CN116240049B - Processing method for producing low-carbon olefin and light aromatic hydrocarbon from crude oil - Google Patents
Processing method for producing low-carbon olefin and light aromatic hydrocarbon from crude oil Download PDFInfo
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 title claims abstract description 93
- 239000010779 crude oil Substances 0.000 title claims abstract description 89
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 74
- 238000003672 processing method Methods 0.000 title description 16
- 239000003921 oil Substances 0.000 claims abstract description 140
- 238000006243 chemical reaction Methods 0.000 claims abstract description 118
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 95
- 238000005336 cracking Methods 0.000 claims abstract description 82
- 238000000034 method Methods 0.000 claims abstract description 69
- 238000000926 separation method Methods 0.000 claims abstract description 65
- 238000004230 steam cracking Methods 0.000 claims abstract description 51
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 38
- 238000001704 evaporation Methods 0.000 claims abstract description 32
- 230000008020 evaporation Effects 0.000 claims abstract description 32
- 238000011033 desalting Methods 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims description 134
- 239000003502 gasoline Substances 0.000 claims description 89
- 239000000047 product Substances 0.000 claims description 80
- 150000001336 alkenes Chemical class 0.000 claims description 70
- 230000008569 process Effects 0.000 claims description 58
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 50
- 239000005977 Ethylene Substances 0.000 claims description 50
- 239000002808 molecular sieve Substances 0.000 claims description 45
- 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 45
- 239000006227 byproduct Substances 0.000 claims description 39
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 38
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 38
- 239000003054 catalyst Substances 0.000 claims description 33
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 25
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 25
- 239000001273 butane Substances 0.000 claims description 23
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 23
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 23
- 238000007233 catalytic pyrolysis Methods 0.000 claims description 21
- 238000005194 fractionation Methods 0.000 claims description 21
- 238000000197 pyrolysis Methods 0.000 claims description 20
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 16
- -1 propylene, butylene Chemical group 0.000 claims description 16
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 9
- 238000002352 steam pyrolysis Methods 0.000 claims description 9
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 8
- 239000001294 propane Substances 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910001868 water Inorganic materials 0.000 claims description 5
- 238000003776 cleavage reaction Methods 0.000 claims description 4
- 238000005243 fluidization Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000011069 regeneration method Methods 0.000 claims description 2
- 230000007017 scission Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 38
- 239000002994 raw material Substances 0.000 abstract description 28
- 238000012545 processing Methods 0.000 abstract description 14
- 238000009826 distribution Methods 0.000 description 42
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 238000011112 process operation Methods 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 9
- 239000003208 petroleum Substances 0.000 description 9
- 239000008096 xylene Substances 0.000 description 9
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 125000003118 aryl group Chemical group 0.000 description 8
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 8
- 239000000295 fuel oil Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 229910052723 transition metal Inorganic materials 0.000 description 8
- 238000005265 energy consumption Methods 0.000 description 7
- 238000007670 refining Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000005292 vacuum distillation Methods 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000000571 coke Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910052746 lanthanum Inorganic materials 0.000 description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 241000269435 Rana <genus> Species 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000003616 anti-epidemic effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003209 petroleum derivative Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000007701 flash-distillation Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 238000007348 radical reaction Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 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
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/04—Thermal processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The method takes whole crude oil as raw material, carries out desalting and dewatering pretreatment, carries out flash evaporation separation to light naphtha and heavy distillate oil after heat exchange with a high-temperature heat exchange medium, and utilizes a catalytic cracking unit, a steam cracking unit, a fixed bed catalytic cracking unit, a hydrocracking and product separation unit, preferably raw materials suitable for cracking and cracking, and the property composition of the cracking and cracking raw materials is highly matched with products such as low-carbon olefin, light aromatic hydrocarbon and the like in molecular structure, thereby realizing deep cracking and cracking conversion of light and heavy fractions and achieving the aims of low processing cost and high yield of the low-carbon olefin and the light aromatic hydrocarbon.
Description
Technical Field
The invention relates to the field of petroleum processing, in particular to a processing method for producing low-carbon olefin and light aromatic hydrocarbon from crude oil.
Background
The demands of light aromatic hydrocarbon which mainly comprises low-carbon olefin and benzene, toluene and xylene and mainly comprises ethylene, propylene and butylene are important basic organic chemical raw materials, and the demands of the light aromatic hydrocarbon are always kept to be high-speed growing. Therefore, the production of low-carbon olefin and light aromatic hydrocarbon from crude oil becomes a main development trend of transformation upgrading, quality improvement and efficiency enhancement of petroleum refining enterprises.
The traditional refinery processing flow mainly comprises devices such as atmospheric and vacuum pressure, catalytic cracking, delayed coking, gasoline and diesel hydrogenation, and the like, has small processing depth and breadth for crude oil, and mainly comprises fuel oil such as gasoline, kerosene, diesel oil and the like. The yield of the basic chemical raw materials such as low-carbon olefin, light aromatic hydrocarbon and the like of the fuel type refinery is about 10 percent by adopting the traditional petroleum processing process flow, and the yield of the basic chemical raw materials directly prepared from crude oil is more than 40 percent, thereby bringing great economic benefit and strong enterprise competitiveness.
CN101253254a discloses a process for producing olefins using whole crude oil feedstock, which is mainly directed to using whole crude oil as feedstock for a steam cracker, preheating crude oil and separating light and heavy petroleum fractions in a conventional steam cracker with little or no coke formation, steam cracking the light fraction to produce light olefins, and discharging the heavy fraction from the cracker together with residuum produced by the cracking.
CN111116286a discloses a method and apparatus for preparing low-carbon olefin from petroleum hydrocarbon, which is mainly optimized for the feeding of steam cracking apparatus, the method includes using a cyclone separating apparatus to separate gasified petroleum hydrocarbon into vapor phase and liquid phase under reduced pressure, the vapor phase entering the steam cracking apparatus to produce low-carbon olefin, thereby realizing improvement of cracking efficiency of petroleum hydrocarbon raw material and reduction of coking of heavy raw material in cracking furnace.
CN111196936a discloses a combined method and device for directly producing olefin from crude oil, firstly adopting pretreatment such as desalting and dewatering to remove water, metal and non-metal impurities in the feed, then sending the improved crude oil into a pyrolysis furnace convection section of a steam pyrolysis device to heat and enter a gas-liquid separator to separate light fraction from heavy fraction, wherein diesel oil and lighter petroleum fraction are sent into the pyrolysis furnace to make steam pyrolysis reaction to produce low-carbon olefin, the liquid heavy fraction separated by the gas-liquid separator is sent into a hydrogenation unit to be further cracked, and hydrogenated tail oil and light petroleum oil produced by cracking are further sent into the pyrolysis furnace to make steam pyrolysis reaction to produce low-carbon olefin. The combined method of steam cracking and hydrocracking can maximally produce low-carbon olefin.
The method has the greatest characteristics that oil refining devices such as atmospheric and vacuum distillation and the like of a traditional refinery are omitted, crude oil is directly supplied to a steam cracking device, components of crude oil and gas are separated, gaseous light fraction enters a steam cracking radiation section for cracking, and liquid heavy fraction is used as raw material of other devices of the refinery, so that the method has the advantages of simplifying process flow, saving construction investment and reducing raw material cost to a certain extent. However, the patent methods have higher requirements on the quality of crude oil, require that the crude oil contains more light fractions, and easily coke on the inner wall of a pipeline and a gas-liquid separator when the heavy fractions are too much; the cracking temperature of the steam cracking device is up to more than 800 ℃, and the heating and cracking of crude oil by using the preheating section and the radiation section lead to high energy consumption of the unit. In addition, the steam cracking device takes light alkane, naphtha, light oil and other petroleum hydrocarbons as raw materials, the temperature is above 800 ℃ (generally not more than 950 ℃), and in the presence of steam, molecular fracture and dehydrogenation reactions occur by utilizing high-temperature pyrolysis reaction, and the steam cracking device takes a free radical reaction mechanism as the main part.
