CN1200082C - Combined technologic process for manufacturing petroleum residue - Google Patents
Combined technologic process for manufacturing petroleum residue Download PDFInfo
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- CN1200082C CN1200082C CN 02130792 CN02130792A CN1200082C CN 1200082 C CN1200082 C CN 1200082C CN 02130792 CN02130792 CN 02130792 CN 02130792 A CN02130792 A CN 02130792A CN 1200082 C CN1200082 C CN 1200082C
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Abstract
The present invention relates to a combined technologic method for processing residual oil. A preheated raw material is introduced into the upper part of a solvent deasphalting extraction tower, and simultaneously, solvents are introduced into the lower part of the extraction tower according to predetermined solvent ratio. The residual oil and the solvents are in contact with each other in the extraction tower in a counterflow mode to be extracted, recovered solvents are removed from deasphalted oil containing a large quantity of solvents, and deoiled asphalt containing a small quantity of solvents is discharged from the bottom of the extraction tower, introduced into a heating furnace and heated without recovering the solvents. Then, the deoiled asphalt is introduced into a reactor of an upflow type viscosity breaking device and subjected to a viscosity breaking reaction in the reactor. A material flow generated in the viscosity breaking reaction is introduced into a fractionation tower of the upflow type viscosity breaking device to fractionate out viscosity broken gas, viscosity broken gasoline and viscosity broken residual oil. Since the solvents in the deoiled asphalt are not recovered with the method, a deoiled asphalt solvent recovering system, namely the heating furnace, is saved, the coking of the deoiled asphalt in a furnace tube is decelerated, the operation period is prolonged, and a path is provided for hard asphalt.
Description
Technical field
The invention belongs to a kind of under the situation that does not have hydrogen the thermal non-catalytic cracking method of hydrocarbon ils, more particularly, be a kind of combined technologic process for manufacturing petroleum residue that improves the residual oil liquid yield.
Background technology
Solvent deasphalting is a kind of important residua upgrading technology.It is a kind of liquid-liquid extraction process of physics, has the ultimate principle of different solubilities that residual oil is separated according to varsol to each component in the residual oil.Solvent deasphalting is by regulating operational condition, the dissolving power of control solvent for use is mainly dissolved stable hydrocarbon and aromatic hydrocarbon, and can remove colloid and bituminous matter most in the residual oil, like this, the deasphalted oil that obtains by solvent deasphalting just has the character of high hydrogen-carbon ratio, low carbon residue, low impurity content, can satisfy the requirement of downstream production process to charging.Typical solvent deasphalting process is: raw material (being generally vacuum residuum) enters the top of extraction tower after heat exchange makes temperature reduce to suitable temperature.Solvent is entered by the extraction tower bottom at a certain temperature.The two is reverse contact flow in tower.Colloid and bituminous matter fall to the bottom of extraction tower.Deasphalted oil enters settling section through upcast.And then reclaiming solvent in deasphalted oil and the de-oiled asphalt respectively, solvent cycle is used.Solvent deasphalting technology is a kind of raw material deep processing technology of existing six more than ten years industrialization history, this technology is mainly used in the production heavy grease in early days, widespread usage along with residual oil deep processing technology, utilize this explained hereafter catalytically cracked material to provide residual oil reasonable utilization ratio, the obvious variation of quality of the de-oiled asphalt of coproduction when improving deasphalted oil (DAO), this gilsonite inferior can not be as petroleum pitch, the oil if act as a fuel, because viscosity height, need call in Macrodilution light oil, very uneconomical.
Viscosity breaking technology is one of heavy oil lighting means, is a kind of special applications of raw material thermal cracking process, and its main purpose is to reduce to greatest extent the viscosity of residual oil, reduces dilution light oil consumption in the merchantable fuels oil.The raw material viscosity breaking is the raw material complete processing that cracking and condensation two class different directions thermal responses take place at a certain temperature.The reduction of viscosity mainly causes owing to non-asphaltene carries out thermo-cracking.
