CN101089144A - Heavy oil and residual oil combined treating process - Google Patents
Heavy oil and residual oil combined treating process Download PDFInfo
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Abstract
The heavy oil and residual oil combined treating process includes the following steps: hydrocracking heavy oil and residual oil material in a suspended bed in mild condition; fractionating the hydrocracked resultant into light fraction, heavy fraction and un-converted vacuum residue, which accounts for 20-45 wt% of the material; catalytically cracking the heavy fraction; and solvent deasphalting the un-converted vacuum residue to obtain deasphalted oil serving as the catalytically cracking material. The process of the present invention has stable hydrocracking operation in suspended bed, can utilize all the fractions in the material, and is suitable for treating various kinds of heavy oil and residual oil.
Description
Technical field
The present invention relates to a kind of heavy, residual oil method for transformation, particularly contain the inferior heavy of high-sulfur, nitrogen, carbon residue, colloid, bituminous matter and heavy metal, the method that residual oil raw material effectively transforms and utilizes.
Background technology
Crude resources worsening shortages in the world wide, crude quality becomes day by day and heavily becomes bad, and the demand of petroleum products is constantly increased, and this just requires limited crude resources is fully effectively utilized.Wherein effective utilization of inferior heavy, residual oil is the key point that makes full use of crude oil.The utilization of inferior heavy, residual oil need be carried out major part lighting and handle except that produced in small quantities pitch, produces the light ends product.To weigh in the prior art at present, the major technique means of residual oil lighting comprise decarburization and hydrogenation.Decarbonization process is subjected to the stock oil property effect bigger, especially when colloid in the stock oil, when asphalt content is high influence particularly evident, and liquid product yield is low, of poor quality, the following process difficulty.And hydrogenation technique can improve the light oil fraction yield, deviates from impurity wherein simultaneously, improves quality product, but has a large amount of tail oils to need post-treatment.Therefore, decarburization and two kinds of technologies of hydrogenation organically being combined is that a kind of more favourable processing is heavy, the method for residual oil.
The fixed bed hydrogenation treatment technology can be used for heavily, residua upgrading, but generally can not handle the too poor raw material of quality, particularly can not handle the higher weight of metal content, residual oil raw material, and the cracking rate is lower, and the yield of light-end products is lower.Because the cracking rate that fixed bed hydrogenation is handled is lower, therefore during with the combination of other technology such as catalytic cracking etc., the cooperation effect of material is relatively poor, generally can only be with the raw material of a large amount of unconverted heavy, residual oil as catalytic cracking, and this has bigger influence to catalytic cracking process.Floating bed hydrocracking can be used for second-rate inferior raw material, and transformation efficiency higher (can reach more than 90%), but because a little less than the hydrogenation, under the situation of higher cracking rate, the coke growing amount is bigger, device is difficult for stable operation.Floating bed hydrocracking also can be used for heavily, the visbreaking process of residual oil, but the cracking rate is very low, does not produce light-end products.
CN1219570A has introduced a kind of combination complete processing, and this technology is residual oil raw material at first to be entered suspended-bed reactor carry out deep processing, and the tail oil that suspension bed comes out is sent into the reaction of defocusing of coker, and the light ends that obtains goes hydrofining again.Though this technology has increased the light oil transformation efficiency, fundamentally do not solve the problem that reduces the device green coke and reduce dry gas output.
In addition, when floating bed hydrocracking combined with coking process, because foreign matter content is higher in the inferior raw material, the suspension bed catalyzer can not be separated and enter coking raw material in addition, and the burnt poor quality of the petroleum coal that makes coking obtain is difficult to use and handle.
Summary of the invention
At the deficiencies in the prior art, the invention provides the combination complete processing of a kind of inferior heavy, residual oil, can handle the inferior raw material that contains high-sulfur, nitrogen, carbon residue, colloid, bituminous matter and heavy metal, and can improve yield of light oil, production equipment can steady running.
