CN103160320B - 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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- CN103160320B CN103160320B CN201110420918.8A CN201110420918A CN103160320B CN 103160320 B CN103160320 B CN 103160320B CN 201110420918 A CN201110420918 A CN 201110420918A CN 103160320 B CN103160320 B CN 103160320B
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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 crude oil that different areas and Different Strata are produced are also 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, based on crude kind is determined optimum processing route and scheme conventionally.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, 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, cannot 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 secondary solvent extracting and obtain secondary fine liquefaction and secondary and extract oil out once extracting oil out, 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 to secondary that 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, there is very bright application prospect; CN123945 discloses a kind of taking light base oil as raw material, adds the method for plasticising solubilizing agent production unsaturated rubber extending oil.USP6,248,929 provide a kind of method of producing high aromatic rubber oil taking dimethyl sulfoxide (DMSO) as solvent.
The high aromatic rubber oil of above-mentioned production mainly adopts solvent extraction process for purification to prepare, and does not relate to other processing method and improves petroleum fractions aromaticity content and add technique.
Summary of the invention
The object of this invention is to provide a kind of method and complete processing thereof that improves petroleum fractions aromaticity content.This invention can improve aromaticity content 1%~30% on former distillate basis, and 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, taking crude oil, long residuum, vacuum residuum and vacuum distillate as raw material, enters in the adiabatic reactor that disperses inner member or sky after being heated to suitable temperature of reaction, and reacted product obtains 360 DEG C~520 DEG C 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, extracts oily aromaticity content out and can reach 30%~80%.
Specifically, technical scheme provided by the invention is: taking any cut between 360 DEG C-520 DEG C of 500 DEG C of residual oil of long residuum, >, the reduced pressure distillates of 350 DEG C of crude oil, > as raw material, be heated to after 360~480 DEG C and enter in the adiabatic reactor that disperses inner member or sky through process furnace, 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 is out cooling through quenching oil, and quenching oil is that cooling rear thermally splitting generates oil, is cooled to 300~380 DEG C; Thermally splitting generates oil and obtains 360~520 DEG C of cuts through fractionation cutting; 360~520 DEG C of cuts and hydrogen mixing post-heating to 250 DEG C~400 DEG C are entered to hydrofining reaction bed, and controlling reaction bed temperature is 250 DEG C~400 DEG C, and 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 obtaining from reactor enters in tower from solvent tower bottom, with enter 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 DEG C of tower top temperatures, 40~70 DEG C of column bottom temperatures; The extraction oil aromaticity content going out from extraction tower underflow can reach 30%~80%.
Or rather, technical scheme of the present invention is: taking any cut between 360 DEG C~520 DEG C of 500 DEG C of residual oil of long residuum, >, the reduced pressure distillates of 350 DEG C of crude oil, > as raw material, be heated to after 390~450 DEG C and enter in the adiabatic reactor that disperses inner member or sky through process furnace, 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 is out cooling through quenching oil, and quenching oil is that cooled thermally splitting generates oil, is cooled to 300~360 DEG C; Thermally splitting generates oil and obtains 360~520 DEG C of cuts through fractionation cutting; 360~520 DEG C of cuts and hydrogen mixing post-heating to 280 DEG C~350 DEG C are entered to hydrofining reaction bed, and controlling reaction bed temperature is 290 DEG C~360 DEG C, and 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 obtaining from reactor enters in tower from solvent tower bottom, with enter 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 DEG C of tower top temperatures, 50~60 DEG C of column bottom temperatures; The aromaticity content of the extraction oil going out from extraction tower underflow can reach 30%~80% (ASTM D2140).
The present invention uses catalyst for refining at 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
3before use, carry out sulfidizing.
The present invention utilizes thermally splitting-hydrofining-solvent treatment combination process to produce, and 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 source.
Embodiment
Further set forth technical solution of the present invention and effect below in conjunction with embodiment.
Petroleum fractions arene content determination adopts ASTM D2140 assay method.
Embodiment 1:
Taking crude oil A as raw material, character, in table 1, is carried out thermocracking process, and thermocracking process operational condition is in table 3.Obtain 360~520 DEG C of cuts through cut cutting, this cut obtains 360~520 DEG C of cuts through hydrogenation, furfural production technology.Each production technique operating parameters is in table 4, table 5.Hydrogenation catalyst character is in table 6.Each cut aromaticity content is in table 7.
Embodiment 2:
Taking crude oil B as raw material, character, in table 1, is carried out thermocracking process, and thermocracking process operational condition is in table 3.Obtain 360~520 DEG C of cuts through cut cutting, this cut obtains 360~520 DEG C of cuts through hydrogenation, furfural production technology.Each production technique operating parameters is in table 4, table 5.Hydrogenation catalyst character is in table 6.Each cut aromaticity content is in table 7.
