CN116554927A - Method and system for producing low-carbon olefin and aromatic hydrocarbon by heavy oil - Google Patents
Method and system for producing low-carbon olefin and aromatic hydrocarbon by heavy oil Download PDFInfo
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- CN116554927A CN116554927A CN202210107418.7A CN202210107418A CN116554927A CN 116554927 A CN116554927 A CN 116554927A CN 202210107418 A CN202210107418 A CN 202210107418A CN 116554927 A CN116554927 A CN 116554927A
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 138
- 239000000295 fuel oil Substances 0.000 title claims abstract description 103
- 238000000034 method Methods 0.000 title claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 title abstract description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 116
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 83
- 239000003921 oil Substances 0.000 claims abstract description 52
- 238000000605 extraction Methods 0.000 claims abstract description 42
- 230000003197 catalytic effect Effects 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 29
- 150000001336 alkenes Chemical class 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 239000002283 diesel fuel Substances 0.000 claims abstract description 11
- -1 ethylene, propylene Chemical group 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 33
- 238000005984 hydrogenation reaction Methods 0.000 claims description 23
- 238000002407 reforming Methods 0.000 claims description 21
- 150000002430 hydrocarbons Chemical class 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005977 Ethylene Substances 0.000 claims description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- 239000004927 clay Substances 0.000 claims description 3
- 239000010779 crude oil Substances 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 15
- 238000005265 energy consumption Methods 0.000 abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000003502 gasoline Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 238000006057 reforming reaction Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 238000007233 catalytic pyrolysis Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present disclosure relates to a method and system for producing light olefins and aromatics from heavy oil, the method comprising: feeding the heavy oil raw material into a catalytic cracking device to contact with a catalytic cracking catalyst for catalytic cracking reaction to obtain ethylene, propylene, a first aromatic hydrocarbon component and catalytic diesel; sending the catalytic diesel into a diesel hydro-conversion device for hydro-conversion treatment to obtain hydro-converted diesel and a second aromatic hydrocarbon component; returning the hydro-converted diesel oil to the catalytic cracking device for continuous reaction; and enabling the first aromatic hydrocarbon component and the second aromatic hydrocarbon component to enter an aromatic hydrocarbon extraction device for extraction treatment to obtain raffinate oil and a first aromatic hydrocarbon product. The method can optimize the product structure, increase the yield of aromatic hydrocarbon and low-carbon olefin, shorten the conversion process, reduce the production energy consumption of chemicals and reduce the oil component ratio in the product.
Description
Technical Field
The present disclosure relates to the field of petrochemical industry, and in particular, to a method and system for producing low-carbon olefins and aromatics from heavy oil.
Background
In recent years, the refining industry enters a period of comprehensively releasing new increased capacity and competing white heat, and is also an industry integration transformation upgrading period, the petroleum demand speed increase is obviously slowed down, the peak value is gradually increased, and the chemical products are advanced and become green. Meanwhile, new energy industries such as fuel for vehicles, hydrogen energy, photoelectricity, wind power and the like are replaced by coal-to-liquid (CNG), ethanol and the like are accelerated to develop, the oil market tends to be saturated, and the demands of chemical products are gradually increased. Therefore, the petrochemical industry has the problem of converting heavy oil into chemical products such as olefin, aromatic hydrocarbon and the like more and more efficiently, and producing less finished oil.
Disclosure of Invention
The purpose of the present disclosure is to provide a method and a system for producing low-carbon olefins and aromatic hydrocarbons from heavy oil, wherein the method can enable heavy oil to be more and more efficiently converted into chemical products such as low-carbon olefins and aromatic hydrocarbons, and reduce the production of finished oil.
In order to achieve the above object, the present disclosure provides a method for producing light olefins and aromatics from heavy oil, the method comprising: enabling the heavy oil raw material to enter a catalytic cracking device to contact a catalytic cracking catalyst for catalytic cracking reaction to obtain ethylene, propylene, a first aromatic hydrocarbon component and catalytic diesel; sending the catalytic diesel into a diesel hydro-conversion device for hydro-conversion treatment to obtain hydro-converted diesel and a second aromatic hydrocarbon component; returning the hydro-converted diesel oil to the catalytic cracking device for continuous reaction; and enabling the first aromatic hydrocarbon component and the second aromatic hydrocarbon component to enter an aromatic hydrocarbon extraction device for extraction treatment to obtain raffinate oil and a first aromatic hydrocarbon product.
