CN102337152A - Processing method of sulfur-containing crude oil - Google Patents
Processing method of sulfur-containing crude oil Download PDFInfo
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- CN102337152A CN102337152A CN2010102336409A CN201010233640A CN102337152A CN 102337152 A CN102337152 A CN 102337152A CN 2010102336409 A CN2010102336409 A CN 2010102336409A CN 201010233640 A CN201010233640 A CN 201010233640A CN 102337152 A CN102337152 A CN 102337152A
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Abstract
A processing method of sulfur-containing crude oil. According to the invention, atmospheric residual oil is used as a raw material for a solvent extraction device and is processed by the solvent extracting technology to obtain solvent refining oil and solvent refining residual oil. According to the invention, low processing temperature of solvent extracting replaces high processing temperature of underpressure distillation, thus reducing energy consumption, saving production cost, avoiding corrosion of sulfur to underpressure distillation equipment at high temperature and prolonging operation period.
Description
Technical field
The invention belongs to a still-process, treating process and cracking process or hydrocracking process and handle the combined method of hydrocarbon ils.More particularly, be a kind of multiple processing combined method of sulphur-bearing crude.
Background technology
Increase along with the Oil extraction amount; Former oil quality worse and worse; Be tending towards poor qualityization, heaviness, show mainly that oil density is big, viscosity is high, heavy metal content is high, sulphur content is high, acid content is high, colloid and asphalt content is high, carbon residue is high, this brings big difficulty for processing of crude oil.In addition, the fast development of global economy, the demand to clean cargo, clean fuel oil increases fast on the one hand; On the other hand, along with the development of road construction, also increasingly high to the road bitumen sticker quantitative requirement of some particular requirements.
Outside de-carbon, the hydrogen, sulphur is the 3rd main ingredient in the component of oil, though on content far below the above two, its content is a very important index.Its sulphur content of common crude oil is many between 0.2 weight % to 5 weight %, but extremely indivedual sulphur content is also arranged up to 7 weight %, usually sulphur content is higher than 0.5 weight % person and is referred to as sulphur-bearing crude, will be higher than 1 weight % person and be referred to as to be the high-sulfur oil.There is the sulphur of free state to exist in the oil, but exists with sulfide and hydrogen sulfide, sulfuric acid, thioether, disulphide and cyclical sulfide etc. mostly.The existence of sulphur is the main root that causes oil and products thereof etching apparatus.For example; Sulphur when sulphur-bearing crude is carried out pyrogenic distillation in the crude oil very easily produces sulfur corrosion; The high temperature corrosion of sulphur generally takes place when temperature surpasses 240 ℃, has had a strong impact on the work-ing life of equipment, has shortened the on-stream time of device widely; Not only delay plant produced, and increase production cost.
In order to maximally utilise resource, voluminous clean fuel oil satisfies social needs, adopts the mode desulfurization of interpolation sweetening agent or hydrogenation etc. usually.A kind of work flow of sulphur-bearing crude is disclosed like CN1160441C: technologies such as atmospheric and vacuum distillation, coking or solvent deasphalting, middle pressure hydrocracking, catalytic cracking are organically combined; Make the refinery can handle sulphur content and reach 1.8～2.8% high-sulfur raw oil; Adopt middle pressure hydrocracking technology when having improved the catalytic cracking charging; Market can also be satisfied to increasingly high diesel and gasoline ratio needs, and finally the low-sulfur light ends that meets product index and environmental protection specification can be produced.Handle sulphur-bearing crude with this method, when carrying out underpressure distillation, be prone to the sulphur high temperature corrosion takes place, had a strong impact on the work-ing life of equipment.CN101213272A discloses a kind of more method of high-value product of from sulphur-bearing crude, making: the heavy hydrocarbon crude oil that will contain high density sulphur under the catalyzer existence condition with the H-H reaction of low pressure; Light oil is therefrom reclaimed, and reaction product is separated and experience further upgrading to produce the lower oil prodn of sulphur content.Handle sulphur-bearing crude with this method; But the heavy metal in the sulphur-bearing crude, bituminous matter and impurity such as colloid, nitrogen need the hydrogen source of labor equally in the hydrotreatment process; Make the hydrogen consumption of hydrogenation crude device big, catalyst deactivation such as demetalization is very fast; The on-stream time of device is short, and process cost is high.
