic cracking unit in described (5) step is: temperature is 460～550 ℃, the agent weight of oil is than 2～20, with 0.5～5 second duration of contact of catalyzer, and pressure 0.1～0.5Mpa.
15, process for treating and mixing residual oil according to claim 1, it is characterized in that the slurry oil that reaction generates in the catalytic cracking unit in described (5) step is after separated the going out of suspension fine particle that it contains, the hydrogenation reaction treatment zone of delivering to described (1) step mixes with hydrogenating materials and carries out hydrogenation jointly.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00123132 CN1123625C (en) | 2000-10-26 | 2000-10-26 | Process for treating and mixing residual oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00123132 CN1123625C (en) | 2000-10-26 | 2000-10-26 | Process for treating and mixing residual oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1351113A CN1351113A (en) | 2002-05-29 |
| CN1123625C true CN1123625C (en) | 2003-10-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00123132 Expired - Lifetime CN1123625C (en) | 2000-10-26 | 2000-10-26 | Process for treating and mixing residual oil |
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| Country | Link |
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| CN (1) | CN1123625C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1965059B (en) * | 2004-05-26 | 2010-06-16 | 国际壳牌研究有限公司 | Process to produce a gas oil by catalytic cracking of a fisher-tropsch product |
| CN101161790B (en) * | 2007-10-30 | 2011-07-20 | 徐州工业职业技术学院 | Method for gaining high conversion rate by catalytic hydrogenation of vacuum residue over-critical extraction slag with zeolite molecular sieve |
| WO2009089681A1 (en) | 2007-12-20 | 2009-07-23 | China Petroleum & Chemical Corporation | Improved integrated process for hydrogenation and catalytic cracking of hydrocarbon oil |
| CN102453545B (en) * | 2010-10-15 | 2013-11-06 | 中国石油化工股份有限公司 | Method for lightening residual oil |
| CN115261068B (en) * | 2021-04-30 | 2024-02-09 | 中国石油化工股份有限公司 | Fixed bed residuum hydrogenation method |
-
2000
- 2000-10-26 CN CN 00123132 patent/CN1123625C/en not_active Expired - Lifetime
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| Publication number | Publication date |
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| CN1351113A (en) | 2002-05-29 |
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