CN103160320A - Processing method for increasing aromatic hydrocarbon content in petroleum fraction - Google Patents
Processing method for increasing aromatic hydrocarbon content in petroleum fraction Download PDFInfo
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- CN103160320A CN103160320A CN2011104209188A CN201110420918A CN103160320A CN 103160320 A CN103160320 A CN 103160320A CN 2011104209188 A CN2011104209188 A CN 2011104209188A CN 201110420918 A CN201110420918 A CN 201110420918A CN 103160320 A CN103160320 A CN 103160320A
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Abstract
The invention relates to a processing method for increasing aromatic hydrocarbon content in a petroleum fraction. According to the invention, crude oil, atmospheric pressure residual oil, residual oil and a reduced pressure distillate are used as raw materials and are subjected to thermal cracking and fractionation so as to obtain a fraction prepared at a temperature of 360 to 520 DEG C; the fraction undergoes hydrorefining and solvent refining so as to obtain a petroleum fraction with a CA value of 30 to 80%; inlet temperature and pressure of thermal cracking are 360 to 480 DEG C and 0.1 to 2.0 MPa, respectively; in hydrorefining, temperature is 250 to 400 DEG C, hydrogen partial pressure is 2.0 to 20 MPa, a volume hourly space velocity is 0.2 to 2.0/h, and a volume ratio of hydrogen to oil is 300: 1 to 1500: 1; a mass ratio of a furfural solvent to a refining solvent is 1: 1.3-3.5; the fraction is subjected to hydrorefining, olefin saturation and aromatic hydrogenation; hydrofined oil undergoes solvent refining for enrichment of aromatic hydrocarbons and polar materials in the oil so as to obtain extract oil; and aromatic hydrocarbon content in the extract oil reaches 30 to 80%.
Description
Technical field
The present invention relates to utilize thermocracking process to improve the method for petroleum fractions aromaticity content.
Background technology
Oil is mainly by alkane, naphthenic hydrocarbon, three kinds of hydrocarbon compositions of aromatic hydrocarbon, three kinds of shared ratios of hydro carbons of the crude oil that different areas and Different Strata are produced also are not quite similar, and are divided into several crude oil such as paraffinic base, cycloalkyl, aromatic base according to three kinds of hydro carbons proportion differences.In petroleum refining process, the based on crude kind is determined optimum processing route and scheme usually.Along with widening of petroleum products range of application, also increasing to the oil product demand of high aromaticity content, the oil product of high aromaticity content mainly contains two sources, and one is the petroleum fractions that aromatic base crude oil is produced, and another kind is the extraction oil that solvent treatment is produced.At present, the aromatic base crude oil proportion is less, and along with the development of oil Refining Technologies, solvent refining unit is also fewer and feweri, causes the oil product source of high aromaticity content also fewer and feweri, can't meet the need of market.
CN1570037A discloses a kind of production technique of high aromatic rubber oil, what relate to is the production technique of the black rubber oil that uses in rubber industry, adopt the catalytic cracking turning oil of slag-mixing amount 20% as raw material, the Extract of lube oil furfural refining unit carries out the method for the high aromatic oil that extracting obtains as solvent.CN 101386687A discloses a kind of aromatic rubber oil and production method thereof, that to subtract three distillates be that raw material carries out solvent extraction and obtains primary purification oil and once extract oil out, carry out the secondary solvent extracting and obtain secondary fine liquefaction and secondary and extract oil out once extracting oil out, the secondary fine liquefaction is through the clay-filtered aromatic rubber oil that just obtains, the standby rubber oil aromaticity content of this legal system is high, polycyclic aromatic hydrocarbon content is less than 3%, and nontoxic without carcinogenesis.CN101597513 discloses a kind of environment-friendly rubber oil and preparation method thereof, that to subtract three distillates be that raw material carries out solvent extraction and obtains primary purification oil and once extract oil out, primary purification oil is carried out secondary that the secondary solvent extracting obtains to be extracted oil out and is environment-friendly rubber oil, the environment-friendly rubber oil aromaticity content of this invention is high, environmental protection, nontoxic, without carcinogenesis, can be used as the substitute of existing aromatic hydrocarbon oil, have very bright application prospect; CN123945 discloses a kind of take light base oil as raw material, adds the method that plasticising solubilizing agent is produced unsaturated rubber extending oil.USP6,248,929 provide a kind of method of producing high aromatic rubber oil take dimethyl sulfoxide (DMSO) as solvent.
