CN114806638A - Production method of low-sulfur marine fuel oil - Google Patents
Production method of low-sulfur marine fuel oil Download PDFInfo
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- CN114806638A CN114806638A CN202110068055.6A CN202110068055A CN114806638A CN 114806638 A CN114806638 A CN 114806638A CN 202110068055 A CN202110068055 A CN 202110068055A CN 114806638 A CN114806638 A CN 114806638A
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- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 49
- 239000011593 sulfur Substances 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- 239000010762 marine fuel oil Substances 0.000 title claims abstract description 17
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 78
- 239000007791 liquid phase Substances 0.000 claims abstract description 75
- 239000000463 material Substances 0.000 claims abstract description 58
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 9
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 62
- 239000003921 oil Substances 0.000 claims description 56
- 239000003054 catalyst Substances 0.000 claims description 36
- 238000000926 separation method Methods 0.000 claims description 22
- 239000010747 number 6 fuel oil Substances 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 13
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 8
- 229920005990 polystyrene resin Polymers 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 4
- 239000002283 diesel fuel Substances 0.000 claims description 3
- 239000001282 iso-butane Substances 0.000 claims description 2
- 239000002358 oil sand bitumen Substances 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 230000000153 supplemental effect Effects 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000000295 fuel oil Substances 0.000 description 10
- 239000002002 slurry Substances 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000004227 thermal cracking Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/302—Viscosity
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/44—Solvents
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- 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
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- 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 provides a method for producing low-sulfur marine fuel oil, which comprises the steps of pretreating inferior hydrocarbon-containing raw materials, and separating to obtain a 1 st liquid-phase material flow; separating the reaction product obtained after the hydrogenation reaction of the 1 st liquid phase material flow to obtain a 2 nd liquid phase material flow and a 3 rd liquid phase material flow; treating the 3 rd liquid phase material flow with a treating agent, and separating to obtain a 4 th liquid phase material flow and a 5 th liquid phase material flow, wherein the 4 th liquid phase material flow is settled and separated to obtain a 6 th liquid phase material flow and a 7 th liquid phase material flow; and (3) circulating and recycling hydrogenated heavy fractions obtained after the 7 th liquid phase material flow is subjected to hydrogenation reaction, and mixing the obtained 2 nd liquid phase material flow, the 5 th liquid phase material flow and the 6 th liquid phase material flow to obtain the low-sulfur marine fuel oil. The production method provided by the invention has the advantages of simple process flow, cheap and easily-obtained raw materials and low production cost, and can meet the requirement of realizing mass production.
Description
Technical Field
The invention belongs to the field of oil refining chemical industry, relates to a fuel oil production method, and particularly relates to a method for producing marine fuel oil by hydrogenation.
Background
The MAPPOL convention provides detailed regulations on the emission control region of fuel oil sulfur content used by a ship, the limit value and the implementation time of the fuel oil sulfur content, and the sulfur content of the fuel oil for the ship is not more than 0.5% when the ship sails in a general region on the sea after 1 month 1 day 2020; when sailing in the emission control area, the sulfur content of the fuel used on the ship should not exceed 0.1 percent. Research shows that the sulfur content of the conventional bunker fuel oil is generally controlled to be 3.5%, and the low-sulfur fuel oil has a huge gap if the use requirement of MAPPOL convention on the sulfur content of the fuel oil is strictly implemented. The current low-sulfur ship fuel production technology mainly uses low-sulfur crude oil as a raw material, and can be used as low-sulfur ship fuel oil or blending components by simple distillation and proper increase of viscosity. On one hand, the low-sulfur crude oil resource is limited, and the low-sulfur ship combustion gap is difficult to make up; on the other hand, the low sulfur crude oil has relatively high price, which is not favorable for realizing the requirement of low cost of the low sulfur fuel oil. In order to meet the requirements of low-cost and large-scale production of low-sulfur marine fuel oil products, a more reasonable low-sulfur marine fuel oil production technology needs to be developed urgently.
The patent CN 106753611A introduces a bunker fuel oil and a production process and a production device thereof, and concretely relates to a bunker fuel oil produced by blending FCC slurry oil, coal tar, catalytic diesel oil, methanol, ethanol, shale oil, vacuum residue oil and an auxiliary agent according to a certain proportion, in order to reduce the influence of catalyst powder in the FCC slurry oil on blended products, the invention adopts an improved electrostatic separation device to realize the de-solidification of the FCC slurry oil. The patent of the invention requires a plurality of blending components, and the implementation difficulty in actual production is larger.