Optionally, the heavy oil raw material comprises one or more of hydrogenated heavy oil, atmospheric residuum, vacuum residuum, atmospheric wax oil, vacuum wax oil and crude oil; the first aromatic hydrocarbon component comprises hydrocarbon compounds with 6-10 carbon atoms; the second aromatic hydrocarbon component comprises a hydrocarbon compound having 6 to 10 carbon atoms.
Alternatively, the heavy oil feedstock has a hydrogen content of 12 wt.% or more, a carbon residue content of 4 wt.% or less, and a metal (Ni+V) content of 13 μg/g or less.
Optionally, the reaction conditions of the catalytic cracking reaction include: the reaction temperature is 500-650 ℃, the reaction pressure is 0.05-0.3 MPa, and the reaction time is 0.1-20 s; the catalytic cracking catalyst comprises one or more of zeolite molecular sieve, inorganic oxide and clay.
Optionally, the reaction conditions of the hydroconversion process include: the reaction temperature is 350-450 ℃, the reaction pressure is 3-10 MPa, the reaction time is 0.1-5 h, and the hydrogen-oil volume ratio is (300-900): 1.
optionally, the method further comprises, before the catalytic cracking reaction, feeding the heavy oil into a heavy oil hydrogenation device for heavy oil hydrogenation treatment to obtain the heavy oil raw material; the reaction conditions for the heavy oil hydrotreatment include: the temperature is 350-500 ℃, the pressure is 8-25 MPa, and the hydrogen-oil volume ratio is (300-900): 1.
optionally, the method further comprises sending the raffinate oil to a reforming device for reforming treatment to obtain a second aromatic hydrocarbon product and hydrogen; returning the hydrogen to the diesel hydroconversion unit; the reaction conditions of the reforming treatment include: the reaction temperature is 500-600 ℃, the reaction pressure is 0.1-0.4 MPa, and the reaction time is 0.1-200 s.
A second aspect of the present disclosure provides a system for producing light olefins and aromatics from heavy oil, the system comprising: the device comprises a catalytic cracking device, a diesel oil hydro-conversion device and an aromatic hydrocarbon extraction device; the catalytic cracking device comprises a heavy oil raw material inlet, a hydro-conversion diesel inlet, an ethylene outlet, a propylene outlet, a first aromatic hydrocarbon component outlet and a catalytic diesel outlet; the diesel hydro-conversion device comprises a catalytic diesel inlet, a hydrogen inlet, a second aromatic hydrocarbon component outlet and a hydro-conversion diesel outlet; the aromatic hydrocarbon extraction device comprises a first aromatic hydrocarbon component inlet, a second aromatic hydrocarbon component inlet, a first aromatic hydrocarbon product outlet and a raffinate oil outlet; the catalytic diesel outlet of the catalytic cracking device is communicated with the catalytic diesel inlet of the diesel hydro-conversion device; the hydroconversion diesel outlet of the diesel hydroconversion device is communicated with the hydroconversion diesel inlet of the catalytic cracking device; the second aromatic hydrocarbon component outlet of the diesel hydro-conversion device is communicated with the second aromatic hydrocarbon component inlet of the aromatic hydrocarbon extraction device, and the first aromatic hydrocarbon component outlet of the catalytic cracking device is communicated with the first aromatic hydrocarbon component inlet of the aromatic hydrocarbon extraction device.
Optionally, the system further comprises a heavy oil hydrogenation device comprising a heavy oil inlet, a hydrogen inlet, and a heavy oil feedstock outlet; the heavy oil raw material outlet of the heavy oil hydrogenation device is communicated with the heavy oil raw material inlet of the catalytic cracking device.
Optionally, the system further comprises a reformer comprising a raffinate oil inlet, a hydrogen outlet, and a second aromatic product outlet; the raffinate oil outlet of the aromatic hydrocarbon extraction device is communicated with the raffinate oil inlet of the reforming device; the hydrogen outlet of the reforming device is communicated with the hydrogen inlet of the diesel hydro-conversion device.