De-oiled asphalt is a kind of special colloidal solution, in this system, the aromatic nucleus that has different side chains interconnects in flakes, interconnect nucleation between sheet and the sheet again, the various higher hydrocabons of these nuclear absorption, the disperse phase of constitution system, the external phase of various small molecules aromatic compounds and alkane constitution system.Since de-oiled asphalt be from raw material behind solvent extraction enrichment bituminous matter and heavy colloid component, under thermal rection condition, de-oiled asphalt is than raw material, heavy component is easily separated out, the coking tendency strengthens.
In recent years, in order to solve the problem of outlet of de-oiled asphalt, bituminous transforms and more and more comes into one's own.For example:
US4428824 has narrated solvent deasphalting technology and viscosity breaking technology anabolic process, this patent raw material after solvent deasphalting is handled, the viscosity breaking process is carried out in deasphalted oil, and then the de-oiled asphalt of solvent deasphalting explained hereafter and deasphalted oil after the viscosity breaking process are reconciled into again the oil fuel of low viscosity and pour point, this technology is for the prolongation cycle, avoided the thermal transition of heavy component-de-oiled asphalt, and the light component that high quality can be used for downstream cracking (as catalytic cracking and hydrocracking etc.) device processing is carried out viscosity breaking, tooling cost increases.
EP0133774 has narrated and has improved the visbreaking severity to reach the viscosity purpose that reduces raw material.This patent mainly is to add hydrogen supply agent in the viscosity breaking process, and thinks that catalytically cracked oil and light cycle oil can adopt as this hydrogen supply agent.But, therefore, will significantly reduce on-stream time, and system is resulted in blockage, weares and teares, and influence quality product because this catalytically cracked oil and light cycle oil contain catalyst fines.
US4298455 has narrated raw material viscosity breaking process under the mitigation condition, and the main method of this patent is to add radical initiator and chain-transfer agent, reduces the reaction severity and reaches the purpose that reduces viscosity.Though can prolong on-stream time under the mitigation condition, the radical initiator and the chain-transfer agent that add are organic compound, have increased cost and expense.
US4767521 and US4773986 have narrated the method that viscosity breaking technology is handled thickness residual oil of using, the main method of this patent is that thickness residual oil is before entering viscosity breaking plant, carry out raw materials pretreatment, adopt solvent-extracted method to remove the heavy constituent of easy coking, most then light constituent enters viscosity breaking plant.Its characteristics are similar to the US4428824 that narrates previously.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of combined technologic process for manufacturing petroleum residue of handling gilsonite.
Method provided by the invention comprises:
Raw material enters the top of solvent deasphalting extraction tower after preheating, solvent enters the bottom of extraction tower by predetermined solvent ratio simultaneously, residual oil and solvent carry out the counter current contact extracting in extraction tower, the deasphalted oil that contains a large amount of solvents comes out to enter downstream unit processing from solvent deasphalting unit after removing solvent, the de-oiled asphalt that contains a small amount of solvent enters the process furnace heating from the discharge of extraction tower bottom without solvent recuperation, enter upflow visbreaking cracking unit reactor then, in reactor, carry out the viscosity breaking reaction, the logistics of reacting through viscosity breaking enters upflow visbreaking cracking unit separation column, fractionates out visbreaking gas, visbreaking gasoline and visbreaking residue.
This method is owing to the solvent that does not reclaim in the de-oiled asphalt, therefore having saved the de-oiled asphalt solvent recovering system is process furnace, and has slowed down the coking of de-oiled asphalt in boiler tube, can accelerate the linear speed of material in boiler tube, prolong operation cycle is for gilsonite provides a kind of outlet.
Description of drawings
Accompanying drawing is a kind of combined technologic process for manufacturing petroleum residue synoptic diagram provided by the invention.
