CN103484160A - Processing method for conversion of residual oil to light fractions - Google Patents
Processing method for conversion of residual oil to light fractions Download PDFInfo
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- CN103484160A CN103484160A CN201210194432.1A CN201210194432A CN103484160A CN 103484160 A CN103484160 A CN 103484160A CN 201210194432 A CN201210194432 A CN 201210194432A CN 103484160 A CN103484160 A CN 103484160A
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Abstract
The present invention relates to a method for conversion of residual oil to light fractions. The method comprises that: pressure reduction residual oil separated from a pressure reduction distillation tower is conveyed into a solvent deasphalting device for treatment to obtain deasphalting oil and deoiled asphalt; the deasphalted oil and normal pressure residual oil or other feeding materials enter a residual oil hydrotreating device, and the hydrogenation product is separated to obtain naphtha, diesel fuel and hydrogenation residual oil; and the hydrogenation residual oil separately enters a catalysis cracking device or the hydrogenation residual oil and other catalysis cracking raw materials enter the catalysis cracking device to be continuously subjected to the reaction, and separation is performed to obtain gasoline, diesel oil, heavy cycle oil and oil slurry products. Compared with the method in the prior art, the method of the present invention has the following characteristics that: the poor-quality pressure reduction residual oil is subjected to an asphalt removing treatment, and then the asphalt-removed pressure reduction residual oil and normal pressure residual oil are subjected to hydrotreating so as to increase treatment capacity of the residual oil hydrotreating device, reduce operation severity, and prolong a service life of the catalyst; and the catalysis cracking device is combined so as to achieve high conversion-to-light fraction of the residual oil.
Description
Technical field
The present invention relates to a kind of residual oil weight-lightening working method, in particular, is a kind of method of utilizing residual hydrocracking, catalytic cracking, solvent deasphalting unit combination process process residual oils.
Background technology
At present the world is being faced with crude oil and becomes and heavily become bad trend, shows the aspects such as foreign matter content is high, viscosity is high, the lighting difficulty is large, and people gradually reduce the demand of heavy fuel oil (HFO), and the demand of lightweight oil is significantly increased.Therefore oil refining enterprise is pursued the conversion of residual oil maximum one after another.
In the whole bag of tricks of residual oil weight-lightening, mainly can be divided into two classes: decarburization and hydrogenation.Decarbonization process mainly comprises coking, solvent deasphalting, heavy oil fluid catalytic cracking etc., and hydrogenation comprises hydrocracking, hydrotreatment etc.The decarbonization process principal feature is that liquid yield is low, poor product quality, coke or bituminous production large, need to carry out aftertreatment.Hydrogenation method can make up above deficiency, not only can hydrocracking residual oil, improve the yield of liquid product, and can also remove heteroatoms wherein.The current comparative maturity of hydrogenation method and to apply more Technology be mainly the residual hydrocracking Technology, but this technique air speed is low, running cost is higher, the process operation cycle is short, general one year, and working properties oil more inferior for a long time, as Ni+V content>110ppm, the residual oil of carbon residue content>17w%.
Walk the refinery of hydrogenation route, the crude oil of general processing is more severe, and foreign matter content is higher, usually first crude oil is carried out to the normal pressure separation, obtains part light ends oil and long residuum.Part long residuum is admitted to the further deep drawing of vacuum distillation tower, obtains vacuum distillate and vacuum residuum.Vacuum residuum or part vacuum residuum enter the residual hydrocracking device with together with remaining long residuum.Because Vacuum Residue Properties is very severe, foreign matter content is higher, so the mixed ratio of vacuum residuum needs strict control, and can significantly reduce the process-cycle of residual hydrocracking device.
In order to be the inferior heavy oil Efficient Conversion clean oil fuel, the refining of petroleum investigator has researched and developed the combined technical method that hydrogenation technique and decarbonization process combine.
CN1393525A has proposed a kind of solvent deasphalting, fixed bed hydrogenation is processed 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 enters fixed bed hydrogenation treatment unit upgrading with together with optional heavy catalytic cycle oil, hydrogenation tail oil is sent into the catalytic cracking unit cracking, in its product, all or part of heavy cycle oil is circulated to fixed bed residual hydrocracking device, and all or part of catalytically cracked oil is circulated to solvent deasphalting unit.Residual oil first carries out the solvent deasphalting processing and carries out hydrotreatment again, can effectively extend the running period of residual hydrocracking device and reduce operating severity, but can cause total liquid yield significantly to reduce, reduce the processing profit, the market outlet of produced simultaneously a large amount of de-oiled asphalt is also very large problem, so should be according to the character of long residuum and vacuum residuum, determine whether to carry out solvent deasphalting or partly carry out the solvent deasphalting processing, vacuum residuum as poor as character carries out the solvent deasphalting processing, and character preferably long residuum directly carry out hydrotreatment.In addition, in refinery's existing apparatus, common solvent deasphalting unit scale is less, and the ratio of residual oil in refinery produces is increasing, and solvent deasphalting unit can not be eaten up residual oil at all fully.