Through the technical scheme, the low-carbon olefin, the first aromatic hydrocarbon component and the catalytic diesel are obtained by carrying out catalytic pyrolysis on heavy oil; then, the catalytic diesel is subjected to hydroconversion to obtain hydroconverted diesel and a second aromatic component; and concentrating and separating the first aromatic hydrocarbon component and the second aromatic hydrocarbon component. By adopting the method disclosed by the invention, the product structure can be optimized, the yields of aromatic hydrocarbon and low-carbon olefin are increased, the conversion process is shortened, the production energy consumption of chemicals is reduced, and the oil component ratio in the product is reduced.
Additional features and advantages of the present disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the disclosure, and are incorporated in and constitute a part of this specification, illustrate the disclosure and together with the description serve to explain, but do not limit the disclosure. In the drawings:
fig. 1 is a schematic flow chart of a specific embodiment of a method for producing light olefins and aromatics from heavy oil provided by the invention.
Fig. 2 is a schematic flow chart of a comparative example of a method for producing light olefins and aromatics from heavy oil provided by the invention.
Description of the reference numerals
1. A catalytic cracking device; 2. a diesel hydro-conversion device; 3. an aromatic hydrocarbon extraction device; 4. a reforming device; 101. heavy oil feedstock; 102. ethylene; 103. propylene; 104. a first aromatic hydrocarbon component; 105. catalyzing diesel oil; 106. a second aromatic hydrocarbon component; 107. hydroconverting diesel; 108. raffinate oil; 109. a first aromatic hydrocarbon product; 110. a second aromatic hydrocarbon product;
21. a catalytic cracking unit; 22-diesel hydrogenation device; 23. a light hydrocarbon separation device; 24. hydrofining device, 25, MTBE (methyl tert-butyl ether) device; 26. an alkylation unit; 150. ethylene; 160. propylene; 201. a first liquefied gas; 202. catalytic gasoline; 203. catalyzing diesel oil; 204. a gasoline component; 205. propane; 206. carbon four; 207. a diesel component; 209. methyl tertiary butyl ether; 210. post-ether carbon four; 211. a second liquefied gas; 212. an alkylate.
Detailed Description
Specific embodiments of the present disclosure are described in detail below with reference to the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the disclosure, are not intended to limit the disclosure.
In this disclosure, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated, unless otherwise indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature.
A first aspect of the present disclosure provides a method for producing light olefins and aromatics from heavy oil, the method comprising: enabling the heavy oil raw material to enter a catalytic cracking device to contact a catalytic cracking catalyst for catalytic cracking reaction to obtain ethylene, propylene, a first aromatic hydrocarbon component and catalytic diesel; sending the catalytic diesel into a diesel hydro-conversion device for hydro-conversion treatment to obtain hydro-converted diesel and a second aromatic hydrocarbon component; returning the hydro-converted diesel oil to the catalytic cracking device for continuous reaction; and enabling the first aromatic hydrocarbon component and the second aromatic hydrocarbon component to enter an aromatic hydrocarbon extraction device for extraction treatment to obtain raffinate oil and a first aromatic hydrocarbon product.
Through the technical scheme, the heavy oil raw material is subjected to catalytic pyrolysis to obtain low-carbon olefin, a first aromatic hydrocarbon component and catalytic diesel; carrying out hydrogenation conversion on the catalytic cracking inferior diesel to obtain hydrogenation converted diesel and a second aromatic hydrocarbon component; and concentrating and separating the first aromatic hydrocarbon component and the second aromatic hydrocarbon component to obtain an aromatic hydrocarbon product and raffinate oil. By adopting the method disclosed by the invention, the product structure can be optimized, specifically, heavy oil is changed from the component of the multi-product oil to the component of the multi-product low-carbon olefin and aromatic hydrocarbon, the ratio of the component of the oil in the product is reduced, the conversion process can be shortened, and the production energy consumption of chemicals can be reduced. The oil components described in the present disclosure refer to, among other things, gasoline, kerosene, and diesel that can be drawn out of the system as products.
In one embodiment, the heavy oil feedstock comprises one or more of hydrogenated heavy oil, atmospheric residuum, vacuum residuum, atmospheric wax oil, vacuum wax oil, and crude oil, preferably hydrogenated heavy oil.
In a further embodiment, the conditions of the heavy oil feedstock include: the hydrogen content in the heavy oil raw material is more than 12 weight percent, preferably 12 to 16 weight percent; the carbon residue content is below 4 wt%, preferably 1-4 wt%; the metal (Ni+V) content is 13. Mu.g/g or less, preferably 1 to 13. Mu.g/g.