Embodiment
The present invention is so concrete enforcement:
(1) raw material enters the top of solvent deasphalting extraction tower after preheating, C3~C7 alkane or alkene solvent enter the bottom of extraction tower by predetermined solvent ratio simultaneously, raw material and solvent carry out the counter current contact extracting in extraction tower, extraction temperature is 40~280 ℃, pressure is 0.1~0.6MPa, and solvent ratio is 1.0~13.0v/v;
(2) deasphalted oil that contains a large amount of solvents is from the outflow of extraction tower top, and the de-oiled asphalt that contains a small amount of solvent enters process furnace from the discharge of extraction tower bottom, and the furnace outlet temperature is 370 ℃~480 ℃, and water injection rate is 1.0~10.0% (weight accounts for furnace charge);
(3) mixture that heated enters reactor from upflow visbreaking cracking unit reactor bottom, the reactor bottom temperature is 350 ℃~470 ℃, head temperature is 340 ℃~460 ℃, the residence time is 10~120 minutes, working pressure is 0.1~1.5MPa, the logistics of reacting through viscosity breaking enters upflow visbreaking cracking separation column from the effusion of upflow visbreaking cracking unit reactor head, fractionates out visbreaking gas, visbreaking gasoline and visbreaking residue.
Described raw material is selected from vacuum residuum, long residuum, visbroken resids, fluid catalytic cracking decant oil, thermal cracking residue, vacuum distillation tower washing oil, coking wax slop, hydrocracking residual oil, furfural treatment and extracts among oil or the preparing ethylene by steam cracking residual oil one or more mixture out.
Described solvent is one or more the mixture in C3~C7 alkane or the alkene.
In step (2), the raw material of process furnace can be only for containing the de-oiled asphalt of a small amount of solvent; The raw material of process furnace can also be except that the de-oiled asphalt that contains a small amount of solvent, adds conventional viscosity breaking raw material again, comprises vacuum residuum, atmospheric residue, full cut heavy crude or pulls out the former wet goods of nose heave matter.
Below in conjunction with accompanying drawing method provided by the invention is described further, but does not limit the present invention.
Accompanying drawing is a kind of combined technologic process for manufacturing petroleum residue synoptic diagram provided by the invention.
Processing method process description of the present invention is as follows: raw material after the preheating and solvent enter solvent deasphalting unit 3 through pipeline 1,2 respectively, the deasphalted oil that contains a large amount of solvents removes to reclaim solvent through pipeline 4, recovered solvent recycles, and enters downstream unit processing through the deasphalted oil that removes solvent.The de-oiled asphalt that has a small amount of solvent enters 6 heating of upflow visbreaking cracking unit process furnace through pipeline 5, the logistics that heated enters reactor through pipeline 7 from upflow visbreaking cracking unit reactor 8 bottoms, the logistics of reacting through viscosity breaking enters upflow visbreaking cracking unit separation column 10 through pipeline 9 from the reactor head effusion, and visbreaking gas, visbreaking gasoline and the visbreaking residue that fractionates out is respectively through pipeline 11,12,13 caterpillars.
The invention has the advantages that:
(1), since the solvent in the gilsonite that solvent deasphalting unit produces do not reclaim, therefore enter process furnace after, can accelerate the linear speed of material in boiler tube, prolong operation cycle.
(2), because the solvent in the gilsonite that solvent deasphalting unit produces does not reclaim, gilsonite directly enters the process furnace of viscosity breaking plant, has saved the de-oiled asphalt solvent recovering system, can reduce investment outlay and the place.
(3), de-oiled asphalt is because the viscosity height, but by method of the present invention, after viscosity breaking is reacted, can be used as oil fuel, for its outlet provides effective processing approach.
The following examples will give further instruction to present method, but therefore not limit present method.
Embodiment 1
The raw material that present embodiment adopts is vacuum residuum A, its character sees 1, the de-oiled asphalt character that table 2 obtains behind propane deasphalting for vacuum residuum A, the deasphalted oil yield is 50% (weight), as can be seen from Table 2, the kinematic viscosity of de-oiled asphalt under 100 ℃ is 5 times of vacuum residuum A, but stable hydrocarbon only has 15.40% as the cracked component, and colloid is up to nearly 50%.
Test is to be to carry out on 10 kilograms/hour medium-sized solvent deasphalting unit and 5 kilograms of/hour viscosity breaking plants in the RIPP processing power.
Table 3 is viscosity breaking technology condition, material balance and the visbreaking residue character of mixture.As can be seen from Table 3, the viscosity of de-oiled asphalt (100 ℃ time) has dropped to 188.5mm
2/ s, the visbreaking effect is obvious.
Embodiment 2
The raw material that present embodiment adopts is vacuum residuum B, its character sees 1, the de-oiled asphalt character that table 2 obtains behind butane deasphalting for vacuum residuum B, the deasphalted oil yield is 63% (weight), as can be seen from Table 2, high about 10 times of the kinematic viscosity ratio vacuum residuum B of de-oiled asphalt under 100 ℃, but stable hydrocarbon only has 5.2% as the cracked component, and colloid is up to 52%.
Test is to be that 10 kilograms/hour medium-sized solvent deasphalting unit and 5 kilograms/hour relax on the thermal crackers and carry out in the RIPP processing power.
Table 3 is viscosity breaking technology condition, material balance and the visbreaking residue character of mixture.As can be seen from Table 3, the viscosity of de-oiled asphalt (100 ℃ time) has dropped to 347.9mm
2/ s, the visbreaking effect is obvious.
Table 1
Embodiment 1 | Embodiment 2 | |
Raw material | Vacuum residuum A | Vacuum residuum B |
Density (20 ℃), g/cm 3 | 0.9207 | 0.9709 |
Kinematic viscosity (100 ℃), mm 2/s | 122 | 765.4 |
Condensation point, ℃ | 38 | 35 |
Hydrocarbon system forms, heavy % | ||
Stable hydrocarbon | 31.7 | 27.0 |
Aromatic hydrocarbons | 35.1 | 35.2 |
Colloid | 33.0 | 35.5 |
Bituminous matter | 0.2 | 2.3 |
Table 2
Embodiment 1 | Embodiment 2 | |
The deasphalted oil yield, heavy % | 50 | 63 |
Solvent | Propane | Butane |
Density (20 ℃), g/cm 3 | 0.9528 | 1.0370 |
Kinematic viscosity (100 ℃), mm 2/s | 620.4 | 7334 |
Hydrocarbon system forms, heavy % | ||
Stable hydrocarbon | 15.4 | 5.2 |
Aromatic hydrocarbons | 35.2 | 39.0 |
Colloid | 49.2 | 52.3 |
Bituminous matter | 0.2 | 3.5 |
Table 3
Embodiment 1 | Embodiment 2 | |
Processing condition | ||
Temperature of reaction, ℃ | 420 | 420 |
Reaction pressure, MPa | 0.40 | 0.40 |
The residence time, minute | 40 | 40 |
Material balance, heavy % | ||
Gas | 1.89 | 2.01 |
Gasoline | 3.08 | 3.94 |
Residual oil | 95.03 | 94.05 |
Visbreaking residue character | ||
Density (20 ℃), g/cm 3 | 0.9785 | 1.0389 |
Kinematic viscosity (100 ℃), mm 2/s | 188.5 | 347.9 |
Condensation point, ℃ | 28 | 29 |
Stability, level | 1.5 | 1.5 |
Compatibleness, level | 1.5 | 1.5 |
Claims (6)
1, a kind of combined technologic process for manufacturing petroleum residue, it is characterized in that raw material enters the top of solvent deasphalting extraction tower after preheating, solvent enters the bottom of extraction tower by predetermined solvent ratio simultaneously, residual oil and solvent carry out the counter current contact extracting in extraction tower, the deasphalted oil that contains a large amount of solvents removes to reclaim solvent, the de-oiled asphalt that contains a small amount of solvent enters the process furnace heating from the discharge of extraction tower bottom without solvent recuperation, enter upflow visbreaking cracking unit reactor then, in reactor, carry out the viscosity breaking reaction, the logistics of reacting through viscosity breaking enters upflow visbreaking cracking unit separation column, fractionates out visbreaking gas, visbreaking gasoline and visbreaking residue.
2,, it is characterized in that described raw material is selected from vacuum residuum, long residuum, visbroken resids, fluid catalytic cracking decant oil, thermal cracking residue, vacuum distillation tower washing oil, coking wax slop, hydrocracking residual oil, furfural treatment and extracts among oil or the preparing ethylene by steam cracking residual oil one or more mixture out according to the method for claim 1.
3,, it is characterized in that described solvent is one or more the mixture in C3~C7 alkane or the alkene according to the method for claim 1.
4,, it is characterized in that the operational condition of solvent deasphalting is: 40~280 ℃ of extraction temperatures, pressure 0.1~0.6MPa, solvent ratio 1.0~13.0v/v according to the method for claim 1.
5, according to the method for claim 1, it is characterized in that 370 ℃~480 ℃ of described furnace outlet temperature, water injection rate accounts for 1.0~10.0 heavy % of furnace charge.
6, according to the method for claim 1, it is characterized in that described upflow visbreaking cracking case bottom temp is 350 ℃~470 ℃, head temperature is 340 ℃~460 ℃, 10~120 minutes residence time, working pressure 0.1~1.5MPa.
Priority Applications (1)
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CN 02130792 CN1200082C (en) | 2002-09-28 | 2002-09-28 | Combined technologic process for manufacturing petroleum residue |
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CN 02130792 CN1200082C (en) | 2002-09-28 | 2002-09-28 | Combined technologic process for manufacturing petroleum residue |
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CN1485412A CN1485412A (en) | 2004-03-31 |
CN1200082C true CN1200082C (en) | 2005-05-04 |
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Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1325605C (en) * | 2005-12-07 | 2007-07-11 | 中国海洋石油总公司 | Oil sand asphalt treating method |
CA2732919C (en) | 2010-03-02 | 2018-12-04 | Meg Energy Corp. | Optimal asphaltene conversion and removal for heavy hydrocarbons |
CN102181304A (en) * | 2011-04-01 | 2011-09-14 | 中石油东北炼化工程有限公司葫芦岛设计院 | Residual oil visbreaking device and method |
AU2012325639A1 (en) * | 2011-10-19 | 2014-05-01 | Meg Energy Corp. | Enhanced methods for Solvent Deasphalting of hydrocarbons |
US9200211B2 (en) | 2012-01-17 | 2015-12-01 | Meg Energy Corp. | Low complexity, high yield conversion of heavy hydrocarbons |
CN103305257B (en) * | 2012-03-16 | 2015-04-15 | 中国石油化工股份有限公司 | Method for reducing viscosity of quenching oil of ethylene unit |
CN103788969B (en) * | 2012-11-01 | 2016-08-03 | 中国石油化工股份有限公司 | A kind of coal and the group technology of petroleum refining side-product copyrolysis |
MX370063B (en) | 2013-02-25 | 2019-11-29 | Meg Energy Corp | Improved separation of solid asphaltenes from heavy liquid hydrocarbons using novel apparatus and process ("ias"). |
CN104449827B (en) * | 2013-09-13 | 2016-12-07 | 中国石油化工股份有限公司 | A kind of system and method reducing ethylene unit quench oil viscosity |
CN104449825B (en) * | 2013-09-13 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of method reducing ethylene unit quenching oil viscosity and improve solvent recovering rate |
CN107297088A (en) * | 2016-04-14 | 2017-10-27 | 黑珀(上海)工业技术有限公司 | A kind of conduction oil cleaning treatment system |
CN114478160B (en) * | 2020-10-26 | 2024-05-07 | 中国石油化工股份有限公司 | Method and system for preparing low-carbon olefin from crude oil |
CN114958418B (en) * | 2021-02-18 | 2023-08-08 | 中国石油化工股份有限公司 | Method for producing residual oil by heating furnace |
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