In order to improve the yield of the low-carbon olefin in the traditional refinery, china petrochemical industry develops a series of heavy oil catalytic cracking technologies, such as processes of DCC (CN 1004878, CN 1034586), CPP (CN 1030326, CN 1159416), HCC (CN 1030313, CN 1215041) and the like, and can process heavy distillate oil obtained by atmospheric and vacuum distillation of crude oil. The reaction temperature of the heavy oil catalytic cracking process is 150-200 ℃ lower than the steam cracking temperature, the energy consumption is lower than that of steam cracking, and the catalyst used by the process has double catalytic activities of a positive carbon ion reaction mechanism and a free radical reaction mechanism, and has higher low-carbon olefin yield. However, because the heavy oil obtained by the atmospheric and vacuum distillation unit is used as a processing raw material, when the heavy oil conversion rate in the DCC process is high, the low-value dry gas and coke yield is also high; CPP technology has the problem that the yield of ethylene and low-value product methane are increased simultaneously; the HCC reaction mechanism is mainly a free radical mechanism, the reaction temperature is higher, the heat balance requirement is difficult to meet only by burning the regenerated catalyst, and the energy consumption is higher than that of a common catalytic cracking process. Therefore, in order to further increase the low-carbon olefins, it is necessary to change the current state of the catalytic cracking process, which is currently mainly processing heavy oil raw materials.
The high-energy consumption devices such as atmospheric and vacuum distillation and the like can be omitted from directly preparing the basic chemical raw materials from crude oil, so that the whole refinery process is short, the energy consumption is low, the construction investment can be saved, and the raw material cost can be reduced; the challenges faced in directly processing crude oil are that heavy fraction in crude oil is difficult to vaporize, fuel oil yield in primary cracking products is high, catalyst deactivation is fast, and dry gas and coke yield is high. The current refinery product mode is changed from the main production of distillate products such as gasoline, aviation kerosene and diesel oil to the main production of molecular products such as light olefins and light aromatics, when the main products are changed, the crude oil atmospheric and vacuum distillation unit for the distillate products are required to be simplified, the separation unit for the molecular products is required to be emphasized, more raw materials suitable for cracking are selected to increase the reaction conversion depth, the fuel yield is reduced, the yields of the light olefins and the light aromatics are increased at the same time, and the existing public patents show that the patents for directly producing the light olefins and the light aromatics from the crude oil are fewer, so that no suitable comprehensive processing technology exists at present.
Disclosure of Invention
The invention aims to provide a processing method for producing low-carbon olefin and light aromatic hydrocarbon from crude oil, which aims to solve the problems that heavy fraction in crude oil is difficult to vaporize, fuel oil yield in a primary cracking product is high, catalyst deactivation is fast, dry gas and coke yield are high and the like when crude oil is directly processed in the prior art.
In order to achieve the above object, the present invention provides a processing method for producing light olefins and light aromatics from crude oil, comprising the steps of:
Step one: crude oil enters a desalting and dewatering pretreatment unit and exchanges heat with a high-temperature heat exchange medium after being desalted and dewatered;
step two: the crude oil enters a flash evaporation unit to be separated into light naphtha and heavy distillate after heat exchange and temperature rise;
step three: sending the light naphtha obtained after flash evaporation in the second step into a steam cracking unit for reaction to produce light olefins and light aromatics and byproduct dry gas;
Step four: sending the heavy distillate oil obtained after the flash evaporation in the second step into a catalytic cracking unit, and sending the heavy distillate oil into a cracking reactor for cracking reaction; the reacted oil gas enters an oil gas fractionation device of a catalytic cracking unit and is separated into dry gas, liquefied gas, pyrolysis gasoline, recycle oil and slurry oil;
step five: separating main product ethylene, byproduct hydrogen, methane and ethane from the dry gas obtained in the step four through a dry gas separation unit;
Step six: separating the liquefied gas obtained in the step four into main products of propylene, butylene, byproducts of propane and butane through a liquefied gas separation unit, further sending the butane into a steam cracking unit for reaction to produce low-carbon olefin, and further sending the byproduct of dry gas, and further sending the butylene into a fixed bed catalytic cracking unit for reaction to produce ethylene and propylene;
Step seven: separating the main product light aromatic hydrocarbon, alkane-rich gasoline and olefin-rich gasoline from the pyrolysis gasoline obtained in the step four through a gasoline separation unit, further sending the alkane-rich gasoline into a steam pyrolysis unit for reaction to produce light olefins and light aromatic hydrocarbon, and further sending the olefin-rich gasoline back into a fixed bed catalytic pyrolysis unit for reaction to produce light olefins and byproduct high-octane gasoline;
Step eight: separating saturated hydrocarbon-rich distillate and aromatic hydrocarbon-rich distillate from the cycle oil obtained in the step four through a cycle oil separation unit; the saturated hydrocarbon-rich distillate oil is further sent back to the catalytic cracking unit to react with the heavy distillate oil obtained after flash evaporation in the cracking reactor to produce low-carbon olefin and light aromatic hydrocarbon, and the aromatic hydrocarbon-rich distillate oil enters the hydrocracking unit to be subjected to hydrocracking conversion to produce light aromatic hydrocarbon, and byproducts of dry gas and liquefied gas.
The invention relates to a processing method for producing light olefins and light aromatics from crude oil, wherein the characteristic factor of the crude oil is 11.5-13.0, preferably 12.0-12.7, and the mass of a fraction of the crude oil at a temperature of less than 200 ℃ is more than 10wt%.
The processing method for producing light olefins and light aromatics from crude oil, disclosed by the invention, has the advantages that the water content of the crude oil is less than 0.5wt% after the crude oil passes through a desalting and dehydrating unit, and the salt content is less than 0.3mg/L.
The processing method for producing low-carbon olefin and light aromatic hydrocarbon from crude oil, disclosed by the invention, comprises the step of carrying out heat exchange on desalted and dehydrated crude oil by a heat exchange medium to reach 220-300 ℃.
The invention relates to a processing method for producing low-carbon olefin and light aromatic hydrocarbon from crude oil, wherein the heat exchange medium is high-temperature pyrolysis oil gas of a catalytic pyrolysis unit.
The invention relates to a processing method for producing light olefins and light aromatic hydrocarbons from crude oil, wherein the distillation range of light naphtha obtained after flash evaporation is from an initial distillation point to 240 ℃, and the distillation range of heavy distillate oil obtained is fraction higher than 240 ℃.
The invention relates to a processing method for producing light olefins and light aromatics from crude oil, wherein the reaction conditions of a steam cracking unit comprise: the reaction temperature is 800-950 ℃, the water-oil ratio is 0.3-0.8, the reaction time is 0.05-2.0 s, and the reaction pressure is 0.12-0.25 MPa.
The invention relates to a processing method for producing light olefins and light aromatic hydrocarbons from crude oil, wherein heavy distillate oil obtained after flash evaporation is subjected to cracking reaction in the presence of a cracking catalyst to obtain cracking oil gas; the cracking catalyst is a composite catalyst formed by mixing a metal modified FAU type molecular sieve, an MFI molecular sieve and an MTT molecular sieve.
The silicon-aluminum molar ratio of the FAU type molecular sieve is 6-12; the silicon-aluminum molar ratio of the MFI molecular sieve is 30-200; the molar ratio of molecular sieve to silicon to aluminum of MTT is 30-100. The mass ratio of the FAU molecular sieve to the MFI molecular sieve to the MTT molecular sieve in the composite catalyst is (1-2): 10: (0-3).
The metal used for the FAU type molecular sieve modification is a rare earth element conventionally added in the art, and specifically can be, for example, lanthanoid elements, specifically can be, for example, selected from La (lanthanum), ce (cerium), pr (praseodymium), nd (neodymium), pm (promethium), sm (samarium), and Eu (europium); preferably, the rare earth in the composite catalyst is selected from lanthanum.