In this embodiment, when the heavy oil satisfies the above conditions, the heavy oil is directly subjected to catalytic cracking reaction as a heavy oil feedstock; when the heavy oil does not meet the conditions, heavy oil is subjected to heavy oil hydrotreatment, the obtained hydrogenated heavy oil is used as a heavy oil raw material to carry out catalytic cracking reaction, specifically, before the catalytic cracking reaction is carried out, the heavy oil is sent into a heavy oil hydrogenation device to carry out heavy oil hydrotreatment, the hydrogenated heavy oil is obtained, and the obtained hydrogenated heavy oil is used as a heavy oil raw material to carry out subsequent reaction; wherein the reaction conditions for the hydrotreatment include: the temperature is 350-500 ℃, preferably 380-440 ℃; the pressure is 8-25 MPa, preferably 10-20 MPa; the hydrogen oil volume ratio is (300-900): 1, preferably (400 to 800): 1.
in order to separate the reaction materials obtained by the catalytic cracking reaction, a separation device can be arranged in the catalytic cracking device or outside the catalytic cracking device; the separation device may be selected as usual in the art, and is not particularly required in this application, for example, the separation device may comprise one or more of a rectifying device, an absorbing device and an extracting device. In one embodiment of the present disclosure, the separation device comprises a rectifying tower and/or a shallow cold absorption tower, and is used for separating the reaction material obtained by the catalytic cracking reaction to obtain the light olefins, the first aromatic component and the catalytic diesel. Wherein the low-carbon olefin contains olefins having 2 to 3 carbon atoms, such as ethylene and propylene; the first aromatic hydrocarbon component contains hydrocarbon compounds having 6 to 10 carbon atoms, preferably aromatic hydrocarbon compounds having 6 to 8 carbon atoms, such as benzene, toluene and xylene. In addition, the reaction materials obtained by the catalytic cracking reaction are separated to obtain a light hydrocarbon component and naphtha, and the light hydrocarbon component and the naphtha can be used as chemical raw materials of other devices for reaction, wherein the light hydrocarbon component is hydrocarbon compounds with 4-5 carbon atoms.
The catalytic cracking device used in the present disclosure may be selected as conventional in the art, and is not particularly limited in this application, and for example, the catalytic cracking device may include one or more of a fluidized bed reactor, a riser reactor, and a downer reactor. In one embodiment of the present disclosure, the catalytic cracking device comprises one or more of a fast fluidized bed, a riser, and a bubbling bed.
In one embodiment, the reaction conditions of the catalytic cracking reaction include: the reaction temperature is 500-650 ℃, preferably 520-600 ℃; the reaction pressure is 0.05-0.3 MPa, preferably 0.1-0.2 MPa; the reaction time is 0.1 to 20s, preferably 0.5 to 15s. In this embodiment, the catalytic cracking conditions described in the present disclosure can be employed to further increase the yield of low-carbon olefins.
In one embodiment, a catalytic cracking catalyst is used in the catalytic cracking reaction, and the catalytic cracking catalyst includes one or more of zeolite molecular sieve, inorganic oxide and clay, preferably a catalytic cracking catalyst containing ZSM-5 molecular sieve. In this embodiment, the use of a catalytic cracking catalyst can enhance the catalytic cracking reaction activity, further enhancing the yield of lower olefins.
In one embodiment, the reaction conditions of the hydroconversion process comprise: the reaction temperature is 350-450 ℃, preferably 380-420 ℃; the reaction pressure is 3-10 MPa, preferably 6-9 MPa; the reaction time is 0.1 to 5 hours, preferably 0.5 to 2 hours; the hydrogen oil volume ratio is (300-900): 1, preferably (450 to 850): 1.
in this embodiment, the diesel hydro-conversion unit used in the present disclosure may be selected as conventional in the art, and is not particularly required in the present application. The catalytic diesel oil can be further converted into the hydroconversion diesel oil and the second aromatic hydrocarbon component by adopting the reaction conditions and the device for hydroconversion treatment, and the aromatic hydrocarbon content in the product can be further increased. Wherein the second aromatic hydrocarbon component comprises hydrocarbon compounds having 6 to 10 carbon atoms, preferably 6 to 8 aromatic hydrocarbons such as benzene, toluene and xylene.