Patent CN 103642539A describes a blending method of bunker fuel oil, which comprises the steps of naturally settling FCC slurry oil and thermal cracking residual oil, filtering with a filter screen, removing catalyst fine powder and other impurities contained in the raw materials, adding hydrogenation tail oil and ethylene tar into a blending tank in advance, gradually heating, stirring until the FCC slurry oil and the thermal cracking residual oil are uniformly mixed, adding the treated FCC slurry oil and the thermal cracking residual oil into the blending tank, raising the temperature, uniformly mixing the components, sequentially adding a desulfurizing agent, a cosolvent and a combustion improver into the blending tank, and uniformly mixing the components to obtain the final product. According to the method, the standing sedimentation is adopted to treat the catalyst powder in the FCC oil slurry, the catalyst powder in the FCC oil slurry is high in content and small in particle size (mostly below 25 mu m), practice proves that the catalyst powder is difficult to remove by adopting the standing sedimentation alone, the requirement on the content of precipitates in the low-sulfur ship fuel index is high, the doping amount of the catalytic oil slurry containing the catalyst powder is limited, and the production process is complex comprehensively.
Disclosure of Invention
The invention aims at the problems that the traditional low-sulfur ship fuel production technology has high cost, and the solid content of a low-sulfur ship fuel product exceeds the standard and the operation period of a device is influenced because the system is easy to be unstable when inferior residual oil is used as a raw material for carrying out deep hydrogenation desulfurization, and the like. The production method provided by the invention has the advantages of simple process flow, cheap and easily-obtained raw materials and low production cost, and can meet the requirement of realizing mass production.
The invention provides a production method of low-sulfur marine fuel oil, which comprises the following steps:
(1) under the contact condition, the inferior hydrocarbon-containing raw material reacts with the resin catalyst, and the material after the reaction is subjected to gas-liquid separation to obtain a 1 st liquid phase material flow;
(2) under the condition that hydrogen and a boiling bed hydrogenation catalyst exist, the 1 st liquid phase material flow obtained in the step (1) enters a boiling bed hydrogenation reaction zone for hydrogenation reaction, and a 2 nd liquid phase material flow and a 3 rd liquid phase material flow are obtained after reaction products are separated;
(3) treating the 3 rd liquid phase material flow obtained in the step (2) with a treating agent under a contact condition, and treating and separating to obtain a 4 th liquid phase material flow and a 5 th liquid phase material flow, wherein the 4 th liquid phase material flow enters a separation tower to be settled and separated to obtain a 6 th liquid phase material flow and a 7 th liquid phase material flow;
(4) feeding the 7 th liquid phase material flow obtained in the step (3) into a supplementary hydrogenation reactor, carrying out hydrogenation reaction in the presence of hydrogen and a supplementary hydrogenation catalyst, and circulating hydrogenated heavy fraction obtained after hydrogenation reaction to a fluidized bed hydrogenation reaction zone for treatment;
(5) and (3) mixing the 2 nd liquid phase flow obtained in the step (2), the 5 th liquid phase flow obtained in the step (3) and the 6 th liquid phase flow to obtain the low-sulfur marine fuel oil.
Further, in the above technical scheme, the poor hydrocarbon-containing raw material in step (1) may be one or more of atmospheric residue, vacuum residue, oil sand bitumen, and may also be one or more of partial wax oil and catalytic diesel oil. The kinematic viscosity (100 ℃) of the inferior hydrocarbon-containing raw material is 2000-8000 mm 2 /s。
Further, in the above technical scheme, the resin catalyst in step (1) may specifically be a polystyrene resin catalyst, and the average pore diameter of the polystyrene resin catalyst is 10-500 nm, preferably 30-100 nm. The preparation method of the catalyst comprises the steps of taking styrene as a monomer, carrying out polymerization reaction to generate a polyethylene polymer, then carrying out sulfonation reaction with concentrated sulfuric acid, and adding a pore-forming agent in the sulfonation process of polystyrene so as to generate a multifunctional structure with large pore diameter and porous channel distribution on the surface and inside of polystyrene resin.