The elements used for modifying the MFI type molecular sieve are nonmetallic elements, alkaline earth elements and transition metal elements which are added conventionally in the field, wherein the nonmetallic elements can be phosphorus elements; the alkaline earth element may Be selected from Be (beryllium), mg (magnesium), ca (calcium), sr (strontium), ba (barium), for example, preferably the alkaline earth element in the composite catalyst is selected from Mg; the transition metal element may be a group ib, iib, ivb, viib, or viib element, and may specifically be selected from Ti (titanium), mn (manganese), fe (iron), co (cobalt), ni (nickel), cu (copper), zn (zinc), for example, and preferably, the transition metal element in the composite catalyst is selected from one or two of the above transition metals.
The elements used for modifying the MTT type molecular sieve are nonmetallic elements and transition metal elements which are added conventionally in the field, wherein the nonmetallic elements can be phosphorus elements; the transition metal element may be a group ib, iib, ivb, viib, or viib element, and may specifically be selected from Ti (titanium), mn (manganese), fe (iron), co (cobalt), ni (nickel), cu (copper), zn (zinc), for example, and preferably, the transition metal element in the composite catalyst is selected from one or two of the above transition metals.
The cracking catalyst is fluidized and circulated back and forth between the cracking reactor and the catalyst regenerator, participates in the reaction in the cracking reactor, and enters the catalyst regenerator to be burnt for recovering the activity after the activity is reduced.
The invention relates to a processing method for producing light olefins and light aromatic hydrocarbons from crude oil, wherein the catalytic cracking unit is a continuous reaction-regeneration catalytic cracking device and comprises a cracking reactor, a catalyst regenerator and an oil gas fractionation device; the cracking reactor is a gas-solid fluidization type reactor combining a conveying bed with a fast bed or a turbulent bed.
The invention relates to a processing method for producing light olefins and light aromatics from crude oil, wherein the reaction conditions of a fixed bed catalytic cracking unit comprise: the reaction temperature is 530-650 ℃, the water-oil ratio is 0.2-0.5, the weight hourly space velocity is 10-30 h -1, and the reaction pressure is 0.10-0.20 MPa.
The invention relates to a processing method for producing light olefins and light aromatics from crude oil, wherein the reaction conditions of a cracking reactor comprise: the reaction temperature is 530-650 ℃, the catalyst-oil ratio is 10-40, the water-oil ratio is 0.2-0.4, the reaction time is 2-8 s, and the reaction pressure is 0.1-0.25 MPa.
The invention relates to a processing method for producing light olefins and light aromatics from crude oil, wherein the reaction conditions of a hydrocracking unit comprise: the reaction temperature is 300-450 ℃, the hydrogen-oil volume ratio is 700-1500, the weight hourly space velocity is 0.6-2.0 h -1, and the reaction pressure is 3.0-10.0 MPa.
The beneficial effects of the invention are as follows:
the method takes whole crude oil as raw material, carries out desalting and dewatering pretreatment, carries out flash evaporation separation to obtain light naphtha and heavy distillate oil after heat exchange with a high-temperature heat exchange medium, utilizes a catalytic cracking unit, a steam cracking unit, a fixed bed catalytic cracking unit, a hydrocracking unit and a product separation unit to preferably select raw materials suitable for cracking and cracking, and highly matches the property composition of the cracking and cracking raw materials with products such as low-carbon olefin, light aromatic hydrocarbon and the like in molecular structure, thereby realizing deep cracking and cracking conversion of the light and heavy distillate, and achieving the aims of low processing cost and high yield of the low-carbon olefin and the light aromatic hydrocarbon.
(1) The simple flash evaporation unit is used for replacing a complex and high-energy-consumption atmospheric and vacuum distillation unit of a conventional refinery, so that the whole crude oil processing flow is short, the energy consumption is low, and the construction investment is saved.
(2) The light naphtha is processed by utilizing a steam cracking unit, and butane and alkane-rich gasoline which are sent out from a separation unit and have high molecular bond energy and are difficult to crack are utilized to effectively crack alkane in light fraction, so that the yield of low-carbon olefin is improved;
(3) The catalytic cracking unit with the circulating fluidization type reactor has strong adaptability to raw materials, high catalytic activity, low operation cost and high yield of low-carbon olefin, and can efficiently crack heavy hydrocarbon.
(4) The method utilizes product separation units such as dry gas, liquefied gas, pyrolysis gasoline, recycle oil and the like to realize the accurate separation of molecular products such as low-carbon olefin, light aromatic hydrocarbon and the like, separates further convertible hydrocarbon according to a molecular structure, and sends the separated hydrocarbon into a proper processing unit for deep pyrolysis and cracking conversion, thereby improving the yields of the low-carbon olefin and the light aromatic hydrocarbon.
(5) And (3) recycling and converting the olefin-rich gasoline in the pyrolysis gasoline and the saturated hydrocarbon-rich fraction in the recycle oil sent out by the separation unit by utilizing the catalytic pyrolysis unit, so as to improve the conversion rate of crude oil and increase the yields of low-carbon olefin and light aromatic hydrocarbon.
(6) The fixed bed catalytic cracking unit is utilized to carry out deep conversion on the olefin-rich gasoline and the butene in the pyrolysis gasoline sent out by the separation unit, so as to realize the aim of producing the low-carbon olefin by taking the micromolecular olefin as the raw material.
(7) The hydrocracking unit is utilized to carry out hydroconversion on aromatic hydrocarbon in the recycle oil, the hydrogenation depth is controlled, and the aim of producing light aromatic hydrocarbon by taking polycyclic aromatic hydrocarbon as a raw material is fulfilled.
(8) The four reaction process units are separated and combined with products, so that the maximum production of basic chemical raw materials such as low-carbon olefin, light aromatic hydrocarbon and the like of crude oil can be realized, 40-65wt% of low-carbon olefin (ethylene, propylene and butylene) and 8-25wt% of light aromatic hydrocarbon (benzene, toluene and xylene) can be obtained through the processing of the combined process, and a conventional refinery can only produce about 20wt% of basic chemical raw materials such as low-carbon olefin, light aromatic hydrocarbon and the like.
Drawings
Fig. 1 is a schematic process flow diagram of embodiment 1 of the present invention.
Wherein, the reference numerals:
1. 36, 8, 9, 11, 13, 15, 17, 18, 19, 20, 22, 24, 26, 27, 28, 29 lines
2 Desalination and dehydration pretreatment unit
4 Heat exchange unit
5 Cracking reactor
7 Oil gas fractionation device
10 Dry gas separation unit
12 Liquefied gas separation unit
14 Steam cracking unit
16 Gasoline separation unit
21 Cycle oil separation unit
23 Hydrocracking unit
25 Flash unit
27 Fixed bed catalytic cracking unit
Detailed Description
The present invention will be specifically described below by way of examples. It is noted herein that the following examples are given solely for the purpose of illustration and are not to be construed as limiting the scope of the invention, as many insubstantial modifications and variations of the invention will become apparent to those skilled in the art in light of the above disclosure.
A process for producing light olefins and light aromatics from crude oil comprising: the crude oil enters a desalting and dewatering pretreatment unit, after desalting and dewatering, the crude oil exchanges heat with a heat exchange medium in a heat exchange unit to raise the temperature, and then enters a flash evaporation unit to be separated into light naphtha and heavy distillate; the light naphtha obtained after flash evaporation is sent into a steam cracking unit for reaction to produce low-carbon olefin and light aromatic hydrocarbon, and a small part of byproduct dry gas is produced; sending the heavy fraction oil obtained after flash evaporation into a catalytic cracking unit, sending the heavy fraction oil into a cracking reactor for cracking reaction, and sending the reacted oil gas into an oil gas fractionation device of the catalytic cracking unit for separation into dry gas, liquefied gas, pyrolysis gasoline, recycle oil and slurry oil; the dry gas is separated into main product ethylene, byproduct hydrogen, methane and ethane through a dry gas separation unit; the liquefied gas passes through a liquefied gas separation unit to separate main products of propylene, butylene and byproducts of propane and butane, and the butane is further sent into a steam cracking unit to react to produce low-carbon olefin, and a small part of byproduct of dry gas is produced; the butene separated by the liquefied gas separation unit is further sent to a fixed bed catalytic cracking unit for reaction to produce ethylene and propylene; the pyrolysis gasoline passes through a gasoline separation unit to separate main products, namely light aromatic hydrocarbon, alkane-rich gasoline and olefin-rich gasoline, wherein the alkane-rich gasoline is further sent to a steam pyrolysis unit to react to produce light olefins and light aromatic hydrocarbon, and the olefin-rich gasoline is further sent to a fixed bed catalytic pyrolysis unit to react to produce light olefins and a small amount of high-octane gasoline as a byproduct; the recycle oil is subjected to a recycle oil separation unit to separate saturated hydrocarbon-rich distillate and aromatic hydrocarbon-rich distillate; the saturated hydrocarbon-rich distillate oil is further sent back to a cracking reactor of a catalytic cracking unit for reaction to produce low-carbon olefin and light aromatic hydrocarbon, and the aromatic hydrocarbon-rich distillate oil enters a hydrocracking unit for hydrocracking and conversion to produce light aromatic hydrocarbon, and a small part of byproduct dry gas and liquefied gas are produced. For crude oil with characteristic factors of 11.5-13.0 (preferably 12.0-12.7), 40-65wt% of low-carbon olefin (ethylene, propylene and butylene) and 8-25wt% of light aromatic hydrocarbon (benzene, toluene and xylene) can be obtained through the processing of the combined process, so that the maximum production of basic organic chemical raw materials is realized.