In one embodiment, the extraction treatment is performed in an extraction column, and the treatment conditions of the extraction treatment include: the temperature is 50-100 ℃, preferably 60-90 ℃; the pressure is 0.1 to 0.4MPa, preferably 0.1 to 0.3MPa. In this embodiment, the first aromatic hydrocarbon component and the second aromatic hydrocarbon component are separated by extraction treatment, so that the aromatic hydrocarbon product can be separated from the aromatic hydrocarbon component, and the content of the aromatic hydrocarbon product can be further increased. In addition, the extraction solvent used in the present disclosure is a conventional extraction solvent in the art, and for example, the solvent for the extraction treatment may be one or more selected from the group consisting of glycol, sulfolane, methylpyrrolidone and dimethylsulfoxide.
In one embodiment, the method further comprises sending the raffinate to a reformer for reforming to obtain a second aromatic hydrocarbon product and hydrogen; returning the hydrogen to a diesel hydro-conversion device; the reaction conditions of the reforming treatment include: the reaction temperature is 500-600 ℃, preferably 500-550 ℃; the reaction pressure is 0.1-0.4 MPa, preferably 0.1-0.25 MPa; the reaction time is 0.1 to 200s, preferably 0.5 to 60s. In this embodiment, the raffinate oil obtained after the extraction treatment is reformed, and the raffinate oil is converted into the second aromatic hydrocarbon product, so that the content of the aromatic hydrocarbon product can be further increased.
In one embodiment, the first aromatic hydrocarbon product and the second aromatic hydrocarbon product obtained by the extraction treatment and the reforming treatment are mixed to be used as aromatic hydrocarbon products, wherein the aromatic hydrocarbon products are hydrocarbon compounds with 6-10 carbon atoms, preferably aromatic hydrocarbons with 6-8 carbon atoms, namely the aromatic hydrocarbon products mainly comprise benzene, toluene and xylene.
In one embodiment, as shown in FIG. 1, a method for producing light olefins and aromatics from heavy oil comprises:
heavy oil is sent into a heavy oil hydrogenation device to carry out heavy oil hydrogenation treatment under the conditions of the temperature of 350-500 ℃ and the pressure of 8-25 MPa, the heavy oil raw material 101 obtained by the hydrogenation treatment is sent into a catalytic cracking device 1 to contact with a catalytic cracking catalyst to carry out catalytic cracking reaction, and ethylene 102, propylene 103, a first aromatic hydrocarbon component 104 and catalytic diesel 105 are obtained, wherein the catalytic cracking temperature is 500-650 ℃ and the pressure is 0.05-0.3 MPa; the catalytic diesel 105 enters a diesel hydro-conversion device 2 to be subjected to hydro-conversion treatment to obtain hydro-converted diesel 107 and a second aromatic hydrocarbon component 106, wherein the hydro-conversion temperature is 350-450 ℃ and the pressure is 3-10 MPa; returning the hydro-converted diesel 107 to the catalytic cracking device 1 for catalytic cracking treatment; respectively feeding the first aromatic hydrocarbon component 104 and the second aromatic hydrocarbon component 106 into an aromatic hydrocarbon extraction device 3 for extraction treatment to obtain raffinate oil 108 and a first aromatic hydrocarbon product 109, wherein the extraction treatment temperature is 50-100 ℃ and the pressure is 0.1-0.4 MPa; the raffinate oil 108 enters the reforming device 4 to be reformed to obtain a second aromatic hydrocarbon product 110, and the first aromatic hydrocarbon product 109 and the second aromatic hydrocarbon product 110 are mixed to be used as aromatic hydrocarbon products, wherein the reforming reaction temperature is 500-600 ℃, and the pressure is 0.1-0.4 MPa.