Further, in the above technical scheme, the reaction conditions in step (1) are as follows: the reaction temperature is 300-430 ℃, and the preferable reaction temperature is 350-420 ℃; the reaction pressure is 0.15MPa to 5.0MPa, and the preferable reaction pressure is 0.45MPa to 3.0 MPa; the volume space velocity is 0.5-4.0 h -1 The preferred volume space velocity is 1.0-3.0 h -1 。
Further, in the above technical scheme, the ebullated-bed hydrogenation reaction zone in step (2) is provided with at least one ebullated-bed hydrogenation reactor, preferably 1 or 2 ebullated-bed hydrogenation reactors, and when more than 2 ebullated-bed hydrogenation reactors are provided, the plurality of ebullated-bed hydrogenation reactors may be connected in series and/or in parallel. The fluidized bed hydrogenation reactor preferably adopts a fluidized bed reactor with a built-in three-phase separator, and particularly can adopt a fluidized bed reactor with a built-in three-phase separator developed by the petrochemical research institute, which is pacified by the petrochemical company Limited in China.
Further, in the above technical scheme, the fluidized bed hydrogenation catalyst in step (2) may be one or more of the existing fluidized bed hydrogenation catalysts in the field, such as fluidized bed hydrogenation catalysts developed by the company of petrochemical industry, ltd, china, and specifically may be commercial brands FES-30 and FEM-10 fluidized bed catalysts developed by the research institute of petrochemical industry, or may be a TEX2720 catalyst purchased from the market. Generally, the fluidized bed hydrogenation catalyst comprises a carrier and an active metal, wherein the active metal can be one or more of nickel, cobalt, molybdenum or tungsten; the catalyst composition may include, in weight percent: 0.5-10% of nickel or cobalt (calculated according to the oxide thereof), 1-25% of molybdenum or tungsten (calculated according to the oxide thereof), and the carrier can be one or more of alumina, silica, alumina-silica or titanium oxide. The catalyst is in the shape of extrudate or sphere, and the bulk density is 0.5-0.9 g/cm 3 The particle diameter (spherical diameter or strip diameter) is 0.04-1.0 mm, and the specific surface area is 80-300 m 2 /g。
Further, in the above technical solution, the operating conditions of the ebullated-bed hydrogenation reaction zone in the step (2) are as follows: the reaction temperature is 380-450 ℃, the reaction pressure is 13-20.0 MPa, and the volume space velocity is 0.2-4.0 h -1 The hydrogen-oil volume ratio is 300-1500, and the preferable operation conditions are as follows: the reaction temperature is 400-440 ℃, the reaction pressure is 14-18.0 MPa, and the volume space velocity is 0.3-1.5 h -1 The volume ratio of hydrogen to oil is 600-1000.
Further, in the above technical solution, the temperature of the division point of the 2 nd liquid phase stream and the 3 rd liquid phase stream in the step (2) is 480 to 560 ℃, preferably 500 to 540 ℃.
Further, in the above technical solution, the treating agent in step (3) may be one or more of propane, n-butane, isobutane, n-pentane, isopentane, and naphtha, preferably one or more of n-butane, isopentane, and naphtha; furthermore, the volume ratio of n-butane to isopentane is 4: 1-1: 4, preferably 2: 1-1: 2.
Further, in the above technical solution, the treatment conditions in step (3) are as follows: the pressure is 4.0-8.0 MPa, the treatment temperature is 130-170 ℃, the volume ratio of the treating agent to the No. 3 liquid phase material flow is 2: 1-10: 1, and the preferable treatment conditions are as follows: the pressure is 4.5-6.5 MPa, the treatment temperature is 135-160 ℃, and the volume ratio of the treating agent to the No. 3 liquid phase material flow is 4: 1-9: 1.
Further, in the above technical scheme, in the step (3), the temperature of the separation tower is controlled to be 160-190 ℃, preferably 150-170 ℃, a 6 th liquid phase material flow is obtained at the top of the separation tower, and a 7 th liquid phase material flow is obtained at the bottom of the separation tower.
Further, in the above technical solution, the operating conditions of the make-up hydrogenation reactor in step (4) are as follows: the reaction temperature is 350-400 ℃, the reaction pressure is 10-15.0 MPa, and the volume airspeed is 0.8-3.0 h -1 The volume ratio of hydrogen to oil is 200-1000, and the preferred operation conditions are as follows: the reaction temperature is 360-380 ℃, the reaction pressure is 11-14.0 MPa, and the volume space velocity is 1.0-2.0 h -1 The volume ratio of the hydrogen to the oil is 250-400.