The present invention is heavy, the residual oil combinational processing method comprises following content:
(1) with inferior heavy, residual oil raw material to carry out floating bed hydrocracking under the mitigation condition, the yield of unconverted vacuum residuum accounts for the 20wt%～45wt% of raw material, is preferably 25wt%～35wt%;
(2) fractionation of floating bed hydrocracking product is a light ends, heavy ends (VGO) and unconverted vacuum residuum;
(3) heavy ends that obtains of step (2) carries out catalytic cracking and handles;
(4) the unconverted vacuum residuum that obtains of step (2) carries out solvent deasphalting and handles, and the heavy ends that deasphalted oil that the solvent deasphalting treating processes obtains and step (2) obtain is jointly as catalytically cracked material.
The slurry oil that catalytic cracking described in the above-mentioned steps (3) is got rid of outward can be used as one of charging of solvent deasphalting, and the de-oiled asphalt that described solvent deasphalting obtains can be used as asphaltic products..
The present invention specifically comprises:
1, floating bed hydrocracking adopts conventional disperse type catalyzer, operates under the demulcent operational condition, obtains suitable transformation efficiency, and raw material can be the inferior raw material of high-sulfur, nitrogen, carbon residue, colloid, bituminous matter and heavy metal.
2, will deliver to vacuum distillation tower from the liquid phase of the hydrotreatment of step 1, in this tower, isolate unconverted vacuum residuum at the bottom of VGO cut and the tower, as the charging of downstream unit.
3, the VGO cut that step 2 is obtained is sent into catalytic cracking unit, before advancing catalytic cracking unit, for avoiding the inactivation of catalyzer, raw material there is strict charging requirement, charging requires to be generally: sulphur content is lower than 0.5%, the carbon residue amount is less than 8%, and metal content is not higher than 40 μ g/g, and nitrogen content is less than 0.3%.In catalytic cracking unit, isolate catalysis gas, diesel oil and catalytic slurry.
4, the unconverted vacuum residuum of step 2 gained is sent into solvent deasphalting unit together with the catalytic slurry that step 3 obtains, obtain deasphalted oil and de-oiled asphalt.Gained deasphalted oil turns back to the further lighting of step 3 catalytic cracking unit again, and de-oiled asphalt can remove processing high grade pitch.
The disperse type catalyzer that floating bed hydrocracking uses in the step 1 of the present invention is the liquid catalyst that contains metal-salt, metal is the metal with hydrogenation activity commonly used, as among W, Mo, Ni, Co, Fe, the Cr etc. one or more, add-on is counted 50～800 μ g/g by metal.The suspension bed reaction conditions is: pressure 5～18MPa, be preferably 10～15MPa, and temperature is 350 ℃～430 ℃, is preferably 400 ℃～420 ℃, the liquid air speed is 0.5～1.5h
-1, being preferably 0.8～1.2h-1, hydrogen to oil volume ratio (under the standard conditions) is 500～1500, is preferably 800～1200.Floating bed hydrocracking reaches required transformation efficiency by the red-tape operati condition.
The present invention 2 is described to be the liquid of treatment step 1 in the vacuum distillation tower, the initial boiling point of VGO cut is generally 290～380 ℃, and final boiling point is generally 490～580 ℃, is preferably 350 ℃～520 ℃ cuts, VGO advances catalytic cracking unit, and vacuum residuum advances solvent deasphalting unit at the bottom of the tower.
The present invention's 3 described catalytic cracking can be adopted the operating method and the operational condition of this area routine.Enter reactor as the VGO cut from the catalytic cracking unit bottom, in device, fully contact upwards mobile with catalyzer.Temperature of reaction is generally 450 ℃～530 ℃, is preferably 480 ℃～510 ℃, and catalyzer is preferably molecular sieve catalyst for sial, silicon magnesium, acidic white earth and molecular sieve catalyst commonly used, can adopt existing various catalytic cracking catalysts.Agent weight of oil ratio is 2～30, is preferably 4～20, and pressure is 0.1～1.0MPa, is preferably 0.3～0.5MPa.Reactor preferably adopts riser reactor, and catalysis gas, the diesel oil of producing removes withdrawing can separately respectively, and catalytic slurry enters downstream unit.