More specifically, the method comprises the steps of:
(1) The crude oil enters a desalting and dewatering pretreatment unit, the water content of the desalted and dewatered crude oil is less than 0.5wt percent, the salt content is less than 0.3mg/L, and the crude oil is sent to a heat exchange unit;
(2) The desalted and dehydrated crude oil enters a heat exchange unit to exchange heat with high-temperature pyrolysis oil gas serving as a heat exchange medium of a catalytic cracking unit, and the temperature reaches 220-300 ℃ after heat exchange;
(3) The crude oil enters a flash evaporation unit to be separated into light naphtha and heavy distillate after heat exchange and temperature rise;
(4) The light naphtha obtained after flash evaporation is further sent into a steam cracking unit for reaction to produce low-carbon olefin and light aromatic hydrocarbon; the reaction conditions of the steam cracking unit include: the reaction temperature is 800-950 ℃ (preferably 820-900 ℃), the water-oil ratio is 0.3-0.8 (preferably 0.4-0.7), the reaction time is 0.05-2.0 s (preferably 0.2-0.4 s), and the reaction pressure is 0.12-0.25 MPa (preferably 0.15-0.23 MPa);
(2) Sending the heavy distillate oil obtained after flash evaporation into a catalytic cracking unit, and sending the heavy distillate oil into a gas-solid fluidization type cracking reactor for cracking reaction, wherein the reaction conditions of the cracking reactor are as follows: the reaction temperature is 530-650 ℃ (preferably 550-600 ℃), the catalyst-oil ratio is 10-40 (preferably 10-20), the water-oil ratio is 0.2-0.4 (preferably 0.3-0.4), the reaction time is 2-8 s (preferably 4-6 s), the reaction pressure is 0.1-0.25 MPa (preferably 0.12-0.20 MPa), and the oil gas after the cracking reaction enters an oil gas fractionation device of a catalytic cracking unit and is separated into dry gas, liquefied gas, cracked gasoline, recycle oil and slurry oil;
(3) Dry gas from the oil gas fractionation device of the catalytic cracking unit enters a dry gas separation unit to separate main product ethylene and byproducts hydrogen, methane and ethane;
(4) The liquefied gas from the oil gas fractionation device of the catalytic cracking unit is separated into main products of propylene, butylene, byproducts of propane and butane through a liquefied gas separation unit, and the butane is further sent into a steam cracking unit for reaction to produce low-carbon olefin, wherein the reaction conditions are as follows: the reaction temperature is 800-950 ℃ (preferably 820-900 ℃), the water-oil ratio is 0.3-0.8 (preferably 0.4-0.7), the reaction time is 0.05-2.0 s (preferably 0.2-0.4 s), and the reaction pressure is 0.12-0.25 MPa (preferably 0.15-0.23 MPa); the butene separated by the liquefied gas separation unit is further sent to a fixed bed catalytic cracking unit for reaction to produce ethylene and propylene; the reaction conditions of the fixed bed catalytic cracking unit include: the reaction temperature is 530-650 ℃ (preferably 540-600 ℃), the water-oil ratio is 0.2-0.5 (preferably 0.3-0.4), the weight hourly space velocity is 10-30 h -1 (preferably 15-25), and the reaction pressure is 0.10-0.20 MPa (preferably 0.10-0.15 MPa).
(5) The pyrolysis gasoline from the oil gas fractionation device of the catalytic pyrolysis unit passes through a gasoline separation unit to separate main products, namely light aromatic hydrocarbon, alkane-rich gasoline and olefin-rich gasoline; the alkane-rich gasoline is further sent into a steam cracking unit for reaction to produce light olefins and light aromatic hydrocarbons, and the reaction conditions are as follows: the reaction temperature is 800-950 ℃ (preferably 820-900 ℃), the water-oil ratio is 0.3-0.8 (preferably 0.4-0.7), the reaction time is 0.05-2.0 s (preferably 0.2-0.4 s), and the reaction pressure is 0.12-0.25 MPa (preferably 0.15-0.23 MPa); the olefin-rich gasoline is further sent into a fixed bed catalytic cracking unit for reaction to produce low-carbon olefin and a small amount of high-octane gasoline as a byproduct; the reaction conditions of the fixed bed catalytic cracking unit include: the reaction temperature is 530-650 ℃ (preferably 540-600 ℃), the water-oil ratio is 0.2-0.5 (preferably 0.3-0.4), the weight hourly space velocity is 10-30 h -1 (preferably 15-25), and the reaction pressure is 0.10-0.20 MPa (preferably 0.10-0.15 MPa).
(6) The recycle oil from the oil gas fractionation device of the catalytic cracking unit passes through a recycle oil separation unit, and the separated saturated hydrocarbon-rich fraction and aromatic hydrocarbon-rich fraction are further sent back to the catalytic cracking unit and mixed with heavy fraction oil to enter a cracking reactor for reaction; the reaction conditions of the cracking reactor are as follows: the reaction temperature is 530-650 ℃ (preferably 550-600 ℃), the catalyst-oil ratio is 10-40 (preferably 10-20), the water-oil ratio is 0.2-0.4 (preferably 0.3-0.4), the reaction time is 2-8 s (preferably 4-6 s), and the reaction pressure is 0.1-0.25 MPa (preferably 0.12-0.20 MPa).
(7) The aromatic-rich fraction obtained by the recycle oil separation unit enters a hydrocracking unit for hydrocracking and converting to produce light aromatic, and a small part of byproduct dry gas and liquefied gas are produced; the reaction conditions of the hydrocracking unit include: the reaction temperature is 300-450 ℃ (preferably 340-400 ℃), the hydrogen-oil volume ratio is 700-1500 (preferably 800-1200), the weight hourly space velocity is 0.6-2.0 h -1 (preferably 0.8-1.5 h -1), and the reaction pressure is 3.0-10.0 MPa (preferably 4-8 MPa).