Further, in the above technical scheme, the supplementary hydrogenation catalyst loaded in the supplementary hydrogenation reactor in step (4) may be one or more of the existing hydrofining catalysts in the field, may be a commercially available product, or may be prepared according to the existing method.
Further, in the above technical scheme, the mass ratio of the hydrogenated heavy components obtained after the reaction obtained in the step (3) in the step (4) to the poor quality hydrocarbon-containing raw material can be generally controlled to be 1:25 to 1:10, and preferably 1:20 to 1: 12.
Compared with the prior art, the method for producing the low-sulfur marine fuel oil has the following advantages:
1. the invention relates to a low-sulfur marine fuel oil production method, which is characterized in that a pretreatment reactor is arranged, an inferior heavy oil raw material is contacted with a treating agent, the molecular structure of a residual oil system can be changed under the action of the treating agent, and the viscosity and the impurity content of the residual oil system are reduced.
2. According to the invention, the heavy fraction obtained after the hydrogenation reaction of the fluidized bed is separated, and then the heavy fraction obtained after the separation is hydrogenated and returns to the hydrogenation reaction zone of the fluidized bed.
3. In the method for producing the low-sulfur marine fuel oil, the low-sulfur marine fuel oil with the sulfur content of less than 0.5 percent can be produced by taking the inferior residual oil as the raw material. Compared with the prior technical routes of blending and producing the bunker fuel oil by using low-sulfur crude oil or high-quality light components and the like, the method has the advantages of lower cost, wider raw material source and low price.
Drawings
FIG. 1 is a schematic diagram of the method for producing low sulfur bunker fuel oil according to the present invention.
Detailed Description
The following detailed description of the embodiments of the present invention will be described with reference to the accompanying drawings and specific examples, but it should be noted that the scope of the present invention is not limited by these embodiments, but is defined by the claims.
All percentages, parts, ratios, etc. referred to in this specification are by weight unless otherwise specifically indicated.
In the context of this specification, any two or more embodiments of the invention may be combined in any combination, and the resulting solution is part of the original disclosure of this specification, and is within the scope of the invention.
As shown in fig. 1, the present invention provides a method for producing low-sulfur bunker fuel oil, comprising the following steps: the inferior hydrocarbon-containing material 1 enters a preprocessor 2 to contact with a resin catalyst for reaction, and the reacted material enters a gas-liquid separator 4 to obtain gas 3 and a 1 st liquid phase material flow 5 after gas-liquid separation; the obtained 1 st liquid phase material flow 5 and hydrogen 6 enter a fluidized bed hydrogenation reaction zone 7 for hydrogenation reaction, and the reaction product enters a gas-liquid separation unit 8 for separation to obtain a 2 nd liquid phase material flow 9 and a 3 rd liquid phase material flow 10; mixing the obtained 3 rd liquid phase material flow 10 with a treating agent 11, then sending the mixture into a processor 12 for treatment, treating and separating to obtain a 4 th liquid phase material flow 13 and a 5 th liquid phase material flow 19, wherein the 4 th liquid phase material flow enters a separation tower 14 for settling and separating to obtain a 6 th liquid phase material flow 15 and a 7 th liquid phase material flow 16; the obtained 7 th liquid phase material flow 16 and hydrogen 6 enter a supplementary hydrogenation reactor 17, hydrogenation reaction is carried out in the presence of a supplementary hydrogenation catalyst, and a hydrogenated 7 th liquid phase material flow 18 obtained after hydrogenation reaction is circulated back to the fluidized bed hydrogenation reaction zone 7 for treatment; the resulting 2 nd liquid phase stream 9, 5 th liquid phase stream 19 and 6 th liquid phase stream 15 can be combined to obtain the low sulfur bunker fuel oil.
The raw materials used in the examples of the present invention and the comparative examples were vacuum residue, and specific raw material properties are shown in table 1.