The present invention 4 is described to be that step 2 gained vacuum residuum is sent into solvent deasphalting unit together with the catalytic slurry that step 3 obtains, and can adopt the operating method and the operational condition of this area routine.Operational condition is generally: temperature is 120 ℃～200 ℃, be preferably 140 ℃～190 ℃, pressure is 2.8～4.2MPa, be preferably 3.5～4MPa, extraction solvent is preferably the mixture of butane and pentane, because of they can operate under comparatively high temps, deviates from the yield height of impurity and asphalt oil, its weight of solvent ratio is 1: 1～8: 1, is preferably 4: 1～6: 1.Tell raffinate oil (deasphalted oil) and pitch.Raffinating oil because of containing higher aromatic hydrocarbons and part colloid, is catalytically cracked material preferably, tell solvent after recirculation return the further lighting of the described catalytic cracking unit of step 3, pitch advances downstream unit and removes to produce high-quality asphalt.
Advantage of the present invention is to have adopted the mutual associating that relaxes several technologies such as floating bed hydrogenation, catalytic cracking, solvent deasphalting, not only widened the field of floating bed hydrogenation, also reduced the severity of device operation, reach substantially not green coke, prolong the operational cycle of floating bed hydrogenation device, ensured the charging of catalytic cracking unit.Improved the catalyzer work-ing life of catalytic cracking unit, reduced dry gas yied, improved the processing power and the liquid yield of device, and obtained high-quality asphalt, the product that is not difficult for utilizing is discharged, and inferior heavy, residual oil are fully effectively used.The inventive method cooperates each unit organic coordination of each combination process, and lighting properly distributed heavy, residual oil is arrived each assembled unit, has avoided the load of some assembled unit lightings too high, distributes and influence stable operation and influence product.
Description of drawings
Fig. 1 is a flow process simplified schematic diagram of the present invention.
Embodiment
Below in conjunction with sketch this process being done one specifies.
As shown in the figure, stock oil 1 at first with liquid catalyst 2 thorough mixing in low-temperature mixed jar 3, enter vulcanizing apparatus 6 through pipeline 4 with pre-hydrogen 5, make the metal component of catalyzer become sulfide, catalyzer is sent into reactor 8 with stock oil and hydrogen by pipeline 7 after tight cure, reaction product 9 enters separator 10, isolated hydrogen-rich gas 11 turns back to hydrogenation system again and recycles after purifying, gained product liquid 12 enters vacuum distillation tower 13, fractionate out VGO14 and vacuum residuum 16, wherein VGO14 and deasphalted oil 22 are mixed into catalytic cracking unit 15 further crackings.In catalytic cracking unit 15, fractionate out LPG17, catalytic gasoline 18, catalytic diesel oil 19, and catalytic slurry 20.Vacuum residuum 16 is mixed into solvent deasphalting unit 21 with catalytically cracked oil 20 again, isolates deasphalted oil 22 and de-oiled asphalt 23, and de-oiled asphalt 23 deasphalting processing unit (plant) 24 more further is processed into high-quality asphalt 25.
In order to further describe advantage of the present invention, enumerate embodiment below.
Embodiment
Test is the normal slag of Tahe with stock oil, and its feedstock property sees Table 1.
Table 1 stock oil character
| Project | Character | Project | Character |
| Density (20 ℃), kg/m 3 | 1001 | Ni | 239.96 |
| Viscosity (100 ℃) mm 2.s -1 | 576.7 | V | 227.4 |
| Carbon residue, wt% | 18.3 | Four components, wt% | |
| Elementary composition, wt% | Saturated branch | 29.0 | |
| C | 85.31 | Fragrance divides | 33.1 |
| H | 9.89 | Colloid | 24.5 |
| S | 3.36 | Bituminous matter | 13.4 |
| N | 1.42 | Boiling range, wt% | |
| Metal content, μ g/g | 350℃～500℃ | 32.1 | |
| Fe | 13.65 | ＞500℃ | 67.9 |
Find out that from feedstock property this raw material is the crude oil with poor quality of high-sulfur, high metal, high carbon residue, raw material at first carries out floating bed hydrogenation, and its operational condition is: temperature: 420 ℃, and pressure: 14MPa, hydrogen-oil ratio (V/V): 800, volume space velocity during liquid: 1h
-1, the catalyzer of floating bed hydrogenation is a phospho-molybdic acid nickel, consumption is 300 μ g/g with the content of metal in raw material.
