CN1290980C - Conversion method for low-grade heavy and residual oil - Google Patents
Conversion method for low-grade heavy and residual oil Download PDFInfo
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- CN1290980C CN1290980C CN 200410076769 CN200410076769A CN1290980C CN 1290980 C CN1290980 C CN 1290980C CN 200410076769 CN200410076769 CN 200410076769 CN 200410076769 A CN200410076769 A CN 200410076769A CN 1290980 C CN1290980 C CN 1290980C
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Abstract
The present invention discloses a sort of method for converting the inferior heavy oil and residual oil, the deasphalted oil and deoiled asphalt is fractionated by the solvent from the raw material of heavy oil and residual oil, wherein the deasphalted oil is delivered to the hydrotreating arrangement of the fixed bed, modifies the matter with the reaction of hydrogen and hydrogenation catalysts, the separated production includes the lightweight cut fraction and hydrocracking tail oil, the hydrocracking tail oil is delivered to the catalytic cracking unit, and cracked with the function of the cracking catalyst, the separated production includes light-weighted cut fraction, heavy recycle oil and slurry oil. The deoiled asphalt which is fractionated by solvent and catalytic slurry oil are delivered to the hydrogenation equipment of the suspension bed together, and are farther produced to get various of light-weighted cut fractions with the function of hydrogen and decentralized energizing agent. This method can effectively reduce the operation severity of the hydrotreating arrangement in the fixed bed and the hydrogenation plant in the suspension bed, and can improve the creation rate and the quality.
Description
Technical field
The present invention relates to a kind of method of producing light ends oil, particularly solvent deasphalting, fixed bed hydrogenation processing, catalytic cracking and floating bed hydrocracking technology are organically combined the method for producing light ends oil by inferior heavy, residual oil.
Background technology
Hydrogenation is the weight that extensively adopts at present, the technological line of residua upgrading production heavy oil FCC raw material.In existing residual hydrogenation method for modifying, the fixed bed residual hydrocracking is a proven technique method the most.
The fixed bed residual hydrocracking has characteristics such as good product quality, technical maturity, and in the residual hydrogenation field, its suitability for industrialized production ability is occupied very high share.But traditional residue fixed-bed hydrogen addition technology because the catalyzer duct is easy to be stopped up by metal impurities, causes catalyst deactivation and is difficult to be applied to process the poor residuum raw material with higher metal and carbon residue content.
For addressing this problem; United States Patent (USP) 5,879,642 have proposed a kind of fixed bed residual hydrogenation technology of using the catalyst protection bed; the catalyst protection bed that this technology is used can remove the organo-metallic impurity of the overwhelming majority, thereby prolongs the work-ing life of integer catalyzer.Because the protection bed is limited to the carrying capacity of metal; processing during than the residual oil raw material of low-metal content (total metal content＜120 μ g/g) this technology can reach the effect in the work-ing life that prolongs integer catalyzer; and for the inferior raw material of processing high metal and carbon residue content, the protection bed still can lose the effect of protection downstream bed because metal stops up duct and coking deactivation rapidly.
U.S. Pat P 5,382, and 349 propose a kind of residue fixed-bed hydrogenation method of using solid Hydrodemetalation catalyst, solid Hydrobon catalyst and the solid hydrodenitrogenation catalyst of grating.This method faces the predicament of the raw material that is difficult to adapt to high metal content and high carbon residue content equally.
The method that above-mentioned patent adopted can not fundamentally solve the problem of the catalyst deactivation that causes owing to metal deposition in the fixed bed Residue Hydrotreating Technology, thereby has limited the raw material sources and the further industrial application of fixed bed residuum hydrodesulfurization technology.
Metal impurities in the residual oil mainly concentrates on bituminous matter (C
7Or C
5Insolubles) in the component, bitum content is the most important factor of decision fixed bed hydrogenation catalyst deactivation speed.Then can more fully remove bituminous matter in the residual oil by solvent deasphalting, remove a bituminous residual oil residual hydrocracking processes that then can be fixed easily so and transform, and its hydrogenation tail oil be good catalytically cracked material.
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 and de-oiled asphalt through solvent extraction, wherein deasphalted oil is sent into fixed bed hydrogenation treatment unit upgrading with catalysis heavy cycle oil, hydrogenation tail oil is sent into the catalytic cracking unit 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, pass through solvent extraction, still have the part catalyst fines to be carried in the deasphalted oil (DAO), after DAO sends into the fixed bed hydrogenation device, 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.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of heavy, residual oil method for transformation is provided, make it can process inferior raw material, improve the yield and the quality of light-end products, avoid beds to stop up, do not produce or produce less low value pitch and coke product.
