CN115125033B - Method and system for simultaneously producing low-carbon olefin and low-sulfur residue type ship combustion - Google Patents
Method and system for simultaneously producing low-carbon olefin and low-sulfur residue type ship combustion Download PDFInfo
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- CN115125033B CN115125033B CN202110315912.8A CN202110315912A CN115125033B CN 115125033 B CN115125033 B CN 115125033B CN 202110315912 A CN202110315912 A CN 202110315912A CN 115125033 B CN115125033 B CN 115125033B
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- 238000000034 method Methods 0.000 title claims abstract description 75
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 69
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 32
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 292
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 201
- 238000002156 mixing Methods 0.000 claims abstract description 57
- 239000002893 slag Substances 0.000 claims abstract description 57
- 239000002994 raw material Substances 0.000 claims abstract description 39
- 239000002002 slurry Substances 0.000 claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000003921 oil Substances 0.000 claims description 306
- 239000003054 catalyst Substances 0.000 claims description 120
- 239000002283 diesel fuel Substances 0.000 claims description 75
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 48
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 38
- 239000001257 hydrogen Substances 0.000 claims description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims description 36
- 238000000926 separation method Methods 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 28
- 229910052717 sulfur Inorganic materials 0.000 claims description 25
- 239000011593 sulfur Substances 0.000 claims description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 15
- 239000005977 Ethylene Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 229910021536 Zeolite Inorganic materials 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 14
- -1 carbon olefins Chemical class 0.000 claims description 14
- 230000003197 catalytic effect Effects 0.000 claims description 14
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 14
- 239000010457 zeolite Substances 0.000 claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 238000005194 fractionation Methods 0.000 claims description 6
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000010937 tungsten Substances 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000004927 clay Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- YCOASTWZYJGKEK-UHFFFAOYSA-N [Co].[Ni].[W] Chemical compound [Co].[Ni].[W] YCOASTWZYJGKEK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 239000010687 lubricating oil Substances 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 2
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 2
- 239000011959 amorphous silica alumina Substances 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 35
- 239000000446 fuel Substances 0.000 abstract description 18
- 150000001336 alkenes Chemical class 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 239000003208 petroleum Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 51
- 238000009826 distribution Methods 0.000 description 29
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 21
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 21
- 238000007233 catalytic pyrolysis Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 13
- 238000011068 loading method Methods 0.000 description 13
- 239000000295 fuel oil Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000005520 cutting process Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000011017 operating method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000004230 steam cracking Methods 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010762 marine fuel oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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 invention relates to the field of petroleum processing, and discloses a method and a system for simultaneously producing low-carbon olefin and low-sulfur residue type ship combustion. The method comprises the following steps: introducing a residual oil raw material into a fixed bed residual oil hydrotreating reaction zone for hydrotreating reaction I, separating residual oil hydrotreating reaction effluent, introducing first hydrogenated wax oil into the fixed bed wax oil hydrotreating reaction zone for hydrotreating reaction II, separating wax oil hydrotreating reaction effluent, introducing second hydrogenated wax oil and partial hydrogenated slag reduction into a catalytic cracking reaction zone for catalytic cracking reaction, and separating catalytic cracking reaction effluent to obtain light olefins; and introducing the catalytic cracking light cycle oil, the catalytic cracking heavy cycle oil, the catalytic cracking slurry oil and partial hydrogenation slag reduction into a ship fuel blending area for blending to obtain the low-sulfur residue type ship fuel. The invention can obviously improve the yield of the low-carbon olefin high-value product and the low-sulfur residue type ship combustion with low production cost.
Description
Technical Field
The invention relates to the field of petroleum processing, in particular to a method and a system for simultaneously producing low-carbon olefin and low-sulfur residue type ship combustion.
Background
The low-carbon olefin represented by ethylene and propylene is a basic raw material in the chemical industry, can be used for producing various organic chemical products, and plays an important role in national economy. In the traditional petrochemical industry, naphtha is mainly used as a raw material to prepare ethylene through steam cracking. However, in recent years, the price of petroleum is increasing and the shale gas extraction technology is maturing, and steam cracking devices using shale gas as raw material are widely used in north america, and the economy of ethylene cracking process using naphtha as raw material is being squeezed.
Compared with the ethylene product market, the impact of propylene by shale gas revolution is smaller, and the gap of the market on propylene is still larger. Therefore, in the period of relatively low price of crude oil, the process technology for producing more propylene is developed, and the method has wide application prospect in the future.
At present, about 60% -65% of propylene in the world is prepared by a steam cracking process, about 30% of propylene is prepared by a catalytic cracking process (including a catalytic cracking process), and the rest of propylene is prepared by processes such as propane dehydrogenation. The main raw materials of the catalytic cracking device comprise wax oil and residual oil, and the catalytic cracking device has certain advantages in raw material cost.
However, the propylene yield of the catalytic cracking device is not high, for example, the yield of propylene in the catalytic cracking unit can reach 20% or even more than 30% by taking intermediate hydrogenated wax oil as a raw material, for example, the yield of propylene in the catalytic cracking unit is generally not more than 20% by taking intermediate hydrogenated residual oil as a raw material. In addition, if a residuum hydrogenation apparatus using only hydrogenated residuum as a catalytic cracking feedstock needs to be operated at a higher reaction severity, the operating cycle or economy of the residuum hydrogenation apparatus may be affected.
It can be seen that it is necessary to increase the propylene yield of the catalytic cracking of the residuum feedstock and to reduce the operating severity of the catalytic cracking feedstock pretreatment unit by selecting an appropriate process route.
CN101063047a discloses a method for hydrotreating-catalytic cracking of heavy raw materials to increase propylene yield, wherein heavy distillate oil and optionally light cycle oil from a catalytic cracking unit can be reacted together in one reaction zone, or can be reacted in two hydrogenation reaction zones filled with different hydrogenation catalysts respectively, and after cooling, separating and fractionating the reaction effluent, the obtained heavy liquid phase fraction is sent to the catalytic cracking unit, and the catalytic cracking reaction product is separated to obtain the final product. The method provided by the invention is suitable for treating wax oil raw materials, and has the defects of short operation period, low impurity removal rate and the like when treating heavy residual oil raw materials.
CN101747935a provides a method for producing low-carbon olefins and monocyclic aromatic hydrocarbons from heavy hydrocarbons, wherein a wax oil raw material and light and heavy cycle oil of a catalytic cracking device are subjected to hydrogenation reaction in a first reaction zone, a reaction effluent is mixed with residual oil and then enters a second reaction zone to be subjected to hydrogenation reaction, and separated heavy fraction obtained by hydrogenation enters the catalytic cracking reaction zone to react to obtain the required products such as low-carbon olefins and monocyclic aromatic hydrocarbons. The method widens the source of the catalytic cracking raw material by introducing residual oil before the second reaction zone, increases the processing amount of low-value residual oil, and solves the problem of heat balance of the catalytic cracking unit.
In addition, with the continuous aggravation of global environmental problems, environmental regulations have been continuously put out at home and abroad to limit the sulfur content of marine fuel oil (hereinafter referred to as "marine fuel"). For example, the international maritime organization (english: international Maritime Organization, abbreviated as IMO) requires that the sulfur content of fuel oil used by a ship traveling in a general area from 1 month 1 in 2020 be not higher than 0.5%.
For the trend of low-sulfur combustion, there are four countermeasures considered by shippers: (1) low sulfur residue marine combustion alternatives; (2) low sulfur light marine combustion alternatives; (3) using LNG fuel; (4) installing an exhaust gas cleaning system (EGC). Among them, the low sulfur residue type marine combustion becomes the preferred scheme of shippers, and will occupy a large proportion in the market, but the global supply is limited by resources and will form a gap.
At present, the high-sulfur residue type ship fuel is mainly obtained by a blending method, and blending components mainly come from non-ideal byproducts such as high-sulfur residue which is difficult to process in a refinery, catalytic slurry oil, low-quality secondary processing distillate oil and the like, wherein the key points of blending are viscosity, stability and metal aluminum and silicon content (catalyst powder in the catalytic slurry oil) meet the quality requirements.
CN109952362a discloses a method for producing low-sulfur residue type ship-fuel, heavy raw materials undergo hydrodemetallization and hydrotreating steps, the obtained effluent undergoes atmospheric and vacuum separation to obtain partial hydrogenation residue reduction, hydrogenated wax oil and at least partial residual hydrogenation residue are used as raw materials of a catalytic cracker, and catalytic cracking light cycle oil, catalytic cracking heavy cycle oil, hydrogenation residue reduction and hydrogenation residue reduction are used as blending components to produce the low-sulfur residue type ship-fuel. When the sulfur content of the raw material is higher, the method needs to operate the residual oil hydrogenation under a higher reaction severity, or a large proportion of hydrogenation slag is needed to be used for blending the low-sulfur residue type ship fuel with qualified sulfur content, which shortens the operation period of a residual oil hydrogenation device or reduces the overall economic benefit.
Moreover, the direct production of residue type ship combustion with the sulfur content of no more than 0.5 percent by adopting the blending component is difficult, and the low-sulfur residue is required to be blended for production. However, if a large amount of high-price low-sulfur straight-run residual oil is blended to produce the residue type ship-fuel, the production cost of the residue type ship-fuel can be greatly increased.
Therefore, there is a need for producing low sulfur residue type marine fires or blending components thereof from sulfur-containing or high sulfur resids to produce low sulfur residue type marine fires at low cost.
Disclosure of Invention
The invention aims to overcome the defect that the prior art can not increase the yield of the low-carbon olefin and simultaneously produce the low-sulfur residue type ship combustion.
In order to achieve the above object, a first aspect of the present invention provides a method for producing both low-carbon olefin and low-sulfur residue type marine combustion, the method comprising:
(1) Introducing a residual oil raw material into a fixed bed residual oil hydrotreating reaction zone in the presence of hydrogen to carry out hydrotreating reaction I, and separating residual oil hydrotreating reaction effluent obtained after the hydrotreating reaction I to obtain a first gas effluent, first hydrogenated naphtha, first hydrogenated diesel oil, first hydrogenated wax oil and hydrogenated slag reduction; controlling the reaction condition of the fixed bed residual oil hydrotreating reaction zone and/or controlling the catalyst grading mode in the fixed bed residual oil hydrotreating reaction zone so that the sulfur content of the hydrogenated slag reduction is no more than 0.8 wt%;
(2) Introducing the first hydrogenated wax oil, optionally together with the first hydrogenated diesel oil, into a fixed bed wax oil hydrotreating reaction zone for hydrotreating reaction II, and separating a wax oil hydrotreating reaction effluent obtained after hydrotreating reaction II to obtain a second gas effluent, second hydrogenated naphtha, second hydrogenated diesel oil and second hydrogenated wax oil;
(3) Introducing the second hydrogenated wax oil, a part of the hydrogenated slag reduction, optionally the second hydrogenated diesel oil into a catalytic cracking reaction zone for catalytic cracking reaction, and separating a catalytic cracking reaction effluent obtained after the catalytic cracking reaction to obtain low-carbon olefin, catalytic cracking naphtha, catalytic cracking light cycle oil, catalytic cracking heavy cycle oil and catalytic cracking slurry oil;
(4) And introducing the catalytic cracking light cycle oil, the catalytic cracking heavy cycle oil, the catalytic cracking slurry oil and the rest of the hydrogenated slag reduction, optionally together with the first hydrogenated diesel oil and/or the second hydrogenated diesel oil, into a ship combustion blending area for blending to obtain the low-sulfur residue type ship combustion.
In a second aspect the invention provides a system for producing both light olefins and low sulphur residue type marine fires, the system comprising:
The fixed bed residuum hydrotreatment reaction zone is used for carrying out hydrotreatment reaction I on a residuum raw material to obtain residuum hydrotreatment reaction effluent;
the first separation zone is used for separating the residual oil hydrotreating reaction effluent to obtain a first gas effluent, first hydrogenated naphtha, first hydrogenated diesel oil, first hydrogenated wax oil and hydrogenated slag reduction;
the fixed bed wax oil hydrotreating reaction zone is used for carrying out hydrotreating reaction II on the first hydrogenated wax oil, optionally together with the first hydrogenated diesel oil to obtain a wax oil hydrotreating reaction effluent;
the second separation zone is used for separating the wax oil hydrotreating reaction effluent to obtain a second gas effluent, second hydrogenated naphtha, second hydrogenated diesel oil and second hydrogenated wax oil;
the catalytic cracking reaction zone is used for carrying out catalytic cracking reaction on the second hydrogenated wax oil, a part of the hydrogenated slag reduction, optionally, the second hydrogenated diesel oil to obtain a catalytic cracking reaction effluent;
the third separation zone is used for separating the catalytic cracking reaction effluent to obtain low-carbon olefin, catalytic cracking naphtha, catalytic cracking light cycle oil, catalytic cracking heavy cycle oil and catalytic cracking slurry oil;
And the ship combustion blending zone is used for blending the catalytic cracking light cycle oil, the catalytic cracking heavy cycle oil, the catalytic cracking slurry oil and the rest of the hydrogenated slag reduction, and optionally, the first hydrogenated diesel oil and/or the second hydrogenated diesel oil to obtain the low-sulfur residue type ship combustion.
The inventor finds that the hydrogenation residue reduction sulfur content obtained in the fixed bed residue hydrotreating reaction zone is strictly controlled by organically combining a fixed bed residue hydrotreating process, a fixed bed wax oil hydrotreating process, a catalytic cracking process and a ship combustion blending technology, so that the yield of high-value products such as propylene, ethylene and the like in the combined process can be remarkably improved, and the ship combustion with low sulfur residue meeting the standard and low cost can be obtained.
Drawings
FIG. 1 is a process flow diagram of a preferred embodiment of the method of the present invention for producing both light olefins and low sulfur residue type marine combustion.
Description of the reference numerals
1. Residuum raw material 2, fixed bed residuum hydrotreatment reaction zone
3. Residuum hydrotreatment reaction effluent 4, first separation zone
5. First gas effluent 6, first hydrogenated naphtha
7. First hydrogenated diesel oil 8 and first hydrogenated wax oil
9. Hydrogenation slag reduction 10 and fixed bed wax oil hydrotreating reaction zone
11. Wax oil hydrotreating reaction effluent 12, second separation zone
13. Second gas effluent 14, second hydrogenated naphtha
15. Second hydrogenated diesel 16, second hydrogenated wax oil
17. Catalytic cracking reaction zone 18, catalytic cracking reaction effluent
19. Third separation zone 20, low carbon olefins
21. Catalytic pyrolysis naphtha 22 and catalytic pyrolysis light cycle oil
23. Catalytic cracking heavy cycle oil 24 and catalytic cracking slurry oil
25. Ship combustion blending area 26, low sulfur residue type ship combustion
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present invention, the pressures are gauge pressures unless otherwise specified.
In the present invention, the particle size of the residuum hydrotreating catalyst refers to the maximum linear distance between two different points on the particle cross section, unless otherwise specified. The particle size of the wax oil hydrotreating catalyst is of similar definition.
In the present invention, the low-carbon olefin includes, but is not limited to, ethylene, propylene, unless otherwise specified.
In the invention, the liquid hourly space velocity is the residual oil volumetric space velocity, i.e. the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil are not calculated when the volumetric space velocity is calculated without corresponding description.
As previously described, a first aspect of the present invention provides a method for producing both low carbon olefins and low sulphur residue type marine combustion, the method comprising:
(1) Introducing a residual oil raw material into a fixed bed residual oil hydrotreating reaction zone in the presence of hydrogen to carry out hydrotreating reaction I, and separating residual oil hydrotreating reaction effluent obtained after the hydrotreating reaction I to obtain a first gas effluent, first hydrogenated naphtha, first hydrogenated diesel oil, first hydrogenated wax oil and hydrogenated slag reduction; controlling the reaction condition of the fixed bed residual oil hydrotreating reaction zone and/or controlling the catalyst grading mode in the fixed bed residual oil hydrotreating reaction zone so that the sulfur content of the hydrogenated slag reduction is no more than 0.8 wt%;
(2) Introducing the first hydrogenated wax oil, optionally together with the first hydrogenated diesel oil, into a fixed bed wax oil hydrotreating reaction zone for hydrotreating reaction II, and separating a wax oil hydrotreating reaction effluent obtained after hydrotreating reaction II to obtain a second gas effluent, second hydrogenated naphtha, second hydrogenated diesel oil and second hydrogenated wax oil;
(3) Introducing the second hydrogenated wax oil, a part of the hydrogenated slag reduction, optionally the second hydrogenated diesel oil into a catalytic cracking reaction zone for catalytic cracking reaction, and separating a catalytic cracking reaction effluent obtained after the catalytic cracking reaction to obtain low-carbon olefin, catalytic cracking naphtha, catalytic cracking light cycle oil, catalytic cracking heavy cycle oil and catalytic cracking slurry oil;
(4) And introducing the catalytic cracking light cycle oil, the catalytic cracking heavy cycle oil, the catalytic cracking slurry oil and the rest of the hydrogenated slag reduction, optionally together with the first hydrogenated diesel oil and/or the second hydrogenated diesel oil, into a ship combustion blending area for blending to obtain the low-sulfur residue type ship combustion.
The invention is not particularly limited to the subsequent treatment of the catalytically cracked naphtha and one skilled in the art may employ operations known in the art, for example, extraction or hydrotreating to remove sulfides after the catalytic cracked naphtha withdrawal unit of the invention and then extracting to obtain monocyclic aromatic hydrocarbons.
Preferably, in step (2), the reaction conditions of the fixed bed wax oil hydrotreating reaction zone and/or the catalyst fractionation in the fixed bed wax oil hydrotreating reaction zone are controlled such that the hydrogen content of the wax oil hydrotreating reaction effluent is less than 13.2 wt%, preferably less than 13.5 wt%. The inventors have found that with this preferred embodiment, the yield of the low carbon olefin product can be made higher.
Preferably, in step (2), the fixed bed wax oil is hydrogenatedThe reaction conditions of the reaction zone include: the hydrogen partial pressure is 6-25MPa, the reaction temperature is 300-460 ℃, and the liquid hourly space velocity is 0.1-5.0h -1 The volume ratio of hydrogen to oil is 200-2000.
More preferably, in step (2), the reaction conditions of the fixed bed wax oil hydrotreating reaction zone include: the hydrogen partial pressure is 10-20MPa, the reaction temperature is 350-440 ℃, and the liquid hourly space velocity is 0.5-2.0h -1 The volume ratio of hydrogen oil is 400-1200.
Preferably, in the step (2), the fixed bed wax oil hydrotreating reaction zone is filled with a wax oil hydrotreating catalyst, and the bulk density of the wax oil hydrotreating catalyst is 0.4-1.3g/cm 3 The average grain diameter is 0.5-50mm, and the specific surface area is 50-400m 2 /g。
In the present invention, the loading type, the loading volume ratio and the loading manner of the wax oil hydrotreating catalyst can be operated in the manner of the prior art, and the present invention exemplarily provides one loading type, the loading volume ratio and the loading manner of the wax oil hydrotreating catalyst, which should not be construed as limiting the present invention.
According to a particularly preferred embodiment, in step (2), the wax oil hydrotreating catalyst is selected from at least one of a guard catalyst I, a wax oil hydrofinishing catalyst.
Preferably, the fixed bed wax oil hydrotreating reaction zone is filled with the protection catalyst I and the wax oil hydrofining catalyst in sequence along the flow direction.
More preferably, the loading volume ratio of the protection catalyst I to the wax oil hydrofining catalyst is 1:9-99.
Preferably, in the step (2), the wax oil hydrotreating catalyst contains a carrier and an active metal element supported on the carrier, the carrier is selected from at least one of alumina, a combination of alumina and silica, and titania, and the active metal element is selected from at least one of nickel, cobalt, molybdenum, and tungsten.
More preferably, in the wax oil hydrotreating catalyst, the total content of nickel and cobalt in terms of oxide is 0 to 30 wt%, the total content of molybdenum and/or tungsten in terms of oxide is 0 to 35 wt%, and the sum of the contents of nickel, cobalt, molybdenum, tungsten in terms of oxide is greater than 0, based on the total weight of the wax oil hydrotreating catalyst.
Preferably, in step (2), the separation conditions of the wax oil hydrotreating reaction effluent are controlled such that the initial boiling point of the second hydrogenated naphtha is 50-70 ℃, the cut points of the second hydrogenated naphtha and the second hydrogenated diesel oil are 160-180 ℃, the cut points of the second hydrogenated diesel oil and the second hydrogenated wax oil are 340-360 ℃, and the final boiling point of the second hydrogenated wax oil is 500-580 ℃.
Preferably, in step (1), the residuum feedstock is selected from at least one of atmospheric residuum, vacuum residuum.
Preferably, in step (1), the reaction conditions of the fixed bed residuum hydroprocessing reaction zone and/or the catalyst fractionation pattern in the fixed bed residuum hydroprocessing reaction zone are controlled such that the sulfur content of the hydrogenated reduced residuum is no more than 0.6 wt.%, more preferably no more than 0.5 wt.%. The inventors have found that with this preferred embodiment, the resulting hydrogenated reduced slag is more readily blended with other marine fuel blending components to yield acceptable low sulfur residue marine fuels.
Preferably, in step (1), the reaction conditions of the fixed bed residuum hydrotreating reaction zone are: the reaction temperature is 300-460 ℃, the hydrogen partial pressure is 6-25MPa, and the liquid hourly space velocity is 0.10-1.0h -1 The volume ratio of hydrogen to oil is 100-1500.
More preferably, in step (1), the reaction conditions of the fixed bed residuum hydroprocessing reaction zone are: the reaction temperature is 350-440 ℃, the hydrogen partial pressure is 12-20MPa, and the liquid hourly space velocity is 0.15-0.4h -1 The volume ratio of hydrogen to oil is 300-1000.
Preferably, in step (1), the fixed bed residuum hydroprocessing reaction zone is charged with a residuum hydroprocessing catalyst having an average particle size of from 0.5 to 50mm and a bulk density of from 0.3 to 1.2g/cm 3 Average pore diameter of 6-30nm and specific surface area of 50-400m 2 /g。
In the present invention, the loading type, loading volume ratio and loading manner of the residuum hydrotreating catalyst may be operated in the manner of the prior art, and the present invention exemplarily provides one loading type, loading volume ratio and loading manner of the residuum hydrotreating catalyst, which should not be construed as limiting the present invention.
Preferably, in step (1), the residuum hydrotreating catalyst is selected from at least one of guard catalyst II, hydrodemetallization catalyst, hydrodesulfurization catalyst, and hydrodechar catalyst.
Preferably, the fixed bed residuum hydrotreating reaction zone is sequentially filled with the protection catalyst II, the hydrodemetallization catalyst, the hydrodesulphurization catalyst and the hydrodecarbon residue catalyst along the stream direction.
More preferably, the packing volume ratio of the protection catalyst II, the hydrodemetallization catalyst, the hydrodesulphurisation catalyst, and the hydrodecarbon residue catalyst is 1:4-8:1-5:2-6.
According to a particularly preferred embodiment, in step (1), the residuum hydroprocessing catalyst contains a support selected from at least one of alumina, silica and titania, and an active metal element selected from group VIB metal elements and/or group VIII metal elements supported on the support.
Preferably, in the residuum hydrotreating catalyst, the active metal element is selected from at least one of a combination of nickel-tungsten, a combination of nickel-tungsten-cobalt, a combination of nickel-molybdenum, and a combination of cobalt-molybdenum.
Preferably, in the residuum hydrotreating catalyst, the carrier further contains at least one element of boron, germanium, zirconium, phosphorus, chlorine, and fluorine.
Preferably, in the residuum hydroprocessing catalyst, the content of the active metal element in terms of oxide is from 1 to 30wt%, preferably from 1 to 25wt%, based on the total weight of the residuum hydroprocessing catalyst.
In the present invention, the resid hydrotreating catalyst may be selected from commercial catalysts conventional in the art or prepared using conventional methods of the prior art, and illustratively, the resid hydrotreating catalyst may employ commercial catalysts of RG series, RDM series, RMS series, RCS series, and RSN series developed by the institute of petrochemical and petrochemical industries, china.
Preferably, in step (1), the separation conditions of the residuum hydrotreating reaction effluent are controlled such that the initial boiling point of the first hydrogenated naphtha is 50 to 70 ℃, the cut point of the first hydrogenated naphtha and the first hydrogenated diesel oil is 160 to 180 ℃, the cut point of the first hydrogenated diesel oil and the first hydrogenated wax oil is 340 to 360 ℃, and the final boiling point of the first hydrogenated wax oil is 500 to 580 ℃.
Preferably, in the step (3), the catalytic cracking reaction zone is filled with a catalytic cracking catalyst, the catalytic cracking catalyst contains zeolite, inorganic oxide and optionally clay, the inorganic oxide is at least one of silicon oxide, aluminum oxide, zirconium oxide, titanium dioxide and amorphous silicon aluminum, the content of the zeolite is 10-50 wt%, the content of the inorganic oxide is 5-90 wt%, and the content of the clay is 0-70 wt%, based on the total weight of the catalytic cracking catalyst.
Preferably, in the catalytic cracking catalyst, the zeolite is at least one selected from a Y-type zeolite containing or not containing a rare earth element, an HY-type zeolite containing or not containing a rare earth element, an ultrastable Y-type zeolite containing or not containing a rare earth element, and a zeolite having an MFI structure.
The apparatus of the catalytic cracking reaction zone and the separation zone, which can use a conventional catalytic cracking system, may include, for example, a reactor, a regenerator and a fractionation system and an absorption stabilization system, and adopts a composite reactor type consisting of a riser and a dense-phase fluidized bed, is not particularly limited.
According to a particularly preferred embodiment, in step (3), the reaction conditions of the catalytic cracking reaction zone are: atomized steam and said residuum sourceThe weight ratio of the materials is 0.05-0.5:1, the weight ratio of the agent to the oil is 6-20:1, the temperature is 500-680 ℃, and the weight hourly space velocity is 1-6h -1 The reaction pressure is 0.05-1MPa.
In the present invention, the catalyst to oil weight ratio is the weight ratio of the sum of the total weight of the catalytic cracking catalyst and the raw material introduced into the catalytic cracking reaction zone, unless otherwise specified. Wherein the feedstock to the catalytic cracking reaction zone comprises the second hydrogenated wax oil, a portion of the hydrogenated reduced slag, optionally, and the second hydrogenated diesel fuel.
Preferably, in the step (3), the separation condition of the catalytic cracking reaction effluent is controlled such that the initial distillation point of the catalytic cracking light cycle oil is 170-190 ℃, the cutting point of the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil is 340-360 ℃, and the final distillation point of the catalytic cracking heavy cycle oil is 500-580 ℃.
Preferably, in step (3), the hydrodewaxed slag introduced into the catalytic cracking reaction zone represents from 5 to 95% by weight, more preferably from 20 to 80% by weight, of the total weight of the hydrodewaxed slag. The inventors have found that with this preferred embodiment, the yield of the low carbon olefin product can be made higher.
The invention has no special limitation on the blending proportion of the components such as the catalytic cracking light cycle oil, the catalytic cracking heavy cycle oil, the catalytic cracking slurry oil, the hydrogenation slag reduction, the first hydrogenation diesel oil and the second hydrogenation diesel oil which are introduced into the ship combustion blending zone, and only needs to ensure that the low sulfur residue type ship combustion obtained after blending can meet the requirements of GB17411-2015 or ISO 8217 and meets the ship fuel standard RMG180 or RMG380.
Preferably, in step (4), the method further comprises: at least one of atmospheric residuum, vacuum residuum, visbreaking residuum, catalytic slurry oil, catalytic heavy cycle oil, catalytic light cycle oil, coker wax oil, ethylene tar and refined extracted oil of lubricating oil solvent is introduced into a ship combustion blending area for blending, so as to obtain the low-sulfur residue type ship combustion.
Preferably, the method further comprises: and separating the first hydrogenated naphtha and/or the second hydrogenated naphtha to obtain light naphtha and heavy naphtha, wherein the light naphtha is recycled to the catalytic cracking reaction zone.
In the present invention, the first hydrogenated naphtha and the second hydrogenated naphtha may be mixed and separated together, or separated separately, to obtain light naphtha and heavy naphtha.
The present invention is not particularly limited to the subsequent treatment of the light naphtha and the heavy naphtha and may be carried out by those skilled in the art using operations known in the art, for example, the light naphtha of the present invention may be introduced into the catalytic cracking reaction zone for the catalytic cracking reaction and the heavy naphtha may be withdrawn from the apparatus for the feed for aromatics extraction.
Preferably, the separation conditions of the first and second hydrogenated naphthas are controlled such that the initial boiling point of the light naphthas is 50 to 70 ℃, the cutting point of the light naphthas and the heavy naphthas is 120 to 140 ℃, and the final boiling point of the heavy naphthas is 170 to 190 ℃.
The following provides a process flow of a preferred embodiment of the method for producing both low carbon olefins and low sulfur residue type marine combustion according to the present invention in combination with fig. 1:
(1) Introducing a residual oil raw material 1 into a fixed bed residual oil hydrotreating reaction zone 2 in the presence of hydrogen to carry out hydrotreating reaction I, and introducing a residual oil hydrotreating reaction effluent 3 obtained after the hydrotreating reaction I into a first separation zone 4 to carry out separation to obtain a first gas effluent 5, first hydrogenated naphtha 6, first hydrogenated diesel oil 7, first hydrogenated wax oil 8 and hydrogenated slag reduction 9;
(2) Introducing the first hydrogenated wax oil 8, optionally together with the first hydrogenated diesel oil 7, into a fixed bed wax oil hydrotreating reaction zone 10 for hydrotreating reaction II, and introducing a wax oil hydrotreating reaction effluent 11 obtained after hydrotreating reaction II into a second separation zone 12 for separation to obtain a second gas effluent 13, second hydrogenated naphtha 14, second hydrogenated diesel oil 15 and second hydrogenated wax oil 16;
(3) Introducing the second hydrogenated wax oil 16 and a part of the hydrogenated slag reduction 9, optionally together with the second hydrogenated diesel oil 15, into a catalytic cracking reaction zone 17 for catalytic cracking reaction, and introducing a catalytic cracking reaction effluent 18 obtained after the catalytic cracking reaction into a third separation zone 19 for separation to obtain low-carbon olefin 20, catalytic cracking naphtha 21, catalytic cracking light cycle oil 22, catalytic cracking heavy cycle oil 23 and catalytic cracking slurry oil 24;
(4) The catalytic cracking light cycle oil 22, the catalytic cracking heavy cycle oil 23, the catalytic cracking slurry oil 24, the rest of the hydrogenated slag reduction 9, and optionally the first hydrogenated diesel oil 7 and/or the second hydrogenated diesel oil 15 are introduced into a ship fuel blending area 25 for blending, so as to obtain the low-sulfur residue type ship fuel 26.
As previously described, a second aspect of the present invention provides a system for producing both low carbon olefins and low sulfur residue type marine fires, the system comprising:
the fixed bed residuum hydrotreatment reaction zone is used for carrying out hydrotreatment reaction I on a residuum raw material to obtain residuum hydrotreatment reaction effluent;
the first separation zone is used for separating the residual oil hydrotreating reaction effluent to obtain a first gas effluent, first hydrogenated naphtha, first hydrogenated diesel oil, first hydrogenated wax oil and hydrogenated slag reduction;
the fixed bed wax oil hydrotreating reaction zone is used for carrying out hydrotreating reaction II on the first hydrogenated wax oil, optionally together with the first hydrogenated diesel oil to obtain a wax oil hydrotreating reaction effluent;
the second separation zone is used for separating the wax oil hydrotreating reaction effluent to obtain a second gas effluent, second hydrogenated naphtha, second hydrogenated diesel oil and second hydrogenated wax oil;
The catalytic cracking reaction zone is used for carrying out catalytic cracking reaction on the second hydrogenated wax oil, a part of the hydrogenated slag reduction, optionally, the second hydrogenated diesel oil to obtain a catalytic cracking reaction effluent;
the third separation zone is used for separating the catalytic cracking reaction effluent to obtain low-carbon olefin, catalytic cracking naphtha, catalytic cracking light cycle oil, catalytic cracking heavy cycle oil and catalytic cracking slurry oil;
and the ship combustion blending zone is used for blending the catalytic cracking light cycle oil, the catalytic cracking heavy cycle oil, the catalytic cracking slurry oil and the rest of the hydrogenated slag reduction, and optionally, the first hydrogenated diesel oil and/or the second hydrogenated diesel oil to obtain the low-sulfur residue type ship combustion.
Preferably, the fixed bed residuum hydroprocessing reaction zone includes at least 1 fixed bed reactor.
According to a particularly preferred embodiment, the fixed bed residuum hydroprocessing reaction zone includes from 3 to 6 fixed bed reactors.
Preferably, the fixed bed wax oil hydroprocessing reaction zone comprises at least 1 fixed bed reactor.
According to a particularly preferred embodiment, the fixed bed wax oil hydroprocessing reaction zone comprises 1-3 fixed bed reactors.
Preferably, the ship's blending zone comprises at least one of a storage device, a transportation device, a mixing device, a filtration device and a measurement device.
Preferably, the system further comprises: and the fourth separation zone is used for separating the first hydrogenated naphtha from the second hydrogenated naphtha to obtain light naphtha and heavy naphtha.
The method of the invention also has the following specific advantages:
1. the invention adopts 100% residual oil raw material (normal slag and/or reduced slag) to produce high-quality catalytic cracking raw material, and can reduce the raw material cost for producing low-carbon olefin to the greatest extent.
2. The invention adopts low-value components such as hydrogenated slag reduction, hydrogenated diesel oil with residual oil hydrogenation, catalytic cracking light cycle oil, catalytic cracking heavy cycle oil, catalytic cracking slurry oil and the like to produce the low-sulfur residue type ship fuel in a blending way, and can reduce the production cost of the ship fuel.
3. The invention realizes deep hydrogenation of wax oil fraction contained in residual oil raw material, first hydrogenated heavy oil cracked in residual oil hydrotreating reaction, catalytic cracking light cycle oil and catalytic cracking heavy cycle oil, thereby providing the best quality raw material for catalytic cracking.
4. The residuum hydrotreatment reaction zone of the invention can be operated under the process conditions of conventional residuum hydrogenation without operating at high severity for producing catalytic cracking feedstock, which is beneficial to long-period operation of residuum hydrogenation equipment.
5. The invention not only can increase the yield of the low-carbon olefin and simultaneously give consideration to the production of the low-sulfur residue type ship fuel, but also can flexibly adjust the production scale of the low-sulfur residue type ship fuel according to the needs.
The invention will be described in detail below by way of examples. In the following examples, various raw materials used without particular description are commercially available.
In the following examples, without corresponding description:
the hydrotreating reaction I is carried out in a fixed bed residual oil hydrotreating medium-sized device;
the hydrotreating reaction II is carried out in a fixed bed wax oil hydrotreating medium-sized device;
the catalytic cracking reaction is carried out in a catalytic cracking medium-sized device.
The blending is performed in a ship-to-ship blending mesoscale unit.
The residuum feedstock was middle east residuum with properties as set forth in table 1.
In a fixed bed residuum hydrotreatment reaction zone, a catalyst A, a catalyst B, a catalyst C and a catalyst D are sequentially filled along the flow direction, wherein the filling volume ratio of the catalyst A to the catalyst B to the catalyst C to the catalyst D is 5:40:25:30;
in a fixed bed wax oil hydrotreating reaction zone, a catalyst A and a catalyst E are sequentially filled along the flow direction, wherein the filling volume ratio of the catalyst A to the catalyst E is 5:95;
The catalysts A-E are produced by a kaolin catalyst factory of China petrochemical catalyst division company, and the properties of the catalysts A-E are shown in Table 2;
wherein, the catalyst A is a protecting catalyst, the catalyst B is a hydrodemetallization catalyst, the catalyst C is a hydrodesulfurization catalyst, the catalyst D is a hydrodecarbonization catalyst, and the catalyst E is a wax oil hydrotreating catalyst.
The catalytic cracking catalysts were MMC-2, which were produced by Qilu division of China petrochemical Co., ltd, and the MMC-2 properties are shown in Table 3.
The dry gas and the liquefied gas can be rectified to obtain low-carbon olefins such as ethylene, propylene and the like.
In the examples below, the feed and product flow rates for each reaction zone were calculated (without hydrogen) at 100g/h based on fresh residuum feed, unless otherwise indicated.
Table 1: residuum feedstock properties
| Properties of (C) | |
| Density (20 ℃), g/cm 3 | 0.9778 |
| Hydrogen content, wt% | 11.05 |
| Carbon residue content, weight percent | 11.60 |
| Sulfur content, wt% | 4.02 |
| Nitrogen content, wt% | 0.22 |
| Content of (nickel+vanadium), μg/g | 70.1 |
Table 2: composition and physicochemical properties of residuum hydrotreating catalyst and wax oil hydrotreating catalyst
| Project | Catalyst A | Catalyst B | Catalyst C | Catalyst D | Catalyst E |
| MO 3 Weight percent | 3.0 | 8.4 | 13.0 | 16.2 | 2.3 |
| NiO, wt% | 0.8 | 1.5 | 3.5 | 4.5 | 2.4 |
| WO 3 Weight percent | - | - | - | - | 26.0 |
| Pore volume, mL/g | 0.80 | 0.66 | 0.64 | 0.64 | 0.28 |
| Specific surface area, m 2 /g | 100 | 157 | 210 | 186 | 150 |
| Bulk density, g/cm 3 | 0.45 | 0.47 | 0.62 | 0.64 | 0.82 |
| Average particle diameter, mm | 3.5 | 1.1 | 1.1 | 1.1 | 1.1 |
Table 3: catalytic cracking catalyst Properties
Example 1
The embodiment provides a method for simultaneously producing low-carbon olefin and low-sulfur residue type ship combustion, which comprises the following steps:
(1) Introducing a residual oil raw material into a fixed bed residual oil hydrotreating reaction zone filled with a residual oil hydrotreating catalyst in the presence of hydrogen to carry out hydrotreating reaction I, and separating residual oil hydrotreating reaction effluent obtained after the hydrotreating reaction I to obtain a first gas effluent, first hydrogenated naphtha, first hydrogenated diesel oil, first hydrogenated wax oil and hydrogenated slag reduction; the cutting point of the first hydrogenated naphtha and the first hydrogenated diesel oil is 175 ℃, and the cutting point of the first hydrogenated diesel oil and the first hydrogenated wax oil is 350 ℃;
(2) Introducing the first hydrogenated wax oil into a fixed bed wax oil hydrotreating reaction zone filled with a wax oil hydrotreating catalyst to carry out hydrotreating reaction II, and separating a wax oil hydrotreating reaction effluent obtained after the hydrotreating reaction II to obtain a second gas effluent, second hydrogenated naphtha, second hydrogenated diesel oil and second hydrogenated wax oil; the cutting point of the second hydrogenated naphtha and the second hydrogenated diesel oil is 175 ℃, and the cutting point of the second hydrogenated diesel oil and the second hydrogenated wax oil is 350 ℃;
(3) Introducing the second hydrogenated wax oil, the second hydrogenated diesel oil and 50 weight percent of the hydrogenated slag serving as raw materials for catalytic pyrolysis into a catalytic pyrolysis reaction zone filled with a catalytic pyrolysis catalyst for catalytic pyrolysis reaction, and separating catalytic pyrolysis reaction effluent obtained after the catalytic pyrolysis reaction to obtain dry gas and liquefied gas, catalytic pyrolysis naphtha, catalytic pyrolysis light cycle oil, catalytic pyrolysis heavy cycle oil and catalytic pyrolysis slurry oil; wherein the cutting points of the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil are 350 ℃;
(4) And introducing the catalytic cracking light cycle oil, the catalytic cracking heavy cycle oil, the catalytic cracking slurry oil, the rest of the hydrogenated slag reduction and the first hydrogenated diesel oil into a ship combustion blending area for blending to obtain the low-sulfur residue type ship combustion.
The reaction conditions and the product distribution of the fixed bed residuum hydrotreatment reaction zone are shown in table 4, the reaction conditions and the product distribution of the fixed bed wax oil hydrotreatment reaction zone are shown in table 5, the properties of the catalytic cracking raw material are shown in table 6, and the reaction conditions and the product distribution of the catalytic cracking reaction zone are shown in table 7; the composition of the components of the marine fuel blending zone and the properties of the marine fuel product with low sulfur residues are shown in table 8;
As can be seen from the data in tables 4-8, 3.9g of ethylene and 13.9g of propylene were obtained per 100g of residuum feedstock in this example, while also obtaining 40.7g of marine combustion conforming to the RMG380 standard.
Comparative example 1
This comparative example is similar to the process of example 1, except that a fixed bed residuum hydrotreating-catalytic cracking process is employed to produce lower olefins, i.e., the residuum feedstock is reacted in a fixed bed residuum hydrotreating reaction zone and separated into a first gaseous effluent, a first hydrogenated naphtha, a first hydrogenated diesel oil, a first hydrogenated wax oil, and a reduced hydrogenation residue, then the first hydrogenated wax oil and 50 wt% of the reduced hydrogenation residue are directly introduced into a catalytic cracking reaction zone for catalytic cracking reaction, and finally the catalytic cracked light cycle oil, the catalytic cracked heavy cycle oil, the catalytic cracked slurry oil, the remainder of the reduced hydrogenation residue, and the first hydrogenated diesel oil are introduced into a ship-to-fuel blending zone for blending to obtain lower sulfur residue type ship-to-fuel.
The reaction conditions and product distribution of the fixed bed residuum hydrotreatment reaction zone are shown in table 4, the properties of the catalytic cracking feedstock are shown in table 6, the reaction conditions and product distribution of the catalytic cracking reaction zone are shown in table 7, and the composition of the components of the ship combustion blending zone and the properties of the low sulfur residue type ship combustion product are shown in table 8.
As can be seen from the data in tables 4-8, 3.4g of ethylene and 12.4g of propylene were obtained per 100g of residuum feedstock in this comparative example, while also obtaining a marine combustion of 43.2g that meets the RMG380 standard.
Example 2
This example is similar to the operating method of example 1, except that in step (2) the first hydrogenated wax oil and the first hydrogenated diesel oil are introduced into a fixed bed wax oil hydrotreating reaction zone packed with a wax oil hydrotreating catalyst; in the step (3), the second hydrogenated wax oil, the second hydrogenated diesel oil and 65 weight percent of the hydrogenated slag reduction are introduced into a catalytic cracking reaction zone filled with a catalytic cracking catalyst as raw materials for catalytic cracking.
The reaction conditions and product distribution of the fixed bed residuum hydrotreatment reaction zone are shown in table 4, the reaction conditions and product distribution of the fixed bed wax oil hydrotreatment reaction zone are shown in table 5, the properties of the catalytic cracking feedstock are shown in table 6, the reaction conditions and product distribution of the catalytic cracking reaction zone are shown in table 7, and the composition of the components and the properties of the low sulfur residue type marine combustion product of the marine combustion blending zone are shown in table 8.
As can be seen from the data in tables 4-8, 5.2g ethylene and 18.7g propylene were obtained per 100g residuum feedstock in this example while still obtaining 23.1g marine fuel meeting the RMG380 standard.
Comparative example 2
This comparative example was similar to the operating method of example 2, except that in step (1), the sulfur content of the hydrogenated slag reduction was 0.93 wt%.
The reaction conditions and product distribution of the fixed bed residuum hydrotreatment reaction zone are shown in table 4, the reaction conditions and product distribution of the fixed bed wax oil hydrotreatment reaction zone are shown in table 5, the properties of the catalytic cracking feedstock are shown in table 6, the reaction conditions and product distribution of the catalytic cracking reaction zone are shown in table 7, and the composition of the components and the properties of the low sulfur residue type marine combustion product of the marine combustion blending zone are shown in table 8.
As can be seen from the data in tables 4-8, 4.1g ethylene and 14.7g propylene were obtained per 100g residuum feedstock in this comparative example, and no marine combustion meeting the RMG180 standard was obtained.
Example 3
This example is similar to the operating method of example 1, except that in step (3), no second hydrogenated diesel oil is introduced; in the step (4), the catalytic cracking light cycle oil, the catalytic cracking heavy cycle oil, the catalytic cracking slurry oil, 50 weight percent of the hydrogenated slag reduction, the first hydrogenated diesel oil and the second hydrogenated diesel oil are introduced into a ship combustion blending area for blending, so that the low-sulfur residue type ship combustion is obtained.
The reaction conditions and product distribution of the fixed bed residuum hydrotreatment reaction zone are shown in table 4, the reaction conditions and product distribution of the fixed bed wax oil hydrotreatment reaction zone are shown in table 5, the properties of the catalytic cracking feedstock are shown in table 6, the reaction conditions and product distribution of the catalytic cracking reaction zone are shown in table 7, and the composition of the components and the properties of the low sulfur residue type marine combustion product of the marine combustion blending zone are shown in table 8.
As can be seen from the data in tables 4-8, 3.7g ethylene and 13.2g propylene were obtained per 100g residuum feedstock in this example while still obtaining a marine combustion of 43.3g conforming to the RMG380 standard.
Example 4
This example is similar to the method of operation of example 2, except that the first and second hydrogenated naphthas are mixed to separate light naphthas and heavy naphthas, the light naphthas also being introduced into the catalytic cracking reaction zone for catalytic cracking reactions.
The reaction conditions and product distribution of the fixed bed residuum hydrotreatment reaction zone are shown in table 4, the reaction conditions and product distribution of the fixed bed wax oil hydrotreatment reaction zone are shown in table 5, the properties of the catalytic cracking feedstock are shown in table 6, the reaction conditions and product distribution of the catalytic cracking reaction zone are shown in table 7, and the composition of the components and the properties of the low sulfur residue type marine combustion product of the marine combustion blending zone are shown in table 8.
As can be seen from the data in tables 4-8, 5.4g ethylene and 18.8g propylene were obtained per 100g residuum feedstock in this example, while still obtaining 23.1g marine combustion in accordance with the RMG380 standard.
Example 5
This example is similar to the operating method of example 2, except that in step (2) the effluent hydrogen content in the fixed bed wax oil hydrogenation reaction zone is 13.08 wt%.
The reaction conditions and product distribution of the fixed bed residuum hydrotreatment reaction zone are shown in table 4, the reaction conditions and product distribution of the fixed bed wax oil hydrotreatment reaction zone are shown in table 5, the properties of the catalytic cracking feedstock are shown in table 6, the reaction conditions and product distribution of the catalytic cracking reaction zone are shown in table 7, and the composition of the components and the properties of the low sulfur residue type marine combustion product of the marine combustion blending zone are shown in table 8.
As can be seen from the data in tables 4-8, 4.8g ethylene and 17.2g propylene were obtained per 100g residuum feedstock in this example while still obtaining 25.7g marine combustion meeting the RMG180 standard.
Example 6
This example is similar to the operating method of example 2 except that in step (3), the hydroprocessed slag as the feedstock to the catalytic cracking reaction zone comprises 90 wt% of the total weight of the hydroprocessed slag.
The reaction conditions and product distribution of the fixed bed residuum hydrotreatment reaction zone are shown in table 4, the reaction conditions and product distribution of the fixed bed wax oil hydrotreatment reaction zone are shown in table 5, the properties of the catalytic cracking feedstock are shown in table 6, the reaction conditions and product distribution of the catalytic cracking reaction zone are shown in table 7, and the composition of the components and the properties of the low sulfur residue type marine combustion product of the marine combustion blending zone are shown in table 8.
As can be seen from the data in tables 4-8, 5.5g ethylene and 19.7g propylene were obtained per 100g residuum feedstock in this example, while 9.1g marine combustion meeting the RMG180 standard was also obtained, but the catalytic cracking light cycle oil, catalytic cracking heavy cycle oil, and catalytic cracking slurry oil remained and could not be blended all together.
Table 4: reaction conditions and product distribution in fixed bed residuum hydrotreatment reaction zone
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Feed flow, g/h | ||||
| Residuum feedstock | 100 | 100 | 100 | 100 |
| Hydrogen gas | 1.7 | 1.9 | 1.7 | 1.9 |
| Totalizing | 101.7 | 101.9 | 101.7 | 101.9 |
| Process conditions | ||||
| Reaction temperature, DEG C | 380 | 390 | 380 | 390 |
| Hydrogen partial pressure, MPa | 15.0 | 15.0 | 15.0 | 15.0 |
| Liquid hourly space velocity, h -1 | 0.20 | 0.20 | 0.20 | 0.20 |
| Hydrogen to oil volume ratio | 700 | 700 | 700 | 700 |
| Product flow, g/h | ||||
| First gaseous effluent | 4.9 | 5.2 | 4.9 | 5.2 |
| First hydrogenated naphtha | 0.9 | 1.3 | 0.9 | 1.3 |
| First hydrogenated diesel oil | 10.5 | 12.8 | 10.5 | 12.8 |
| First hydrogenated wax oil | 43.8 | 45.5 | 43.8 | 45.5 |
| Hydrogenation slag reduction | 41.6 | 37.1 | 41.6 | 37.1 |
| Totalizing | 101.7 | 101.9 | 101.7 | 101.9 |
| Hydrogenation slag sulfur content, wt% | 0.59 | 0.25 | 0.59 | 0.25 |
Table 4 (continuous 1): reaction conditions and product distribution in fixed bed residuum hydrotreatment reaction zone
| Example 5 | Example 6 | Comparative example 1 | Comparative example 2 | |
| Feed flow, g/h | ||||
| Residuum feedstock | 100 | 100 | 100 | 100 |
| Hydrogen gas | 1.9 | 1.9 | 1.8 | 1.6 |
| Totalizing | 101.9 | 101.9 | 101.8 | 101.6 |
| Process conditions | ||||
| Reaction temperature, DEG C | 390 | 390 | 380 | 373 |
| Hydrogen partial pressure, MPa | 15.0 | 15.0 | 15.0 | 15.0 |
| Liquid hourly space velocity, h -1 | 0.20 | 0.20 | 0.20 | 0.20 |
| Hydrogen to oil volume ratio | 700 | 700 | 700 | 700 |
| Product flow, g/h | ||||
| First gaseous effluent | 5.2 | 5.2 | 5.1 | 4.8 |
| First hydrogenated naphtha | 1.3 | 1.3 | 0.9 | 0.8 |
| First hydrogenated diesel oil | 12.8 | 12.8 | 11.1 | 9.2 |
| First hydrogenated wax oil | 45.5 | 45.5 | 44.9 | 43.3 |
| Hydrogenation slag reduction | 37.1 | 37.1 | 39.8 | 43.5 |
| Totalizing | 101.9 | 101.9 | 101.8 | 101.6 |
| Hydrogenation slag sulfur content, wt% | 0.25 | 0.25 | 0.51 | 0.93 |
Table 5: reaction condition and product distribution of fixed bed wax oil hydrotreatment reaction zone
Table 5 (continuation 1): reaction condition and product distribution of fixed bed wax oil hydrotreatment reaction zone
| Example 5 | Example 6 | Comparative example 2 | |
| Feed flow, g/h | |||
| First hydrogenated wax oil | 45.5 | 45.5 | 43.3 |
| First hydrogenated diesel oil | 12.8 | 12.8 | - |
| Hydrogen gas | 0.5 | 0.5 | 0.4 |
| Totalizing | 58.8 | 58.8 | 43.7 |
| Process conditions | |||
| Reaction temperature, DEG C | 365 | 375 | 375 |
| Hydrogen partial pressure, MPa | 12.0 | 14.0 | 14.0 |
| Liquid hourly space velocity, h -1 | 1.3 | 1.0 | 1.0 |
| Hydrogen to oil volume ratio | 700 | 700 | 700 |
| Effluent hydrogen content, wt% | 13.08 | 13.65 | 13.58 |
| Product flow, g/h | |||
| Second gaseous effluent | 0.3 | 0.5 | 0.4 |
| Second hydrogenated naphtha | 0.2 | 0.5 | 0.3 |
| Second hydrogenated diesel oil | 14.8 | 15.7 | 3.0 |
| Second hydrogenated wax oil | 43.5 | 42.1 | 40.0 |
| Totalizing | 58.8 | 58.8 | 43.7 |
Table 6: catalytic cracking reaction zone feedstock properties
| Properties of (C) | Example 1 | Example 2 | Example 3 | Example 4 |
| Density (20 ℃), g/cm 3 | 0.8956 | 0.8872 | 0.8979 | 0.8820 |
| Hydrogen content, wt% | 13.01 | 13.20 | 12.96 | 13.21 |
| Carbon residue, weight percent | 2.94 | 2.34 | 3.08 | 2.31 |
| Sulfur content, wt% | 0.19 | 0.07 | 0.20 | 0.07 |
| Nitrogen content, wt% | 0.069 | 0.058 | 0.073 | 0.058 |
| Content of (nickel+vanadium), μg/g | 3.3 | 1.7 | 3.5 | 1.7 |
Table 6 (continuous 1): catalytic cracking reaction zone feedstock properties
| Properties of (C) | Example 5 | Example 6 | Comparative example 1 | Comparative example 2 |
| Density (20 ℃), g/cm 3 | 0.9020 | 0.8931 | 0.9191 | 0.9075 |
| Hydrogen content, wt% | 12.87 | 13.07 | 12.49 | 12.75 |
| Carbon residue, weight percent | 2.34 | 2.92 | 2.73 | 4.22 |
| Sulfur content, wt% | 0.07 | 0.09 | 0.16 | 0.40 |
| Nitrogen content, wt% | 0.058 | 0.072 | 0.064 | 0.097 |
| Content of (nickel+vanadium), μg/g | 1.7 | 2.1 | 2.8 | 7.1 |
Table 7: reaction conditions and product distribution in catalytic cracking reaction zone
| Project | Example 1 | Example 2 | Example 3 | Example 4 |
| Raw material flow, g/h | ||||
| Second hydrogenated wax oil | 40.4 | 42.1 | 40.4 | 42.1 |
| Second addingHydrogen diesel oil | 3.1 | 15.7 | - | 15.7 |
| Hydrogenation slag reduction | 20.8 | 24.1 | 20.8 | 24.1 |
| Light naphtha | - | - | - | 0.6 |
| Totalizing | 64.3 | 81.9 | 61.2 | 82.5 |
| Reaction pressure, MPa | 0.08 | 0.08 | 0.08 | 0.08 |
| Reaction temperature, DEG C | 565 | 565 | 565 | 565 |
| Weight hourly space velocity, h -1 | 4 | 4 | 4 | 4 |
| Weight ratio of agent to oil | 12 | 12 | 12 | 12 |
| Atomization steam content (based on fresh residuum raw materials), weight percent | 25 | 25 | 25 | 25 |
| Product flow, g/h | ||||
| Dry gas + liquefied gas | 35.6 | 47.6 | 33.9 | 48.0 |
| Catalytic pyrolysis naphtha | 14.4 | 18.1 | 13.7 | 18.3 |
| Catalytic cracking light cycle oil | 6.6 | 7.7 | 6.3 | 7.7 |
| Catalytic cracking heavy cycle oil+catalytic slurry oil | 2.8 | 2.4 | 2.6 | 2.4 |
| Coke | 4.9 | 6.1 | 4.7 | 6.1 |
| Totals to | 64.3 | 81.9 | 61.2 | 82.5 |
| Ethylene | 3.9 | 5.2 | 3.7 | 5.4 |
| Propylene | 13.9 | 18.7 | 13.2 | 18.8 |
Table 7 (continuation 1): reaction conditions and product distribution in catalytic cracking reaction zone
Table 8: component composition of marine fuel blending zone and low sulfur residue marine fuel product properties
| Example 1 | Example 2 | Example 3 | Example 4 | |
| Feed flow, g/h | ||||
| Hydrogenation slag reduction | 20.8 | 13.0 | 20.8 | 13.0 |
| Light cycle oil | 6.6 | 7.7 | 6.3 | 7.7 |
| Heavy cycle oil + slurry oil | 2.8 | 2.4 | 2.6 | 2.4 |
| First hydrogenated diesel oil | 10.5 | - | 10.5 | - |
| Second hydrogenated diesel oil | - | - | 3.1 | - |
| Totalizing | 40.7 | 23.1 | 43.3 | 23.1 |
| Properties of marine combustion | ||||
| Silicon+aluminum, μg/g | 40.8 | 51.5 | 36.5 | 51.5 |
| Sulfur content, wt% | 0.40 | 0.21 | 0.38 | 0.21 |
| Viscosity at 50 ℃ of mm 2 /s | 270 | 352 | 192 | 352 |
| Carbon Aromatic Index (CCAI) | 795 | 813 | 733 | 813 |
Table 8 (continuation 1): component composition of marine fuel blending zone and low sulfur residue marine fuel product properties
| Example 5 | Example 6 | Comparative example 1 | Comparative example 2 | |
| Feed flow, g/h | ||||
| Hydrogenation slag reduction | 13.0 | 3.7 | 19.9 | 13.0 |
| Light cycle oil | 9.1 | 4.3 | 8.8 | 7.8 |
| Heavy cycle oil + slurry oil | 3.6 | 1.1 | 3.4 | 3.1 |
| First hydrogenated diesel oil | - | - | 11.1 | 9.2 |
| Second hydrogenated diesel oil | - | - | - | 3.0 |
| Totalizing | 25.7 | 9.1 | 43.2 | 36.1 |
| Properties of marine combustion | ||||
| Si+Al，μg/g | 58.3 | 58.4 | 47.6 | 51.4 |
| Sulfur content, wt% | 0.21 | 0.21 | 0.33 | 0.61 |
| Viscosity at 50 ℃ of mm 2 /s | 121 | 102 | 209 | 132 |
| Carbon Aromatic Index (CCAI) | 828 | 827 | 797 | 797 |
From the results in tables 4 to 8, it can be seen that: the invention organically combines the fixed bed residual oil hydrotreating process, the fixed bed wax oil hydrotreating process, the catalytic cracking process and the ship combustion blending technology, strictly controls the sulfur content of the hydrogenated slag reduction obtained in the fixed bed residual oil hydrotreating reaction zone, not only can remarkably improve the yield of high-value products such as propylene, ethylene and the like in the combined process, but also can obtain the low-sulfur residue type ship combustion meeting the standard and having low cost.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (38)
1. A method for producing both low-carbon olefins and low-sulfur residues on a marine vessel, comprising:
(1) Introducing a residual oil raw material into a fixed bed residual oil hydrotreating reaction zone in the presence of hydrogen to carry out hydrotreating reaction I, and separating residual oil hydrotreating reaction effluent obtained after the hydrotreating reaction I to obtain a first gas effluent, first hydrogenated naphtha, first hydrogenated diesel oil, first hydrogenated wax oil and hydrogenated slag reduction; controlling the reaction condition of the fixed bed residual oil hydrotreating reaction zone and/or controlling the catalyst grading mode in the fixed bed residual oil hydrotreating reaction zone so that the sulfur content of the hydrogenated slag reduction is no more than 0.8 wt%;
(2) Introducing the first hydrogenated wax oil, optionally together with the first hydrogenated diesel oil, into a fixed bed wax oil hydrotreating reaction zone for hydrotreating reaction II, and separating a wax oil hydrotreating reaction effluent obtained after hydrotreating reaction II to obtain a second gas effluent, second hydrogenated naphtha, second hydrogenated diesel oil and second hydrogenated wax oil;
(3) Introducing the second hydrogenated wax oil, a part of the hydrogenated slag reduction, optionally the second hydrogenated diesel oil into a catalytic cracking reaction zone for catalytic cracking reaction, and separating a catalytic cracking reaction effluent obtained after the catalytic cracking reaction to obtain low-carbon olefin, catalytic cracking naphtha, catalytic cracking light cycle oil, catalytic cracking heavy cycle oil and catalytic cracking slurry oil;
(4) And introducing the catalytic cracking light cycle oil, the catalytic cracking heavy cycle oil, the catalytic cracking slurry oil and the rest of the hydrogenated slag reduction, optionally together with the first hydrogenated diesel oil and/or the second hydrogenated diesel oil, into a ship combustion blending area for blending to obtain the low-sulfur residue type ship combustion.
2. The process according to claim 1, wherein in step (2) the reaction conditions of the fixed bed wax oil hydroprocessing reaction zone and/or the catalyst fractionation pattern in the fixed bed wax oil hydroprocessing reaction zone are controlled such that the hydrogen content of the wax oil hydroprocessing reaction effluent is less than 13.2 wt%.
3. The process according to claim 2, wherein the reaction conditions of the fixed bed wax oil hydroprocessing reaction zone and/or the catalyst fractionation pattern in the fixed bed wax oil hydroprocessing reaction zone are controlled such that the hydrogen content of the wax oil hydroprocessing reaction effluent is less than 13.5 wt%.
4. A process according to any one of claims 1 to 3, wherein in step (2) the reaction conditions of the fixed bed wax oil hydroprocessing reaction zone comprise: the hydrogen partial pressure is 6-25MPa, the reaction temperature is 300-460 ℃, and the liquid hourly space velocity is 0.1-5.0h -1 The volume ratio of hydrogen to oil is 200-2000.
5. The process of claim 4, wherein in step (2), the reaction conditions of the fixed bed wax oil hydroprocessing reaction zone comprise: the hydrogen partial pressure is 10-20MPa, the reaction temperature is 350-440 ℃, and the liquid hourly space velocity is 0.5-2.0h -1 The volume ratio of hydrogen oil is 400-1200.
6. A process according to any one of claims 1 to 3, wherein in step (2) the fixed bed wax oil hydroprocessing reaction zone is charged with a wax oil hydroprocessing catalyst having a bulk density of from 0.4 to 1.3g/cm 3 The average grain diameter is 0.5-50mm, and the specific surface area is 50-400m 2 /g。
7. The method according to claim 6, wherein in step (2), the wax oil hydrotreating catalyst is selected from at least one of a guard catalyst I, a wax oil hydrofinishing catalyst.
8. The method according to claim 7, wherein in step (2), the wax oil hydrotreating catalyst contains a support selected from at least one of alumina, a combination of alumina-silica, and titania, and an active metal element selected from at least one of nickel, cobalt, molybdenum, and tungsten, supported on the support.
9. The process according to claim 7, wherein in the wax oil hydrotreating catalyst the content of nickel and/or cobalt in oxide is 0-30 wt.%, the content of molybdenum and/or tungsten in oxide is 0-35 wt.%, and the sum of the contents of nickel, cobalt, molybdenum, tungsten in oxide is greater than 0, based on the total weight of the wax oil hydrotreating catalyst.
10. A process according to any one of claims 1 to 3, wherein in step (2) the separation conditions of the wax oil hydrotreating reaction effluent are controlled such that the initial boiling point of the second hydrogenated naphtha is 50-70 ℃, the cut point of the second hydrogenated naphtha and the second hydrogenated diesel is 160-180 ℃, the cut point of the second hydrogenated diesel and the second hydrogenated wax oil is 340-360 ℃, and the final boiling point of the second hydrogenated wax oil is 500-580 ℃.
11. A process according to any one of claims 1 to 3, wherein in step (1) the residuum feedstock is selected from at least one of atmospheric residuum, vacuum residuum.
12. A process according to any one of claims 1 to 3, wherein in step (1) the reaction conditions of the fixed bed residuum hydroprocessing reaction zone and/or the catalyst fractionation pattern in the fixed bed residuum hydroprocessing reaction zone is controlled such that the sulfur content of the hydrogenated reduced slag is no more than 0.6 wt%.
13. A process according to any one of claims 1 to 3 wherein in step (1) the reaction conditions of the fixed bed residuum hydroprocessing reaction zone are: the reaction temperature is 300-460 ℃, the hydrogen partial pressure is 6-25MPa, and the liquid hourly space velocity is 0.10-1.0h -1 The volume ratio of hydrogen to oil is 100-1500.