Example 1
The crude oil enters a desalting and dewatering pretreatment unit 2 through a pipeline 1, the water content after desalting and dewatering is less than 0.5wt%, the salt content is less than 0.3mg/L, the crude oil enters a heat exchange unit 4 through a pipeline 3 to exchange heat with a heat exchange medium, the temperature reaches 220-300 ℃ after heat exchange, and the crude oil enters a flash evaporation unit 25 to be separated into light naphtha (initial distillation point-240 ℃) and heavy distillate oil (> 240 ℃); the light naphtha obtained after flash evaporation is further sent into a steam cracking unit 14 through a pipeline 26 to react to produce light olefins and light aromatics, and a small amount of byproduct dry gas is produced; the heavy distillate oil obtained after flash evaporation enters a cracking reactor 5 of a catalytic cracking unit through a pipeline 28 for cracking reaction, the reacted oil gas enters an oil gas fractionation device 7 of the catalytic cracking unit through a pipeline 6 and is separated into dry gas, liquefied gas, pyrolysis gasoline, recycle oil and slurry oil, and the slurry oil is sent out of the device through a pipeline 8; the dry gas enters a dry gas separation unit 10 through a pipeline 9 to separate main product ethylene and byproducts hydrogen, methane and ethane; the liquefied gas is separated into main products of propylene, butylene, byproducts of propane and butane by a liquefied gas separation unit 12 through a pipeline 11, and the butane is further sent into a steam cracking unit 14 through a pipeline 13 to react to produce low-carbon olefin, and a small part of byproduct of dry gas is produced; the butene is further sent to a fixed bed catalytic cracking unit 27 for reaction to produce ethylene and propylene through a pipeline 29; the pyrolysis gasoline enters a gasoline separation unit 16 through a pipeline 15 to separate main products of light aromatic hydrocarbon, alkane-rich gasoline and olefin-rich gasoline, the light aromatic hydrocarbon is sent out of the device through a pipeline 19, the alkane-rich gasoline is further sent into a steam cracking unit 14 through a pipeline 17 to react to produce low-carbon olefin and light aromatic hydrocarbon, and the olefin-rich gasoline is further sent into a fixed bed catalytic cracking unit 27 through a pipeline 18 to react to produce ethylene, propylene and a small amount of high-octane gasoline; the recycle oil enters a recycle oil separation unit 21 through a pipeline 20 to separate saturated hydrocarbon-rich distillate and aromatic hydrocarbon-rich distillate; the saturated hydrocarbon-rich distillate oil is further sent back to the catalytic cracking unit through a pipeline 24 and is mixed with the heavy distillate oil separated by the flash evaporation unit, and then enters the cracking reactor 5 to react to produce light olefins and light aromatics, and the aromatic hydrocarbon-rich distillate oil enters the hydrocracking unit 23 through a pipeline 22 to be hydrocracked and converted to produce light aromatics, and a small part of byproduct dry gas and liquefied gas are produced.
The feedstock used in this example was crude oil with a characteristic factor of 13.0, and its properties are shown in Table 1.1.
The catalyst for the cleavage reaction of this example (catalyst grade: LPS-67C, purchased from Petroleum Rana catalyst division, china) was: FAU type molecular sieve with 1wt% lanthanum, MFI type molecular sieve with 4wt% phosphorus, 0.5wt% magnesium, 3wt% iron and 0.1wt% titanium, and MTT type molecular sieve with 2wt% phosphorus and 1wt% zinc; the mass ratio of the FAU type molecular sieve to the MFI type molecular sieve to the MTT type molecular sieve in the composite catalyst is 1:10:3, the silicon-aluminum molar ratio of the MFI type molecular sieve is 30, and the silicon-aluminum molar ratio of the MTT type molecular sieve is 60.
TABLE 1.1 raw oil Properties
The flash distillation of the unit mass crude oil is used as a reference, 68.09wt% of heavy distillate oil is fed into a cracking reactor of a catalytic cracking unit for cracking reaction, the process operation conditions of the cracking reactor of the catalytic cracking unit are shown in table 1.2, and the product distribution of the catalytic cracking unit is shown in table 1.3. The 31.91wt% light naphtha obtained after flash evaporation enters a steam cracking unit to react to produce light olefins and light aromatics, and a small amount of dry gas is produced as a byproduct (the process operation conditions and the main product distribution are shown in tables 1.7 and 1.8).
TABLE 1.2 Process operating conditions for catalytic cracking unit cracking reactor
TABLE 1.3 product distribution in wt% of catalytic cracking units (based on unit weight heavy distillate)
The yield of the catalytic cracking dry gas from the oil gas fractionation device of the catalytic cracking unit is 11.20 weight percent based on the unit weight of heavy distillate oil, wherein the yield of ethylene is 7.32 weight percent (see table 1.3); wherein the yield of the catalytic cracking liquefied gas is 49.58wt%, the yield of propylene is 22.49wt%, the yield of butylene is 12.71wt%, and the yield of butane is 9.95wt% (see table 1.3); the composition of the dry gas entering the dry gas separation unit is shown in table 1.4, and the separated dry gas is used as hydrogen, methane, ethane and ethylene products respectively.
TABLE 1.4 composition of dry gas entering the dry gas separation unit/wt%
The composition of the liquefied gas entering the liquefied gas separation unit is shown in table 1.5, main products of propylene, butylene and byproducts of propane and butane are obtained after separation, the separated butane enters a steam cracking device for reaction to produce low-carbon olefin, and a small part of byproduct dry gas (the process operation conditions and the main product distribution are shown in table 1.7 and table 1.8) enters a fixed bed catalytic cracking unit for reaction to produce ethylene and propylene (the process operation conditions and the main product distribution are shown in table 1.9 and table 1.10).
TABLE 1.5 composition of liquefied gas entering the liquefied gas separation unit/wt%
The yield of the catalytic pyrolysis gasoline from the oil gas fractionation device of the catalytic pyrolysis unit is 22.45wt% (see table 1.3), the composition of the gasoline entering the gasoline separation unit and the composition of the separated alkane-rich gasoline and the separated alkene-rich gasoline are shown in table 1.6, the separated alkane-rich gasoline enters the steam pyrolysis device to react to produce low-carbon olefin and light aromatic hydrocarbon (the process operation conditions and the main product distribution are shown in table 1.7 and table 1.8), and the separated alkene-rich gasoline enters the fixed bed catalytic pyrolysis unit to react to produce ethylene, propylene and a small amount of high-octane gasoline (the process operation conditions and the main product distribution are shown in table 1.9 and table 1.10).
TABLE 1.6 composition of gasoline entering separation unit and composition of separated alkane-rich, olefin-rich gasoline and light aromatic hydrocarbon/wt%
Table 1.7 shows the process conditions for the reaction of light naphtha, butane and alkane rich gasoline in the steam cracking unit and Table 1.8 shows the main product distribution of the steam cracking unit.
TABLE 1.7 Process operating conditions of steam cracking units
TABLE 1.8 Main product distribution/wt% of steam cracking units
Table 1.9 shows the process conditions for the reaction of butene with olefin-rich gasoline in a fixed bed catalytic cracking unit, and Table 1.10 shows the main product distribution of the fixed bed catalytic cracking unit.
TABLE 1.9 Process operating conditions for fixed bed catalytic cracking units
TABLE 1.10 Main product distribution/wt% of fixed bed catalytic cracking units
The yield of the catalytic pyrolysis recycle oil from the oil-gas fractionation device of the catalytic pyrolysis unit is 6.53wt% (see table 1.3) based on the unit weight of the heavy distillate, and the composition of the recycle oil entering the recycle oil separation unit and the composition of the separated saturated hydrocarbon-rich distillate and aromatic hydrocarbon-rich distillate are shown in table 1.11. The separated saturated hydrocarbon-rich distillate oil and the heavy distillate oil separated by the flash evaporation unit are mixed and enter a catalytic cracking reactor to react to produce light olefins and light aromatics (the process operating conditions and the main product distribution are shown in tables 1.2 and 1.3), the aromatic hydrocarbon-rich distillate oil enters a hydrocracking unit to be subjected to hydrocracking conversion to produce light aromatics, and a small part of byproduct dry gas and liquefied gas are produced.
TABLE 1.11 composition of cycle oil and composition of saturated hydrocarbon-rich fraction and aromatic hydrocarbon-rich fraction after separation/wt%
Table 1.12 shows the process conditions for the reaction of the aromatic-rich distillate into the hydrocracking unit, and Table 1.13 shows the main product distribution of the hydrocracking unit.