Inferior heavy of the present invention, residual oil method for transformation may further comprise the steps:
A, weight, residual oil raw material obtain deasphalted oil and de-oiled asphalt through solvent extraction;
The deasphalted oil that obtains among b, the step a enters the fixed bed hydrogenation treatment unit, carries out hydro-upgrading under hydrogen and fixed bed hydrogenation catalyst action, and separated product obtains light ends and hydrogenation tail oil;
The hydrogenation tail oil that obtains among c, the step b enters catalytic cracking unit, under the catalytic cracking catalyst effect, carry out cracking, separated product obtains light ends, heavy cycle oil and slurry oil, wherein heavy cycle oil is in the catalytic cracking unit internal recycling, or partly or entirely is circulated to the fixed bed hydrogenation treatment unit;
The part or all of slurry oil that the pitch that obtains among d, the step a obtains in step c enters the floating bed hydrogenation device, carries out hydrocracking under hydrogen and disperse type catalyzer effect, and the product separation obtains light ends and residue.
The weight of addressing among the step a, residual oil raw material comprise the organism that residual oil, heavy-gravity heavy crude oil and oil sands bitumen, shale oil, the dry distillation of coal and gelatin liquefaction that crude distillation obtains obtain, particularly metal content surpasses 120 μ g/g in the raw material, and carbon residue is greater than weight, the residual oil of 10wt%.Solvent for use is selected from C
3～C
8In alkane or alkene, condensate oil, light naphthar, the petroleum naphtha one or more are preferably C
4～C
7In alkane or alkene, condensate oil, light naphthar, the petroleum naphtha one or more.
Heavy, 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 enter extraction tower again by pre-mixing earlier and separate.
The operational condition of solvent extraction is among the present invention: extraction temperature is 80～260 ℃, and pressure is 2.0～6.0MPa, and agent oil volume ratio is 1.0～10.0; Be preferably 120～210 ℃ of extraction temperatures, pressure is 4.0～5.0MPa, and agent oil volume ratio is 4.0～8.0.
Solvent deasphalting adopts old process, can be that single hop also can be two sections.
The solvent deasphalting unit controlling index is the content of heptane insolubles in the deasphalted oil (DAO), generally is lower than 1wt%, is preferably 0.1wt%, is preferably to be lower than 0.05wt%; And the DAO productive rate is generally 50～95wt%, is preferably 60～80wt%.Substantially asphaltenes not among the DAO like this, the bed hydroprocessing device that can be fixed easily processing is converted into high-quality FCC charging, and the pitch that removes also can satisfy floating bed hydrogenation device charging requirement.
Fixed bed hydrogenation treatment technology described in the step b is conventional fixed bed residual hydrogenation technology, and its operational condition will conventional fixed bed Residue Hydrotreating Technology condition relax, and is generally: 320～410 ℃ of temperature of reaction, preferably 340～390 ℃; Reaction pressure is 8.0～16.0MPa, is preferably 10.0～15.0MPa; Hydrogen to oil volume ratio is 500～2000, is preferably 700～1500; Volume space velocity is 0.1～2.0h during liquid
-1, be preferably 0.2～1.5h
-1The fixed bed hydrogenation catalyzer that is adopted be meant have hydrodemetallation (HDM), the single catalyst or the series catalyst of hydrogenating desulfurization, hydrodenitrification and hydrocracking function.These catalyzer generally all are to be carrier with porous refractory inorganic oxide such as aluminum oxide, the oxide compound of group vib (as W, Mo) and/or group VIII metal (as Co, Ni) is an active ingredient, optionally adds the catalyzer of other various auxiliary agents such as P, Si, elements such as F, B.For example CEN, the FZC series Hydrodemetalation catalyst of being produced by Fushun Petrochemical Research Institute pilot scale base just belongs to this class catalyzer by serial hydrogenating desulfurization of ZTS, the ZTN of the production of first fertilizer plant of Qilu Petrochemical company and hydrodenitrogenation catalyst.At present in fixed bed residual hydrogenation technology, it often is the supporting use of multiple catalyzer, Hydrodemetalation catalyst, Hydrobon catalyst, hydrodenitrogenation catalyst, hydrocracking catalyst are wherein arranged, and the filling order generally is that stock oil is contacted with hydrodemetallation (HDM), hydrogenating desulfurization, hydrodenitrification successively.Technology with these several catalyst mix fillings is also arranged certainly.When concrete enforcement is of the present invention, can suitably adjust processing condition and the loading amount of catalyzer and the proportioning of different catalysts of fixed bed residual hydrogenation according to raw materials used character.