CN1351129A discloses a kind of residual oil-refining and method for transformation, residual oil is carried out to stage treatment, it is the difference of based on crude character, crude oil enters respectively the different tripping device of two covers with more bad crude oil preferably, crude separation goes out gas preferably, distillate and the long residuum of different boiling range scopes, more bad crude oil separates gas, distillate and the vacuum residuum of different boiling range scopes, the vacuum residuum that more bad crude separation goes out enters solvent deasphalting unit and processes, enter the residual hydrocracking device together with the long residuum that the deasphalted oil obtained obtains with the better crude separation of character or vacuum residuum, hydrogenated residue is sent into catalytic cracking unit again and is further reacted.The method at least needs two cover crude separating devices, can significantly increase the construction cost of device; For refinery, process flexibility also can be affected simultaneously.
Summary of the invention
Purpose of the present invention is developed a kind of residual oil weight-lightening working method exactly, a kind of solvent deasphalting, residual hydrocracking and catalytic cracking combined technique, not only can improve the clean or white yield, but also can effectively extend the runtime of residual hydrocracking device and reduce operating severity.
The specific embodiment of the invention step comprises the steps:
(1) vacuum distillation tower is separated to the vacuum residuum obtained and send into the solvent deasphalting unit processing, obtain deasphalted oil and de-oiled asphalt;
(2) deasphalted oil separates the long residuum obtained and sends into the residual hydrocracking device and process with atmospheric tower, and the hydrogenation resultant is separated, and separates and obtains gas, petroleum naphtha, diesel oil and hydrogenated residue;
(3) hydrogenated residue is sent into catalytic cracking unit again and is carried out lighting.
In step (1), generally to guarantee that the cut point of vacuum residuum is at 450 ~ 600 ℃.In step (2), generally to guarantee that the cut point of long residuum is at 300 ~ 400 ℃, can guarantee like this gasoline in logistics, diesel oil and other distillates are fully cut out.
In step (1), the applicable rotating disk contact tower of described solvent deasphalting or tray column.Residual oil enters from top, and extraction solvent enters from bottom.The extraction medium adopted normally contains the light hydrocarbon solvent of alkane compound, and using more is C
3~ C
8alkane, as propane, butane, pentane etc. or mixture.The preferred butane of the present invention, pentane or its mixing.Typical operation conditions is: pressure is 0.1 ~ 6MPa, and temperature is 50 ~ 250 ℃, and total extraction solvent is 1.2 ~ 9 with the weight of oil ratio.
In step (2), described residual hydrocracking technology can be any technology of the present invention that is applicable to, as wherein a kind of of fixed bed residual hydrocracking technology, expanded bed residual hydrocracking technology and moving-bed residual hydrocracking technology.At present, fixed bed residual hydrocracking technology is comparatively ripe and application is wider, so take fixed bed residual hydrocracking technology, is example.Device adopts the catalyzer grading loading, and filling comprises the catalyzer of the catalyzer such as protective material, metal remover, sweetening agent and denitrfying agent.Catalyzer is generally that to take porous inorganic oxide be carrier as aluminum oxide, and group VIB and VIII family metal oxide, as the oxide compound of W, Mo, Co, Ni etc. is load, optionally add the catalyzer of the auxiliary agents such as P, Si, F.
The normal operating condition of residual hydrocracking device is: hydrogen partial pressure 7～20MPa, temperature of reaction is 300～435 ℃, volume space velocity 0.1～1.5hr
-1, hydrogen and residual oil volume ratio are 500～1700.Residual oil and hydrogen are from the reaction of residual hydrogenation equipment opening for feed access to plant, and reaction product can be separated into dry gas, hydrotreated naphtha, hydrogenated diesel oil and hydrogenated residue.
In step (3), described catalytic cracking can be catalytic cracking family, as a set of or several covering devices in heavy oil fluid catalytic cracking, catalytic pyrolysis, maximizing iso-paraffins catalytic cracking etc.The condition of catalytic cracking is: 470～650 ℃ of temperature of reaction, in 0.5～5 second reaction times, catalyst oil is than 3～10,650～800 ℃ of regeneration temperatures.Hydrogenated residue can enter separately catalytic cracking unit, also can together with other catalytically cracked material, enter.The reaction product separation obtains dry gas, liquefied gas, catalytic gasoline, catalytic diesel oil, heavy catalytic cycle oil and slurry oil, also can be cut according to actual needs.
