CN1151239C - Process for lightening heavy oil or residual oil - Google Patents
Process for lightening heavy oil or residual oil Download PDFInfo
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- CN1151239C CN1151239C CNB011141697A CN01114169A CN1151239C CN 1151239 C CN1151239 C CN 1151239C CN B011141697 A CNB011141697 A CN B011141697A CN 01114169 A CN01114169 A CN 01114169A CN 1151239 C CN1151239 C CN 1151239C
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Abstract
The present invention discloses a lightening technique of heavy oil and residual oil with a hydrogen supply agent. Weight oil and residual oil are cracked into light oil products with a suspension bed by a hydrogenation method; the products are fractionated to obtain fractions with the boiling range of 170 to 350 DEG C.; the fractions are hydrogenized to be used as a hydrogen supply agent which is circularly returned to a hydrogenation reactor with a suspension bed.
Description
The present invention relates to a kind of working method of heavy, residual oil, use weight, the dreg-oil suspension bed hydrogenation cracking processing method of hydrogen supply agent especially.
Floating bed hydrocracking is handled and is weighed, residual oil is that characteristics have obtained extensive studies with its high-speed, high conversion.Yet the high conversion floating bed hydrocracking technology of operation down often faces the disadvantageous effect that high green coke brings.
In order to address this is that, some process using add the processing method of pressed powder as the green coke carrier.Chinese patent CN1035836 proposes ferrous sulfate and coal are ground in oil, makes a kind of iron-coal paste shape additive, mixes with heavy oil then and carries out floating bed hydrogenation.Iron-coal paste shape additive only has faint hydrogenation activity, and effectively the process of inhibition green coke is mainly used to the carrier as green coke, and the additive that accounts for charging (2～4) w% finally is enriched in the tail oil with coke and is difficult to utilize again.
Chinese patent CN1219569 proposes to use the decentralized metal catalyst with higher hydrogenation activity can effectively suppress green coke reaction heavy, residuum (cracking) process.And because only several hectogammas of catalyzer usage quantity can be avoided the too much and unserviceable difficult problem of solids in the tail oil.However, be subjected to dissolving and the restriction of diffusion and the influence of other factors of hydrogen in heavy oil, hydrogenation reaction can not be carried out thoroughly, and the process transformation efficiency surpasses after the 80w%, and the green coke amount also will be above 1w%.Under this green coke amount, continuous apparatus often can not smooth running.
The gelatin liquefaction technology adopts higher hydrogen dividing potential drop to make carbon change into hydro carbons, even process makes under the situation of spent hydroprocessing catalyst, the hydrogen dividing potential drop is also often up to 18～35MPa.Raising process hydrogen dividing potential drop is to suppress the method for floating bed hydrocracking green coke reaction equally, but the increase of facility investment and running cost then greatly reduces the economy of technology.
The object of the present invention is to provide a kind of transformation efficiency height, green coke amount few, weight, dreg-oil suspension bed lighting working method that can long-term operation.
Heavy, residual oil lighting working method flow process of the present invention is:
A, a small amount of (being lower than 1000 μ g/g) decentralized metal catalyst (comprising water soluble metal catalyst and oil soluble metal catalyzer) is sent into the floating bed hydrogenation reactor with heavy, residual oil raw material after mixing, (6～20MPa), heavy, residual oil is cracked into light-end products under higher conversion (more than the 80w%) to introduce hydrogen supply agent and high pressure hydrogen;
It is 170～350 ℃ distillate or wherein a certain narrow fraction section that b, the material that comes out from suspended-bed reactor cut out the boiling range scope through water distilling apparatus;
C, this distillate is sent into the fixed bed hydrogenation device, adopt conventional diesel oil hydrogenation condition;
D, be that 170～350 ℃ distillate loops back the floating bed hydrocracking reactor by a certain percentage, also can be used as the hydrogen supply agent of the inventive method behind the diesel oil fraction hydrogenating of the diesel oil distillate of catalytic cracking production and thermally splitting product the boiling range behind the hydrogenation.
The weight that the present invention relates to, residual oil can be the residual oils that crude distillation obtains, heavy-gravity heavy crude oil, the also organism that obtains of oil sands bitumen, shale oil and the dry distillation of coal.
Wherein, the disperse type catalyzer that uses in heavy, the hydrogenation of residual oil suspended bed process can be the heteropolyacid salt aqueous solution of periodic table of elements VIB, VIIB and two or more metallic compounds of group VIII, as phospho-molybdic acid nickel, phospho-wolframic acid nickel etc.; Also can be the oil soluble organic compound of periodic table of elements VIB, VIIB and two or more metals of group VIII, as many carbonyl compound, naphthenate compound and the porphyrin class inner complex of molybdenum, nickel, cobalt.In weight metal, the content of catalyzer in raw material is 50～1600 μ g/g, is preferably 150～800 μ g/g.
Wherein distillate hydrogenation adopts the Solid Bed method of hydrotreating, and catalyzer that uses and operational condition can be the catalyzer and the processing condition of routine.
Disperse type catalyzer and stock oil thorough mixing, the total add-on of catalyst metal is no more than 1000 μ g/g.The stock oil that contains catalyzer is sent into the floating bed hydrogenation reactor with hydrogen supply agent, hydrogen; Or catalyzer and stock oil and hydrogen supply agent mix the back simultaneously and enter the floating bed hydrogenation reactor with hydrogen.Hydrogenation and scission reaction take place in heavy, residual oil in reactor, change into low boiler cut to greatest extent.The floating bed hydrogenation reactor operating condition is: pressure 6～20Mpa, preferred 6～12MPa, 400～490 ℃ of temperature, preferred 420～460 ℃, liquid hourly space velocity 0.2～2.0h
-1, hydrogen to oil volume ratio (under the standard pressure) 200～1200.
The logistics of coming out from the floating bed hydrogenation reactor is sent in the distillation tower, cut out 170～350 ℃ of cuts and other cut, 170～350 ℃ of cuts are sent into fixed bed hydrogenation reactor, hydrogenation under 3～10MPa hydrogen pressure, hydrogenation products loops back the floating bed hydrogenation reactor as hydrogen supply agent of the present invention by a certain percentage with it.The ratio that hydrogen supply agent circulation add-on accounts for the total liquid feeding of floating bed hydrogenation reactor is 10m%～90m%, is preferably 20m%～70m%, is preferably 30m%～60m%.
Fig. 1 is a hydrogen supply agent method hydrogenation of residual oil suspended bed process flow diagram of the present invention.
Below in conjunction with Fig. 1 process of the present invention is described in detail:
Residual oil raw material and decentralized metallic catalyst enter blender 3 from pipeline 1 and 2 respectively. Blender 3 can be an agitator tank, also can be a homogenizer or static mixer or other conventional mixing apparatus, and residual oil and catalyst mix is even. If material viscosity is large especially, be difficult to use the conventional method mixing below 100 ℃, also can first catalyst be mixed with a small amount of reduced crude, and then mix with full-bodied charging. Charging after mixing enters heater 9 through pipeline 4 and pump 5, pipeline 6, pipeline 8, and hydrogen enters system via pipeline 7, and hydrogen supply agent is sent into heater 9 through pipeline 16, pipeline 6 and pipeline 8. Charging is heated to 350～440 ℃ in heater 9, then enter reactor 11 through pipeline 10. Reactor operating condition is hydrogen pressure 6～20MPa, feeding liquid hourly space velocity 0.2～2.0h-1, 400～490 ℃ of reaction temperatures, hydrogen-oil ratio 200～1200 (volume ratio). Product enters fractionating column 13 via pipeline 12, tells boiling spread and is 170～350 ℃ of products and go fixed bed reactors 15 to carry out that hydrogenation is full to be closed through pipeline 14, and the partial hydrogenation product loops back the floating bed hydrogenation reaction zone through pipeline 16.
Advantage of the present invention is:
1, uses simultaneously disperse type catalyzer and the hydrogen supply agent with higher hydrogenation activity, improved significantly the ability of process coke inhibiting reaction, the operation of make heavily, dreg-oil suspension bed hydrogenation cracking technique can be under higher conversion ratio, obtain light-end products to greatest extent and do not produce coke, but the long period steady running.
2, in the floating bed hydrogenation process, adopt disperse type catalyzer, effectively suppressed the green coke of process, thereby so that substantially do not contained solid particle in the tail oil.
3, the hydrogen supply agent that uses of process is raw material pyrolysis product hydrogenation gained, adds hydrogen supply agent for need use, and can be recycled, and has avoided using pure hydrogen supply agent such as naphthane and the adverse effect of the high cost that causes.
For further specifying all main points of the present invention, enumerate following examples.
Test raw material character sees Table 1.This residual oil sulphur content height as shown in Table 1, the metal content height, only nickel, vanadium and iron promptly reach more than the 190 μ g/g, and asphalt content reaches 8.4m%, and carbon residue surpasses 20m%, and nitrogen content is also higher, is a kind of more unmanageable poor residuum.
Table 1 test vacuum residuum character in the sand
| Project | Numerical value | Project | Numerical value |
| Density (20 ℃), Kg/m 3 | 1024.8 | Four proximate analysis m% | |
| Carbon residue, m% | 20.73 | Stable hydrocarbon | 9.9 |
| C，m％ | 83.52 | Aromatic hydrocarbons | 52.2 |
| H，m％ | 10.43 | Colloid | 29.5 |
| S，m％ | 4.95 | Bituminous matter | 8.4 |
| N，m％ | 0.35 | Boiling range, ℃ | 538 + |
| Metal content m% | |||
| Fe，10 -6 | 8.16 | ||
| Ni，10 -6 | 43.4 | ||
| V，10 -6 | 143.6 |
This test investigate subtract in the sand slag at catalyst-free and hydrogen supply agent, only have catalyzer, only have hydrogen supply agent and catalyzer and hydrogen supply agent all to have four kinds of hydrocracking and coke forming properties under the condition.Transformation efficiency is to obtain each distillate yield sum after the reaction product cutting, wherein the hydrogen supply agent of deduction adding.Hydrogen supply agent is the hydrogenation products of the diesel oil distillate in the present embodiment crackate.Diesel oil fixed bed hydrogenation catalyzer is 3926 Hydrobon catalysts that Fushun No.3 Petroleum Factory produces, and processing condition are: pressure 7MPa, 340 ℃ of temperature, volume space velocity 1.5h
-1, hydrogen-oil ratio is 500.Wherein the suspension bed hydrogenation process condition value is the numerical value (down together) that does not contain hydrogen supply agent.Coke forming property characterizes to measure the toluene insolubles that generates in the oil.Test is carried out on small-sized floating bed hydrogenation device, and the device general flow chart is seen Fig. 1.Test-results sees Table 2.
Subtract the floating bed hydrogenation test-results under four kinds of conditions of slag in table 2 sand
| Embodiment |
| 1 | 2 | 3 | 4 | |
| Hydrogen supply agent (hydrogenated diesel oil) m% | 0 | 0 | 50 | 32 |
| Catalyzer (the phospho-molybdic acid nickel aqueous solution) μ g/g | 0 | 400 | 0 | 400 |
| Reaction conditions: | ||||
| Temperature ℃ | 430 | 435 | 440 | 440 |
| | 10 | 10 | 10 | 10 |
| Air speed h -1 | 1.0 | 1.0 | 1.0 | 1.0 |
| Hydrogen-oil ratio v/v | 800 | 800 | 800 | 800 |
| Products distribution: | ||||
| ＜170 ℃ of cut m% | 13.9 | 12.2 | 10.3 | 10.3 |
| 170～350 ℃ of cut m% | 20.7 | 32.3 | 31.9 | 30.8 |
| 350～538 ℃ of cut m% | 27.3 | 34.3 | 44.7 | 42.7 |
| Transformation efficiency m% | 61.9 | 78.8 | 86.9 | 83.8 |
| Toluene insolubles m% | 1.89 | 1.03 | 1.17 | 0.31 |
Can significantly reduce the green coke amount of residual oil under the floating bed hydrogenation high conversion after decentralized metal catalyst and hydrogen supply agent are used in the test-results explanation simultaneously, thereby assurance device can smooth running continuously under high conversion.
Mass spectrometric measurement result after table 3 diesel oil distillate first hydrogenation front and back and twice circulation
| |
5 | 6 | 7 |
| Before the hydrogenation | Behind the hydrogenation | Behind twice circulation hydrogenation | |
| Naphthenic hydrocarbon | 17.4 | 33.2 | 36.1 |
| Mononuclear aromatics | 23.0 | 34.4 | 42.1 |
| Double ring arene | 28.7 | 2.5 | 2.3 |
The test result explanation is based on the tetraline class, mononuclear aromatics with strong hydrogen transference ability repeatedly can occupy suitable ratio after the circulation in diesel oil distillate, after adjusting 170～350 ℃ of diesel oil additional proportions, this diesel oil distillate fully can instead of pure tetraline class hydrogen supply agent, makes the art of this patent obtain better economic.
Embodiment 7～10
This test is investigated under different disperse type catalyzers and the different hydrogen supply agent additional proportions, subtracts the situation of slag hydrocracking and green coke in the sand.Test-results sees Table 4.
Test-results on the continuous floating bed hydrogenation device of table 4
| Embodiment | 7 | 8 | 9 | 10 |
| Catalyzer | The phospho-molybdic acid nickel aqueous solution | With 7 | Molybdenum naphthenate and cobalt naphthenate | With 9 |
| Catalyst metal add-on μ g/g | 400 | 800 | 400 | 800 |
| Hydrogen supply agent m% | 49.7 | 36.0 | 22.1 | 75.0 |
| Reaction conditions: | ||||
| | 8 | 8 | 8 | 8 |
| Air speed h -1 | 1.0 | 1.0 | 1.0 | 1.0 |
| Temperature ℃ | 445 | 440 | 440 | 450 |
| Hydrogen-oil ratio v/v | 800 | 800 | 800 | 800 |
| Distribution of reaction products: m% |
| ＜170 ℃ of cuts | 19.1 | 15.6 | 17.7 | 21.3 |
| 170～350 ℃ of cuts | 31.5 | 30.5 | 30.2 | 34.2 |
| 350～538 ℃ of cuts | 40.5 | 41.2 | 39.6 | 36.6 |
| Transformation efficiency m% | 91.1 | 87.3 | 87.5 | 92.1 |
| Toluene insolubles m% | 0.85 | 0.76 | 0.85 | 0.95 |
Wherein hydrogen supply agent is a diesel oil fraction hydrogenating product in the present embodiment, and hydroconversion condition and catalyzer are the same.
The test-results explanation, can reach residual oil and have lower green coke level under higher transformation efficiency by adjusting hydrogen supply agent additional proportion and reactor operating parameters using under water-soluble or the oil soluble disperse type catalyzer condition, therefore smooth operation for a long time.
Claims (9)
1, a kind of heavy, residual oil lightening method reacts under weight, dreg-oil suspension bed hydrogenation cracking condition, it is characterized in that using simultaneously disperse type catalyzer and hydrogen supply agent, and hydrogen supply agent is the diesel oil distillate after the hydrofining, and conversion of raw material is 80～95%; Described heavy, dreg-oil suspension bed hydrogenation cracking condition is: volume space velocity 0.2～2.0h when pressure 6～20MPa, 400～490 ℃ of temperature, feeding liquid
-1, hydrogen to oil volume ratio 200～1200.
2, in accordance with the method for claim 1, it is characterized in that described disperse type catalyzer is water-soluble or the oil soluble metal catalyzer, catalyzer directly is dispersed in weight, the residual oil by add-on.
3,, it is characterized in that described catalyzer is the heteropolyacid salt aqueous solution or the organometallic compound of periodic table of elements VIB, VIIB and two or more metals of group VIII according to claim 1 or 2 described methods.
4, in accordance with the method for claim 3, it is characterized in that described metal is selected from Mo, Ni, Co, W, Cr or Fe.
5, in accordance with the method for claim 1, it is characterized in that described catalyst levels counts 50～1600 μ g/g with metal.
6, in accordance with the method for claim 1, it is characterized in that described hydrogen supply agent comes from the diesel oil distillate of the diesel oil distillate of the diesel oil distillate of floating bed hydrocracking product, catalytic cracking production, thermally splitting product or two or more mixture wherein.
7, in accordance with the method for claim 1, it is characterized in that the ratio that the hydrogen supply agent add-on accounts for the total liquid feeding of floating bed hydrogenation reactor is 10m%～90m%.
8, in accordance with the method for claim 1, it is characterized in that the ratio that the hydrogen supply agent add-on accounts for the total liquid feeding of floating bed hydrogenation reactor is 30m%～60m%.
9, in accordance with the method for claim 1, it is characterized in that described diesel oil fraction hydrogenating purified condition is: adopt the Solid Bed method of hydrotreating, operate under 3～10MPa hydrogen pressure, catalyzer is aluminum oxide or the siliceous aluminium oxide catalyst that supports molybdenum, nickel, cobalt, tungsten metal.
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| CNB011141697A CN1151239C (en) | 2001-07-02 | 2001-07-02 | Process for lightening heavy oil or residual oil |
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|---|---|---|---|
| CNB011141697A CN1151239C (en) | 2001-07-02 | 2001-07-02 | Process for lightening heavy oil or residual oil |
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| CN1151239C true CN1151239C (en) | 2004-05-26 |
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| CN100351347C (en) * | 2003-04-07 | 2007-11-28 | 石油大学(华东) | High decentralization type catalyzer utilized in suspension bed isocracking process |
| CN101724450B (en) * | 2008-10-28 | 2013-05-01 | 中国石油化工股份有限公司 | Method for modifying heavy oil |
| CN101724449B (en) * | 2008-10-29 | 2013-04-10 | 中国石油化工股份有限公司 | Combined technological method for heavy oil modification |
| CN102585897B (en) * | 2012-01-12 | 2014-06-04 | 何巨堂 | Method for conversion of low-hydrogen heavy oil to light fractions by hydrogenation with hydrogen-supplying hydrocarbons |
| CN104422748B (en) * | 2013-09-03 | 2016-05-25 | 中国石油化工股份有限公司 | A kind of method of hydrogen supply agent to response matrix hydrogen supply capacity of evaluating |
| CN105273749A (en) * | 2014-06-30 | 2016-01-27 | 湖南万通科技有限公司 | Preparation method for light oil |
| CN105331390A (en) * | 2015-11-27 | 2016-02-17 | 中国海洋石油总公司 | Method for delaying coking by supplying hydrogen |
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| CN114381302A (en) * | 2020-10-19 | 2022-04-22 | 中国石油大学(北京) | Heavy oil lightening method |
| CN114381301A (en) * | 2020-10-19 | 2022-04-22 | 中国石油大学(北京) | Heavy oil lightening method coupled with hydrogen donor |
| CN114381303A (en) * | 2020-10-19 | 2022-04-22 | 中国石油大学(北京) | Heavy oil lightening method |
| CN114381299A (en) * | 2020-10-19 | 2022-04-22 | 中国石油大学(北京) | Heavy oil lightening method |
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