Catalytic cracking unit described in the step c comprises a reactor, a revivifier and a separation column at least.Wherein 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, as silica-alumina catalyst, silica-magnesia catalyst, acid-treated carclazyte and molecular sieve cracking catalyst, molecular sieve cracking catalyst preferably, wherein molecular sieve optional self-contained or do not contain rare earth Y or HY molecular sieve, the super-stable Y molecular sieves that contains or do not contain rare earth, ZSM-5 series molecular sieve, have the high-silica zeolite of five-membered ring structure and in the beta-molecular sieve one or more.Adopt molecular sieve cracking catalyst active high, 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 fixed 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 fixed bed hydrogenation treatment unit hydro-upgrading in the cracking of catalytic cracking unit internal recycling; 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 goes out the mixture of pitch and catalytic slurry as solvent extraction, and the part by weight of its medium pitch 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, as phospho-molybdic acid nickel, phospho-wolframic acid nickel etc.; Described oil-soluble catalyst can be the oil soluble organic compound of two or more metals in periodic table of elements VIB, VIIB and the group VIII metal, as contains many carbonyl compound, naphthenate compound or the porphyrin class inner complex of two or more metals in molybdenum, nickel, the 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: pressure 8～32MPa, 400～490 ℃ of temperature of reaction, volume space velocity 0.1～2.0h during liquid
-1, hydrogen to oil volume ratio (under the standard pressure) 200～1200.Be preferably pressure 12～24MPa, 410～470 ℃ of temperature of reaction, volume space velocity 0.5～1.5h during liquid
-1Hydrogen to oil volume ratio (under the standard pressure) 400～1000.
The fractionation of floating bed hydrogenation product obtains various light ends, and the cracking tail oil loops back suspended-bed reactor or as the personal fuel in refinery.
Advantage of the present invention is:
1, solvent deasphalting and fixed bed hydrogenation is combined, can utilize solvent extraction to remove bituminous matters whole in the poor residuum and most metal on the one hand, make fixed bed hydrogenation can process the inferior raw material that the containing metal amount surpasses 120 μ g/g, enlarge the raw material sources of fixed bed hydrogenation technology, utilize fixed bed hydrogenation on the other hand good take off percentage of admixture and take off carbon yield obtain high-quality hydrogenated products, be the fine catalytically cracked material;
2, the present invention's charging that deasphalted oil is handled as fixed bed hydrogenation, the Macrodilution agent that can avoid conventional fixed bed hydrogenation device to add when handling inferior raw material has on the one hand enlarged the processing power of installing; Owing to metal content in the charging reduces significantly, reduce metal and stopped up the risk that the solid catalyst duct makes its inactivation on the other hand, prolonged the fixed bed device on-stream time; In addition, compare with patent CN 1393525A, catalytic slurry is not circulated to solvent deasphalting unit, can avoid the part catalytic cracking catalyst powder deposition that carries among the DAO on the fixed bed hydrogenation beds and the bed pressure drop that causes raises and stop up like this.
3, 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;
4, will be from the de-oiled asphalt of solvent deasphalting unit with from the charging of the catalytically cracked oil of catalytic cracking unit as the floating bed hydrogenation device, in the presence of disperse type catalyzer, make the saturated or hydrocracking production light-end products of its hydrogenation, improved the yield of light-end products, made low value bituminous productive rate reach minimum;
5, adopt solvent deasphalting-fixed bed hydrogenation processing-catalytic cracking-floating bed hydrogenation combination process can handle the high carbon residue inferior heavy of high metal, residual oil, improved light-end products yield and quality, do not produce or produce less low value pitch and coke product.
Description of drawings
Fig. 1 is the process flow diagram that the present invention is heavy, residual oil transforms.