TABLE 1.12 Process operating conditions for hydrocracking Unit reactions of aromatic-rich distillate
TABLE 1.13 Main product distribution/wt% of hydrocracking Unit
The yields of the low-carbon olefins (ethylene+propylene+butylene, ethylene+propylene) and the light aromatic hydrocarbons (benzene+toluene+xylene) in the cracking and cracking processes are shown in table 1.14, 28.95wt% of the low-carbon olefins (ethylene+propylene+butylene) and 10.81wt% of the light aromatic hydrocarbons are obtained by catalytic cracking based on the unit mass of crude oil, 20.63wt% of the low-carbon olefins (ethylene+propylene+butylene) and 7.48wt% of the light aromatic hydrocarbons are obtained by steam cracking, 7.66wt% of the low-carbon olefins (ethylene+propylene+butylene) and 1.43wt% of the high-octane gasoline are obtained by fixed bed catalytic cracking, and 2.36wt% of the light aromatic hydrocarbons are obtained by hydrocracking.
TABLE 1.14 yields of light olefins and aromatics for cracking and cracking processes (based on crude oil unit mass)
The yield of the low-carbon olefin (ethylene+propylene+butylene, ethylene+propylene) and the yield of the light aromatic hydrocarbon (benzene+toluene+xylene) obtained by adopting the combined process are shown in table 1.15 on the basis of crude oil of unit mass, compared with the yield of the low-carbon olefin and the yield of the light aromatic hydrocarbon in the existing refining integrated refinery (constant force petrochemical 20Mt/a refining integrated project is comprehensively put into production, china petrochemical organic raw material science and technology center station, petrochemical technology and economy, 2019, 35 (04): 37. Anti-epidemic situation acts as a qualified product of all chemical devices of the constant force petrochemical (large connection) 150 ten thousand t/a ethylene project, petrochemical design, 2020, 37 (01): 14.) is improved, the yield of the low-carbon olefin (ethylene+propylene+butylene) is improved by 37.95 percent, the yield of the ethylene+propylene is improved by 34.13 percent, and the yield of the low-carbon olefin and the light aromatic hydrocarbon is improved by 35.90 percent.
Table 1.15 comparison of the combined Process and the yields of light aromatic hydrocarbons and light olefins in the present refinery
Example 2
The process flow profile is identical to that of example 1.
The feedstock used in this example was crude oil with a characteristic factor of 11.5, the properties of which are shown in Table 2.1.
The catalyst for the cleavage reaction of this example (catalyst grade: LPS-67C, purchased from Petroleum Rana catalyst division, china) was: FAU type molecular sieve with 3wt% lanthanum, MFI type molecular sieve with 2wt% phosphorus, 1wt% magnesium, 4wt% iron and 1wt% nickel, and MTT type molecular sieve with 2wt% phosphorus and 0.5wt% zinc; the mass ratio of the FAU type molecular sieve to the MFI type molecular sieve to the MTT type molecular sieve in the composite catalyst is 2:10:1, the silicon-aluminum molar ratio of the MFI type molecular sieve is 100, and the silicon-aluminum molar ratio of the MTT type molecular sieve is 70.
TABLE 2.1 raw oil Properties
The unit mass of crude oil is taken as a reference, 78.05wt% of heavy distillate oil obtained after flash evaporation enters a cracking reactor of a catalytic cracking unit for cracking reaction, the process operation conditions of the cracking reactor of the catalytic cracking unit are shown in table 2.2, and the product distribution of the catalytic cracking unit is shown in table 2.3. The 21.95wt% light naphtha obtained after flash evaporation enters a steam cracking unit to react to produce light olefins and light aromatics, and a small amount of dry gas is produced as a byproduct (the process operation conditions and the main product distribution are shown in tables 2.7 and 2.8).
TABLE 2.2 Process operating conditions for catalytic cracking unit cracking reactor
TABLE 2.3 product distribution in wt% of catalytic cracking units (based on unit weight heavy distillate)
The yield of the catalytic cracking dry gas from the oil gas fractionation device of the catalytic cracking unit is 6.25 weight percent based on the unit weight of heavy distillate oil, wherein the yield of ethylene is 3.14 weight percent (see table 2.3); wherein the yield of the catalytic cracking liquefied gas is 38.55wt%, the yield of propylene is 15.90wt%, the yield of butylene is 12.54wt%, and the yield of butane is 7.21wt% (see table 2.3); the composition of the dry gas entering the dry gas separation unit is shown in table 2.4, and the separated dry gas is used as hydrogen, methane, ethane and ethylene products respectively.
TABLE 2.4 composition of dry gas entering the dry gas separation unit/wt%
The composition of the liquefied gas entering the liquefied gas separation unit is shown in table 2.5, main products of propylene, butylene and byproducts of propane and butane are obtained after separation, the separated butane enters a steam cracking device for reaction to produce low-carbon olefin, and a small part of byproduct dry gas (the process operation conditions and the main product distribution are shown in table 2.7 and table 2.8) enters a fixed bed catalytic cracking unit for reaction to produce ethylene and propylene (the process operation conditions and the main product distribution are shown in table 2.9 and table 2.10).
TABLE 2.5 composition of liquefied gas entering the liquefied gas separation unit/wt%
The yield of the catalytic pyrolysis gasoline from the oil gas fractionation device of the catalytic pyrolysis unit is 30.71wt% (see table 2.3) based on the unit weight of heavy distillate oil, the composition of the gasoline entering the gasoline separation unit and the composition of the separated alkane-rich gasoline and the separated alkene-rich gasoline are shown in table 2.6, the separated alkane-rich gasoline enters the steam pyrolysis device to react to produce low-carbon olefin and light aromatic hydrocarbon (the process operation conditions and the main product distribution are shown in table 2.7 and table 2.8), and the separated alkene-rich gasoline enters the fixed bed catalytic pyrolysis unit to react to produce ethylene, propylene and a small amount of high-octane gasoline (the process operation conditions and the main product distribution are shown in table 2.9 and table 2.10).
TABLE 2.6 composition of gasoline entering separation unit and composition of separated alkane-rich, olefin-rich gasoline and light aromatic hydrocarbon/wt%
Table 2.7 shows the process conditions for the reaction of light naphtha, butane and alkane rich gasoline in the steam cracking unit and Table 2.8 shows the main product distribution of the steam cracking unit.
TABLE 2.7 Process operating conditions of steam cracking units
TABLE 2.8 Main product distribution/wt% of steam cracking units
Table 2.9 shows the process conditions for the reaction of butene with olefin-rich gasoline in a fixed bed catalytic cracking unit, and Table 2.10 shows the main product distribution of the fixed bed catalytic cracking unit.
TABLE 2.9 Process operating conditions for fixed bed catalytic cracking units
TABLE 2.10 Main product distribution/wt% of fixed bed catalytic cracking units
The yield of the catalytic pyrolysis recycle oil from the oil-gas fractionation device of the catalytic pyrolysis unit is 10.91wt% (see table 2.3) based on the unit weight of the heavy distillate, and the composition of the recycle oil entering the recycle oil separation unit and the composition of the separated saturated hydrocarbon-rich distillate and aromatic hydrocarbon-rich distillate are shown in table 2.11. The separated saturated hydrocarbon-rich distillate oil and the heavy distillate oil separated by the flash evaporation unit are mixed and enter a catalytic cracking reactor to react to produce light olefins and light aromatics (the process operating conditions and the main product distribution are shown in tables 2.2 and 2.3), the aromatic hydrocarbon-rich distillate oil enters a hydrocracking unit to be subjected to hydrocracking conversion to produce light aromatics, and a small part of byproduct dry gas and liquefied gas are produced.
TABLE 2.11 composition of cycle oil and composition of saturated hydrocarbon-rich fraction and aromatic hydrocarbon-rich fraction after separation/wt%
Table 2.12 shows the process conditions for the reaction of the aromatic-rich distillate into the hydrocracking unit, and Table 2.13 shows the main product distribution of the hydrocracking unit.
TABLE 2.12 Process operating conditions for hydrocracking Unit reactions of aromatic-rich distillate
TABLE 2.13 Main product distribution/wt% of hydrocracking Unit
The yields of the low-carbon olefin (ethylene+propylene+butylene, ethylene+propylene) and the light aromatic hydrocarbon (benzene+toluene+xylene) in the cracking and cracking processes are shown in table 2.14, based on the unit mass of crude oil, 26.80wt% of the low-carbon olefin (ethylene+propylene+butylene) and 12.79wt% of the light aromatic hydrocarbon are obtained by catalytic cracking, 12.46wt% of the low-carbon olefin (ethylene+propylene+butylene) and 6.62wt% of the light aromatic hydrocarbon are obtained by steam cracking, 14.50wt% of the low-carbon olefin (ethylene+propylene+butylene) and 2.07wt% of the high-octane gasoline are obtained by fixed bed catalytic cracking, and 4.16wt% of the light aromatic hydrocarbon is obtained by hydrocracking.