Enter vacuum distillation tower through the product of floating bed hydrogenation and carry out vacuum fractionation, the green coke situation characterizes with toluene insolubles, and product characteristics sees Table 2.
Table 2 suspension bed generates oily narrow fraction character
| Project | ＜180 ℃ (petroleum naphtha heats up in a steamer) | 180-350 ℃ (diesel oil distillate) | 350-500 ℃ (VGO cut) | ＞500 ℃ (vacuum residue fraction) |
| Density (20 ℃) g.cm -1 | 0.7710 | 0.8567 | 0.9197 | |
| Carbon residue wt% | ＜0.01 | 32.95 | ||
| Viscosity (100 ℃, mm 2/s) | 3.419 | 6.463 | ||
| Acidity, (mgKOH/100ml) | 4.49 | 16.16 | ＞1500 | |
| Yield | 10.3 | 23.7 | 36.5 | 28.8 |
| Existent gum (mg/100ml) | 222 | |||
| Ultimate analysis wt% | ||||
| C | 84.69 | 85.79 | 86.24 | 85.33 |
| H | 13.94 | 13.13 | 12.08 | 9.86 |
| S | 0.18 | 0.26 | 0.48 | 2.3 |
| N | 0.0984 | 0.1577 | 0.2143 | 0.6529 |
| Metallic element μ g.g -1 | ||||
| Fe | 0.11 | 13.54 | ||
| Ni | 0.08 | 239.86 | ||
| V | 0.06 | 227.32 | ||
| Four proximate analyses, wt% | ||||
| Stable hydrocarbon | 37.9 | |||
| Aromatic hydrocarbon | 31.6 | |||
| Colloid | 26.7 | |||
| Bituminous matter | 3.5 | |||
| Toluene insolubles, wt% | 0.001 |
From generating oil nature, the VGO cut meets catalytic cracking unit charging requirement fully, VGO and deasphalted oil are mixed laggard catalytic cracking unit carry out lighting, mixing oil character sees Table 3, catalytic cracking condition is: temperature of reaction 500, pressure 0.1MPa, agent-oil ratio (wt) 5.5,1 second duration of contact of agent oil.Catalytic cracking reaction the results are shown in table 4.
Table 3 catalytic cracking mixing raw material oil nature
| S/N/CCR，wt％ | 0.52/0.24/0.06 |
| Ni+V，μg/g | 0.08 |
| Stable hydrocarbon/aromatic hydrocarbon | 58.3/31.6 |
| Colloid/bituminous matter | 8.7/1.4 |
Table 4 catalytic cracking reaction products distribution
| Product distributes, wt% | The result |
| Dry gas | 2.2 |
| Liquefied gas | 9.6 |
| Gasoline | 41.3 |
| Diesel oil | 37.6 |
| Yield of light oil | 78.9 |
| Slurry oil | 5.2 |
| Coke | 3.1 |
To be mixed into solvent deasphalting unit greater than 500 ℃ vacuum residuum and catalytic slurry, mixing oil character sees Table 5, the solvent deasphalting operational condition can be selected flexibly according to the purpose product, operational condition in this example is: solvent is butane and 1: 1 mixture of pentane mol ratio, 140 ℃ of temperature, pressure is 4MPa, and the weight of solvent ratio is 5.5, and the solvent deasphalting product property sees Table 6.
Table 5 solvent deasphalting mixing raw material oil nature
| S/N/CCR，wt％ | 2.1/0.6/32.3 |
| Ni+V，μg/g | 88.4 |
| Stable hydrocarbon/aromatic hydrocarbon, wt% | 34.2/30.8 |
| Colloid/bituminous matter, wt% | 29.3/5.7 |
Table 6 solvent deasphalting product property
| Project | Deasphalted oil | De-oiled asphalt | Project | Deasphalted oil | De-oiled asphalt |
| Density, g.cm -1 | 0.9475 | 1.1328 | Fe，μg/g | 0.52 | 6.23 |
| Carbon residue, wt% | 5.55 | 40 | Ni，μg/g | 5.28 | 30.38 |
| Yield, wt% | 67.3 | 32.7 | V，μg/g | 18.06 | 52.65 |
| S，wt％ | 0.83 | 2.3 | Penetration degree | ||
| N，wt％ | 0.26 | 0.6 | Softening temperature | 136 |
Comparative example
Original technology products therefrom yield A and combination process products therefrom yield B of the present invention are compared, the results are shown in Table 7.
Table 7 comparative example product yield
| Yield wt% | A | B |
| Gas | 9.8 | 3.6 |
| ＜350 ℃ of cuts | 24.6 | 33.3 |
| 350 ℃～500 ℃ cuts | 32.2 | 44.3 |
| Yield of light oil | 56.8 | 77.6 |
| ＞500 ℃ of cuts | 33.1 | 18.7 |
| Total liquid is received | 89.9 | 96.3 |
| Loss | 0.3 | 0.1 |
As can be seen from the comparative examples, the more original technology yield of light oil of combination process of the present invention has increased by 20 percentage points, and factor of created gase is very low, is a kind of feasible heavy residual oil complete processing.
Claims (10)
1, a kind of heavy, residual oil combinational processing method comprises following content:
(1) with inferior heavy, residual oil raw material to carry out floating bed hydrocracking under the mitigation condition, the yield of unconverted vacuum residuum accounts for the 20wt%～45wt% of raw material;
(2) fractionation of floating bed hydrocracking product is a light ends, heavy ends (VGO) and unconverted vacuum residuum;
(3) heavy ends that obtains of step (2) carries out catalytic cracking and handles;
(4) the unconverted vacuum residuum that obtains of step (2) carries out solvent deasphalting and handles, and the heavy ends that deasphalted oil that the solvent deasphalting treating processes obtains and step (2) obtain is jointly as catalytically cracked material.
2, in accordance with the method for claim 1, it is characterized in that the yield of the unconverted vacuum residuum described in the step (1) accounts for the 25wt%～35wt% of raw material.
3, in accordance with the method for claim 1, it is characterized in that slurry oil that the catalytic cracking described in the step (3) gets rid of is as one of charging of solvent deasphalting outward.
4, in accordance with the method for claim 1, it is characterized in that the disperse type catalyzer that the described floating bed hydrocracking of step (1) uses is the liquid catalyst that contains metal-salt, metal is one or more among W, Mo, Ni, Co, Fe and the Cr, and add-on is counted 50～800 μ g/g by metal; The suspension bed reaction conditions is: pressure 5～18MPa, and temperature is 350 ℃～430 ℃, the liquid air speed is 0.5～1.5h
-1, hydrogen to oil volume ratio is 500～1500; Floating bed hydrocracking reaches required transformation efficiency by the red-tape operati condition.
5, in accordance with the method for claim 4, it is characterized in that described suspension bed reaction conditions is: pressure is 10～15MPa, and temperature is 400 ℃～420 ℃, and the liquid air speed is 0.8～1.2h
-1, hydrogen to oil volume ratio is 800～1200.
6, in accordance with the method for claim 1, it is characterized in that the initial boiling point of the described VGO cut of step (2) is 290～380 ℃, final boiling point is 490～580 ℃.
7, in accordance with the method for claim 1, it is characterized in that the described Hydrocarbon Content by Catalytic Cracking Operation condition of step (3) is: temperature of reaction is 450 ℃～530 ℃, and agent weight of oil ratio is 2～30, and pressure is 0.1～1.0MPa.
8, in accordance with the method for claim 7, it is characterized in that described Hydrocarbon Content by Catalytic Cracking Operation condition is: temperature of reaction is 480 ℃～510 ℃, and agent weight of oil ratio is 4～20, and pressure is 0.3～0.5MPa.
9, in accordance with the method for claim 1, it is characterized in that the described solvent deasphalting operational condition of step (4) is: temperature is 120 ℃～200 ℃, pressure is 2.8～4.2MPa, and extraction solvent is the mixture of butane and pentane, and the weight of solvent ratio is 1: 1～8: 1.
10, in accordance with the method for claim 9, it is characterized in that described solvent deasphalting operational condition is: temperature is 140 ℃～190 ℃, and pressure is 3.5～4MPa, and extraction solvent is the mixture of butane and pentane, and the weight of solvent ratio is 4: 1～6: 1.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102652169A (en) * | 2009-12-11 | 2012-08-29 | 环球油品公司 | Process and apparatus for producing hydrocarbon fuel and composition |
| CN101724463B (en) * | 2008-10-29 | 2012-11-21 | 中国石油化工股份有限公司 | Combined process method for performing hydro-cracking and catalytic cracking on suspension bed residual oil |
| CN103429708A (en) * | 2011-03-23 | 2013-12-04 | 沙特阿拉伯石油公司 | Integrated hydrocracking and fluidized catalytic cracking system and process |
| US9101854B2 (en) | 2011-03-23 | 2015-08-11 | Saudi Arabian Oil Company | Cracking system and process integrating hydrocracking and fluidized catalytic cracking |
| CN105838416A (en) * | 2009-06-23 | 2016-08-10 | 鲁姆斯科技公司 | Multistage resid hydrocracking |
| CN106433779A (en) * | 2016-12-07 | 2017-02-22 | 北京神雾环境能源科技集团股份有限公司 | System and method for maximum production of light fuel by coal tar |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101724463B (en) * | 2008-10-29 | 2012-11-21 | 中国石油化工股份有限公司 | Combined process method for performing hydro-cracking and catalytic cracking on suspension bed residual oil |
| CN105838416A (en) * | 2009-06-23 | 2016-08-10 | 鲁姆斯科技公司 | Multistage resid hydrocracking |
| CN105838416B (en) * | 2009-06-23 | 2018-12-28 | 鲁姆斯科技公司 | Multistage residual hydrocracking |
| CN102652169A (en) * | 2009-12-11 | 2012-08-29 | 环球油品公司 | Process and apparatus for producing hydrocarbon fuel and composition |
| CN102652169B (en) * | 2009-12-11 | 2015-06-10 | 环球油品公司 | Process and apparatus for producing hydrocarbon fuel and composition |
| CN103429708A (en) * | 2011-03-23 | 2013-12-04 | 沙特阿拉伯石油公司 | Integrated hydrocracking and fluidized catalytic cracking system and process |
| US9101854B2 (en) | 2011-03-23 | 2015-08-11 | Saudi Arabian Oil Company | Cracking system and process integrating hydrocracking and fluidized catalytic cracking |
| US9101853B2 (en) | 2011-03-23 | 2015-08-11 | Saudi Arabian Oil Company | Integrated hydrocracking and fluidized catalytic cracking system and process |
| CN103429708B (en) * | 2011-03-23 | 2016-03-09 | 沙特阿拉伯石油公司 | The hydrocracking integrated and fluid catalytic cracking system and method |
| US10232285B2 (en) | 2011-03-23 | 2019-03-19 | Saudi Arabian Oil Company | Integrated hydrocracking and fluidized catalytic cracking system |
| CN106433779A (en) * | 2016-12-07 | 2017-02-22 | 北京神雾环境能源科技集团股份有限公司 | System and method for maximum production of light fuel by coal tar |
| CN106433779B (en) * | 2016-12-07 | 2018-09-07 | 神雾科技集团股份有限公司 | A kind of coal tar maximizes the system and method for production light Fuel |
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