Summary of the invention
The working method that the purpose of this invention is to provide a kind of sulphur-bearing crude, to be solved is the prior art medium-sour crude particularly high-sulfur crude oil the high temperature corrosion of sulphur be prone to take place when underpressure distillation, and problem such as the vacuum distillate yield is low.
Method provided by the present invention: comprising:
(1) sulphur-bearing crude gets into the air distillation unit, obtains atmospheric distillate and long residuum,
(2) long residuum gets into the solvent extraction unit, obtains solvent-refined oil and solvent treatment irreducible oil,
(3) solvent-refined oil of step (2) gained gets into catalytic cracking unit or hydrogen cracking unit, obtains the hydrocarbon fraction of lighting,
(4) the solvent treatment irreducible oil of step (2) gained is the properties-correcting agent of high-modulus asphalt.
The present invention the crude oil that will handle be sulphur-bearing crude, the sulphur content in the said sulphur-bearing crude is more than or equal to 0.5 weight %.The crude oil that preferred institute will handle is high-sulfur crude oil, and the sulphur content in the promptly said sulphur-bearing crude be more than or equal to 1.0 weight %, and preferably further, the sulphur content in the said sulphur-bearing crude is 1.0 weight %～5.0 weight %.
The present invention distills sulphur-bearing crude in the air distillation unit, at the bottom of atmospheric distillation tower, obtain the long residuum greater than 350 ℃.Because under normal pressure; Crude oil promptly has tangible decomposing phenomenon since 350 ℃, so generally, it is distilled under reduced pressure that boiling point is higher than 350 ℃ cut; And the top temperature of decompression distillation system up to 500 ℃～560 ℃; When Sulfur-Containing Crude particularly during high-sulfur crude oil, can there be the uniform corrosion and the local erosion of high temperature sulphur in its vacuum furnace and the vacuum distillation tower simultaneously, serious to equipment damage.The present invention carries out low-temperature solvent extracting separation with the long residuum of sulphur-bearing crude, to replace the higher service temperature of underpressure distillation, has avoided the sulfur corrosion temperature range in the sulphur-bearing crude, thereby reduces the corrosion of device.
Solvent extraction process is based on the physical separating process of " similar compatibility " principle, its objective is very high colloid and the bituminous matter of heavy metal, sulphur, nitrogen and carbon residue that removes in the long residuum, for other complete processing provides better raw material.Solvent-refined oil is rich in saturated branch and divides with fragrance; Carbon residue and metal content are lower, are good catalytic cracking or/and the raw material of hydrogen cracking, and the solvent treatment irreducible oil has concentrated the sulphur of the overwhelming majority, bituminous matter, heavy metal etc. in the residual oil; Its softening temperature can reach more than 110 ℃, and penetration degree is less.
In the solvent extraction unit, said long residuum and premix solvent, the volume ratio of premix solvent and long residuum are 0.1～6: 1, preferred 0.2～4: 1; Get into extraction tower through the long residuum after the dilution; Contacting mixing with solvent in extraction tower inside is separated; The volume ratio of solvent and long residuum is 3～12: 1, after extraction tower cat head and bottom stream are isolated solvent, obtains solvent-refined oil and solvent treatment irreducible oil respectively; Extraction tower pressure is 2.0～8.0MPa, and the extracting tower top temperature is 40～190 ℃, and the extracting column bottom temperature is 30～180 ℃.Preferably in extraction tower, the volume ratio of solvent and long residuum is 4～8: 1; Extraction tower pressure is 3.0～5.0MPa, and the extracting tower top temperature is 60～170 ℃, and the extracting column bottom temperature is 50～160 ℃.
Said long residuum gets into extraction tower from extraction tower top; Solvent gets into from the extraction tower bottom; Both are separated in the inner reverse contact mixing of extraction tower; Saturated branch is dissolved in the solvent with the fragrance branch, and draws from the extraction tower top, after flash distillation, stripping are isolated solvent, obtains solvent-refined oil.With the long residuum is benchmark, and the yield of said solvent-refined oil is 50 weight %～85 weight %.The boiling range of solvent-refined oil is 340 ℃～720 ℃.This solvent-refined oil can be used as the raw material of catalytic cracking or/and the raw material of hydrogen cracking.Catalytic cracking unit of the present invention and hydrogen cracking unit; Be conventional catalytic cracking unit and hydrogen cracking unit; Described solvent-refined oil can be independent, also can after other raw materials mix, get into above-mentioned machining cell, obtains the hydrocarbon fraction of lighting.Draw from extraction tower bottom through extractive heavy constituent, after flash distillation, stripping are isolated solvent, obtain asphalt content height, softening temperature is high, penetration degree is low solvent treatment irreducible oil, as the properties-correcting agent of producing high-modulus asphalt.Said solvent treatment irreducible oil mixes with matrix pitch and obtains high-modulus asphalt, and the weight ratio of matrix pitch and solvent treatment irreducible oil is 40: 60～60: 40.
In another preferred embodiment; Squeeze into secondary solvent in the bottom of extraction tower and contact with the heavy constituent of decline are reverse, the saturated branch that further extracting is wherein carried secretly reaches the abundant dissolved purpose of saturated branch; The volume ratio of secondary solvent and long residuum is 0.1～6: 1, preferred 0.2～2: 1.
Premix solvent, solvent and secondary solvent are selected from C
3～C
5In alkane or the alkene one or more.Preferably, premix solvent, solvent and secondary solvent are selected from C
4In alkane or the alkene one or more.
Advantage of the present invention:
(1) the present invention with solvent extraction than low processing temperature substitute underpressure distillation than high processing temperature, not only reduced energy consumption, practiced thrift production cost, and when having avoided the sulphur high temperature in the crude oil to the corrosion of vacuum distillation equipment, prolonged on-stream time.
(2) productive rate of heavy oil lighting of the present invention is high, compares with the underpressure distillation of routine, and solvent-refined oil yield of the present invention is far above the yield of vacuum distillate, and quality is suitable with vacuum distillate.
(3) the present invention can produce the properties-correcting agent of the high-modulus asphalt that satisfies the road construction needs simultaneously.Because avoided Pintsch process and the condensation reaction under the underpressure distillation, the solvent treatment irreducible oil of gained of the present invention all is being superior to by the asphalt modifier that subtracts the slag gained aspect high-temperature behavior and the low-temperature performance as asphalt modifier.
Embodiment
Below in conjunction with embodiment, method of the present invention is further explained, but therefore do not limited the present invention.
Embodiment 1
Present embodiment adopts a kind of sulphur-bearing crude as raw material, and its sulphur content is 2.2 weight %.This crude oil gets into the air distillation unit, obtains atmospheric distillate and long residuum.The character of gained long residuum is listed in table 1; Can find out that from table 1 this long residuum sulphur content is up to 3.10 weight %, carbon residue is 19.8 weight %; Nickel content is that 48 μ g/g, content of vanadium are 314 μ g/g, is the inferior heavy oil of a kind of high-sulfur, high metal and high carbon residue.
In the solvent extraction unit; Long residuum mixes the back and gets into from extraction tower top with premix solvent (the premix solvent is 0.3: 1 with raw oil by volume); Main solvent gets into (main solvent and raw oil are 6: 1 by volume) from the extraction tower bottom; Secondary solvent gets into (secondary solvent and raw oil are 0.3: 1 by volume) from the extraction tower bottom, and the tower temperature is 135 ℃/125 ℃ (at the bottom of cat head/tower), and pressure is 4.0MPa; Be to carry out solvent extraction under the condition of 30min in the residence time; Obtain solvent-laden light phase solution and heavy phase solution, light phase solution and heavy phase solution obtain solvent-refined oil and solvent treatment irreducible oil through flash distillation, stripping after reclaiming solvent respectively, recycle after the solvent recuperation.The composition of premix solvent, main solvent and secondary solvent is listed in table 2.The solvent-refined oil yield that obtains accounts for 50 weight % of raw material; Its character is listed in table 3, can find out from table 3, and the carbon residue of gained solvent-refined oil is merely 2.1 weight %; Nickel content is that 1.5 μ g/g, content of vanadium are 7.6 μ g/g, is the high quality raw material of catalytic cracking unit.
The solvent treatment irreducible oil yield of gained accounts for 50 quality % of raw material, and asphalt content is 29.0 quality %, and softening temperature is 119.1 ℃.With the solvent treatment irreducible oil is properties-correcting agent, is matrix pitch with No. 90 pitches liking the mountain range crude production, obtains high-modulus asphalt.Wherein matrix pitch penetration degree be 82 (25 ℃, 100g, 5s)/(1/10mm), performance is classified as PG58-22.The dynamic shear modulus that the gained high-modulus asphalt is 60 ℃ is 23.3kPa, and its performance classification can reach PG82-22.
Comparative Examples 1
Different with embodiment 1 is, long residuum is without solvent extraction process, but directly gets into the vacuum distillation tower deep drawing of reducing pressure, and obtains 350 ℃～540 ℃ vacuum distillate and＞540 ℃ vacuum residuum respectively.Temperature is 190～330 ℃ at the bottom of the underpressure distillation still, after underpressure distillation finishes, at the bottom of the underpressure distillation still, obviously has coking material to generate.The vacuum distillate yield that obtains accounts for 31.1 quality % of long residuum, and its carbon residue is 1.3 quality %, and nickel content＜0.1 μ g/g, content of vanadium are 3.1 μ g/g.＞540 ℃ vacuum residuum and No. 90 pitches of joyful mountain range crude production are concocted with certain proportion, and the dynamic shear modulus that obtains 60 ℃ of blended products is 14.5kPa, and its performance classification can be PG76-16.The main character of vacuum distillate, vacuum residuum and high-modulus asphalt is listed in table 3.
Can find out by the data in the table 3, though Comparative Examples 1 gained reduced pressure distillate oil properties slightly is superior to embodiment 1 gained solvent-refined oil,, the yield of vacuum distillate than the yield of solvent-refined oil low nearly 20 weight %.In addition, the carbon residue of embodiment 1 gained solvent treatment irreducible oil is far below the carbon residue of Comparative Examples 1 gained vacuum residuum; With the solvent treatment irreducible oil is the high-modulus asphalt that properties-correcting agent is produced; Its 60 ℃ of dynamic shear modulus can reach 23kPa; Its performance classification can reach PG82-22, and the high-modulus asphalt of producing with＞540 ℃ of vacuum residuum properties-correcting agent, its 60 ℃ of dynamic shear modulus have only 14.5kPa; Its performance is classified as PG76-16, and high-temperature behavior and low-temperature performance are all poor than the high-modulus asphalt of embodiment 1 gained.The most important thing is; The service temperature of embodiment 1 solvent extraction is far below the temperature of Comparative Examples 1 underpressure distillation; Do not pass through the pyroreaction temperature range of sulfur corrosion; About 240 ℃ sulfur corrosion reaction zone has then been passed through in underpressure distillation, and vacuum distillation process has scission reaction to take place, and the operating parameters fluctuation is big, have coking material to generate at the bottom of the still.
Embodiment 2
Adopt the long residuum identical with embodiment 1; In the solvent extraction unit; Long residuum mixes the back and gets into from extraction tower top with premix solvent (the premix solvent is 0.5: 1 with raw oil by volume), main solvent gets into (main solvent and raw oil are 5.5: 1 by volume) from the extraction tower bottom, and secondary solvent gets into (secondary solvent and raw oil are 0.3: 1 by volume) from the extraction tower bottom; The tower temperature is 125 ℃/115 ℃ (at the bottom of cat head/tower); Pressure is 4.0MPa, in the residence time is to carry out solvent extraction under the condition of 30min, obtains solvent-laden light phase solution and heavy phase solution; Light phase solution and heavy phase solution obtain solvent-refined oil and solvent treatment irreducible oil through flash distillation, stripping after reclaiming solvent respectively, recycle after the solvent recuperation.The composition of premix solvent, main solvent and secondary solvent is listed in table 2.The solvent-refined oil yield that obtains accounts for 54.1 weight % of raw material; Its character is listed in table 4, can find out from table 4, and the carbon residue of gained solvent-refined oil is merely 2.4 weight %; Nickel content is that 1.9 μ g/g, content of vanadium are 9.9 μ g/g, is the high quality raw material of catalytic cracking unit.
The solvent treatment irreducible oil yield of gained accounts for 46 quality % of raw material, and asphalt content is 41.0 quality %, and softening temperature is 137.5 ℃.With the solvent treatment irreducible oil is properties-correcting agent, is matrix pitch with No. 90 pitches liking the mountain range crude production, obtains high-modulus asphalt.Wherein matrix pitch penetration degree be 82 (25 ℃, 100g, 5s)/(1/10mm), PG is classified as PG58-22.The dynamic shear modulus that the gained high-modulus asphalt is 60 ℃ is 25.2kPa, and its performance classification can reach PG82-16.
Comparative Examples 2
Different with embodiment 2 is; Long residuum obtains 350～540 ℃ vacuum distillate and＞540 ℃ vacuum residuum earlier through underpressure distillation, and temperature is 190～330 ℃ at the bottom of the underpressure distillation still; After underpressure distillation finishes, at the bottom of the underpressure distillation still, obviously there is coking material to generate.Operate as the raw material of solvent extraction vacuum residuum according to the solvent extraction condition among the embodiment 2, obtain solvent-refined oil and solvent treatment irreducible oil.With the mixture of vacuum distillate and the solvent-refined oil raw material as catalytic cracking/hydrogen cracking, the yield of its mixture accounts for 54.7 quality % of long residuum, and its carbon residue is 2.65 weight %, and nickel content is 2.0 μ g/g, and content of vanadium is 11.1 μ g/g.The solvent treatment irreducible oil of gained after the vacuum residuum extracting and No. 90 pitches of joyful mountain range crude production are concocted with certain proportion, and the dynamic shear modulus that obtains 60 ℃ of blended products is 14.6kPa, and its performance classification can be PG76-16.The main character of vacuum distillate, vacuum residuum and high-modulus asphalt is listed in table 4.
Can be found out that by the data in the table 4 yield of embodiment 2 gained solvent-refined oils is suitable with Comparative Examples 2 gained vacuum distillate solubilizing agent treated oil total recoverys, both character is also close.But embodiment 2 is the extractings of long residuum direct solvent, does not pass through underpressure distillation, has promptly avoided sulphur generation corrosive high-temperature operation temperature range in the crude oil, has also omitted a underpressure distillation operating unit.