The high aromatic rubber oil of above-mentioned production mainly adopts the solvent extraction process for purification to prepare, and does not relate to other processing method and improves the petroleum fractions aromaticity content and add technique.
Summary of the invention
The purpose of this invention is to provide a kind of method and complete processing thereof that improves the petroleum fractions aromaticity content.This invention can improve aromaticity content 1%～30% on former distillate basis, the high aromaticity content cut of preparing is through complete processing of the present invention, and can produce aromaticity content is 30%～80% petroleum fractions.
The present invention enters after being heated to suitable temperature of reaction in the adiabatic reactor that disperses inner member or sky take crude oil, long residuum, vacuum residuum and vacuum distillate as raw material, and reacted product obtains 360 ℃～520 ℃ cuts through cooling, fractionation; This cut removes the heteroatomss such as S, N, O through hydrofining, and carries out olefin saturated and aromatic hydrogenation; Hydrofined oil is extracted oil out through solvent treatment extracting enrichment polyaromatic component, and the aromaticity content of extracting oil out can reach 30%～80%.
Specifically, technical scheme provided by the invention is: take crude oil,＞long residuum of 350 ℃,＞360 ℃-520 ℃, 500 ℃ of residual oil, reduced pressure distillate between any cut as raw material, be heated to through process furnace and enter after 360～480 ℃ in the adiabatic reactor that disperses inner member or sky, disperseing inner member is bubble deck, valve tray, traverse baffle or filler, control raw material 10～180 minutes residence time in reactor, pressure 0.1～2.0MPa; Reactor reactant flow out is cooling through quenching oil, and quenching oil is that cooling rear thermally splitting generates oil, is cooled to 300～380 ℃; Thermally splitting generates oil and obtains 360～520 ℃ of cuts through the fractionation cutting; 360～520 ℃ of cuts and hydrogen mixing post-heating to 250 ℃～400 ℃ are entered the hydrofining reaction bed, and controlling the reaction bed temperature is 250 ℃～400 ℃, and the hydrogen dividing potential drop is 2.0～20MPa, and volume space velocity is 0.2～2.0h
-1, hydrogen to oil volume ratio 300: 1～1500: 1; The hydrogenated oil that obtains from reactor enters in tower from the solvent tower bottom, with advance tower furfural counter current contact from top and carry out heat and mass, operational condition is: solvent ratio 1: 1.3～3.5 (mass ratio), 70～100 ℃ of tower top temperatures, 40～70 ℃ of column bottom temperatures; The extraction oil aromaticity content that goes out from the extraction tower underflow can reach 30%～80%.
Or rather, technical scheme of the present invention is: take crude oil,＞long residuum of 350 ℃,＞360 ℃～520 ℃, 500 ℃ of residual oil, reduced pressure distillate between any cut as raw material, be heated to through process furnace and enter after 390～450 ℃ in the adiabatic reactor that disperses inner member or sky, inner member is bubble deck, valve tray, traverse baffle or filler, control raw material 20～90 minutes residence time in reactor, pressure 0.1～1.6MPa; Reactor reactant flow out is cooling through quenching oil, and quenching oil is that cooled thermally splitting generates oil, is cooled to 300～360 ℃; Thermally splitting generates oil and obtains 360～520 ℃ of cuts through the fractionation cutting; 360～520 ℃ of cuts and hydrogen mixing post-heating to 280 ℃～350 ℃ are entered the hydrofining reaction bed, and controlling the reaction bed temperature is 290 ℃～360 ℃, and the hydrogen dividing potential drop is 5.0～16MPa, and volume space velocity is 0.5～1.0h
-1, hydrogen to oil volume ratio 300: 1～800: 1; The hydrogenated oil that obtains from reactor enters in tower from the solvent tower bottom, with advance tower furfural counter current contact from top and carry out heat and mass, operational condition is: solvent ratio 1: 1.9～2.6 (mass ratio), 80～90 ℃ of tower top temperatures, 50～60 ℃ of column bottom temperatures; The aromaticity content of the extraction oil that goes out from the extraction tower underflow can reach 30%～80% (ASTM D2140).
The present invention uses catalyst for refining at the hydrofining reaction bed, and the active metal component of catalyzer is W, Ni, and Co, one or two or more kinds combination in Mo accounts for 10%～40% of catalyst weight in oxide compound active metal component content, and carrier is Al
2O
3Carry out sulfidizing before use.
The present invention utilizes thermally splitting-hydrofining-solvent treatment combination process production, can improve equal distillate aromaticity content value 10%～55%, and the aromaticity content of oil product can reach 30%～80%, and the method can be widened high aromaticity content petroleum fractions and originate.