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 extraction device 3, and solvent extraction can be that one-part form also can two-part, obtains deasphalted oil (DAO) 4 and de-oiled asphalt 8; Mix with hydrogen 9 after deasphalted oil 4 preheatings and send into fixed bed hydrogenation treatment unit 5, under conventional fixed bed hydrogenation catalyzer and hydroprocessing technique condition, heteroatoms and carbon residues such as DAO hydrogenation and removing sulphur, nitrogen, product obtains light ends 10 and hydrogenation tail oil 11 through separation; Hydrogenation tail oil 11 enters 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 can partly or entirely be circulated to fixed bed hydrogenation treatment unit 5, also can partly or entirely loop back catalytic cracking unit 6, partly or entirely catalytic slurry 15 is sent into floating bed hydrogenation cracker 7 with being mixed from the de-oiled asphalt 8 of solvent extraction device and high pressure hydrogen 9, under the disperse type catalyzer effect, de-oiled asphalt and catalytic slurry hydrocracking are light-end products 12, and a spot of hydrogenation residues 13 is as refinery's fuel.
For further specifying all main points of the present invention, enumerate following examples, but not thereby limiting the invention.
Two kinds of typical inferior heavy, residual oil are used in test, and its feedstock property sees Table 1.Two kinds of residual oil have metal content height, carbon residue height and the high characteristics of sulphur content as shown in Table 1, wherein subtract in the sand slag only the content of nickel, vanadium and iron promptly reach 190 μ g/g, and the normal slag of Tahe is more up to more than the 320 μ g/g; Both asphalt contents surpass 8wt%, and carbon residue content surpasses 18wt%, are that conventional fixed bed Residue Hydrotreating Technology is difficult to the directly poor residuum of processing.
Table 1 feedstock property
| Project | The normal slag of Tahe | Subtract slag in the sand |
| Density (20 ℃), kg.m -3 | 1001.0 | 1024.8 |
| Carbon residue, wt% | 18.3 | 20.7 |
| Ultimate analysis, wt% | ||
| C | 86.31 | 83.52 |
| H | 10.74 | 10.43 |
| S | 2.53 | 4.95 |
| N | 0.42 | 0.35 |
| Metallic element, μ g.g -1 | ||
| Ni | 38.6 | 43.4 |
| V | 287.4 | 143.6 |
| Four proximate analyses, wt% | ||
| Stable hydrocarbon | 29.0 | 9.9 |
| Aromatic hydrocarbon | 33.1 | 52.2 |
| Colloid | 24.5 | 29.5 |
| Bituminous matter | 13.4 | 8.4 |
| Raw material is formed, wt% | ||
| 350 ℃～500 ℃ cuts | 32.1 | 0 |
| ＞500 ℃ of cuts | 67.9 | 100.0 |
Embodiment 1～2
The change of properties of the deasphalted oil that two kinds of residual oil raw materials of this test investigation obtain under different solvents extracting condition.Data results shows that the DAO yield of two kinds of residual oil raw materials is respectively 76wt% and 80wt%, and the DAO N.heptane insolubles is 0, and the content of Ni and V is low, is the raw material of good fixed bed hydrogenation treatment unit.
Table 2 solvent extraction testing data
| Project | Embodiment 1 | Embodiment 2 |
| Raw material | The normal slag of Tahe | Subtract slag in the sand |
| Solvent | Normal butane | Skellysolve A |
| The solvent deasphalting condition | ||
| Temperature, ℃ | 140 | 190 |
| Pressure, MPa | 4.0 | 4.0 |
| Solvent ratio, v/v | 5 | 7 |
| The DAO yield, wt% | 76 | 80 |
| DAO character | ||
| Density (20 ℃), g/cm 3 | 0.9566 | 0.9732 |
| Conradson carbon residue, wt% | 12.1 | 13.3 |
| S，wt％ | 1.95 | 3.96 |
| N，wt％ | 0.22 | 0.18 |
| Ni，μg·g -1 | 3.5 | 3.4 |
| V，μg.g -1 | 37.0 | 23.1 |
| N.heptane insolubles, wt% | 0 | 0 |
| The de-oiled asphalt softening temperature, ℃ | 150 | 155 |
Embodiment 3～4
This description of test embodiment 1 and 2 resulting DAO carry out the situation that fixed bed hydrogenation is handled.
The fixed bed hydrogenation catalyzer that uses in the test is CEN, the FZC series Hydrodemetalation catalyst of being produced by Fushun Petrochemical Research Institute pilot scale base, by the hydrodenitrification of ZTN, ZTS series, the Hydrobon 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.Admission space 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。
The fixed bed hydrogenation test shows, subtract this class of slag in normal slag of Tahe and the sand and have the inferior raw material of the high carbon residue of high metal through behind the solvent extraction, the DAO that obtains can be used as the high-quality charging of fixed bed hydrogenation device, satisfies the requirement of device long-term operation, and produces superior in quality RFCC raw material.