A second aspect of the present disclosure provides a system for producing light olefins and aromatics from heavy oil, the system comprising: the device comprises a catalytic cracking device, a diesel oil hydro-conversion device and an aromatic hydrocarbon extraction device; the catalytic cracking device comprises a heavy oil raw material inlet, a hydro-conversion diesel inlet, an ethylene outlet, a propylene outlet, a first aromatic hydrocarbon component outlet and a catalytic diesel outlet; the diesel hydro-conversion device comprises a catalytic diesel inlet, a hydrogen inlet, a second aromatic hydrocarbon component outlet and a hydro-conversion diesel outlet; the aromatic hydrocarbon extraction device comprises a first aromatic hydrocarbon component inlet, a second aromatic hydrocarbon component inlet, a first aromatic hydrocarbon product outlet and a raffinate oil outlet; the catalytic diesel outlet of the catalytic cracking device is communicated with the catalytic diesel inlet of the diesel hydro-conversion device, so that the catalytic diesel enters the diesel hydro-conversion device for hydro-conversion treatment; the hydrogenation conversion diesel outlet of the diesel hydrogenation conversion device is communicated with the hydrogenation conversion diesel inlet of the catalytic cracking device and is used for returning catalytic diesel to the catalytic cracking device for catalytic cracking reaction; the second aromatic hydrocarbon component outlet of the diesel hydro-conversion device is communicated with the second aromatic hydrocarbon component inlet of the aromatic hydrocarbon extraction device, so that the second aromatic hydrocarbon component is sent into the aromatic hydrocarbon extraction device for extraction treatment; the first aromatic hydrocarbon component outlet of the catalytic cracking device is communicated with the first aromatic hydrocarbon component inlet of the aromatic hydrocarbon extraction device and is used for sending the first aromatic hydrocarbon component into the aromatic hydrocarbon extraction device for extraction treatment.
In one embodiment, the system further comprises a heavy oil hydrogenation unit comprising a heavy oil inlet, a hydrogen inlet, and a heavy oil feedstock outlet; the heavy oil raw material outlet of the heavy oil hydrogenation device is communicated with the heavy oil raw material inlet of the catalytic cracking device and is used for conveying the heavy oil raw material obtained by the hydrotreatment into the catalytic cracking device.
In one embodiment, the system further comprises a reformer comprising a raffinate oil inlet, a hydrogen outlet, and a second aromatic product outlet; the raffinate oil outlet of the aromatic hydrocarbon extraction device is communicated with the raffinate oil inlet of the reforming device and is used for sending raffinate oil into the reforming device for reforming treatment; the hydrogen outlet of the reforming device is communicated with the hydrogen inlet of the diesel hydro-conversion device and is used for returning the hydrogen separated in the reforming device to the diesel hydro-conversion device.
The following examples further illustrate the invention but are not intended to limit it.
The reagents used hereinafter are all chemically pure reagents unless otherwise specified. The heavy oils selected in example 1 and comparative example 1 described below were each an atmospheric residue having a hydrogen content of 11.5 wt.%, a carbon residue content of 6 wt.%, and a metal (Ni+V) content of 15. Mu.g/g.
Example 1
The system for producing the low-carbon olefin and the aromatic hydrocarbon by the heavy oil shown in fig. 1 is used for producing ethylene, propylene and the aromatic hydrocarbon, and the specific method is as follows:
feeding the atmospheric residuum and hydrogen into a heavy oil hydrogenation device, wherein the volume ratio of the hydrogen to the oil is 700:1, carrying out hydrotreating under the condition of 1 to obtain a heavy oil raw material 101; the resulting heavy oil feedstock 101 had a hydrogen content of 13 wt.%, a carbon residue content of 3.5 wt.%, and a metal (Ni+V) content of 10. Mu.g/g; the heavy oil raw material 101 is sent to a catalytic cracking device 1 to be contacted with a catalytic cracking catalyst containing ZSM-5 molecular sieve for catalytic cracking reaction, so as to obtain catalytic cracking reaction materials, and then the catalytic cracking reaction materials are separated to obtain ethylene 102, propylene 103, a first aromatic hydrocarbon component 104 and catalytic diesel 105. Wherein the reaction temperature of the catalytic cracking reaction is 550 ℃, the pressure is 0.2MPa, and the reaction time is 10s.
The catalytic diesel 105 and hydrogen are sent into a diesel hydro-conversion device 2 for hydro-conversion treatment, and hydro-conversion diesel 107 and a second aromatic hydrocarbon component 106 are obtained after separation, wherein the hydro-conversion temperature is 380 ℃, the pressure is 8MPa, the time is 1.5h, and the volume ratio of hydrogen to oil is 600:1, a step of; returning the hydro-converted diesel 107 to the catalytic cracking device 1 for catalytic cracking treatment; feeding the first aromatic hydrocarbon component 104 and the second aromatic hydrocarbon component 106 into an aromatic hydrocarbon extraction device 3 for extraction treatment to obtain raffinate oil 108 and a first aromatic hydrocarbon product 109, wherein the solvent is sulfolane, the temperature is 80 ℃, and the pressure is 0.25MPa;
the raffinate oil 108 is sent to the reformer 4 for reforming treatment to obtain a second aromatic hydrocarbon product 110, wherein the reforming reaction temperature is 500 ℃, the pressure is 0.15MPa, and the time is 20s. The obtained products and their indexes are shown in Table 1.
Example 2
The method for producing ethylene, propylene and aromatic hydrocarbon by the system for producing light olefins and aromatic hydrocarbon by heavy oil is the same as in example 1, except that the atmospheric residuum is directly fed as heavy oil raw material into a catalytic cracking device for catalytic cracking reaction. The obtained products and their indexes are shown in Table 1.
Example 3
The process for producing ethylene, propylene and aromatics in a system for producing light olefins and aromatics from heavy oil is the same as in example 1, except that the raffinate oil is not subjected to reforming treatment. The obtained products and their indexes are shown in Table 1.
Comparative example 1
The system for producing olefins and aromatics using the heavy oil processing method conventionally employed in the art as shown in FIG. 2 specifically comprises the steps of:
heavy oil enters a heavy oil hydrogenation device to be subjected to heavy oil hydrogenation treatment at 400 ℃ and 16MPa to obtain a heavy oil raw material 101; feeding the heavy oil raw material 101 to a catalytic cracking device 21 to obtain ethylene 150, first liquefied gas 201, catalytic gasoline 202 and catalytic diesel 203, wherein the catalytic cracking temperature is 510 ℃ and the pressure is 0.2MPa;
the first liquefied gas 201 enters a light hydrocarbon separation device 23 to separate propylene 160, propane 205 and carbon four 206; feeding carbon four 206 into an MTBE unit 25 to produce methyl tertiary butyl ether 209 and ether post-carbon four 210;
passing the post-ether carbon number four 210 to an alkylation unit 26 to produce a second liquefied gas 211 and an alkylate 212;
the catalytic gasoline 202 is sent to the hydrofining apparatus 24 to obtain a gasoline component 204;
the catalytic diesel 203 enters the diesel hydrogenation device 22 for treatment to produce a diesel component 207, wherein the diesel hydrogenation reaction temperature is 380 ℃ and the reaction pressure is 10MPa. The obtained products and their indexes are shown in Table 1.
TABLE 1 raw materials and product index
Pouring 1 : the chemical refers to ethylene, propylene and aromatic hydrocarbons.
As can be seen from table 1, by comparing examples 1 to 3 with comparative example 1, the heavy oil processing method of the present disclosure can optimize the product structure, specifically, convert heavy oil raw materials from original productive oil components to chemicals, wherein the chemical compositions are as follows: ethylene, propylene and aromatics, and do not produce oil components; meanwhile, the energy consumption of the chemical product in unit yield of the embodiment 1 of the disclosure is reduced by at least 44.8% compared with that of the chemical product in the comparative example 1, and the energy saving and consumption reduction effects are remarkable. As can be seen from a comparison of the data of example 1 and example 2, when the reaction is performed using a heavy oil feedstock conforming to the standard, the yield of light olefins and the total amount of chemicals can be significantly increased. As can be seen from a comparison of the data of example 1 and example 3, the reforming reaction of the raffinate oil can increase the aromatics production and can increase the total chemicals.
The preferred embodiments of the present disclosure have been described in detail above with reference to the accompanying drawings, but the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solutions of the present disclosure within the scope of the technical concept of the present disclosure, and all the simple modifications belong to the protection scope of the present disclosure.
In addition, the specific features described in the foregoing embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present disclosure does not further describe various possible combinations.
Moreover, any combination between the various embodiments of the present disclosure is possible as long as it does not depart from the spirit of the present disclosure, which should also be construed as the disclosure of the present disclosure.
Claims (10)
1. A method for producing light olefins and aromatics from heavy oil, the method comprising:
enabling the heavy oil raw material to enter a catalytic cracking device to contact a catalytic cracking catalyst for catalytic cracking reaction to obtain ethylene, propylene, a first aromatic hydrocarbon component and catalytic diesel;
sending the catalytic diesel into a diesel hydro-conversion device for hydro-conversion treatment to obtain hydro-converted diesel and a second aromatic hydrocarbon component;
returning the hydro-converted diesel oil to the catalytic cracking device for continuous reaction;
and enabling the first aromatic hydrocarbon component and the second aromatic hydrocarbon component to enter an aromatic hydrocarbon extraction device for extraction treatment to obtain raffinate oil and a first aromatic hydrocarbon product.
2. The method of claim 1, wherein the heavy oil feedstock comprises one or more of hydrogenated heavy oil, atmospheric residuum, vacuum residuum, atmospheric wax oil, vacuum wax oil, and crude oil;
the first aromatic hydrocarbon component comprises hydrocarbon compounds with 6-10 carbon atoms;
the second aromatic hydrocarbon component comprises a hydrocarbon compound having 6 to 10 carbon atoms.
3. The method according to claim 1, wherein the heavy oil feedstock has a hydrogen content of 12 wt.% or more, a carbon residue content of 4 wt.% or less, and a metal (ni+v) content of 13 μg/g or less.
4. The method according to claim 1, wherein the reaction conditions of the catalytic cracking reaction comprise: the reaction temperature is 500-650 ℃, the reaction pressure is 0.05-0.3 MPa, and the reaction time is 0.1-20 s;
the catalytic cracking catalyst comprises one or more of zeolite molecular sieve, inorganic oxide and clay.
5. The process of claim 1, wherein the reaction conditions of the hydroconversion process comprise: the reaction temperature is 350-450 ℃, the reaction pressure is 3-10 MPa, the reaction time is 0.1-5 h, and the hydrogen-oil volume ratio is (300-900): 1.
6. the method of claim 1 further comprising, prior to conducting the catalytic cracking reaction, feeding the heavy oil to a heavy oil hydrotreater for heavy oil hydrotreatment to obtain the heavy oil feedstock;
the reaction conditions for the heavy oil hydrotreatment include: the temperature is 350-500 ℃, the pressure is 8-25 MPa, and the hydrogen-oil volume ratio is (300-900): 1.
7. the process of claim 1 further comprising sending the raffinate to a reformer for reforming to produce a second aromatic product and hydrogen; returning the hydrogen to the diesel hydroconversion unit;
the reaction conditions of the reforming treatment include: the reaction temperature is 500-600 ℃, the reaction pressure is 0.1-0.4 MPa, and the reaction time is 0.1-200 s.
8. A system for producing light olefins and aromatics from heavy oil, the system comprising: the device comprises a catalytic cracking device, a diesel oil hydro-conversion device and an aromatic hydrocarbon extraction device;
the catalytic cracking device comprises a heavy oil raw material inlet, a hydro-conversion diesel inlet, an ethylene outlet, a propylene outlet, a first aromatic hydrocarbon component outlet and a catalytic diesel outlet;
the diesel hydro-conversion device comprises a catalytic diesel inlet, a hydrogen inlet, a second aromatic hydrocarbon component outlet and a hydro-conversion diesel outlet;
the aromatic hydrocarbon extraction device comprises a first aromatic hydrocarbon component inlet, a second aromatic hydrocarbon component inlet, a first aromatic hydrocarbon product outlet and a raffinate oil outlet;
the catalytic diesel outlet of the catalytic cracking device is communicated with the catalytic diesel inlet of the diesel hydro-conversion device; the hydroconversion diesel outlet of the diesel hydroconversion device is communicated with the hydroconversion diesel inlet of the catalytic cracking device; the second aromatic hydrocarbon component outlet of the diesel hydro-conversion device is communicated with the second aromatic hydrocarbon component inlet of the aromatic hydrocarbon extraction device, and the first aromatic hydrocarbon component outlet of the catalytic cracking device is communicated with the first aromatic hydrocarbon component inlet of the aromatic hydrocarbon extraction device.
9. The system of claim 8, further comprising a heavy oil hydrogenation unit comprising a heavy oil inlet, a hydrogen inlet, and a heavy oil feedstock outlet; the heavy oil raw material outlet of the heavy oil hydrogenation device is communicated with the heavy oil raw material inlet of the catalytic cracking device.
10. The system of claim 8, further comprising a reformer comprising a raffinate oil inlet, a hydrogen outlet, and a second aromatic product outlet;
the raffinate oil outlet of the aromatic hydrocarbon extraction device is communicated with the raffinate oil inlet of the reforming device;
the hydrogen outlet of the reforming device is communicated with the hydrogen inlet of the diesel hydro-conversion device.
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