The present invention is the poor residuum hydrocracking that is applicable to high metal, high carbon residue, high condensed ring material.Compared with prior art, the present invention's vacuum residuum that character is poor has partly carried out the solvent deasphalting processing, reduced the foreign matter content subtracted in slag, result has not only increased the feed throughput of residual hydrocracking device, but also reduced the operating severity installed, extend the running life of residual hydrocracking device catalyzer, realized the high conversion of residual oil.
Embodiment
In embodiment and Comparative Examples, the device related to and condition all adopt following apparatus and condition.
Test is carried out respectively on solvent extraction apparatus, residual hydrocracking pilot plant and small riser formula catalytic cracking unit.
Vacuum residuum carries out the solvent deasphalting processing at solvent deasphalting unit, and the solvent of employing is pentane.
The solvent deasphalting condition is:
Temperature: 200 ℃, pressure is: 1.0MPa, solvent ratio: 5(v/v)
The residual hydrocracking pilot plant is inlet device, divides filling protective material, metal remover, sweetening agent and denitrfying agent at the bottom of being provided with 4 reactors, 1 high score, 1.Comparative Examples is the same with the catalyzer in embodiment, and the grating ratio is 5:40:30:25, and catalyzer is that independently develop in laboratory.
In order to guarantee residual hydrocracking device catalyzer work-ing life and quality product, charging requires:
S≯4.4w%，MCR≯16.5w%，Ni+V≯85ppm
Operational condition is:
Temperature: 392 ℃, pressure is: 17.0MPa, and hydrogen-oil ratio: 1000(v/v), air speed: ≮ 0.22hr
-1, hydrogen purity: 97v%
The normal slag of hydrogenation (>360 ℃) is controlled index: S ≯ 0.6w%, MCR ≯ 6.0w%, Ni+V ≯ 15ppm
The catalyzer that catalytic cracking unit is used is independent development catalyzer, and in order to guarantee each product property of catalytic cracking, the charging of catalytic cracking unit requires index:
S≮0.6w%，MCR≮6.0w%，Ni+V≮15ppm
Operational condition is:
Temperature: 505 ℃, pressure is: 0.15MPa, agent-oil ratio: 5.5(w/w), agent oil duration of contact: 1s tests the normal slag (>360 ℃) adopted and subtracts slag (>520 ℃) and picks up from the CNPC refinery.
Table 1 test raw material oil
| Character | Long residuum | Vacuum residuum |
| Density (20 ℃), kg/m 3 | 0.957 | 1.040 |
| S，m％ | 3.73 | 4.82 |
| N，m％ | 0.37 | 0.45 |
| Carbon residue (MCR), m% | 14.2 | 24.5 |
| Metal (Ni+V), ppm | 69.5 | 137.6 |
Comparative Examples:
In Comparative Examples, long residuum and vacuum residuum do not carry out the solvent deasphalting processing, directly send into the residual hydrocracking pilot plant.By test, can know, specified criteria and product qualified under, to the ratio 20w% that mixes at most vacuum residuum in long residuum.Be cut into<160 ℃ of cuts of product after hydrogenation, 160 ℃ ~ 360 ℃ cuts,>360 ℃ of cuts, wherein>360 ℃ of cuts are sent into catalytic cracking unit and are continued reaction, obtain dry gas, catalytic gasoline, catalytic diesel oil, heavy cycle oil and slurry oil.Each stage raw material, product property are in Table 2.
Embodiment:
Vacuum residuum is sent into to solvent deasphalting unit and carry out the diasphaltene processing, tested according to given condition, the solvent-deasphalted oils yield obtained and character are in Table 1.Solvent-deasphalted oils is incorporated in long residuum, then carries out residual hydrocracking.By test, can know, in the situation that guarantee that product is qualified, deasphalted oil can be mixed with arbitrary proportion, and the situation that is 50w% at mixed ratio, and air speed can be increased to 0.28hr
-1.The same with Comparative Examples, be cut into<160 ℃ of cuts of product after hydrogenation, 160 ℃ ~ 360 ℃ cuts,>360 ℃ of cuts, wherein>360 ℃ of cuts are sent into catalytic cracking unit and are continued reaction, obtain dry gas, catalytic gasoline, catalytic diesel oil, heavy cycle oil and slurry oil.Each stage character is in Table 2.
Table 2 processing condition and raw material, product property
By table 2, can know, under same residual hydrocracking device, catalytic cracking unit operational condition and control of product index, vacuum residuum, after solvent deasphalting is processed, meets the charging requirement of residual hydrocracking device, and the charging mixed ratio has been brought up to 50w% by original 20w%.Simultaneously, residual hydrocracking device air speed is also by original 0.22hr
-1brought up to 0.28hr
-1, amplification reaches 27.2%, the increase that all is greatly improved of the processing treatment ability of residual oil and the lightweight rate of vacuum residuum.