Fixed bed hydrogenation used among table 3 embodiment is handled catalyzer
| Catalyzer | Pore volume, ml/g | Specific surface, m 2/g | Tap density, g/ml | Active ingredient is formed, wt% | |||
| NiO | MoO 3 | P | |||||
| Protective material | CEN-2 | 1.18 | 150 | 0.41 | 2.5 | - | - |
| CEN-4 | 1.22 | 133 | 0.42 | 2.0 | - | - | |
| FZC-16 | 0.49 | 156 | 0.76 | 2.5 | - | - | |
| The hydrodemetallation (HDM) agent | CEN-5 | 0.66 | 136 | 0.55 | 3.1 | - | - |
| CEN-6 | 0.62 | 150 | 0.60 | 3.1 | 8.9 | - | |
| The hydrogenating desulfurization agent | ZTS-01 | 0.38 | 145 | 0.85 | 4.0 | 18.7 | 2.0 |
| ZTS-02 | 0.39 | 145 | 0.85 | 4.4 | 19.2 | 1.8 | |
| ZTS-03 | 0.38 | 147 | 0.84 | 4.4 | 18.8 | 2.0 | |
| Hydrodenitrogenation catalyst | ZTN-01 | 0.40 | 220 | 0.85 | 9.1 | 22.5 | - |
The fixed bed hydrogenation testing data of table 4 embodiment 1 and embodiment 2DAO
| Embodiment | Embodiment 3 | Embodiment 4 | ||
| Raw material | Embodiment 1DAO | Embodiment 2DAO | ||
| Reaction conditions | ||||
| The hydrogen dividing potential drop, MPa | 8.0 | 8.0 | 8.0 | 8.0 |
| Temperature of reaction, ℃ | 380 | 385 | 380 | 385 |
| Volume space velocity, h -1 | 0.5 | 0.5 | 0.5 | 0.5 |
| Hydrogen-oil ratio, v/v | 1000 | 1000 | 1000 | 1000 |
| Runtime, hour | 100 | 1400 | 100 | 1400 |
| Liquid product distributes, wt% | ||||
| Gasoline | 0.5 | 0.6 | 1.0 | 1.0 |
| Diesel oil | 10.1 | 10.1 | 9.7 | 9.8 |
| Hydrogenation tail oil | 89.4 | 89.3 | 89.3 | 89.2 |
| Hydrogenation tail oil character | ||||
| Density (20 ℃), kg.m -3 | 937.2 | 938.6 | 953.1 | 953.4 |
| Sulphur, wt% | 0.05 | 0.05 | 0.05 | 0.05 |
| Nitrogen, wt% | 0.12 | 0.12 | 0.15 | 0.15 |
| Carbon residue, wt% | 2.91 | 3.05 | 2.80 | 2.82 |
| (Ni+V)，μg·g -1 | 6.0 | 6.0 | 4.6 | 4.6 |
Embodiment 5～6
The hydrogenation tail oil of this test explanation embodiment 3 and embodiment 4 carries out the FCC test on small-sized riser fluid catalytic cracking situation.The FCC tests unit capacity is 1kg/h, adopts circulating reaction-reproduction operation pattern.Catalytic cracking catalyst is the CHV-1 catalyzer that oil-refining chemical total stone catalyst plant in Chang Ling is produced.
Table 5 hydrogenation tail oil FCC tests data
| Numbering | Embodiment 5 | Embodiment 6 |
| Raw material | Tahe fixed bed hydrogenation tail oil | Fixed bed hydrogenation tail oil in the sand |
| Operational condition | ||
| Temperature of reaction, ℃ | 500 | 500 |
| Reaction times, second | 2.7 | 2.7 |
| Agent weight of oil ratio | 6.0 | 6.0 |
| Product distributes, wt% | ||
| Dry gas | 2.31 | 3.41 |
| Liquefied gas | 10.24 | 11.71 |
| Gasoline | 46.64 | 43.13 |
| Diesel oil | 27.09 | 25.28 |
| Slurry oil | 5.22 | 6.77 |
| Coke | 8.11 | 9.23 |
| Loss | 0.39 | 0.47 |
| Amount to | 100.00 | 100.00 |
| Total light hydrocarbon yield, wt% | 83.97 | 80.12 |
| Light oil yield, wt% | 73.73 | 68.41 |
Embodiment 7～10
The de-oiled asphalt of this test explanation embodiment 1 and embodiment 2 is through floating bed hydrogenation cracked situation.