Table 1 long residuum main character
The composition of table 2 solvent (volume %)
| Propane | Propylene | Trimethylmethane | Normal butane | Anti-butylene | N-butene | 1,3 divinyl |
| 0.63 | 0.07 | 87.45 | 0.41 | 3.35 | 7.59 | 0.48 |
Table 3
Table 4
Claims (10)
1. the working method of a sulphur-bearing crude comprises:
(1) sulphur-bearing crude gets into the air distillation unit, obtains atmospheric distillate and long residuum,
(2) long residuum gets into the solvent extraction unit, obtains solvent-refined oil and solvent treatment irreducible oil,
(3) solvent-refined oil of step (2) gained gets into catalytic cracking unit or hydrogen cracking unit, obtains the hydrocarbon fraction of lighting,
(4) the solvent treatment irreducible oil of step (2) gained is the properties-correcting agent of high-modulus asphalt.
2. according to the described method of claim 1, it is characterized in that said long residuum and premix solvent; The volume ratio of premix solvent and long residuum is 0.1～6: 1; Get into extraction tower through the long residuum after the dilution, contact mixing with solvent in extraction tower inside and be separated, the volume ratio of solvent and long residuum is 3～12: 1; After extraction tower cat head and bottom stream are isolated solvent, obtain solvent-refined oil and solvent treatment irreducible oil respectively; Extraction tower pressure is 2.0～8.0MPa, and the extracting tower top temperature is 40 ℃～190 ℃, and the extracting column bottom temperature is 30 ℃～180 ℃.
3. according to the described method of claim 2, it is characterized in that the volume ratio of premix solvent and long residuum is 0.2～4: 1; In the extraction tower, the volume ratio of solvent and long residuum is 4～8: 1; Extraction tower pressure is 3.0～5.0MPa, and the extracting tower top temperature is 60 ℃～170 ℃, and the extracting column bottom temperature is 50 ℃～160 ℃.
4. according to claim 1 or 2 described methods, it is characterized in that premix solvent and solvent are selected from C
3～C
5In alkane or the alkene one or more.
5. according to the described method of claim 4, it is characterized in that premix solvent and solvent are selected from C
4In alkane or the alkene one or more.
6. according to the described method of claim 1, it is characterized in that the sulphur content in the said sulphur-bearing crude is more than or equal to 0.5 weight %.
7. according to the described method of claim 6, it is characterized in that the sulphur content in the said sulphur-bearing crude is more than or equal to 1.0 weight %.
8. according to the described method of claim 1, it is characterized in that, is benchmark with the long residuum, and the yield of said solvent-refined oil is 50 weight %～85 weight %, and the boiling range of said solvent-refined oil is 340 ℃～720 ℃.
9. according to the described method of claim 1, it is characterized in that get into secondary solvent by the bottom of extraction tower, the volume ratio of secondary solvent and long residuum is 0.1～6: 1.
10. according to the described method of claim 1, it is characterized in that said solvent treatment irreducible oil mixes with matrix pitch and obtains high-modulus asphalt, the weight ratio of matrix pitch and solvent treatment irreducible oil is 40: 60～60: 40.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5089114A (en) * | 1988-11-22 | 1992-02-18 | Instituto Mexicano Del Petroleo | Method for processing heavy crude oils |
| CN1351131A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | Technological route for treating S-contained crude oil |
| CN1654603A (en) * | 2004-02-13 | 2005-08-17 | 中国石油化工股份有限公司 | Conversion method for low-grade heavy and residual oil |
| CN101050383A (en) * | 2007-04-30 | 2007-10-10 | 中国石油化工股份有限公司 | Combined technique for processing heavy oil |
-
2010
- 2010-07-22 CN CN2010102336409A patent/CN102337152A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5089114A (en) * | 1988-11-22 | 1992-02-18 | Instituto Mexicano Del Petroleo | Method for processing heavy crude oils |
| CN1351131A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | Technological route for treating S-contained crude oil |
| CN1654603A (en) * | 2004-02-13 | 2005-08-17 | 中国石油化工股份有限公司 | Conversion method for low-grade heavy and residual oil |
| CN101050383A (en) * | 2007-04-30 | 2007-10-10 | 中国石油化工股份有限公司 | Combined technique for processing heavy oil |
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Application publication date: 20120201 |