CN101942338A - Combined process method for heavy oil modification - Google Patents
Combined process method for heavy oil modification Download PDFInfo
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- CN101942338A CN101942338A CN2009100124963A CN200910012496A CN101942338A CN 101942338 A CN101942338 A CN 101942338A CN 2009100124963 A CN2009100124963 A CN 2009100124963A CN 200910012496 A CN200910012496 A CN 200910012496A CN 101942338 A CN101942338 A CN 101942338A
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Abstract
The invention discloses a combined process method for heavy oil modification, which comprises the following steps of: mixing heavy oil raw materials and a hydrogen supply solvent for supercritical treatment, and making the heavy oil subjected to the supercritical treatment enter a catalytic cracking unit for treatment; and performing a cracking reaction in the presence of a cracking catalyst, and separating reaction products to obtain dry gas, liquefied gas, gasoline, diesel oil, heavy cycle oil and slurry oil, wherein the heavy cycle oil partially or totally cycles for the supercritical treatment, and the slurry oil partially or totally cycles for the supercritical treatment. The supercritical treatment method for the heavy oil raw materials comprises the step of mixing the heavy oil raw materials and the hydrogen supply solvent for the supercritical treatment, wherein the hydrogen supply solvent comprises tetrahydronaphthalene or decahydronaphthalene. The method has the advantages of capacity of effectively improving the utilization rate of poor-quality heavy oil, low coking rate, stable production process, and suitability for light treatment of various heavy and poor-quality raw materials.
Description
Technical field
The present invention relates to a kind of combined technical method of heavy oil modification, particularly the combination process of inferior heavy oil upgrading.
Background technology
At present, because petroleum resources are day by day exhausted, and Economic development constantly increases the demand of oil, shows petroleum resources day precious.And along with the heaviness of crude resources, in the refining process of oil, the productive rate of residual oil is higher, is generally 40%-50%.In addition, more heavy crude is arranged in world's crude oil reserve, it forms the overwhelming majority is residual oil, and is the very high poor residuum of foreign matter content.
The industrialized method of handling these residual oil or heavy oil comprises at present: method or combined methods such as catalytic cracking, residual hydrogenation, delayed coking, viscosity breaking.Along with residual oil is more and more inferior, sulphur, nitrogen and metals content impurity are more and more higher, and existing working method deals with all weak point; On the other hand, the energy inferior such as oil-sand, pitch, synthetic crude also enter into the ranks of refining of petroleum, need suitable method to handle the great energy of these reserves, alleviate the demand of social development to produce more light-end products.
CN200610026906.6 discloses a kind of method of preparing light oil from supercritical water modified vacuum residuum, in supercritical water, carries out the thermally splitting of vacuum residuum and handles.Though this method is carried out heat cracking reaction in supercritical water, compare with common thermal cracking process and reduced the coking side reaction, for inferior raw material, coking rate is still higher.
Existing residual hydrocracking---heavy oil catalytic cracking process is that the residual oil behind the hydrogenation is entered further processing in the catalytic cracking unit.Because the heavy cycle oil that produces in the catalytic cracking contains polycyclic aromatic hydrocarbons, thereby light oil yield is low, the green coke amount is big, has increased the revivifier load, has reduced the treatment capacity and the economic benefit of heavy oil catalytically cracking equipment.The sulphur content of heavy cycle oil is higher in addition, exceeds one times than hydrogenation tail oil approximately, and the heavy cycle oil circulation also makes the product sulphur content rise.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of combination process of heavy oil modification, the impurity of the inventive method in can effective elimination heavy oil, and coking rate is low.
The combined technical method of heavy oil modification of the present invention comprises following content: heavy oil feedstock at first mixes with hydrogen supply dissolvent and carries out first supercritical processing, entering catalytic cracking unit through the heavy oil after the first supercritical processing handles, 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, and wherein heavy cycle oil partly or entirely is circulated to first supercritical processing; Slurry oil partly or entirely is circulated to first supercritical processing.Slurry oil can direct cycle to first supercritical processing, also can will steam thing and be circulated to first supercritical processing after fractionation by distillation go out resistates.All enter catalytic cracking unit through the heavy oil behind process separating solid substances of the material after the first supercritical processing and the fractionation light constituent.
In the combination process of heavy oil modification of the present invention, it is that heavy oil feedstock mixes with hydrogen supply dissolvent and carries out first supercritical processing that heavy oil feedstock carries out the first supercritical processing method, hydrogen supply dissolvent comprises naphthane or perhydronaphthalene, heavy oil feedstock is 1: 0.5～1: 10 with the mixed weight ratio of hydrogen supply dissolvent, the first supercritical processing condition is to handle 0.2～5 hour down for 300～500 ℃ at pressure 15～40MPa and temperature, handles and carries out the fractionation processing after product is isolated solid impurity.The first supercritical processing condition is the supercritical state of hydrogen supply dissolvent or near the condition of criticality, hydrogen supply dissolvent can and provide hydrogen with coking precursor thorough mixing in the heavy oil feedstock in coking precursor scission reaction under this condition, prevent its coking, and then reduce coking rate.