The floating bed hydrogenation test is carried out on the 1kg/h continuous apparatus, used oil-soluble catalyst is the oil soluble disperse type catalyzer that organo-metallic Mo, Ni compound are re-dubbed in the table 6, and catalyzer is formed: dimethylglyoxime closes nickel/diethyl diamino molybdenum dithiophosphate=1.3/6; Used water-soluble catalyst is the water-soluble disperse type catalyzer of the aqueous solution preparation of phospho-molybdic acid nickel heteropolyacid salt, and catalyzer is formed: Mo 6.00wt%, Ni 0.70wt%, P 0.26wt%.
The floating bed hydrogenation test-results of table 6 de-oiled asphalt and catalytic slurry mixing raw material
| Embodiment | 7 | 8 | 9 | 10 |
| Asphalt stock | The Tahe de-oiled asphalt | De-oiled asphalt in the sand | ||
| The catalytic slurry add-on, wt% | 0 | 46.0 | 22.1 | 75.0 |
| Reaction conditions | ||||
| Pressure, MPa | 20 | 16 | 14 | 16 |
| Air speed, h -1 | 1.35 | 0.85 | 1.0 | 0.85 |
| Temperature, ℃ | 445 | 440 | 440 | 445 |
| Hydrogen-oil ratio, v/v | 1000 | 800 | 600 | 800 |
| Catalyst type | Oil soluble Mo/Ni | Water-soluble Mo/Ni | Water-soluble Mo/Ni | Oil soluble Mo/Ni |
| The catalyzer add-on, μ gg -1 | 600 | 1200 | 1500 | 400 |
| Distribution of reaction products: wt% | ||||
| ＜180℃ | 19.1 | 15.6 | 17.7 | 21.3 |
| 180～350℃ | 31.5 | 30.5 | 30.2 | 34.2 |
| 350～524℃ | 40.5 | 41.2 | 39.6 | 36.6 |
| Transformation efficiency, wt% | 91.1 | 87.3 | 87.5 | 92.1 |
| Toluene insolubles, wt% | 1.15 | 0.46 | 0.85 | 0.55 |
The test-results explanation, by adjusting catalytic slurry additional proportion and reactor operating parameters, the green coke level is extremely low with higher transformation efficiency hydrocracking can to make pitch, the continuously long-term smooth operation of assurance device.
Claims (11)
1, a kind of method for transformation of heavy, residual oil may further comprise the steps:
A, weight, residual oil raw material obtain deasphalted oil and de-oiled asphalt through solvent extraction;
The fixed bed hydrogenation treatment unit is sent in the deasphalted oil that obtains among b, the step a, carries out hydro-upgrading under hydrogen and fixed bed hydrogenation catalyst action, and separated product obtains light ends and hydrogenation tail oil;
The hydrogenation tail oil that obtains among c, the step b is sent into catalytic cracking unit, carries out cracking under the catalytic cracking catalyst effect, and separated product obtains light ends, heavy cycle oil and slurry oil; Wherein the heavy cycle oil of gained is in the catalytic cracking unit internal recycling, or partly or entirely is circulated to the fixed bed hydrogenation treatment unit described in the step b;
The part or all of slurry oil that the de-oiled asphalt that obtains among d, the step a obtains in step c enters the floating bed hydrogenation device, carries out hydrocracking under hydrogen and disperse type catalyzer effect, and separated product obtains light ends and residue; Described disperse type catalyzer is water-soluble catalyst or oil-soluble catalyst.
2, in accordance with the method for claim 1, it is characterized in that solvent for use is selected from C among the step a
3～C
8In alkane or alkene, condensate oil, light naphthar, the petroleum naphtha one or more.