TABLE 2.14 yields of light olefins and aromatics for cracking and cracking processes (based on crude oil unit mass)
The yield of the low-carbon olefin (ethylene+propylene+butylene, ethylene+propylene) and the yield of the light aromatic hydrocarbon (benzene+toluene+xylene) obtained by adopting the combined process are shown in Table 2.15 on the basis of crude oil of unit mass, compared with the yield of the low-carbon olefin and the yield of the light aromatic hydrocarbon in the existing refining integrated refinery (constant force petrochemical 20Mt/a refining integrated project is comprehensively put into production, china petrochemical organic raw material science and technology center station, petrochemical technology and economy, 2019, 35 (04): 37. Anti-epidemic situation acts as a qualified product produced by all chemical devices of the constant force petrochemical (large connection) 150 ten thousand t/a ethylene project, petrochemical design, 2020, 37 (01): 14.) the yield of the low-carbon olefin (ethylene+propylene+butylene) is increased by 32.48 percent, the yield of the ethylene+propylene is increased by 23.90 percent, and the yield of the low-carbon olefin and the light aromatic hydrocarbon is increased by 33.35 percent.
Table 2.15 comparison of the combined Process and the yield of light aromatic hydrocarbons/wt% of light olefins in the present refinery
Example 3
The process flow profile is identical to that of example 1.
The feedstock used in this example was crude oil with a characteristic factor of 12.3, the properties of which are shown in Table 3.1.
The catalyst for the cleavage reaction of this example (catalyst grade: LPS-67C, purchased from Petroleum Rana catalyst division, china) was: an FAU type molecular sieve with 2wt% of lanthanum, an MFI type molecular sieve with 3wt% of phosphorus, 0.8wt% of magnesium, 5wt% of iron and 0.5wt% of nickel, and an MTT type molecular sieve with 2wt% of phosphorus and 0.7wt% of zinc; the mass ratio of the FAU type molecular sieve to the MFI type molecular sieve to the MTT type molecular sieve in the composite catalyst is 2:10:2, the silicon-aluminum molar ratio of the MFI type molecular sieve is 80, and the silicon-aluminum molar ratio of the MTT type molecular sieve is 65.
TABLE 3.1 raw oil Properties
The flash distillation of the unit mass crude oil is used as a reference, and 66.59wt% of heavy distillate oil is fed into a cracking reactor of a catalytic cracking unit for cracking reaction, wherein the table 3.2 shows the process operation conditions of the cracking reactor of the catalytic cracking unit, and the table 3.3 shows the product distribution of the catalytic cracking unit. The 33.41wt% light naphtha obtained after flash evaporation enters a steam cracking unit to react to produce light olefins and light aromatics, and a small amount of dry gas is produced as a byproduct (the process operation conditions and the main product distribution are shown in tables 3.7 and 3.8).
TABLE 3.2 Process operating conditions for catalytic cracking unit cracking reactor
TABLE 3 product distribution in wt% of catalytic cracking units (based on unit weight heavy distillate)
The yield of the catalytic cracking dry gas from the oil gas fractionation device of the catalytic cracking unit is 8.34 weight percent based on the unit weight of heavy distillate oil, wherein the yield of ethylene is 4.79 weight percent (see table 3.3); wherein the catalytic cracking liquefied gas yield is 43.52wt%, the propylene yield is 19.54wt%, the butene yield is 12.64wt%, and the butane yield is 7.76wt% (see table 3.3); the composition of the dry gas entering the dry gas separation unit is shown in table 3.4, and the separated dry gas is used as hydrogen, methane, ethane and ethylene products respectively.
TABLE 3.4 composition of dry gas entering the dry gas separation unit/wt%
The composition of the liquefied gas entering the liquefied gas separation unit is shown in table 3.5, main products of propylene, butylene and byproducts of propane and butane are obtained after separation, the separated butane enters a steam cracking device for reaction to produce low-carbon olefin, and a small part of byproduct dry gas (the process operation conditions and the main product distribution are shown in table 3.7 and table 3.8) enters a fixed bed catalytic cracking unit for reaction to produce ethylene and propylene (the process operation conditions and the main product distribution are shown in table 3.9 and table 3.10).
TABLE 3.5 composition of liquefied gas entering the liquefied gas separation unit/wt%
The yield of the catalytic pyrolysis gasoline from the oil gas fractionation device of the catalytic pyrolysis unit is 28.09wt% (see table 3.3), the composition of the gasoline entering the gasoline separation unit and the composition of the separated alkane-rich gasoline and the separated alkene-rich gasoline are shown in table 3.6, the separated alkane-rich gasoline enters the steam pyrolysis device to react to produce low-carbon olefin and light aromatic hydrocarbon (the process operation conditions and the main product distribution are shown in table 3.7 and table 3.8), and the separated alkene-rich gasoline enters the fixed bed catalytic pyrolysis unit to react to produce ethylene, propylene and a small amount of high-octane gasoline (the process operation conditions and the main product distribution are shown in table 3.9 and table 3.10).
TABLE 3.6 composition of gasoline entering separation unit and composition of separated alkane-rich, olefin-rich gasoline and light aromatic hydrocarbon/wt%
Table 3.7 shows the process operating conditions for the reaction of light naphtha, butane and alkane rich gasoline in the steam cracking unit and Table 3.8 shows the main product distribution of the steam cracking unit.
TABLE 3.7 Process operating conditions of steam cracking units
TABLE 3.8 Main product distribution/wt% of steam cracking units
Table 3.9 shows the process conditions for the reaction of butene with olefin-rich gasoline in a fixed bed catalytic cracking unit, and Table 3.10 shows the main product distribution of the fixed bed catalytic cracking unit.
TABLE 3.9 Process operating conditions for fixed bed catalytic cracking units
TABLE 3.10 Main product distribution/wt% of fixed bed catalytic cracking units
The yield of the catalytic pyrolysis cycle oil from the oil-gas fractionation device of the catalytic pyrolysis unit is 8.09wt% (see table 3.3) based on the unit weight of the heavy distillate oil, and the composition of the cycle oil entering the cycle oil separation unit and the composition of the separated saturated hydrocarbon-rich distillate oil and aromatic hydrocarbon-rich distillate oil are shown in table 3.11. The separated saturated hydrocarbon-rich distillate oil and the heavy distillate oil separated by the flash evaporation unit are mixed and enter a catalytic cracking reactor to react to produce light olefins and light aromatics (the process operating conditions and the main product distribution are shown in tables 3.2 and 3.3), the aromatic hydrocarbon-rich distillate oil enters a hydrocracking unit to be subjected to hydrocracking conversion to produce light aromatics, and a small part of byproduct dry gas and liquefied gas are produced.
TABLE 3.11 composition of cycle oil and composition of saturated hydrocarbon-rich fraction and aromatic hydrocarbon-rich fraction after separation/wt%
Table 3.12 shows the process conditions for the reaction of the aromatic-rich distillate into the hydrocracking unit, and Table 3.13 shows the main product distribution of the hydrocracking unit.
TABLE 3.12 Process operating conditions for hydrocracking Unit reactions of aromatic-rich distillate
TABLE 3.13 Main product distribution/wt% of hydrocracking Unit
The yields of the low-carbon olefins (ethylene+propylene+butylene, ethylene+propylene) and the light aromatic hydrocarbons (benzene+toluene+xylene) in the cracking and cracking processes are shown in Table 3.14, 28.86wt% of the low-carbon olefins (ethylene+propylene+butylene) and 13.16wt% of the light aromatic hydrocarbons are obtained by catalytic cracking based on the unit mass of crude oil, 15.26wt% of the low-carbon olefins (ethylene+propylene+butylene) and 7.50wt% of the light aromatic hydrocarbons are obtained by steam cracking, 10.95wt% of the low-carbon olefins (ethylene+propylene+butylene) and 1.76wt% of the high-octane gasoline are obtained by fixed bed catalytic cracking, and 3.04wt% of the light aromatic hydrocarbons are obtained by hydrocracking.