14. The method of claim 13, wherein in step (1), the fixed bed slagThe reaction conditions of the oil hydrotreating reaction zone are as follows: the reaction temperature is 350-440 ℃, the hydrogen partial pressure is 12-20MPa, and the liquid hourly space velocity is 0.15-0.4h -1 The volume ratio of hydrogen to oil is 300-1000.
15. A process according to any one of claims 1 to 3, wherein in step (1) the fixed bed residuum hydroprocessing reaction zone is charged with residuum hydroprocessing catalyst having an average particle size of from 0.5 to 50mm and a bulk density of from 0.3 to 1.2g/cm 3 Average pore diameter of 6-30nm and specific surface area of 50-400m 2 /g。
16. The process of claim 15, wherein in step (1), the residuum hydrotreating catalyst is selected from at least one of guard catalyst II, hydrodemetallization catalyst, hydrodesulphurisation catalyst, and hydrodecarbon residue catalyst.
17. The process according to claim 16, wherein in step (1), the residuum hydrotreating catalyst contains a support selected from at least one of alumina, silica, and titania, and an active metal element selected from group vi B metal elements and/or group viii metal elements supported on the support.
18. The method of claim 17, wherein in the residuum hydroprocessing catalyst the active metal element is selected from at least one of a nickel-tungsten combination, a nickel-tungsten-cobalt combination, a nickel-molybdenum combination, a cobalt-molybdenum combination.
19. The process of claim 17 wherein in the residuum hydroprocessing catalyst the support further comprises at least one element from the group consisting of boron, germanium, zirconium, phosphorus, chlorine, and fluorine.
20. The process according to claim 18, wherein the content of the active metal element in oxide is 1 to 30wt% based on the total weight of the resid hydrotreating catalyst in the resid hydrotreating catalyst.
21. The process according to claim 20, wherein the content of the active metal element in oxide is 1 to 25wt% based on the total weight of the resid hydrotreating catalyst in the resid hydrotreating catalyst.
22. A process according to any one of claims 1 to 3, wherein in step (1) the separation conditions of the residuum hydrotreatment reaction effluent are controlled such that the initial boiling point of the first hydrogenated naphtha is 50-70 ℃, the cut point of the first hydrogenated naphtha and the first hydrogenated diesel is 160-180 ℃, the cut point of the first hydrogenated diesel and the first hydrogenated wax oil is 340-360 ℃, and the final boiling point of the first hydrogenated wax oil is 500-580 ℃.
23. A process according to any one of claims 1 to 3, wherein in step (3) the catalytic cracking reaction zone is packed with a catalytic cracking catalyst comprising zeolite, inorganic oxide and optionally clay, the inorganic oxide being selected from at least one of silica, alumina, zirconia, titania and amorphous silica alumina, the zeolite being present in an amount of 10 to 50 wt%, the inorganic oxide being present in an amount of 5 to 90 wt% and the clay being present in an amount of 0 to 70 wt%, based on the total weight of the catalytic cracking catalyst.
24. The method according to claim 23, wherein in the catalytic cracking catalyst, the zeolite is at least one selected from a Y-type zeolite with or without rare earth elements, an HY-type zeolite with or without rare earth elements, an ultrastable Y-type zeolite with or without rare earth elements, and a zeolite having MFI structure.
25. The method of claim 23, wherein, inIn the step (3), the reaction conditions of the catalytic cracking reaction zone are as follows: the weight ratio of the atomized steam to the residual oil raw material is 0.05-0.5:1, the weight ratio of the agent to the oil is 6-20:1, the temperature is 500-680 ℃, and the weight hourly space velocity is 1-6h -1 The reaction pressure is 0.05-1MPa.
26. A process according to any one of claims 1 to 3, wherein in step (3), the separation conditions of the catalytic cracking reaction effluent are controlled such that the initial boiling point of the catalytic cracking light cycle oil is 170 to 190 ℃, the cut points of the catalytic cracking light cycle oil and the catalytic cracking heavy cycle oil are 340 to 360 ℃, and the final boiling point of the catalytic cracking heavy cycle oil is 500 to 580 ℃.
27. A process according to any one of claims 1 to 3, wherein in step (3) the hydrodewaxed slag introduced into the catalytic cracking reaction zone comprises 5 to 95% by weight of the total weight of the hydrodewaxed slag.
28. The process of claim 27, wherein in step (3), the hydropulped slag introduced into the catalytic cracking reaction zone comprises 20-80 wt% of the total weight of the hydropulped slag.
29. A method according to any one of claims 1-3, wherein in step (4), the method further comprises: at least one of atmospheric residuum, vacuum residuum, visbreaking residuum, catalytic slurry oil, catalytic heavy cycle oil, catalytic light cycle oil, coker wax oil, ethylene tar and refined extracted oil of lubricating oil solvent is introduced into a ship combustion blending area for blending, so as to obtain the low-sulfur residue type ship combustion.
30. A method according to any one of claims 1-3, wherein the method further comprises: and separating the first hydrogenated naphtha and/or the second hydrogenated naphtha to obtain light naphtha and heavy naphtha, wherein the light naphtha is recycled to the catalytic cracking reaction zone.
31. The process of claim 30, wherein the separation conditions of the first and second hydrogenated naphthas are controlled such that the light naphthas have an initial boiling point of 50-70 ℃, the light naphthas and heavy naphthas have cut points of 120-140 ℃, and the heavy naphthas have an end boiling point of 170-190 ℃.
32. A system for producing both low carbon olefins and low sulfur residue type marine combustion, the system comprising:
the fixed bed residuum hydrotreatment reaction zone is used for carrying out hydrotreatment reaction I on a residuum raw material to obtain residuum hydrotreatment reaction effluent;
the first separation zone is used for separating the residual oil hydrotreating reaction effluent to obtain a first gas effluent, first hydrogenated naphtha, first hydrogenated diesel oil, first hydrogenated wax oil and hydrogenated slag reduction;
the fixed bed wax oil hydrotreating reaction zone is used for carrying out hydrotreating reaction II on the first hydrogenated wax oil, optionally together with the first hydrogenated diesel oil to obtain a wax oil hydrotreating reaction effluent;
The second separation zone is used for separating the wax oil hydrotreating reaction effluent to obtain a second gas effluent, second hydrogenated naphtha, second hydrogenated diesel oil and second hydrogenated wax oil;
the catalytic cracking reaction zone is used for carrying out catalytic cracking reaction on the second hydrogenated wax oil, a part of the hydrogenated slag reduction, optionally, the second hydrogenated diesel oil to obtain a catalytic cracking reaction effluent;
the third separation zone is used for separating the catalytic cracking reaction effluent to obtain low-carbon olefin, catalytic cracking naphtha, catalytic cracking light cycle oil, catalytic cracking heavy cycle oil and catalytic cracking slurry oil;
and the ship combustion blending zone is used for blending the catalytic cracking light cycle oil, the catalytic cracking heavy cycle oil, the catalytic cracking slurry oil and the rest of the hydrogenated slag reduction, and optionally, the first hydrogenated diesel oil and/or the second hydrogenated diesel oil to obtain the low-sulfur residue type ship combustion.
33. The system of claim 32, wherein the fixed bed residuum hydroprocessing reaction zone comprises at least 1 fixed bed reactor.
34. The system of claim 33, wherein the fixed bed residuum hydroprocessing reaction zone comprises from 3 to 6 fixed bed reactors.
35. The system of any of claims 32-34, wherein the fixed bed wax oil hydroprocessing reaction zone comprises at least 1 fixed bed reactor.
36. The system of claim 35, wherein the fixed bed wax oil hydroprocessing reaction zone comprises 1-3 fixed bed reactors.
37. The system of any of claims 32-34, wherein the marine combustion blending zone comprises at least one of a storage device, a transportation device, a mixing device, a filtration device, and a measurement device.
38. The system according to any one of claims 32-34, wherein the system further comprises:
and the fourth separation zone is used for separating the first hydrogenated naphtha and/or the second hydrogenated naphtha to obtain light naphtha and heavy naphtha.
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| CN101747935A (en) * | 2008-12-18 | 2010-06-23 | 中国石油化工股份有限公司 | Method for producing light olefins and monocyclic aromatic hydrocarbons from heavy hydrocarbons |
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| CN112538384A (en) * | 2019-09-20 | 2021-03-23 | 中国石油化工股份有限公司 | Hydrotreating-catalytic cracking combined process method for increasing yield of isobutane and light aromatic hydrocarbons |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101747935A (en) * | 2008-12-18 | 2010-06-23 | 中国石油化工股份有限公司 | Method for producing light olefins and monocyclic aromatic hydrocarbons from heavy hydrocarbons |
| CN109952362A (en) * | 2016-10-20 | 2019-06-28 | Ifp 新能源公司 | The method for transformation of production marine fuel including fixed bed hydrogenation processing, separation hydrotreating residue oil fraction and catalytic cracking step |
| CN108018080A (en) * | 2016-10-28 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of combined method and system for handling residual oil |
| CN112538384A (en) * | 2019-09-20 | 2021-03-23 | 中国石油化工股份有限公司 | Hydrotreating-catalytic cracking combined process method for increasing yield of isobutane and light aromatic hydrocarbons |
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