Claims (6)
1. a residual oil weight-lightening working method, step comprises:
(1) vacuum still is separated to the vacuum residuum obtained and send into the solvent deasphalting unit processing, obtain deasphalted oil and de-oiled asphalt;
(2) deasphalted oil and long residuum or other charging, enter the residual hydrocracking device together, and the hydrogenated products separation obtains petroleum naphtha, diesel oil and hydrogenated residue;
(3) separately or enter catalytic cracking unit continue reaction with other catalytically cracked material together with, separation obtains gasoline, diesel oil, heavy cycle oil and slurry oil product to hydrogenated residue.
2. require described residual oil weight-lightening working method according to right 1, the long residuum described in its characterization step (1), (2) is residual oil or the heavy oil that boiling range is greater than 300 ~ 400 ℃, and vacuum residuum is residual oil or the heavy oil that boiling range is greater than 450 ~ 600 ℃.
3. require described residual oil weight-lightening working method according to right 1, residual oil or heavy oil that the long residuum described in its characterization step (1), (2) is 340 ~ 380 ℃ of boiling ranges, residual oil or heavy oil that vacuum residuum is 500 ~ 560 ℃ of boiling ranges.
4. residual oil weight-lightening working method according to claim 1, it is characterized in that: the described residual hydrocracking device of step (2) is fixed bed residual hydrocracking device, expanded bed residual hydrocracking device or moving-bed residual hydrocracking device, adopt the catalyzer grading loading, filling comprises protective material, metal remover and sweetening agent at interior multiple catalysts; Catalyzer is to take the porous, inorganic aluminum oxide as carrier, and the oxide compound of load group VIB and the metal W of VIII family, Mo, Co, Ni optionally adds the catalyzer of P, Si or F auxiliary agent; Hydrogen partial pressure 7～20MPa, temperature of reaction is 300 ~ 435 ℃, volume space velocity 0.1～1.5hr-1, hydrogen and residual oil volume ratio are 500～1700.
5. require described residual oil weight-lightening working method according to right 1, it is characterized in that: the described solvent de-asphalting process of step (1) is used rotating disk contact tower or tray column, hydrocarbon oil feed enters from top, and the extraction medium that extraction solvent adopts is the light hydrocarbon solvent that contains alkane compound, typical operation conditions is: pressure is 0.1 ~ 6MPa, temperature is 50 ~ 250 ℃, and total extraction solvent is 1.2 ~ 9 with the weight of oil ratio.
6. residual oil weight-lightening working method according to claim 1, it is characterized in that: the operational condition of the described catalytic cracking unit of step (3) is: 470～650 ℃ of temperature of reaction, 0.5～5 second reaction times, catalyst oil is than 3～10,650～800 ℃ of regeneration temperatures, the catalyzer that uses be the synthetic zeolite catalysts cracking catalyzer.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449840A (en) * | 2014-11-05 | 2015-03-25 | 中国石油大学(北京) | Method for processing low-grade heavy oil |
| CN114479929A (en) * | 2020-10-27 | 2022-05-13 | 中国石油天然气股份有限公司 | Continuous modification and viscosity reduction process for crude oil |
| CN114790401A (en) * | 2022-02-28 | 2022-07-26 | 中国海洋石油集团有限公司 | Combined method for heavy oil modification |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1117071A (en) * | 1994-05-19 | 1996-02-21 | 国际壳牌研究有限公司 | Process for the conversion of a residual hydrocarbon oil |
| CN101045884A (en) * | 2006-03-31 | 2007-10-03 | 中国石油化工股份有限公司 | Process of producing clean diesel oil and low carbon olefin with residual oil and heavy fraction oil |
-
2012
- 2012-06-13 CN CN201210194432.1A patent/CN103484160A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1117071A (en) * | 1994-05-19 | 1996-02-21 | 国际壳牌研究有限公司 | Process for the conversion of a residual hydrocarbon oil |
| CN101045884A (en) * | 2006-03-31 | 2007-10-03 | 中国石油化工股份有限公司 | Process of producing clean diesel oil and low carbon olefin with residual oil and heavy fraction oil |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104449840A (en) * | 2014-11-05 | 2015-03-25 | 中国石油大学(北京) | Method for processing low-grade heavy oil |
| CN114479929A (en) * | 2020-10-27 | 2022-05-13 | 中国石油天然气股份有限公司 | Continuous modification and viscosity reduction process for crude oil |
| CN114479929B (en) * | 2020-10-27 | 2023-09-26 | 中国石油天然气股份有限公司 | Crude oil continuous modification and viscosity reduction process |
| CN114790401A (en) * | 2022-02-28 | 2022-07-26 | 中国海洋石油集团有限公司 | Combined method for heavy oil modification |
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Application publication date: 20140101 |