The treating agent used in the pretreatment reactors in the examples and the comparative examples of the invention is a polystyrene resin catalyst, the polystyrene resin catalyst has an average pore diameter of 30-100 nm, an average diameter of 0.45mm and a specific surface area of 21m 2 G, average pore volume 0.26cm 3 (ii) in terms of/g. The polystyrene resin catalyst can be prepared according to the prior method, and D072 styrene resin can be washed by distilled water to be colorless, and then H with the volume concentration of 30 percent 2 SO 4 Washing to strong acidity, and washing with distilled waterNeutralizing, washing with NaOH with volume concentration of 45%, washing with distilled water to neutrality, soaking in sodium metaaluminate compound, soaking the washed styrene resin in 500mL of sulfuric acid solution, stirring at room temperature for 12 hr, washing with distilled water to neutrality, and drying in drying oven at 100 deg.C for 8 hr.
The fluidized bed hydrogenation reaction zone uses a fluidized bed reactor, in particular to a fluidized bed hydrogenation reactor with a built-in three-phase separator developed by the company of petrochemical industry limited in China. The fluidized bed hydrogenation catalyst adopts a commercial grade FES-30 microspheric fluidized bed hydrogenation catalyst developed by the comforting petrochemical research institute. The supplementary hydrogenation reactor adopts FF-66 hydrogenation catalyst developed by the research institute of the comforting petrochemical industry.
Example 1
Example 1 using vacuum residue as a raw material, by using the method of the present invention, vacuum residue first enters a pretreatment reactor for a pretreatment reaction, and the reaction conditions of the pretreatment reactor are as follows: reaction temperature: the reaction pressure is 0.65MPa at 360 ℃, and the volume space velocity is 1.5h -1 Then, after gas-liquid separation, the liquid phase enters a fluidized bed hydrogenation reactor for deep impurity removal reaction, and the reaction conditions of the hydrogenation reaction zone are as follows: reaction temperature: the reaction pressure is 14MPa at 420 ℃, and the volume space velocity is 0.45h -1 Hydrogen to oil volume ratio 800. The split point temperature of the 2 nd and 3 rd liquid phase streams is 510 ℃; the treating agent is n-butane and isopentane, the volume ratio of n-butane to isopentane is 1:1, the pressure is 5.0MPa, the treating temperature is 145 ℃, the solvent ratio is 5:1, and the operating temperature of the separation tower is 155 ℃. Operating conditions of the make-up hydrogenation reactor: the reaction temperature is 370 ℃, the reaction pressure is 13.0MPa, and the volume space velocity is 1.8h -1 Hydrogen to oil volume ratio 300. And (3) recycling the hydrogenated heavy fraction to the fluidized bed hydrogenation reactor, wherein the mass ratio of the hydrogenated heavy fraction to the vacuum residue is 1: 15. The specific test results are shown in tables 2 and 3.
Example 2
Example 1 using vacuum residue as a raw material, according to the method of the present invention, vacuum residue first enters a pretreatment reactor for a pretreatment reaction, and the reaction conditions of the pretreatment reactor are as follows: reaction temperature: reaction at 360 DEG CThe pressure is 0.65MPa, and the volume space velocity is 1.5h -1 Then, after gas-liquid separation, the liquid phase enters a fluidized bed hydrogenation reactor for deep impurity removal reaction, and the reaction conditions of the hydrogenation reaction zone are as follows: reaction temperature: the reaction pressure is 14MPa at 420 ℃, and the volume space velocity is 0.45h -1 Hydrogen to oil volume ratio 800. The split point temperature of the 2 nd and 3 rd liquid phase streams was 510 ℃. The treating agent is naphtha, the pressure is 5.0MPa, the temperature is 145 ℃, the solvent ratio is 5:1, and the operation temperature of the separation tower is 155 ℃; operating conditions of the make-up hydrogenation reactor: the reaction temperature is 370 ℃, the reaction pressure is 13.0MPa, and the volume space velocity is 1.5h -1 Hydrogen-oil volume ratio 300; and (3) recycling the hydrogenated heavy fraction to the fluidized bed hydrogenation reactor, wherein the mass ratio of the hydrogenated heavy fraction to the vacuum residue is 1: 12. The specific test results are shown in tables 2 and 3.