Embodiment 3:
Taking crude oil C as raw material, character, in table 1, is carried out thermocracking process, and thermocracking process operational condition is in table 3.Obtain 360~520 DEG C of cuts through cut cutting, this cut obtains 360~20 DEG C of cuts through hydrogenation, furfural production technology.Each production technique operating parameters is in table 4, table 5.Hydrogenation catalyst character is in table 6.Each cut aromaticity content is in table 7.
Embodiment 4:
Taking long residuum D as raw material, character, in table 1, is carried out thermocracking process, and thermocracking process operational condition is in table 3.Obtain 360~520 DEG C of cuts through cut cutting, this cut obtains 360~520 DEG C of cuts through hydrogenation, furfural production technology.Each production technique operating parameters is in table 4, table 5.Hydrogenation catalyst character is in table 6.Each cut aromaticity content is in table 7.
Embodiment 5:
Taking long residuum E as raw material, character, in table 1, is carried out thermocracking process, and thermocracking process operational condition is in table 3.Obtain 360~520 DEG C of cuts through cut cutting, this cut obtains 360~520 DEG C of cuts through hydrogenation, furfural production technology.Each production technique operating parameters is in table 4, table 5.Hydrogenation catalyst character is in table 6.Each cut aromaticity content is in table 7.
Embodiment 6:
Taking long residuum F as raw material, character, in table 1, is carried out thermocracking process, and thermocracking process operational condition is in table 3.Obtain 360~520 DEG C of cuts through cut cutting, this cut obtains 360~520 DEG C of cuts through hydrogenation, furfural production technology.Each production technique operating parameters is in table 4, table 5.Hydrogenation catalyst character is in table 6.Each cut aromaticity content is in table 7.
Embodiment 7:
Taking vacuum residuum G as raw material, character, in table 1, is carried out thermocracking process, and thermocracking process operational condition is in table 3.Obtain 360~520 DEG C of cuts through cut cutting, this cut obtains 360~520 DEG C of cuts through hydrogenation, furfural production technology.Each production technique operating parameters is in table 4, table 5.Hydrogenation catalyst character is in table 6.Each cut aromaticity content is in table 7.
Embodiment 8:
Taking vacuum residuum H as raw material, character, in table 1, is carried out thermocracking process, and thermocracking process operational condition is in table 3.Obtain 360~520 DEG C of cuts through cut cutting, this cut obtains 360~520 DEG C of cuts through hydrogenation, furfural production technology.Each production technique operating parameters is in table 4, table 5.Hydrogenation catalyst character is in table 6.Each cut aromaticity content is in table 7.
Embodiment 9:
Taking vacuum residuum I as raw material, character, in table 1, is carried out thermocracking process, and thermocracking process operational condition is in table 3.Obtain 360~520 DEG C of cuts through cut cutting, this cut obtains 360~520 DEG C of cuts through hydrogenation, furfural production technology.Each production technique operating parameters is in table 4, table 5.Hydrogenation catalyst character is in table 6.Each cut aromaticity content is in table 7.
Embodiment 10:
Taking 360 DEG C~520 DEG C decompression petroleum fractions J as raw material, character, in table 1, is carried out thermocracking process, and thermocracking process operational condition is in table 3.Obtain 360~520 DEG C of cuts through cut cutting, this cut obtains 360~520 DEG C of cuts through hydrogenation, furfural production technology.Each production technique operating parameters is in table 4, table 5.Hydrogenation catalyst character is in table 6.Each cut aromaticity content is in table 7.
Embodiment 11:
Taking 360 DEG C~520 DEG C decompression petroleum fractions K as raw material, character, in table 1, is carried out thermocracking process, and thermocracking process operational condition is in table 3.Obtain 360~520 DEG C of cuts through cut cutting, this cut obtains 360~520 DEG C of cuts through hydrogenation, furfural production technology.Each production technique operating parameters is in table 4, table 5.Hydrogenation catalyst character is in table 6.Each cut aromaticity content is in table 7.
Embodiment 12:
Taking 360 DEG C~520 DEG C decompression petroleum fractions L as raw material, character, in table 1, is carried out thermocracking process, and thermocracking process operational condition is in table 3.Obtain 360~520 DEG C of cuts through cut cutting, this cut obtains 360~520 DEG C of cuts through hydrogenation, furfural production technology.Each production technique operating parameters is in table 4, table 5.Hydrogenation catalyst character is in table 6.Each cut aromaticity content is in table 7.
Embodiment 13:
Taking 360 DEG C~520 DEG C decompression petroleum fractions M as raw material, character, in table 1, is carried out thermocracking process, and thermocracking process operational condition is in table 3.Obtain 360~520 DEG C of cuts through cut cutting, this cut obtains 360~520 DEG C of cuts through hydrogenation, furfural production technology.Each production technique operating parameters is in table 4, table 5.Hydrogenation catalyst character is in table 6.Each cut aromaticity content is in table 7.
Comparative example 1:
Taking crude oil A as raw material, character, in table 1, is carried out cut cutting, and cut obtains 360-520 DEG C of cut through furfural production technology, and each cut aromaticity content is in table 2.Embodiment 1 is compared with comparative example 1: 360-400 DEG C of cut aromaticity content increased by 10%, 400-450 DEG C of cut aromaticity content and increased by 17%, 450-520 DEG C of cut aromaticity content and increased by 20%.
Comparative example 2:
Taking crude oil B as raw material, character, in table 1, is carried out cut cutting, and cut obtains 360-520 DEG C of cut through furfural production technology, and each cut aromaticity content is in table 2.Embodiment 2 is compared with comparative example 2: 360-400 DEG C of cut aromaticity content increased by 27%, 400-450 DEG C of cut aromaticity content and increased by 55%, 450-520 DEG C of cut aromaticity content and increased by 18%.
Comparative example 3:
Taking crude oil C as raw material, character, in table 1, is carried out cut cutting, and cut obtains 360-520 DEG C of cut through furfural production technology, and each cut aromaticity content is in table 2.Embodiment 3 is compared with comparative example 3: 360-400 DEG C of cut aromaticity content increased by 32%, 400-450 DEG C of cut aromaticity content and increased by 27%, 450-520 DEG C of cut aromaticity content and increased by 18%.
Comparative example 4:
Taking long residuum D as raw material, character, in table 1, is carried out cut cutting, and cut obtains 360-520 DEG C of cut through furfural production technology, and each cut aromaticity content is in table 2.Embodiment 4 is compared with comparative example 4: 360-400 DEG C of cut aromaticity content increased by 19%, 400-450 DEG C of cut aromaticity content and increased by 42%, 450-520 DEG C of cut aromaticity content and increased by 45%.
Comparative example 5:
Taking long residuum E as raw material, character, in table 1, is carried out cut cutting, and cut obtains 360-520 DEG C of cut through furfural production technology, and each cut aromaticity content is in table 2.Embodiment 5 is compared with comparative example 5: 360-400 DEG C of cut aromaticity content increased by 21%, 400-450 DEG C of cut aromaticity content and increased by 25%, 450-520 DEG C of cut aromaticity content and increased by 45%.
Comparative example 6:
Taking long residuum F as raw material, character, in table 1, is carried out cut cutting, and cut obtains 360-520 DEG C of cut through furfural production technology, and each cut aromaticity content is in table 2.Embodiment 6 is compared with comparative example 6: 360-400 DEG C of cut aromaticity content increased by 27%, 400-450 DEG C of cut aromaticity content and increased by 18%, 450-520 DEG C of cut aromaticity content and increased by 20%.
The analysis of table 1 feedstock property
Table 2 comparative example 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. one kind is improved the working method of petroleum fractions aromaticity content, it is characterized in that: taking any cut between 360 DEG C-520 DEG C of long residuum, >500 DEG C residual oil, the reduced pressure distillates of crude oil, >350 DEG C as raw material, through heat cracking reaction, fractionation obtains 360~520 DEG C of cuts; This cut obtains CA value through hydrofining, solvent treatment and reaches 30%-80% petroleum fractions;
The processing condition of heat cracking reaction are: temperature in is 360 DEG C~480 DEG C, 10~180 minutes residence time, pressure 0.1~2.0MPa;
Entering the processing condition that hydrofining reaction bed carries out hydrofining reaction under Hydrobon catalyst effect is: temperature is 250 DEG C~400 DEG C, and 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; 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 oxide compound active metallic content, and carrier is Al
2o
3, before use, carry out sulfidizing;
Carrying out the refining processing condition of furfural solvent is: solvent quality is than 1:1.3~3.5,70~100 DEG C of tower top temperatures, 40~70 DEG C 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 heat cracking reaction are: temperature in is 390 DEG C~450 DEG C, 20~90 minutes residence time, pressure 0.1~1.6MPa;
Entering the processing condition that hydrofining reaction bed carries out hydrofining reaction is: temperature is 290 DEG C~360 DEG C, and 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 quality is than 1:1.9~2.6,80~90 DEG C of tower top temperatures, 50~60 DEG C of column bottom temperatures.
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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 |
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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 |
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