TABLE 3.14 yields of light olefins and aromatics for cracking and cracking processes (based on crude oil unit mass)
The yield of the low-carbon olefin (ethylene+propylene+butylene, ethylene+propylene) and the yield of the light aromatic hydrocarbon (benzene+toluene+xylene) obtained by adopting the combined process are shown in Table 3.15 on the basis of crude oil of unit mass, compared with the yield of the low-carbon olefin and the yield of the light aromatic hydrocarbon in the existing refining integrated refinery (constant force petrochemical 20Mt/a refining integrated project is comprehensively put into production, china petrochemical organic raw material science and technology center station, petrochemical technology and economy, 2019, 35 (04): 37. Anti-epidemic situation acts as a qualified product of all chemical devices of the constant force petrochemical (large connection) 150 ten thousand t/a ethylene project, petrochemical design, 2020, 37 (01): 14.) is improved, the yield of the low-carbon olefin (ethylene+propylene+butylene) is improved by 34.56 percent, the yield of the ethylene+propylene is improved by 29.36 percent, and the yield of the low-carbon olefin and the light aromatic hydrocarbon is improved by 35.56 percent.
Table 3.15 comparison of the combined Process and the yield of light aromatic hydrocarbons/wt% of light olefins in the present refinery
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (5)
1. A process for producing light olefins and light aromatics from crude oil, comprising the steps of:
Step one: crude oil enters a desalting and dewatering pretreatment unit and exchanges heat with a high-temperature heat exchange medium after being desalted and dewatered;
step two: the crude oil enters a flash evaporation unit to be separated into light naphtha and heavy distillate after heat exchange and temperature rise;
step three: sending the light naphtha obtained after flash evaporation in the second step into a steam cracking unit for reaction to produce light olefins and light aromatics and byproduct dry gas;
Step four: sending the heavy distillate oil obtained after the flash evaporation in the second step into a catalytic cracking unit, and sending the heavy distillate oil into a cracking reactor for cracking reaction; the reacted oil gas enters an oil gas fractionation device of a catalytic cracking unit and is separated into dry gas, liquefied gas, pyrolysis gasoline, recycle oil and slurry oil;
step five: separating main product ethylene, byproduct hydrogen, methane and ethane from the dry gas obtained in the step four through a dry gas separation unit;
Step six: separating the liquefied gas obtained in the step four into main products of propylene, butylene, byproducts of propane and butane through a liquefied gas separation unit, further sending the butane into a steam cracking unit for reaction to produce low-carbon olefin, and further sending the byproduct of dry gas, and further sending the butylene into a fixed bed catalytic cracking unit for reaction to produce ethylene and propylene;
Step seven: separating the main product light aromatic hydrocarbon, alkane-rich gasoline and olefin-rich gasoline from the pyrolysis gasoline obtained in the step four through a gasoline separation unit, further sending the alkane-rich gasoline into a steam pyrolysis unit for reaction to produce light olefins and light aromatic hydrocarbon, and further sending the olefin-rich gasoline back into a fixed bed catalytic pyrolysis unit for reaction to produce light olefins and byproduct high-octane gasoline;
step eight: separating saturated hydrocarbon-rich distillate and aromatic hydrocarbon-rich distillate from the cycle oil obtained in the step four through a cycle oil separation unit; the saturated hydrocarbon-rich distillate oil is further sent back to the catalytic cracking unit and enters a cracking reactor together with the heavy distillate oil obtained after flash evaporation to react, low-carbon olefin and light aromatic hydrocarbon are produced, the aromatic hydrocarbon-rich distillate oil enters a hydrocracking unit to be subjected to hydrocracking conversion, light aromatic hydrocarbon is produced, and dry gas and liquefied gas are produced as byproducts;
The characteristic factor of the crude oil is 11.5-13.0, and the mass of the fraction of the crude oil at the temperature of less than 200 ℃ is more than 10wt%;
The light naphtha obtained after flash evaporation has a distillation range of between an initial distillation point and 240 ℃, and the heavy distillate oil obtained has a distillation range of more than 240 ℃;
The reaction conditions of the steam cracking unit include: the reaction temperature is 800-950 ℃, the water-oil ratio is 0.3-0.8, the reaction time is 0.05-2.0 s, and the reaction pressure is 0.12-0.25 MPa;
Carrying out cracking reaction on the heavy distillate oil obtained after flash evaporation in the presence of a cracking catalyst to obtain cracking oil gas; the cracking catalyst is a composite catalyst formed by mixing a metal modified FAU type molecular sieve, an MFI molecular sieve and an MTT molecular sieve; the silicon-aluminum molar ratio of the FAU type molecular sieve is 6-12; the silicon-aluminum molar ratio of the MFI molecular sieve is 30-200; the silicon-aluminum mole ratio of the MTT molecular sieve is 30-100; the mass ratio of the FAU molecular sieve to the MFI molecular sieve to the MTT molecular sieve in the composite catalyst is (1-2): 10: (0-3);
The catalytic cracking unit is a continuous reaction-regeneration catalytic cracking device and comprises a cracking reactor, a catalyst regenerator and an oil gas fractionation device; the cracking reactor is a gas-solid fluidization type reactor combined by a conveying bed and a rapid bed or a turbulent bed;
The reaction conditions of the fixed bed catalytic cracking unit include: the reaction temperature is 530-650 ℃, the water-oil ratio is 0.2-0.5, the weight hourly space velocity is 10-30 h -1, and the reaction pressure is 0.10-0.20 MPa;
The reaction conditions of the cleavage reactor include: the reaction temperature is 530-650 ℃, the agent-oil ratio is 10-40, the water-oil ratio is 0.2-0.4, the reaction time is 2-8 s, and the reaction pressure is 0.1-0.25 MPa;
The reaction conditions of the hydrocracking unit include: the reaction temperature is 300-450 ℃, the hydrogen-oil volume ratio is 700-1500, the weight hourly space velocity is 0.6-2.0 h -1, and the reaction pressure is 3.0-10.0 MPa.
2. The process for producing light olefins and light aromatics from crude oil according to claim 1, wherein said crude oil has a characteristic factor of 12.0-12.7 and a fraction less than 200 ℃ in crude oil has a mass of greater than 10wt%.
3. The process for producing light olefins and light aromatics from crude oil according to claim 1, wherein the crude oil has a water content of less than 0.5wt% and a salt content of less than 0.3mg/L after passing through a desalting and dewatering unit.
4. The process for producing light olefins and light aromatics from crude oil according to claim 1, wherein said desalted and dehydrated crude oil is subjected to heat exchange with a heat exchange medium to 220-300 ℃.
5. The process for producing light olefins and aromatics from crude oil according to claim 1, wherein said heat exchange medium is pyrolysis oil gas of a catalytic cracking unit.
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| CN105349179A (en) * | 2015-10-28 | 2016-02-24 | 中国石油大学(华东) | Combined process of heavy petroleum hydrocarbon catalytic cracking and light petroleum hydrocarbon steam cracking |
| CN111825514A (en) * | 2020-08-12 | 2020-10-27 | 浙江科茂环境科技有限公司 | Method for maximizing production of ethylene or propylene |
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| CN101362669A (en) * | 2007-08-09 | 2009-02-11 | 中国石油化工股份有限公司 | Catalytic conversion method of ethylene, propylene and aromatic hydrocarbon preparation |
| CN105349179A (en) * | 2015-10-28 | 2016-02-24 | 中国石油大学(华东) | Combined process of heavy petroleum hydrocarbon catalytic cracking and light petroleum hydrocarbon steam cracking |
| CN111825514A (en) * | 2020-08-12 | 2020-10-27 | 浙江科茂环境科技有限公司 | Method for maximizing production of ethylene or propylene |
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