3, in accordance with the method for claim 1, it is characterized in that the operational condition of solvent extraction among the step a is: extraction temperature is 80～260 ℃, and pressure is 2.0～6.0MPa, and agent oil volume ratio is 1.0～10.0;
4, in accordance with the method for claim 1, it is characterized in that the operational condition that the fixed bed hydrogenation described in the step b is handled is: 320～410 ℃ of temperature of reaction; Reaction pressure is 8.0～16.0MPa; Hydrogen to oil volume ratio is 500～2000; Volume space velocity is 0.1～2.0h during liquid
-1
5, in accordance with the method for claim 1, it is characterized in that the operational condition that the fixed bed hydrogenation described in the step b is handled is: 340～390 ℃ of temperature of reaction; Reaction pressure is 10.0～15.0MPa; Hydrogen to oil volume ratio is 700～1500; Volume space velocity is 0.2～1.5h during liquid
-1
6, in accordance with the method for claim 1, it is characterized in that the catalytic cracking unit described in the step c comprises a reactor, a revivifier and a separation column at least, its reaction conditions is: 470～570 ℃ of temperature of reaction, 1～5 second reaction times, agent weight of oil than 3～10,650～750 ℃ of regeneration temperatures.
7, in accordance with the method for claim 1, it is characterized in that in the floating bed hydrogenation charging described in the steps d, the part by weight of pitch and catalytic slurry is 0.1～10.0.
8, in accordance with the method for claim 1, it is characterized in that in the floating bed hydrogenation charging described in the steps d, the part by weight of pitch and catalytic slurry is 0.3～8.0.
9, in accordance with the method for claim 1, it is characterized in that described water-soluble catalyst is phospho-molybdic acid nickel or phospho-wolframic acid nickel, described oil-soluble catalyst is many carbonyl compound, naphthenate compound or the porphyrin class inner complex that contains two or more metals in molybdenum, nickel, the cobalt.
10, in accordance with the method for claim 1, it is characterized in that the disperse type catalyzer that the floating bed hydrogenation process is used in the steps d, in weight metal, the content in raw material is 50～3000 μ g/g.
11, in accordance with the method for claim 1, it is characterized in that the operational condition of floating bed hydrogenation process in the steps d is: pressure 8～32MPa, 400～490 ℃ of temperature of reaction, volume space velocity 0.1～2.0h during liquid
-1, hydrogen to oil volume ratio 200～1200.
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| 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 |
| US8597500B2 (en) * | 2008-03-13 | 2013-12-03 | China Petroleum & Chemical Corporation | Process for converting inferior feedstock to high quality fuel oil |
| CN101875856B (en) * | 2009-04-30 | 2013-03-20 | 中国石油化工股份有限公司 | Wax oil hydrogenated treatment and catalytic cracking combined method |
| CN102337152A (en) * | 2010-07-22 | 2012-02-01 | 中国石油化工股份有限公司 | Processing method of sulfur-containing crude oil |
| CN103540358B (en) * | 2012-07-12 | 2016-05-11 | 中国石油天然气股份有限公司 | Residual oil conversion-Aromatics Extractive Project group technology |
| US20140221713A1 (en) * | 2013-02-04 | 2014-08-07 | Lummus Technology Inc. | Residue hydrocracking processing |
| CN105567319B (en) * | 2014-10-11 | 2017-07-25 | 中国石油化工股份有限公司 | A kind of method for handling mink cell focus |
| CN105623725B (en) * | 2014-10-27 | 2017-11-03 | 中国石油化工股份有限公司 | A kind of group technology of heavy/Residual cracking |
| KR20220092544A (en) * | 2019-10-31 | 2022-07-01 | 차이나 페트로리움 앤드 케미컬 코포레이션 | Method and system for hydrotreatment of deoiled asphalt |
| CN112745946B (en) * | 2019-10-31 | 2022-06-28 | 中国石油化工股份有限公司 | Method and system for processing heavy raw oil |
| WO2021083302A1 (en) * | 2019-10-31 | 2021-05-06 | 中国石油化工股份有限公司 | Aromatic-enriched distillate oil processing method and system |
| CN112745947B (en) * | 2019-10-31 | 2022-06-28 | 中国石油化工股份有限公司 | Method and system for processing heavy raw oil |
| CN114426880B (en) * | 2020-09-28 | 2023-12-12 | 中国石油化工股份有限公司 | Fixed bed residuum hydrogenation method for producing catalytic cracking raw material |
| CN114426881A (en) * | 2020-09-28 | 2022-05-03 | 中国石油化工股份有限公司 | Residual oil hydrogenation method |
| CN114437797B (en) * | 2020-10-16 | 2023-05-26 | 中国石油化工股份有限公司 | Production method of blending components of marine fuel oil |
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