Embodiment
Further set forth technical solution of the present invention and effect below in conjunction with embodiment.
The petroleum fractions arene content determination adopts ASTM D2140 assay method.
Embodiment 1:
Take crude oil A as raw material, character sees Table 1, carries out thermocracking process, and the thermocracking process operational condition sees Table 3.Obtain 360～520 ℃ of cuts through the cut cutting, this cut obtains 360～520 ℃ of cuts through hydrogenation, furfural production technology.Each production technique operating parameters sees Table 4, table 5.Hydrogenation catalyst character sees Table 6.Each cut aromaticity content sees Table 7.
Embodiment 2:
Take crude oil B as raw material, character sees Table 1, carries out thermocracking process, and the thermocracking process operational condition sees Table 3.Obtain 360～520 ℃ of cuts through the cut cutting, this cut obtains 360～520 ℃ of cuts through hydrogenation, furfural production technology.Each production technique operating parameters sees Table 4, table 5.Hydrogenation catalyst character sees Table 6.Each cut aromaticity content sees Table 7.
Embodiment 3:
Take crude oil C as raw material, character sees Table 1, carries out thermocracking process, and the thermocracking process operational condition sees Table 3.Obtain 360～520 ℃ of cuts through the cut cutting, this cut obtains 360～20 ℃ of cuts through hydrogenation, furfural production technology.Each production technique operating parameters sees Table 4, table 5.Hydrogenation catalyst character sees Table 6.Each cut aromaticity content sees Table 7.
Embodiment 4:
Take long residuum D as raw material, character sees Table 1, carries out thermocracking process, and the thermocracking process operational condition sees Table 3.Obtain 360～520 ℃ of cuts through the cut cutting, this cut obtains 360～520 ℃ of cuts through hydrogenation, furfural production technology.Each production technique operating parameters sees Table 4, table 5.Hydrogenation catalyst character sees Table 6.Each cut aromaticity content sees Table 7.
Embodiment 5:
Take long residuum E as raw material, character sees Table 1, carries out thermocracking process, and the thermocracking process operational condition sees Table 3.Obtain 360～520 ℃ of cuts through the cut cutting, this cut obtains 360～520 ℃ of cuts through hydrogenation, furfural production technology.Each production technique operating parameters sees Table 4, table 5.Hydrogenation catalyst character sees Table 6.Each cut aromaticity content sees Table 7.
Embodiment 6:
Take long residuum F as raw material, character sees Table 1, carries out thermocracking process, and the thermocracking process operational condition sees Table 3.Obtain 360～520 ℃ of cuts through the cut cutting, this cut obtains 360～520 ℃ of cuts through hydrogenation, furfural production technology.Each production technique operating parameters sees Table 4, table 5.Hydrogenation catalyst character sees Table 6.Each cut aromaticity content sees Table 7.
Embodiment 7:
Take vacuum residuum G as raw material, character sees Table 1, carries out thermocracking process, and the thermocracking process operational condition sees Table 3.Obtain 360～520 ℃ of cuts through the cut cutting, this cut obtains 360～520 ℃ of cuts through hydrogenation, furfural production technology.Each production technique operating parameters sees Table 4, table 5.Hydrogenation catalyst character sees Table 6.Each cut aromaticity content sees Table 7.
Embodiment 8:
Take vacuum residuum H as raw material, character sees Table 1, carries out thermocracking process, and the thermocracking process operational condition sees Table 3.Obtain 360～520 ℃ of cuts through the cut cutting, this cut obtains 360～520 ℃ of cuts through hydrogenation, furfural production technology.Each production technique operating parameters sees Table 4, table 5.Hydrogenation catalyst character sees Table 6.Each cut aromaticity content sees Table 7.
Embodiment 9:
Take vacuum residuum I as raw material, character sees Table 1, carries out thermocracking process, and the thermocracking process operational condition sees Table 3.Obtain 360～520 ℃ of cuts through the cut cutting, this cut obtains 360～520 ℃ of cuts through hydrogenation, furfural production technology.Each production technique operating parameters sees Table 4, table 5.Hydrogenation catalyst character sees Table 6.Each cut aromaticity content sees Table 7.
Embodiment 10:
Take 360 ℃～520 ℃ decompression petroleum fractions J as raw material, character sees Table 1, carries out thermocracking process, and the thermocracking process operational condition sees Table 3.Obtain 360～520 ℃ of cuts through the cut cutting, this cut obtains 360～520 ℃ of cuts through hydrogenation, furfural production technology.Each production technique operating parameters sees Table 4, table 5.Hydrogenation catalyst character sees Table 6.Each cut aromaticity content sees Table 7.
Embodiment 11:
Take 360 ℃～520 ℃ decompression petroleum fractions K as raw material, character sees Table 1, carries out thermocracking process, and the thermocracking process operational condition sees Table 3.Obtain 360～520 ℃ of cuts through the cut cutting, this cut obtains 360～520 ℃ of cuts through hydrogenation, furfural production technology.Each production technique operating parameters sees Table 4, table 5.Hydrogenation catalyst character sees Table 6.Each cut aromaticity content sees Table 7.
Embodiment 12:
Take 360 ℃～520 ℃ decompression petroleum fractions L as raw material, character sees Table 1, carries out thermocracking process, and the thermocracking process operational condition sees Table 3.Obtain 360～520 ℃ of cuts through the cut cutting, this cut obtains 360～520 ℃ of cuts through hydrogenation, furfural production technology.Each production technique operating parameters sees Table 4, table 5.Hydrogenation catalyst character sees Table 6.Each cut aromaticity content sees Table 7.
Embodiment 13:
Take 360 ℃～520 ℃ decompression petroleum fractions M as raw material, character sees Table 1, carries out thermocracking process, and the thermocracking process operational condition sees Table 3.Obtain 360～520 ℃ of cuts through the cut cutting, this cut obtains 360～520 ℃ of cuts through hydrogenation, furfural production technology.Each production technique operating parameters sees Table 4, table 5.Hydrogenation catalyst character sees Table 6.Each cut aromaticity content sees Table 7.
Comparative Examples 1:
Take crude oil A as raw material, character sees Table 1, carries out the cut cutting, and cut obtains 360-520 ℃ of cut through furfural production technology, and each cut aromaticity content sees Table 2.Embodiment 1 compares with Comparative Examples 1: 360-400 ℃ of cut aromaticity content increased by 10%, 400-450 ℃ of cut aromaticity content and increased by 17%, 450-520 ℃ of cut aromaticity content and increased by 20%.
Comparative Examples 2:
Take crude oil B as raw material, character sees Table 1, carries out the cut cutting, and cut obtains 360-520 ℃ of cut through furfural production technology, and each cut aromaticity content sees Table 2.Embodiment 2 compares with Comparative Examples 2: 360-400 ℃ of cut aromaticity content increased by 27%, 400-450 ℃ of cut aromaticity content and increased by 55%, 450-520 ℃ of cut aromaticity content and increased by 18%.
Comparative Examples 3:
Take crude oil C as raw material, character sees Table 1, carries out the cut cutting, and cut obtains 360-520 ℃ of cut through furfural production technology, and each cut aromaticity content sees Table 2.Embodiment 3 compares with Comparative Examples 3: 360-400 ℃ of cut aromaticity content increased by 32%, 400-450 ℃ of cut aromaticity content and increased by 27%, 450-520 ℃ of cut aromaticity content and increased by 18%.
Comparative Examples 4:
Take long residuum D as raw material, character sees Table 1, carries out the cut cutting, and cut obtains 360-520 ℃ of cut through furfural production technology, and each cut aromaticity content sees Table 2.Embodiment 4 compares with Comparative Examples 4: 360-400 ℃ of cut aromaticity content increased by 19%, 400-450 ℃ of cut aromaticity content and increased by 42%, 450-520 ℃ of cut aromaticity content and increased by 45%.
Comparative Examples 5:
Take long residuum E as raw material, character sees Table 1, carries out the cut cutting, and cut obtains 360-520 ℃ of cut through furfural production technology, and each cut aromaticity content sees Table 2.Embodiment 5 compares with Comparative Examples 5: 360-400 ℃ of cut aromaticity content increased by 21%, 400-450 ℃ of cut aromaticity content and increased by 25%, 450-520 ℃ of cut aromaticity content and increased by 45%.
Comparative Examples 6:
Take long residuum F as raw material, character sees Table 1, carries out the cut cutting, and cut obtains 360-520 ℃ of cut through furfural production technology, and each cut aromaticity content sees Table 2.Embodiment 6 compares with Comparative Examples 6: 360-400 ℃ of cut aromaticity content increased by 27%, 400-450 ℃ of cut aromaticity content and increased by 18%, 450-520 ℃ of cut aromaticity content and increased by 20%.