Example 3
Example 1 using vacuum residue as a raw material, according to the method of the present invention, vacuum residue first enters a pretreatment reactor for a pretreatment reaction, and the reaction conditions of the pretreatment reactor are as follows: reaction temperature: the reaction pressure is 0.65MPa at 360 ℃, and the volume space velocity is 1.5h -1 Then, after gas-liquid separation, the liquid phase enters a fluidized bed hydrogenation reactor for deep impurity removal reaction, and the reaction conditions of the hydrogenation reaction zone are as follows: reaction temperature: 430 ℃, the reaction pressure is 14MPa, and the volume space velocity is 0.45h -1 Hydrogen to oil volume ratio 800. The split point temperature of the 2 nd and 3 rd liquid phase streams is 530 ℃. The treating agent is naphtha. The pressure is 5.0MPa, the temperature is 145 ℃, the solvent ratio is 5:1, and the operating temperature of the separation tower is 165 ℃; operating conditions of the make-up hydrogenation reactor: the reaction temperature is 370 ℃, the reaction pressure is 13.0MPa, and the volume space velocity is 1.3h -1 Hydrogen to oil volume ratio 300; and (3) recycling the hydrogenated heavy fraction to the fluidized bed hydrogenation reactor, wherein the mass ratio of the hydrogenated heavy fraction to the vacuum residue is 1: 12. The specific test results are shown in tables 2 and 3.
Comparative example 1
The process is substantially the same as example 1, except that a pretreatment reactor and a supplementary hydrogenation reactor are not provided, and the separated 7 th liquid phase is directly sent to a fluidized bed hydrogenation reaction zone without supplementary hydrogenation. The specific test results are shown in tables 2 and 3.
Comparative example 2
Essentially the same as example 1, except that no pretreatment reactor was provided, the poor quality hydrocarbonaceous feedstock was passed directly to the ebullated bed hydrogenation reaction zone without any treatment. The specific test results are shown in tables 2 and 3.
TABLE 1 Properties of the raw materials
TABLE 2 results of the reaction
TABLE 3 operating cycle of ebullated bed reactor for different embodiments
The embodiment and the comparative example show that the production method for producing the low-sulfur marine fuel oil by the fluidized bed hydrogenation reduces the difficulty of residual oil macromolecule hydrogenation reaction by arranging the pretreatment reactor, improves the stability of a fluidized bed hydrogenation system by arranging the hydrogen supplement hydrogenation reactor to circulate the hydrogenated heavy oil back to the fluidized bed reactor, reduces the content of toluene insoluble substances in the generated oil, improves the online rate of an auxiliary fractionation system of a fluidized bed hydrogenation unit while realizing the production of the low-sulfur marine fuel oil by deep desulfurization, and improves the operation stability.
Claims (12)
1. A method for producing low-sulfur marine fuel oil, comprising the following steps:
(1) under the contact condition, the inferior hydrocarbon-containing raw material reacts with the resin catalyst, and the material after the reaction is subjected to gas-liquid separation to obtain a 1 st liquid phase material flow;
(2) under the condition that hydrogen and a boiling bed hydrogenation catalyst exist, the 1 st liquid phase material flow obtained in the step (1) enters a boiling bed hydrogenation reaction zone for hydrogenation reaction, and a 2 nd liquid phase material flow and a 3 rd liquid phase material flow are obtained after reaction products are separated;
(3) treating the 3 rd liquid phase material flow obtained in the step (2) with a treating agent under a contact condition, and treating and separating to obtain a 4 th liquid phase material flow and a 5 th liquid phase material flow, wherein the 4 th liquid phase material flow enters a separation tower to be settled and separated to obtain a 6 th liquid phase material flow and a 7 th liquid phase material flow;
(4) feeding the 7 th liquid phase material flow obtained in the step (3) into a supplementary hydrogenation reactor, carrying out hydrogenation reaction in the presence of hydrogen and a supplementary hydrogenation catalyst, and circulating hydrogenated heavy fraction obtained after hydrogenation reaction to a fluidized bed hydrogenation reaction zone for treatment;
(5) and (3) mixing the 2 nd liquid phase flow obtained in the step (2), the 5 th liquid phase flow obtained in the step (3) and the 6 th liquid phase flow to obtain the low-sulfur marine fuel oil.
2. The method for producing low-sulfur bunker fuel oil according to claim 1, wherein said low-quality hydrocarbon-containing feedstock in step (1) is one or more selected from the group consisting of atmospheric residue, vacuum residue, oil sand bitumen, and optionally one or more selected from the group consisting of partial wax oil and catalytic diesel oil.