Catalytic cracking process is conventional processing condition and reaction unit, and concrete is riser catalytic cracking technology as catalytic cracking, or the catalytic cracking process of voluminous isoparaffin, or double lifting leg technology or catalytic pyrolysis (DCC) technology etc.
In the combination process of heavy oil modification of the present invention, described heavy oil feedstock is the residual oil of various crude oil, and various oil-sand, pitch, synthetic crude, coal tar, shale oil or oli oil etc., or two or more mixture of above-mentioned raw materials.
The cut (being mainly diesel oil distillate) that the supercritical reaction effluent is isolated to be contained hydrogen supply dissolvent or lose the hydrogen hydrogen supply dissolvent can partly or entirely loop back super critical reaction process, also can recycle behind the hydrogenation carrying out.The hydrogen supply dissolvent cyclical operation can reduce the consumption of fresh hydrogen supply dissolvent.Internal circulating load generally can be 0.1～5 times of fresh hydrogen supply dissolvent volume, can determine according to concrete optimization of the required reaction effect of overcritical process.
In the combination process of heavy oil modification of the present invention, can also add entry in the supercritical reaction system, the add-on of water can be handled 0.1 times～10 times of raw material weight for supercritical reaction.Water under reaction conditions can with reaction generating portion hydrogen such as coke in the reaction system, under the high pressure-temperature condition, the hydrogen that generates can react with the hydrogen supply dissolvent that loses hydrogen, makes the hydrogen supply dissolvent recuperation section hydrogen supply capacity that loses hydrogen, thereby can reduce the consumption of hydrogen supply dissolvent and improve reaction efficiency.Water and hydrogen supply dissolvent have formed the coordinated effect.
In the combination process of heavy oil modification of the present invention, the hydrogen supply dissolvent that can adopt method such as fractionation will comprise superfluous hydrogen supply dissolvent in the mixture behind the supercritical reaction or lose hydrogen separates, can directly recycle after the separation, or recycle after replenishing fresh hydrogen supply dissolvent, or it is recycled through behind the catalytic cracking process.
In the combination process of heavy oil modification of the present invention, the first supercritical processing conversion unit can use this area popular response device, can be continuously stirred tank reactor (CSTR) (CSTR), tank reactor etc. intermittently as the first supercritical processing reactor, reaction process is carried out agitation as appropriate, the air atmosphere that can be aided with lower concentration in the reactor is to increase reaction effect.
The combination process of heavy oil modification of the present invention is with first supercritical processing and catalytic cracking combination, in the supercritical state of hydrogen supply dissolvent or near carrying out under the critical phase conditions, the fused effect and the reaction effect of coking precursor in hydrogen supply dissolvent and the heavy oil have been improved, reduced the coking tendency, strengthened reaction effect simultaneously, improve the ability that removes impurity, can handle heavy oil feedstock more inferior.
In the combination process of heavy oil modification of the present invention, with catalytic cracking and first supercritical processing combination, first supercritical processing can effectively reduce and alleviate the load of catalytic cracking, compares with the technology of independent employing catalytic cracking, and the processing condition of catalytic cracking can obtain relaxing in the combination process.In the supercritical state of hydrogen supply dissolvent or near carrying out under the critical phase conditions, the fused effect and the reaction effect of coking precursor in hydrogen supply dissolvent and the heavy oil have been improved, reduced the coking tendency, strengthened reaction effect simultaneously, improve the ability that removes impurity, can handle heavy oil feedstock more inferior.Heavy catalytic cycle oil and slurry oil loop back first supercritical processing, can further optimize the catalytic cracking reaction environment, improve the quality of products.Hydrogen supply dissolvent and water use simultaneously, can reach the coordinated effect, make hydrogen supply dissolvent can partly recover hydrogen supply capacity under response behaviour, reduce the consumption of hydrogen supply dissolvent, improve reaction effect.The cut of hydrogen supply dissolvent loops back first supercritical processing after containing hydrogen supply dissolvent or losing hydrogen, can recover the hydrogen supply capacity of hydrogen supply dissolvent on the one hand, can improve the reaction environment of catalytic cracking on the other hand, improves the stability of Hydrocarbon Content by Catalytic Cracking Operation.Can also improve simultaneously whole light oil yield, further with the heavy oil feedstock lighting.
Description of drawings
Fig. 1 is a kind of concrete process flow diagram of the combination process of heavy oil modification of the present invention.
Embodiment
Further specify the solution of the present invention and effect below in conjunction with the drawings and specific embodiments.
As shown in Figure 1, heavy oil feedstock is through with after the identical filtration of common process etc. is handled, mix with additive (additive comprises hydrogen supply dissolvent and water etc.), then after the material heating, enter CSTR (continuously stirred tank reactor (CSTR)), pressurize, heat up and begin and stir rotating speed 800 commentaries on classics/min, be forced into 15～40MPa, be warming up to 300～500 ℃.Reacted product enters separator after isolating solid impurity after filtration, and gas phase is separated with liquid phase, and the solid impurity that filters to isolate etc. can burn or as the raw material of needle coke, liquid phase enters separation column.Separation column is isolated the hydrogen supply dissolvent of light-end products (gasoline fraction and diesel oil distillate) and surplus or is lost the hydrogen supply dissolvent of hydrogen.Heavy oil fraction after the fractionation enters catalytic cracking process, and operational condition is 470～520 ℃ of temperature, pressure 0.1～0.3MPa, agent-oil ratio (catalyzer and stock oil weight ratio) 3～6: 1, air speed 5～15h
-1
Embodiment-1
Tahe residual oil is through with after the identical filtration of common process etc. is handled, heavy oil feedstock carries out first supercritical processing again, joins motionless mixer with naphthane, (keeps excessive naphthane, the weight ratio finish of heavy oil feedstock and naphthane was than 1: 6), after the material heating, enter CSTR (continuously stirred tank reactor (CSTR)) then, pressurize, heat up and begin and stir, rotating speed 800 commentaries on classics/min, be forced into 20MPa, be warming up to 400 ℃, the reaction times is 3h.Reacted product enters separator after filtering, and gas phase is separated with liquid phase, and the solid impurity that filters to isolate etc. can burn or as the raw material of needle coke, liquid phase enters separation column.Separation column is isolated various light ends (gasoline fraction and diesel oil distillate) and superfluous hydrogen supply dissolvent.Superfluous hydrogen supply dissolvent can recycle, and the heavy oil fraction that fractionation obtains is as the charging of catalytic cracking.Reaction effect sees Table 1.
Embodiment-2
With Tahe residual oil is raw material, supercritical process step same embodiment-1.Heavy oil feedstock carries out first supercritical processing, and hydrogen supply dissolvent is a perhydronaphthalene, and heavy oil feedstock and hydrogen supply dissolvent weight ratio are 1: 2, reaction pressure is 35MPa, temperature of reaction is 450 ℃, and the reaction times is 0.5h (CSTR is the continuously feeding discharging, and the reaction times is the material mean residence time).The isolated heavy oil fraction of separation column enters catalytic cracking, and operational condition is 510 ℃ of temperature, pressure 0.2MPa, agent-oil ratio 5: 1, air speed 10h
-1Reaction product isolated obtains dry gas, liquefied gas, gasoline, diesel oil, heavy cycle oil and slurry oil, and wherein heavy cycle oil is circulated to first supercritical processing; Slurry oil is after fractionation by distillation goes out resistates, and the thing that steams of slurry oil is back to first supercritical processing, heavy cycle oil: slurry oil steams thing: heavy oil feedstock=3: 5: 92 (weight).After method processing of the present invention, catalytic cracking reaction the results are shown in Table 2.
Embodiment-3
Press the identical method of embodiment 2, also add water when using perhydronaphthalene, the weight ratio of water and first supercritical processing charging is 2: 1, and catalytic cracking reaction the results are shown in Table 2.
Comparative example
The method identical with embodiment 2 only makes water in the first supercritical processing process, do not use the hydrogen supply dissolvent perhydronaphthalene, and catalytic cracking reaction the results are shown in Table 2.
Table 1 embodiment 1 reaction result
| Raw material | Embodiment-1 | |
| Density (20 ℃), kgm -3 | 1023.4 | 978.3 |
| Carbon residue, quality % | 19.3 | 9.8 |
| Viscosity (100 ℃) mm 2·s -1 | 576.7 | 104.4 |
| S, quality % | 3.6 | 0.9 |
| N, quality % | 0.7 | 0.24 |
| Ni，μg·g -1 | 38.6 | 3.5 |
| V，μg·g -1 | 110.4 | 8.1 |
| Colloid, quality % | 24.5 | 14.7 |
| Bituminous matter, quality % | 16.4 | 5.2 |
| Coke yield, quality % | - | 3.7 |
Table 2 embodiment 2,3 and comparative example reaction result
Claims (10)
1. the combined technical method of a heavy oil modification, it is characterized in that: heavy oil feedstock at first mixes with hydrogen supply dissolvent and carries out first supercritical processing, entering catalytic cracking unit through the heavy oil after the first supercritical processing handles, 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, and wherein heavy cycle oil partly or entirely is circulated to first supercritical processing; Slurry oil partly or entirely is circulated to first supercritical processing.
2. in accordance with the method for claim 1, it is characterized in that: slurry oil direct cycles to first supercritical processing, perhaps after fractionation by distillation goes out resistates, will steam thing and be circulated to first supercritical processing.
3. it is characterized in that in accordance with the method for claim 1: all enter catalytic cracking unit through the heavy oil behind process separating solid substances of the material after the first supercritical processing and the fractionation light constituent.
4. in accordance with the method for claim 1, it is characterized in that: it is that heavy oil feedstock mixes with hydrogen supply dissolvent and carries out first supercritical processing that heavy oil feedstock carries out the first supercritical processing method, hydrogen supply dissolvent comprises naphthane or perhydronaphthalene, heavy oil feedstock is 1: 0.5～1: 10 with the mixed weight ratio of hydrogen supply dissolvent, and the first supercritical processing condition is to handle 0.2～5 hour down for 300～500 ℃ at pressure 15～40MPa and temperature.
5. in accordance with the method for claim 1, it is characterized in that: heavy oil feedstock is the residual oil of various crude oil, and various oil-sand, pitch, synthetic crude, coal tar, shale oil or oli oil, or two or more mixture of above-mentioned raw materials.
6. in accordance with the method for claim 1, it is characterized in that: the isolated cut that contains hydrogen supply dissolvent or mistake hydrogen hydrogen supply dissolvent of supercritical reaction effluent partly or entirely loops back super critical reaction process, perhaps carries out recycling behind the hydrogenation.
7. it is characterized in that in accordance with the method for claim 6: the amount that recycles is 0.1～5 times for fresh hydrogen supply dissolvent volume.
8. in accordance with the method for claim 1, it is characterized in that: add entry in the supercritical reaction system, the add-on of water is 0.1 times～10 times that supercritical reaction is handled raw material weight.
9. it is characterized in that in accordance with the method for claim 1: the first supercritical processing conversion unit is continuously stirred tank reactor (CSTR) or tank reactor intermittently.
10. in accordance with the method for claim 1, it is characterized in that: catalytic cracking is a riser catalytic cracking technology, or the catalytic cracking process of voluminous isoparaffin, or double lifting leg technology or Deep Catalytic Cracking process.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111954708A (en) * | 2018-04-11 | 2020-11-17 | 沙特阿拉伯石油公司 | Supercritical water method integrated with visbreaking furnace |
| CN113214863A (en) * | 2020-07-10 | 2021-08-06 | 中国石油大学(北京) | Distillate oil supercritical/subcritical fluid enhanced hydrogenation method |
| CN113789191A (en) * | 2021-09-13 | 2021-12-14 | 延安大学 | Heavy oil viscosity reducing and desulfurizing method based on supercritical methanol |
| CN113801689A (en) * | 2021-09-10 | 2021-12-17 | 中海油天津化工研究设计院有限公司 | Method for treating heavy oil by supercritical hydrothermal modification and delayed coking technology |
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| CN101077980A (en) * | 2006-05-26 | 2007-11-28 | 华东理工大学 | Method for preparing light oil from supercritical water modified vacuum residuum |
| US20080099377A1 (en) * | 2006-10-31 | 2008-05-01 | Chevron U.S.A. Inc. | Process for upgrading heavy hydrocarbon oils |
| JP2008297466A (en) * | 2007-05-31 | 2008-12-11 | Japan Energy Corp | Method for cracking hydrocarbon oil |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101077980A (en) * | 2006-05-26 | 2007-11-28 | 华东理工大学 | Method for preparing light oil from supercritical water modified vacuum residuum |
| US20080099377A1 (en) * | 2006-10-31 | 2008-05-01 | Chevron U.S.A. Inc. | Process for upgrading heavy hydrocarbon oils |
| JP2008297466A (en) * | 2007-05-31 | 2008-12-11 | Japan Energy Corp | Method for cracking hydrocarbon oil |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111954708A (en) * | 2018-04-11 | 2020-11-17 | 沙特阿拉伯石油公司 | Supercritical water method integrated with visbreaking furnace |
| CN113214863A (en) * | 2020-07-10 | 2021-08-06 | 中国石油大学(北京) | Distillate oil supercritical/subcritical fluid enhanced hydrogenation method |
| CN113801689A (en) * | 2021-09-10 | 2021-12-17 | 中海油天津化工研究设计院有限公司 | Method for treating heavy oil by supercritical hydrothermal modification and delayed coking technology |
| CN113801689B (en) * | 2021-09-10 | 2022-10-18 | 中海油天津化工研究设计院有限公司 | Method for treating heavy oil by supercritical hydrothermal modification and delayed coking technology |
| CN113789191A (en) * | 2021-09-13 | 2021-12-14 | 延安大学 | Heavy oil viscosity reducing and desulfurizing method based on supercritical methanol |
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