The analysis of table 1 feedstock property
Table 2 Comparative Examples petroleum fractions aromaticity content
Table 3 thermally splitting operating parameters and property analysis
Table 4 hydrofining operational condition and property analysis
Table 5 furfural operational condition and chaff essential oil property analysis
The analysis of table 6 catalyst property
Table 7 embodiment petroleum fractions aromaticity content is analyzed
Claims (2)
1. working method that improves the petroleum fractions aromaticity content, it is characterized in that: take crude oil,＞long residuum of 350 ℃,＞360 ℃-520 ℃, 500 ℃ of residual oil, reduced pressure distillate between any cut as raw material, through heat cracking reaction, fractionation obtains 360～520 ℃ of cuts; This cut obtains the CA value through hydrofining, solvent treatment and reaches the 30%-80% petroleum fractions;
The processing condition of heat cracking reaction are: temperature in is 360 ℃～480 ℃, 10～180 minutes residence time, pressure 0.1～2.0MPa;
Entering the hydrofining reaction bed carries out hydrofining reaction under the Hydrobon catalyst effect processing condition is: temperature is 250 ℃～400 ℃, and the hydrogen dividing potential drop is 2.0～20MPa, and volume space velocity is 0.2～2.0h
-1, hydrogen to oil volume ratio 300: 1～1500: 1; The hydrofining reaction bed uses Hydrobon catalyst, and the active metal component of catalyzer is W, Ni, and Co, a kind of or its combination in Mo accounts for 10～40% of catalyst weight in the oxide compound active metallic content, and carrier is Al
2O
3, carry out sulfidizing before use;
Carrying out the refining processing condition of furfural solvent is: solvent quality is than 1: 1.3～3.5,70～100 ℃ of tower top temperatures, 40～70 ℃ of column bottom temperatures.
2. according to the working method of raising petroleum fractions aromaticity content claimed in claim 1, it is characterized in that:
The processing condition of thermal response are: temperature in is 390 ℃～450 ℃, 20～90 minutes residence time, pressure 0.1～1.6MPa;
Entering the processing condition that the hydrofining reaction bed carries out hydrofining reaction is: temperature is 290 ℃～360 ℃, and the hydrogen dividing potential drop is 5～16MPa, and volume space velocity is 0.5～1.0h
-1, hydrogen to oil volume ratio 300: 1～800: 1;
Carrying out the refining processing condition of furfural solvent is: solvent ratio 1: 1.9～2.6 (mass ratio), 80～90 ℃ of tower top temperatures, 50～60 ℃ of column bottom temperatures.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111595928A (en) * | 2020-04-29 | 2020-08-28 | 中国石油天然气股份有限公司 | Method for judging thermal cracking degree of crude oil |
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| US4297204A (en) * | 1978-02-17 | 1981-10-27 | Linde Aktiengesellschaft | Thermal cracking with post hydrogenation and recycle of heavy fractions |
| US4619757A (en) * | 1982-08-31 | 1986-10-28 | Linde Aktiengesellschaft | Two stage hydrotreating pretreatment in production of olefins from heavy hydrocarbons |
| US5167847A (en) * | 1990-05-21 | 1992-12-01 | Exxon Research And Engineering Company | Process for producing transformer oil from a hydrocracked stock |
| CN1448483A (en) * | 2002-04-04 | 2003-10-15 | 中国石油化工股份有限公司 | Composition process of deep processing residual oil |
| CN101646750A (en) * | 2007-04-19 | 2010-02-10 | 昭和电工株式会社 | Hydrogenation method and petrochemical process |
-
2011
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4297204A (en) * | 1978-02-17 | 1981-10-27 | Linde Aktiengesellschaft | Thermal cracking with post hydrogenation and recycle of heavy fractions |
| US4619757A (en) * | 1982-08-31 | 1986-10-28 | Linde Aktiengesellschaft | Two stage hydrotreating pretreatment in production of olefins from heavy hydrocarbons |
| US5167847A (en) * | 1990-05-21 | 1992-12-01 | Exxon Research And Engineering Company | Process for producing transformer oil from a hydrocracked stock |
| CN1448483A (en) * | 2002-04-04 | 2003-10-15 | 中国石油化工股份有限公司 | Composition process of deep processing residual oil |
| CN101646750A (en) * | 2007-04-19 | 2010-02-10 | 昭和电工株式会社 | Hydrogenation method and petrochemical process |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111595928A (en) * | 2020-04-29 | 2020-08-28 | 中国石油天然气股份有限公司 | Method for judging thermal cracking degree of crude oil |
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