3. The method for producing low-sulfur bunker fuel oil according to claim 1, wherein the resin catalyst in the step (1) is a polystyrene resin catalyst having an average pore diameter of 10 to 500nm, preferably 30 to 100 nm.
4. The method for producing low-sulfur bunker fuel oil according to claim 1, wherein the reaction conditions in step (1) are as follows: the reaction temperature is 300-430 ℃, and the preferable reaction temperature is 350-420 ℃; the reaction pressure is 0.15MPa to 5.0MPa, and the preferable reaction pressure is 0.45MPa to 3.0 MPa; the volume space velocity is 0.5-4.0 h -1 The preferred volume space velocity is 1.0-3.0 h -1 。
5. The method for producing low-sulfur bunker fuel oil according to claim 1, wherein said ebullated-bed hydrogenation reaction zone in step (2) is provided with at least one ebullated-bed hydrogenation reactor, preferably 1 or 2 ebullated-bed hydrogenation reactors, and when more than 2 ebullated-bed hydrogenation reactors are provided, said plurality of ebullated-bed hydrogenation reactors are connected in series and/or in parallel.
6. The process for producing low-sulfur bunker fuel oil according to claim 1, wherein the operating conditions of the ebullated-bed hydrogenation reaction zone in the step (2) are as follows: the reaction temperature is 380-450 ℃, the reaction pressure is 13-20.0 MPa, and the volume space velocity is 0.2-4.0 h -1 The hydrogen-oil volume ratio is 300-1500, and the preferable operation conditions are as follows: the reaction temperature is 400-440 ℃, the reaction pressure is 14-18.0 MPa, and the volume space velocity is 0.3-1.5 h -1 The volume ratio of hydrogen to oil is 600-1000.
7. The process for the production of low sulfur bunker fuel oil according to claim 1, wherein the temperature of the division point of the 2 nd and 3 rd liquid phase streams in step (2) is 480 to 560 ℃, preferably 500 to 540 ℃.
8. The method for producing low-sulfur bunker fuel oil according to claim 1, wherein said treating agent in step (3) is one or more selected from propane, n-butane, isobutane, n-pentane, isopentane, naphtha, preferably one or more selected from n-butane, isopentane, naphtha; furthermore, the volume ratio of n-butane to isopentane is 4: 1-1: 4, preferably 2: 1-1: 2.
9. The method for producing low-sulfur bunker fuel oil according to claim 1, wherein the treatment conditions in the step (3) are as follows: the pressure is 4.0-8.0 MPa, the treatment temperature is 130-170 ℃, the volume ratio of the treating agent to the No. 3 liquid phase material flow is 2: 1-10: 1, and the preferable treatment conditions are as follows: the pressure is 4.5-6.5 MPa, the treatment temperature is 135-160 ℃, and the volume ratio of the treating agent to the No. 3 liquid phase material flow is 4: 1-9: 1.
10. The method for producing low-sulfur bunker fuel oil according to claim 1, wherein the temperature of the separation tower in the step (3) is controlled to be 160-190 ℃, preferably 150-170 ℃, a 6 th liquid phase flow is obtained at the top of the separation tower, and a 7 th liquid phase flow is obtained at the bottom of the separation tower.
11. The process for the production of low sulfur bunker fuel oil of claim 1 wherein said supplemental hydrogenation reactor operating conditions in step (4) are as follows: the reaction temperature is 350-400 ℃, the reaction pressure is 10-15.0 MPa, and the volume airspeed is 0.8-3.0 h -1 The volume ratio of hydrogen to oil is 200-1000, and the preferred operation conditions are as follows: the reaction temperature is 360-380 ℃, the reaction pressure is 11-14.0 MPa, and the volume space velocity is 1.0-2.0 h -1 The volume ratio of the hydrogen to the oil is 250-400.
12. The method for producing low-sulfur bunker fuel oil according to claim 1, wherein the mass ratio of hydrogenated heavy components obtained after the reaction in the step (3) in the step (4) to the poor-quality hydrocarbon-containing raw material is controlled to be 1:25 to 1:10, preferably 1:20 to 1: 12.
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| CN111088068A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Production method of low-sulfur marine fuel oil |
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| CN111088068A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Production method of low-sulfur marine fuel oil |
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Effective date of registration: 20231113 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |