CN114752409B - Production method of low-sulfur marine fuel oil - Google Patents
Production method of low-sulfur marine fuel oil Download PDFInfo
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- CN114752409B CN114752409B CN202210024871.1A CN202210024871A CN114752409B CN 114752409 B CN114752409 B CN 114752409B CN 202210024871 A CN202210024871 A CN 202210024871A CN 114752409 B CN114752409 B CN 114752409B
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- 239000011593 sulfur Substances 0.000 title claims abstract description 52
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 52
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 80
- 238000000034 method Methods 0.000 claims abstract description 30
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- 238000002156 mixing Methods 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
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- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 235000009165 saligot Nutrition 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
-
- 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
- C10G2300/201—Impurities
- C10G2300/205—Metal content
- C10G2300/206—Asphaltenes
-
- 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
-
- 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
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)
- Catalysts (AREA)
Abstract
The invention discloses a production method of low-sulfur marine fuel oil, which comprises the following steps: under the condition of hydrogen, residual oil raw materials enter a hydrogenation reaction zone to be sequentially contacted with an asphaltene conversion catalyst and a hydrodesulfurization catalyst for reaction, and fractions with the temperature of more than 350 ℃ obtained after reaction effluent is separated are directly used as low-sulfur marine fuel oil components or used as blending components for producing marine fuel oil. The production method adopts a catalyst grading scheme to process the vacuum residue to produce the low-sulfur marine fuel oil. The matching use of the asphaltene conversion catalyst and the high-activity hydrodesulfurization catalyst is adopted, the stability of a system is ensured by selectively converting the asphaltene and breaking and hydrogenating the polycyclic aromatic hydrocarbon, and meanwhile, the sulfur in the raw material is further removed, so that the requirement of low-sulfur ship combustion is met.
Description
Technical Field
The invention belongs to the field of petrochemical industry, relates to a method for producing marine fuel oil, and particularly relates to a method for producing low-sulfur marine fuel oil by hydrogenation.
Background
The 70 th meeting of the International maritime organization maritime environmental protection Committee decides that regulations not exceeding 0.50% of the sulfur content of marine fuel are implemented on a global scale from 1/2020. This means that low sulfur fuel oil will gradually replace the common high sulfur fuel oil for ships as the mainstream fuel oil in the market. China is a large fuel oil consumption country and is also the biggest low-sulfur fuel oil producing country in the world, and a low-cost low-sulfur ship fuel production technology is the research target.
The boiling bed residual oil hydrogenation technology has the characteristics of uniform temperature in a reactor, long running period, flexible device operation and the like, is an important technology for processing high-sulfur, high-carbon residue and high-metal heavy crude oil, realizes higher desulfurization rate, and is an efficient process scheme for economically producing low-sulfur ship fuel. At present, two fuel oils of RME180 and RMG380 are used for sailing ships. The main specifications that determine the quality of fuel oils include viscosity, sulfur content, total deposits, carbon residue, and pour point, among others. The total deposits are a key indicator because deposits in the oil can exacerbate equipment wear and injector plugging, and can accumulate in storage tanks, filter screens, or equipment, causing poor oil circulation from the tank to the burner. The index of the total deposit (aging method) of the two fuel oils is less than or equal to 0.1 percent. How to reach the index requirement or lower of the total deposit under the condition of ensuring high desulfurization rate is the research direction of the people.
The precipitate is a soft carbon material that forms during catalytic and thermal cracking under severe operating conditions and high conversion. Research has shown that the formation of precipitates during residue conversion is related to asphaltenes in the residue. The precipitate has a structure similar to that of asphaltene, and the asphaltene separated from the precipitate has a shorter alkyl chain and higher aromaticity than the asphaltene in the vacuum residue. Thus, selective conversion of asphaltenes is critical to reducing sediment formation.
CN201880075001.9 discloses a method and system for upgrading of unconverted heavy oil of hydrocrackers. Providing an unconverted heavy oil feed from a hydroprocessing system, wherein the unconverted heavy oil feed comprises a hydrocracker resid; optionally, adding a first aromatic feed to the unconverted heavy oil feed to form a mixture; passing the unconverted heavy oil feed or the mixture directly to a separation process to remove insolubles, thereby forming an unconverted heavy oil stream; optionally, combining a second aromatic feed with the unconverted heavy oil stream to form a second mixture; subjecting the unconverted heavy oil stream or the second mixture to heavy oil hydrogenationA treatment process to form a hydrotreated heavy oil stream from the unconverted heavy oil stream or the second mixture; wherein at least one of the first aromatic feed or the second aromatic feed is combined with the unconverted heavy oil feed or the unconverted heavy oil stream; and optionally, recovering or further treating the hydrotreated heavy oil stream. The heavy oil hydroprocessing process typically comprises a catalyst selected from the group consisting of demetallization catalysts, desulfurization catalysts, or combinations thereof. Demetallization catalysts have a relatively high pore volume (generally)>0.6 cc/g), larger average mesopore diameter: (>180 angstroms) and a low surface area (<150m 2 /g), the active metal content (Mo and Ni) is low, where the Mo content is generally<6 wt.% Ni content<2% by weight. The transition and conversion catalysts generally have a pore volume of from 0.5 to 0.8cc/g and a surface area of from 100 to 180m 2 (ii) a/g and an average mesopore diameter of 100 to 200 angstroms. The active Mo content is generally from 5 to 9% by weight and the Ni content from 1.5 to 2.5% by weight. The pore volume of the deep conversion catalyst is generally<0.7cc/g, surface area of>150m 2 In terms of/g, and an average mesopore diameter of<150 angstroms. The active Mo content is generally>7.5% by weight of nickel>2% by weight. This patent reduces sediment levels by adding aromatic species to the unconverted oil which cannot be directly used to produce low sulfur boat fuel, followed by filtration.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for producing low-sulfur marine fuel oil, which adopts a catalyst grading scheme to process vacuum residue to produce the low-sulfur marine fuel oil. The matching use of the asphaltene conversion catalyst and the high-activity hydrodesulfurization catalyst is adopted, the stability of a system is ensured by selectively converting the asphaltene and breaking and hydrogenating the polycyclic aromatic hydrocarbon, and meanwhile, the sulfur in the raw material is further removed, so that the requirement of low-sulfur ship combustion is met.
The invention provides a production method of low-sulfur marine fuel oil, which comprises the following steps: under the condition of hydrogen, residual oil raw materials enter a hydrogenation reaction zone to be sequentially contacted with an asphaltene conversion catalyst and a hydrodesulfurization catalyst for reaction, and fractions with the temperature of more than 350 ℃ obtained after reaction effluent is separated are directly used as low-sulfur marine fuel oil components or used as blending components for producing marine fuel oil;
the asphaltene conversion catalyst comprises a carrier and active metal, wherein the carrier comprises a carrier substrate and a coating, the coating is a composite material containing carbon and silicon oxide, and a space network structure is formed between the coating and the carrier substrate in an sp3 hybridization mode; the carrier matrix is one or more of a metal oxide carrier and a carbon carrier, and is preferably a metal oxide carrier;
the hydrodesulfurization catalyst comprises a silicon-aluminum material and a first metal and a second metal which are loaded on the silicon-aluminum material; wherein the first metal is selected from at least one of group IVB metal, group VIB metal and group VIII metal, preferably the group VIB metal; the second metal is selected from at least one of VIB group metals and VIII group metals.
Further, in the above technical scheme, in the asphaltene conversion catalyst, based on the total weight content of the carrier, the content of the carrier matrix is 80-99 wt%, preferably 85-95 wt%, and the content of the coating is 1-20%, preferably 5-15%; in the coating, the weight ratio of carbon to silicon oxide is 1:0.1 to 1:1.5, preferably 1:0.5 to 1:1.
further, in the above technical solution, in the asphaltene conversion catalyst, the carrier matrix may be one or more of a metal oxide carrier and a carbon carrier, and is preferably a metal oxide carrier. The metal oxide carrier may be one or more of alumina, titania, zirconia and iron oxide in any combination, preferably alumina, and more preferably modified alumina, and the modification may be one or more of substances capable of adjusting the surface properties of alumina, specifically one or more of silicon, phosphorus, boron, fluorine, silicon, titanium, zirconium, magnesium and the like.
Furthermore, in the above technical scheme, in the asphaltene conversion catalyst, the specific surface of the carrier is 140-220 m 2 Per gram, pore volume is 0.6-0.9 mL/g, carbon content is 0.5-10%, silicon oxide content is 0.5-10%, and abrasion index is less than 0.5%.
Further, in the above technical scheme, in the asphaltene conversion catalyst, the active metal component is one or more of group VIB metals and group VIII metals.
Further, in the above technical solution, in the asphaltene conversion catalyst, the content of the active metal component can be adjusted according to actual needs, and the adjustment of the content of the active metal component is the ordinary skill of those skilled in the art. Generally, the content of the metal component of group VIB is between 4 and 15 wt.%; the content of the VIII group metal component is 1wt% -5 wt%.
Further, in the above technical solution, in the asphaltene conversion catalyst, the group VIB metal is typically Mo and/or W, and the group VIII metal is typically Ni and/or Co.
Further, in the above technical scheme, the properties of the asphaltene conversion catalyst are as follows: the specific surface area is 120 to 200m 2 Per gram, pore volume is 0.5-0.8 mL/g, carbon content is 0.3-9%, silicon dioxide content is 0.3-9%, and abrasion index is less than 0.5%.
Further, in the technical scheme, the specific surface area of the hydrodesulfurization catalyst is 160-250 m 2 The ratio of the molar mass to the molar mass is preferably 160 to 230m 2 The pore volume is 0.4 to 0.7mL/g, preferably 0.45 to 0.65mL/g, the total acid value of the catalyst is 0.3 to 0.6mol/g, preferably 0.35 to 0.6mol/g, and the ratio of the B acid to the L acid is 0.3 to 1.0, preferably 0.3 to 0.8.
Further, in the above technical scheme, in the hydrodesulfurization catalyst, the content of the group VIB metal in terms of oxide is 6 to 15%, preferably 8 to 15%, based on the weight of the catalyst; the content of the VIII group metal is 2 to 10 percent, preferably 2 to 6 percent, calculated by oxide, and the content of the IVB group metal is 0.1 to 4.0 percent, preferably 0.5 to 4.0 percent, calculated by oxide.
Further, in the above technical scheme, the properties of the residual oil feedstock are as follows: the metal (Ni + V) is not less than 180. Mu.g/g, preferably (Ni + V) is not less than 200. Mu.g/g, the sulfur content is not less than 4wt%, preferably the sulfur content is not less than 4.5wt%, the carbon residue is not less than 18wt%, preferably the carbon residue is not less than 20wt%.
Further, in the above technical scheme, the hydrogenation reaction zone is provided with more than one reactor, preferably more than 2 reactors, and further preferably 2 to 3 reactors, the reactor may be one or more of a fixed bed hydrogenation reactor, a boiling bed hydrogenation reactor, and a suspension bed hydrogenation reactor, and preferably a boiling bed hydrogenation reactor. When more than 2 reactors are arranged, the first reactor is filled with asphaltene conversion catalyst and the other reactors are filled with hydrodesulfurization catalyst according to the contact sequence of the reactors and the materials.
Further, in the above technical solution, the reaction conditions of the hydrogenation reaction zone are as follows: the reaction pressure is 13-18 MPaG, the reaction temperature is 380-430 ℃, and the liquid hourly space velocity is 0.1-0.6 h -1 The volume ratio of hydrogen to oil is 400-800.
Further, in the above technical scheme, the preparation method of the asphaltene conversion catalyst comprises the following steps:
(a) Mixing a silicon-containing compound, an organic carbon precursor and water, and uniformly mixing to obtain a coating liquid;
(b) Introducing the coating liquid obtained in the step (a) onto a carrier matrix, and further drying and roasting to obtain a carrier;
(c) Introducing an active metal component to the carrier obtained in the step (b), and further roasting to obtain the asphaltene conversion catalyst.
In the preparation method of the asphaltene conversion catalyst, the content of silicon in the coating liquid in the step (a) is 50-150 g/L in terms of oxide, and the content of carbon precursor is 100-500 g/L.
In the preparation method of the asphaltene conversion catalyst, the silicon-containing compound in the step (a) can be one or more of silica sol, water glass and white carbon black, preferably silica sol, and more preferably the silica sol can be one of acidic silica sol or alkaline silica sol; the silica sol has a silica content of 20 to 40wt%, preferably 25 to 35wt%, calculated as oxide. In the above method for preparing the asphaltene conversion catalyst, the organic carbon precursor in step (a) is an organic compound containing three elements of carbon, hydrogen and oxygen, and further the organic carbon precursor contains carbonThe molecular formula of the organic compound of the three elements of hydrogen and oxygen is (C) 6 H 10 O 5 )n、(C 2 H 4 O)n、HO(C 2 H 4 O)nH、(C 6 H 10 O 6 )n、(C 2 H 6 O) n is one or more of; among them, the organic compound containing three elements of carbon, hydrogen and oxygen has an average molecular weight of 5000 to 2500000, preferably 10000 to 2000000.
In the preparation method of the asphaltene conversion catalyst, the organic carbon precursor in the step (a) can be one or more of saccharides, flour, polyvinyl alcohol, polyethylene glycol and cellulose ether; preferably a carbohydrate and/or flour. The saccharide can be one or more of monosaccharide, disaccharide and polysaccharide, specifically one or more of starch and glucose, and preferably starch. The starch can be one or more of mung bean starch, cassava starch, sweet potato starch, wheat starch, water chestnut starch, lotus root starch and corn starch, preferably corn starch and/or wheat starch, and further preferably wheat starch, and the particle size of the starch is larger than 250 meshes, preferably larger than 300 meshes, and further preferably larger than 350 meshes. The cellulose ether can be one or more of methyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl cellulose, ethyl cellulose, benzyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, cyanoethyl cellulose, benzyl cyanoethyl cellulose, carboxymethyl hydroxyethyl cellulose, phenyl cellulose, etc.
In the above preparation method of the asphaltene conversion catalyst, the carrier matrix in step (b) may be one or more of a metal oxide carrier and a carbon carrier, and is preferably a metal oxide carrier. The metal oxide carrier can be one or more of alumina, titanium oxide, zirconium oxide and iron oxide in any combination, preferably alumina, and more preferably modified alumina, wherein the modification can be one or more of substances capable of adjusting the surface property of alumina, and specifically can be one or more of silicon, phosphorus, boron, fluorine, titanium, zirconium and the like.
In the above method for preparing the asphaltene conversion catalyst, the step (b) of introducing the coating solution obtained in the step (a) onto the carrier substrate may be carried out by any of the existing methods, such as spraying, dipping, and pulling, and preferably by dipping.
In the above preparation method of the asphaltene conversion catalyst, the shape of the carrier matrix in step (b) is not limited, and the carrier matrix can be in any form such as spherical shape, cylindrical bar shape, clover, etc., and can be selected by those skilled in the art according to actual needs.
In the above preparation method of the asphaltene conversion catalyst, the drying conditions in step (b) are such that the drying temperature is 80 to 200 ℃, preferably 120 to 160 ℃; the drying time is 2 to 10 hours, preferably 4 to 8 hours.
In the preparation method of the asphaltene conversion catalyst, the calcination in the step (b) is carried out in an inert atmosphere, wherein the inert atmosphere can be one or more of nitrogen, helium, neon and argon, and nitrogen is preferred. The roasting temperature is 600-950 ℃, preferably 650-900 ℃, the roasting time is 2-8 h, preferably 3-6 h, and the volume space velocity of the inert atmosphere is 100-500 h -1 Preferably 100 to 300h -1 。
In the above method for preparing the asphaltene conversion catalyst, the active metal component introduced in step (c) can be prepared by any method, such as impregnation, kneading, coprecipitation, etc., preferably impregnation, which can be one of saturation impregnation and supersaturation impregnation.
In the preparation method of the asphaltene conversion catalyst, the roasting temperature in the step (c) is 400-600 ℃, preferably 400-550 ℃; the treatment time is 2 to 8 hours, preferably 2 to 5 hours. More preferably, the firing is performed in the presence of a vapor-containing gas, wherein the vapor-containing gas is water vapor or a mixed gas of water vapor and a carrier gas, and the volume ratio of water vapor to carrier gas in the mixed gas is 1; the carrier gas is one or more of nitrogen, helium, neon, argon, krypton and xenon. The volume space velocity of the gas containing water vapor is 100 to 800h -1 Preferably 200～500h -1 。
Further, in the above technical scheme, the preparation method of the hydrodesulfurization catalyst comprises the following steps:
(1) Adding an acidic aluminum source into a silicon source, and then mixing with a first metal salt solution to obtain a mixed solution A;
(2) Contacting the mixed solution A with an alkaline aluminum source in the presence of water to obtain slurry B;
(3) Carrying out hydrothermal treatment on the slurry B to obtain a carrier precursor;
(4) Uniformly mixing the carrier precursor obtained in the step (3), a forming agent and an adhesive, forming, drying and roasting to obtain a carrier;
(5) And mixing the carrier with a second metal salt solution, and further drying and roasting to obtain the catalyst.
According to the present invention, in step (1), an acidic aluminum source is added to the silicon source, instead of adding the silicon source to the acidic aluminum source, which would otherwise result in the formation of a large amount of precipitate.
Further, in the preparation method of the hydrodesulfurization catalyst, in the step (1), the silicon source is a water-soluble or water-dispersible basic silicon-containing compound (preferably a water-soluble or water-dispersible basic inorganic silicon-containing compound, more preferably one or more selected from water-soluble silicate, water glass, and silica sol, and preferably water glass).
Further, in the above method for producing a hydrodesulfurization catalyst, the silicon source is used in the form of an aqueous solution. The silicon source (as SiO 2) is present in a concentration of 5 to 30 wt.% (preferably 15 to 30 wt.%), based on the total weight of the aqueous solution, and the modulus is generally 2.5 to 3.2.
In the preparation method of the hydrodesulfurization catalyst, the acidic aluminum source is a water-soluble acidic aluminum-containing compound (preferably a water-soluble acidic inorganic aluminum-containing compound, particularly a water-soluble strong inorganic acid aluminum salt, more preferably one or more selected from aluminum sulfate, aluminum nitrate and aluminum chloride, and preferably aluminum sulfate).
Further, in the above-mentioned method for producing a hydrodesulfurization catalyst, the source of acidic aluminum is used in the form of an aqueous solution, and the concentration of the source of acidic aluminum (calculated as Al2O 3) is 30 to 100g/L (preferably 30 to 80 g/L) based on the total weight of the aqueous solution.
Further, in the above method for producing a hydrodesulfurization catalyst, the weight ratio of the silicon source (in terms of SiO 2) to the acidic aluminum source (in terms of Al2O 3) is 1 to 1 (preferably 1 to 7).
Further, in the above-described method for producing a hydrodesulfurization catalyst, in order to achieve the technical effects of the present invention more favorably, in particular, in order to obtain a support precursor having a larger pore volume and a lower impurity content, an acid (preferably, the acidic aluminum source is added to the silicon source, and then the acid is added to obtain the mixed solution a) is further added in step (1).
Further, in the above method for preparing a hydrodesulfurization catalyst, the acid is a water-soluble acid (preferably a water-soluble inorganic acid, more preferably one or more selected from sulfuric acid, nitric acid, and hydrochloric acid, and preferably sulfuric acid).
Further, in the above-mentioned method for producing a hydrodesulfurization catalyst, the acid is used in the form of an aqueous solution. The concentration of the acid is 2-6wt% (preferably 2-5wt% based on the total weight of the aqueous solution).
Further, in the above method for producing a hydrodesulfurization catalyst, the acid is added in an amount such that the pH of the mixed solution a is 2 to 4 (preferably 3 to 4).
Further, in the above-mentioned method for producing a hydrodesulfurization catalyst, in the step (1), the mixed solution A generally has an aluminum content of 5 to 20gAl2O3/L in terms of Al2O3 and a silicon content of 5 to 40gSiO2/L in terms of SiO 2.
Further, in the preparation method of the hydrodesulfurization catalyst, in the step (2), the alkali aluminum source is a water-soluble alkali aluminum-containing compound (preferably a water-soluble alkali inorganic aluminum-containing compound, especially an alkali metal meta-aluminate, more preferably one or more selected from sodium meta-aluminate and potassium meta-aluminate, and preferably sodium meta-aluminate).
Further, in the above method for producing a hydrodesulfurization catalyst, the alkali aluminum source is used in the form of an aqueous solution. The alkaline aluminum source (as Al2O 3) has a concentration of 130 to 350g/L (preferably 150 to 250 g/L) based on the total weight of the aqueous solution and a caustic ratio of generally 1.15 to 1.35, preferably 1.15 to 1.30.
Further, in the above method for producing a hydrodesulfurization catalyst, the amount of the mixed liquid a is 40 to 70vol% (preferably 40 to 65 vol%) based on the total volume of the mixed liquid a, the alkali aluminum source and water.
Further, in the above method for producing a hydrodesulfurization catalyst, the amount of the alkali aluminum source is 20 to 40vol% (preferably 25 to 40 vol%) based on the total volume of the mixed solution a, the alkali aluminum source and water.
Further, in the above method for producing a hydrodesulfurization catalyst, the amount of water is 10 to 20vol% (preferably 13 to 20 vol%) based on the total volume of the mixed solution a, the alkali aluminum source and water.
Further, in the above method for preparing a hydrodesulfurization catalyst, the mixed solution a and the alkali aluminum source are added to water sequentially or simultaneously (preferably, the mixed solution a and the alkali aluminum source are added to water in a concurrent flow manner).
Further, in the above method for preparing a hydrodesulfurization catalyst, the flow rate of the mixed solution A is 15 to 50mL/min (preferably 20 to 40 mL/min).
Further, in the above-mentioned method for producing a hydrodesulfurization catalyst, the flow rate of the addition of the alkali aluminum source is controlled so that the pH of the slurry B is maintained at 7.5 to 10.5 (preferably 8.0 to 10.5, and more preferably 8.5 to 10.5).
Further, in the above-described method for producing a hydrodesulfurization catalyst, in order to achieve the technical effects of the present invention more favorably, particularly in order to obtain a support precursor having a larger pore volume, a water-soluble carbonate (preferably, the mixed solution a and the alkaline aluminum source are added to water, and then the water-soluble carbonate is added to obtain the slurry B) is further added in the step (2).
Further, in the preparation method of the hydrodesulfurization catalyst, the water-soluble carbonate is selected from one or more carbonates of alkali metals and ammonium (preferably, one or more carbonates selected from sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium carbonate and ammonium bicarbonate, preferably sodium carbonate).
Further, in the above method for producing a hydrodesulfurization catalyst, the water-soluble carbonate is used in the form of a solid.
Further, in the above-mentioned method for producing a hydrodesulfurization catalyst, the water-soluble carbonate is added in an amount such that the slurry B has a pH of 10.5 to 12 (preferably 11 to 12).
Further, in the above-described method for producing a hydrodesulfurization catalyst, in step (3), the support precursor is separated from the reaction system of the hydrothermal treatment, washed to neutrality, and then dried. Here, the washing may be performed by a washing method conventional in the art, preferably by deionized water, and further preferably at 50 ℃ to 90 ℃. In addition, the separation can adopt one of the means which can realize the separation of liquid-solid two-phase materials in the field, such as filtration, centrifugal separation and the like, and concretely, the separation can adopt a filtration separation mode to separate, solid-phase materials and liquid-phase materials are obtained after separation, and the solid-phase materials are washed and dried to obtain the carrier precursor.
Further, in the above method for preparing a hydrodesulfurization catalyst, the drying conditions include: the drying temperature is 100-150 ℃, and the drying time is 6-10 hours.
Further, in the above-mentioned method for producing a hydrodesulfurization catalyst, in the step (1), the temperature is 25 to 50 ℃ (preferably 25 to 40 ℃) and the pressure is normal pressure.
Further, in the above-mentioned method for producing a hydrodesulfurization catalyst, in the step (2), the temperature is 50 to 90 ℃ (preferably 50 to 80 ℃) and the pressure is normal pressure.
Further, in the above-mentioned method for producing a hydrodesulfurization catalyst, in the step (3), the temperature is 180 to 300 ℃ (preferably 180 to 280 ℃, more preferably 180 to 250 ℃) and the pressure is 0.1 to 0.5MPa (preferably 0.1 to 0.3 MPa).
Further, in the above-mentioned method for preparing a hydrodesulfurization catalyst, in order to achieve the technical effects of the present invention more excellently, in the step (3), the hydrothermal treatment time is 0.5 to 20 hours (preferably 2 to 16 hours).
Furthermore, in the preparation method of the hydrodesulfurization catalyst, an auxiliary agent, such as one or more of P2O5, B2O3 or TiO2, can be added according to actual needs. For this purpose, these precursors may be added during the reaction of step (1) in the form of water-soluble inorganic salts. Specific examples of the inorganic salt include borate, sulfate, and nitrate. The addition amount of these auxiliaries can be arbitrarily adjusted according to the requirements of the subsequent catalyst and the like. In general, these auxiliaries are generally present in a weight content, calculated as oxide, of from 1 to 8% by weight, preferably from 2 to 6% by weight, relative to 100% by weight of the total weight of the support precursor.
Further, in the preparation method of the hydrodesulfurization catalyst, in the step (1), the first metal is selected from at least one of group IVB metals, group VIB metals and group VIII metals, and further, the first metal salt is a soluble metal salt, such as any one of sulfate or nitrate. The first metal may specifically be one or more of Ni, co, fe, and Zr, and further, the first metal salt may be one or more of nickel nitrate, cobalt nitrate, nickel sulfate, cobalt sulfate, iron nitrate, iron sulfate, zirconium nitrate, and zirconium sulfate.
Further, in the preparation method of the hydrodesulfurization catalyst, the forming agent in the step (4) is one or more of cellulose and starch, preferably cellulose, and more preferably methyl cellulose.
Further, in the preparation method of the hydrodesulfurization catalyst, the binder in the step (4) is an organic acid, specifically, one or more of acetic acid, citric acid and the like, and preferably citric acid.
Further, in the preparation method of the hydrodesulfurization catalyst, the drying temperature in the step (4) is 100 to 150 ℃, and the drying time is 4 to 10 hours. The baking temperature is 500 to 950 ℃, preferably 550 to 900 ℃, and the baking time is 2 to 6 hours.
Further, in the preparation method of the hydrodesulfurization catalyst, the molding in the step (4) may adopt a molding mode commonly used in the existing catalyst preparation, and the specific molding shape may be selected according to actual needs, such as a spherical shape, a strip shape, a clover shape, and the like.
Further, in the preparation method of the hydrodesulfurization catalyst, the drying temperature in the step (5) is 100 to 150 ℃, and the drying time is 4 to 10 hours.
Further, in the above method for preparing a hydrodesulfurization catalyst, the calcination in step (5) is performed in a mixed atmosphere of steam and an oxygen-containing gas, and the volume ratio of the oxygen-containing gas to the steam is 5:1 to 1, wherein the oxygen-containing gas is any one of oxygen and air. The baking temperature is 400 to 650 ℃, preferably 400 to 550 ℃; the roasting time is 3 to 8h.
Compared with the prior art, the method for producing the low-sulfur marine fuel oil has the following advantages:
1. in the low-sulfur marine fuel oil production method provided by the invention, the problem of high total sediment of the marine fuel oil obtained in the conventional production method is solved by adopting a grading scheme of an asphaltene conversion catalyst and a hydrodesulfurization catalyst, and a residual oil raw material is firstly contacted with the asphaltene conversion catalyst to ensure that the asphaltene is selectively subjected to hydroconversion on the basis of high-temperature fracture, so that the polycondensation reaction of the asphaltene is reduced, and simultaneously, impurities, particularly metals, in the raw material are effectively removed. Then the catalyst contacts with a hydrodesulfurization catalyst, the acidity of the catalyst is enhanced to promote the polycyclic aromatic hydrocarbon in the asphaltene to be further converted, heteroatoms such as sulfur, nitrogen and the like are effectively removed, meanwhile, the generation of sediments in the generated oil is reduced, and the purpose of producing low-sulfur ship fuel by residual oil conversion is realized.
2. In the method for producing the low-sulfur marine fuel oil, the surface of a carrier matrix is coated with a coating in the asphaltene conversion catalyst, so that the carrier matrix-silicon-carbon composite carrier is prepared. The coating comprises carbon and silicon, the silicon in the coating plays a role of a bridge, and aluminum and/or silicon in the carrier matrix and the carbon form a space net structure in an sp3 hybridization mode, so that the carbon layer and the carrier matrix are combined more firmly, the smoothness and the mechanical strength of the surface of the material are improved, the wear resistance of the material is improved, and the problem that the carbon layer and the carrier matrix in the existing carbon-containing composite material are not tightly combined is effectively solved. In the preparation method, a saturated dipping mode is adopted for coating, the silica gel cluster and the organic carbon precursor are coated on the outer layer of the carrier matrix, water in coating liquid enters the pore channels of the carrier matrix, and in the subsequent drying process, the water escapes in the form of water vapor to break through the coating at the pore opening, so that the coating has a rich multistage pore channel structure and is convenient for the diffusion of reactants; the roasting process is carried out in the atmosphere containing water vapor, and the carbon layer on the outer surface of the carrier has weak adsorption capacity on the active metal, so that the active metal migrates into the pore channels of the carrier material, and the active metal distribution of the prepared catalyst has the characteristic of less surface layer and more middle part.
3. In the production method of the low-sulfur marine fuel oil, the first metal component is firstly introduced into the hydrodesulfurization catalyst in the preparation of the carrier, and occupies neutral and alkaline surface hydroxyl groups in the silicon-aluminum material, so that the acidity of the carrier is modulated. Then when the second metal solution is soaked, the second metal is dispersed more uniformly due to the occupying effect of the first metal on the carrier, and the roasting condition of mixing water vapor and oxygen is adopted to remove non-framework aluminum and non-framework silicon, so that a multi-stage pore channel structure can be formed, an acid center is exposed, and meanwhile, the acidity of the catalyst is enhanced, and the hydrogenation performance of the catalyst is improved. In the preparation of the carrier, firstly, a silicon source is acidified by adopting an acidic aluminum source and then a metal salt, cations (sodium ions and the like) in silicic acid polymers enveloped in a ring or a cage in the silicon source are dissociated, acidified silica gel groups are adsorbed on aluminum hydroxide colloid, so that the sodium ions are effectively separated from the silica gel groups, and meanwhile, the added metal is multivalent, has high charge energy and plays a role of isolating the dissociated sodium ions with the acidic aluminum source, so that the subsequent sodium ions are more easily removed, the difficulty in removing sodium by subsequent washing is greatly reduced, and the water consumption for washing can be reduced. More importantly, sodium ions are effectively removed, metal ions are supplemented, the hydroxyl distribution of the silicon-aluminum-metal composite material is changed, the carrier has higher acidity and has large pore volume and mesoporous-macroporous multilevel pore channels, and the characteristics of high B acid content, low sodium content and the like are improved by the composite addition of silicon and metal. The catalyst prepared by the method has good hydrogenation performance, particularly desulfurization performance, and is suitable for hydrogenation process for producing low-sulfur marine oil from heavy and poor-quality residual oil.
4. In the method for producing the low-sulfur marine fuel oil, the acidified silica gel groups are adsorbed on the aluminum hydroxide colloid in the preparation method of the hydrodesulfurization catalyst, so that crystal nuclei are provided for subsequent reactions, the increase of crystal grains of the prepared carrier precursor is promoted, and the carrier precursor with large pore volume and large pore diameter is formed. By adjusting the pH value of the slurry, the slurry system form is changed into a gelatinous thixotropic form from a flowing state at the beginning in the high-temperature treatment process, the slurry system form is changed into the flowing state after being treated for a period of time, and a silicon-aluminum material and water form a changeable silicon-aluminum-oxygen network structure in the process of being changed into the gelatinous thixotropic form, so that the preparation of the carrier precursor with large pore volume is facilitated.
Detailed Description
The following detailed description of the embodiments of the present invention will be described with reference to specific examples, but it should be noted that the scope of the present invention is not limited by the embodiments, but is defined by the claims.
In the context of the present specification, the pore volume and specific surface area of the silicoaluminum material were analyzed using a low-temperature nitrogen adsorption method.
In the context of the present specification, the pore volume, specific surface area and pore size distribution are measured using cryogenic nitrogen adsorption. Total acid, B acid and L acid were measured by pyridine infrared adsorption. Sodium oxide and silica were measured using fluorescence analysis. The active metal content was measured spectrophotometrically. The wear index was measured using an air jet method. The C content was measured by oxidation.
All percentages, parts, ratios, etc. referred to in this specification are by weight and pressures are gauge pressures 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.
Example 1
(1) Preparation of asphaltene conversion catalyst
Mixing silica sol with the silicon oxide content of 30wt%, water and wheat starch with the granularity of 400 meshes and the molecular weight of 60000, and uniformly mixing to obtain coating liquid with the silicon oxide content of 80g/L and the wheat starch content of 200 g/L;
the coating liquid is dipped on a 0.3-0.8mm spherical alumina carrier substrate (the specific surface is 161 m) 2 Per g, pore volume 0.76mL/g, abrasion index 3.32%), dried at 120 deg.C for 6h, and then at a volume space velocity of 200h -1 Roasting at 700 deg.c for 3 hr to obtain the catalytic carrier material AS-1.
Weighing 23.78g of phosphoric acid, adding 800mL of distilled water, then sequentially adding 77.50g of molybdenum oxide and 35.52g of basic nickel carbonate, heating and stirring until the molybdenum oxide and the basic nickel carbonate are completely dissolved, and then using the distilled water to fix the volume of the solution to 1000mL to obtain a solution L-1.
Impregnating the L1 solution onto AS-1 in a saturated impregnation mode, drying at 120 ℃ for 6 hours, roasting in a mixed gas atmosphere with the volume ratio of water vapor to nitrogen being 1 -1 The calcination temperature of the catalyst is 450 ℃, the calcination time is 3 hours, the catalyst ASC-1 of the invention is obtained, and the analysis result is shown in Table 1.
(2) Preparation of hydrodesulfurization catalyst
The preparation concentration is 40gAl 2 O 3 L aluminium sulphate solution and a concentration of 60gSiO 2 L/mouldSilica sol solution with the number of 2.8 is used for standby, and first metal salt solution with the concentration of 50gNiO/L is prepared for standby. The caustic ratio is 1.20, the concentration is 150 gAl 2 O 3 and/L of sodium metaaluminate solution for later use.
1.5L of the solution with the concentration of 60gSiO is measured 2 Adding the/L silica sol solution into a container, and slowly adding 1L of 40gAl under stirring 2 O 3 Aluminum sulfate solution/L, during which aluminum hydroxide colloids are formed, but the solution is still in liquid form. And then adding a first metal salt solution with the concentration of 50gNiO/L to adjust the pH value to 3, wherein the dosage is 0.1L, and completing acidification treatment to obtain a mixed solution A.
Adding 1000mL of deionized water into a 5000mL reactor as bottom water, starting stirring and heating, heating the deionized water to 60 ℃, adding the mixed solution A into the reactor at a rate of 20mL/min, simultaneously adding the prepared sodium metaaluminate solution in a concurrent flow manner, controlling the pH value of the reaction to be 9.0 by adjusting the flow rate of the sodium metaaluminate, and keeping the temperature and the pH value of slurry in the reactor constant. After the reaction is finished, the using amount of sodium metaaluminate is 500mL, and 48g of ammonium carbonate is added into the reactor under the stirring condition to adjust the pH value to 10.5. The slurry is put into a reactor and treated for 2 hours under the condition of stirring at the treatment temperature of 220 ℃ and the treatment pressure of 0.3 MPa. And washing the treated slurry with hot water at 90 ℃ until the liquid is neutral, and drying at 120 ℃ for 6h to obtain a dried sample PO-1 of the silicon-aluminum-metal composite material.
And taking 500g of the prepared PO-1 silicon-aluminum-metal composite material dry sample, adding 3.9g of hydroxypropyl methyl cellulose, 10.54g of citric acid and 470g of purified water, uniformly mixing, then forming a sphere, and roasting the sphere-formed sample at 650 ℃ for 3h to obtain the carrier S1 with the particle size of 0.3-0.8 mm.
Weighing 50.29g of phosphoric acid, adding 800mL of distilled water, then sequentially adding 177.57g of molybdenum oxide and 75.12g of basic nickel carbonate, heating and stirring until the molybdenum oxide and the basic nickel carbonate are completely dissolved, and then using the distilled water to fix the volume of the solution to 1000mL to obtain a solution L2. The support S1 was saturated with the solution L2 and dried at 110 ℃ for 2h, at a volume ratio of air to water vapor of 3:1, roasting for 5 hours at the roasting temperature of 480 ℃ to obtain the catalyst SC1, wherein the specific properties are shown in a table 2.
Example 2
(1) Preparation of asphaltene conversion catalyst
The same AS example 1 except that the silica content of the coating solution was changed to 100g/L and the wheat starch content was changed to 180g/L, the catalytic carrier material AS-2 of the present invention and the catalyst ASC-2 of the present invention were obtained, and the analysis results are shown in Table 1.
(2) Preparation of hydrodesulfurization catalyst
The other conditions were the same as in example 1 except that: changing the silica sol into a water glass solution, changing the dosage of the first metal salt into 0.05L, adjusting the acidification pH to 4.0, controlling the flow rate of the mixed solution A to be 30mL/min, and heating deionized water in a reactor to 70 ℃ to obtain a silicon-aluminum-metal composite material dry sample PO-2.
And taking 500g of the prepared PO-2 silicon-aluminum-metal composite material dry sample, adding 7.0g of wheat starch, 12.8g of acetic acid (85 wt%) and 450g of purified water, uniformly mixing, then forming a sphere, and roasting the sphere sample at 600 ℃ for 4 hours to obtain the carrier S2 with the granularity of 0.3-0.8 mm.
The support S2 was saturated with the solution L2 and dried at 110 ℃ for 2h, at a volume ratio of air to water vapor of 4:1, roasting for 4 hours at the roasting temperature of 580 ℃ to obtain the catalyst SC2, wherein the specific properties are shown in Table 2.
Example 3
(1) Preparation of asphaltene conversion catalyst
Otherwise, as in example 1, the spherical alumina carrier substrate was changed to 148 m (specific surface area) 2 (iv)/g, pore volume 0.76mL/g, abrasion index 3.56%), and starch was changed to polyvinyl alcohol having an average molecular weight of 120000 to obtain the catalytic support material AS-3 of the present invention and the catalyst ASC-3 of the present invention, and the analysis results thereof are shown in Table 1.
(2) Preparation of hydrodesulfurization catalyst
The other conditions were the same as in example 1 except that: changing the silica sol to 40gSiO 2 and/L, adjusting the acidification pH to 3.5, adjusting the flow rate of the mixed solution A to 15mL/min, adding 61g of ammonium carbonate into the reactor under the stirring condition to adjust the pH value to 11.0, adjusting the treatment temperature to 250 ℃, and adjusting the treatment pressure to 0.4MPa to obtain the silicon-aluminum-metal composite material dry sample PO-3.
And taking 500g of prepared PO-3 silicon-aluminum-metal composite material dry sample, adding 10.0g of wheat starch, 8.8g of tartaric acid and 480g of purified water, uniformly mixing, then forming a sphere, and roasting the sphere-formed sample at 700 ℃ for 4 hours to obtain a carrier AS3 with the granularity of 0.3-0.8 mm.
The support AS3 was saturated with the solution L1 and dried at 110 ℃ for 2h, in a volume ratio of air to water vapor of 1:1, roasting for 3 hours at the roasting temperature of 500 ℃ to obtain a catalyst ASC3, wherein the specific properties are shown in a table 2.
Example 4
(1) Preparation of asphaltene conversion catalyst
The other example is the same as example 1 except that the space velocity of the nitrogen volume is changed to 300h -1 The roasting temperature is changed to 800 ℃, and the roasting time is changed to 4 hours, so AS to obtain the catalytic carrier material AS-4.
Weighing 41.79g of phosphoric acid, adding 800mL of distilled water, then sequentially adding 106.82g of molybdenum oxide and 48.96g of basic nickel carbonate, heating and stirring until the molybdenum oxide and the basic nickel carbonate are completely dissolved, and then using the distilled water to fix the volume of the solution to 1000mL to obtain a solution L-3. The L-1 solution was changed to an L-3 solution to obtain the catalyst ASC-4 of the present invention, and the analytical results are shown in Table 1.
(2) Preparation of hydrodesulfurization catalyst
The preparation concentration is 30gAl 2 O 3 Aluminum sulfate solution/L and a concentration of 60gSiO 2 The silica sol solution with the modulus of 2.8 and the concentration of 30g ZrO is prepared for standby 2 The first metal salt solution is ready for use. The caustic ratio was 1.25, the concentration was 130 gAl 2 O 3 and/L of sodium metaaluminate solution for later use.
1.5L of the solution with the concentration of 60gSiO is measured 2 Adding the/L silica sol solution into a container, and slowly adding 1L of 30gAl under stirring 2 O 3 Aluminum sulfate solution/L, during which aluminum hydroxide colloids are formed, but the solution is still in liquid form. Then, 30g of ZrO was added 2 Adjusting the pH value of the first metal salt solution to 3.5 by 0.05L, and completing acidification treatment to obtain mixed solution A.
Adding 800mL of deionized water serving as bottom water into a 5000mL reactor, starting stirring and heating, heating the deionized water to 70 ℃, adding the mixed solution A into the reactor at a rate of 25mL/min, simultaneously adding the prepared sodium metaaluminate solution in a concurrent flow manner, controlling the pH value of the reaction to be 8.0 by adjusting the flow rate of the sodium metaaluminate, and keeping the temperature and the pH value of slurry in the reactor constant. After the reaction is finished, the dosage of sodium metaaluminate is 560mL, and 76g of ammonium carbonate is added into the reactor under the stirring condition to adjust the pH value to 10.5. The slurry is put into a reactor and treated for 4 hours under the condition of stirring at the treatment temperature of 240 ℃ and the treatment pressure of 0.3 MPa. And washing the treated slurry with hot water at 90 ℃ until the liquid is neutral, and drying at 120 ℃ for 6h to obtain a dried sample PO-4 of the silicon-aluminum-metal composite material.
And taking 500g of the prepared PO-4 silicon-aluminum-metal composite material dry sample, adding 5.1g of hydroxypropyl methyl cellulose, 8.76g of tartaric acid and 490g of purified water, uniformly mixing, then forming a sphere, and roasting the sphere-formed sample at 550 ℃ for 3h to obtain the carrier S4 with the particle size of 0.3-0.8 mm.
Weighing 50.47g of phosphoric acid, adding 800mL of distilled water, then sequentially adding 137.06g of molybdenum oxide and 48.76g of basic cobalt carbonate, heating and stirring until the molybdenum oxide and the basic cobalt carbonate are completely dissolved, and then using the distilled water to fix the volume of the solution to 1000mL to obtain a solution L4. The support S4 is saturated with the solution L4, dried at 110 ℃ for 2h and dried at a volume ratio of air to water vapor of 4:1, roasting for 4 hours at the roasting temperature of 450 ℃ to obtain the catalyst SC4, wherein the specific properties are shown in Table 2.
Example 5
(1) Preparation of asphaltene conversion catalyst
The other steps are the same as example 4, except that the volume ratio of the water vapor to the nitrogen is changed to 1 and 3, and the volume space velocity of the mixed gas is changed to 450h -1 The catalyst calcination temperature was 550 ℃ to obtain the catalytic carrier material AS-5 of the present invention and the catalyst ASC-5 of the present invention, and the analytical results are shown in the table.
(2) Preparation of hydrodesulfurization catalyst
The other conditions were the same as in example 4 except that: changing the silica sol into water glass, adjusting the acidification pH value to 3.0, adjusting the adding amount of reactor bottom water to 1000mL, heating deionized water to 70 ℃, adjusting the treatment temperature to 260 ℃ and adjusting the treatment pressure to 0.5MPa to obtain a silicon-aluminum material dried sample PO-5, wherein the properties of the silicon-aluminum material dried sample are shown in Table 1.
And taking 500g of the prepared PO-5 silicon-aluminum-metal composite material dry sample, adding 12.3g of methyl cellulose, 5.5g of citric acid and 460g of purified water, uniformly mixing, then forming a sphere, and roasting the sphere-formed sample at 700 ℃ for 4 hours to obtain the carrier S5 with the particle size of 0.3-0.8 mm.
The support S5 was saturated with the solution L4 and dried at 110 ℃ for 2h, at a volume ratio of air to water vapor of 2:1, roasting the mixture for 5 hours at the roasting temperature of 420 ℃ to obtain the catalyst SC5, wherein the specific properties are shown in a table 2.
Comparative example 1
(1) Preparation of asphaltene conversion catalyst
The spherical alumina carrier is not coated, and the L-1 solution is directly impregnated into the spherical alumina carrier (the specific surface is 161 m) 2 Per g, pore volume 0.76mL/g, abrasion index 3.32%), drying at 120 deg.C for 6h, and then at a nitrogen gas volume space velocity of 300h -1 The calcination temperature of the catalyst is 450 ℃, the calcination time is 3 hours, the catalyst ASFC-1 is obtained, and the analysis result is shown in Table 1.
(2) Preparation of hydrodesulfurization catalyst
The preparation concentration is 40gAl 2 O 3 Aluminum sulfate solution/L and a concentration of 60gSiO 2 The silica sol solution with the modulus of 2.8 is ready for use. The caustic ratio is 1.20, the concentration is 150 gAl 2 O 3 and/L of sodium metaaluminate solution for later use.
Adding 1000mL of deionized water into a 5000mL reactor as bottom water, starting stirring and heating, heating the deionized water to 60 ℃, adding aluminum sulfate into the reactor at 20mL/min and 30mL/min of silica sol, simultaneously adding the prepared sodium metaaluminate solution in a concurrent flow manner, controlling the pH value of the reaction to be 9.0 by adjusting the flow rate of the sodium metaaluminate, and keeping the temperature of slurry in the reactor and the pH value constant. After the reaction is finished, the using amount of sodium metaaluminate is 500mL, and 48g of ammonium carbonate is added into the reactor under the stirring condition to adjust the pH value to 10.5. The slurry is put into a reactor and treated for 2 hours under the condition of stirring at the treatment temperature of 220 ℃ and the treatment pressure of 0.3 MPa. Washing the treated slurry with hot water at 90 ℃ until the liquid is neutral, and drying at 120 ℃ for 6 hours to obtain a dried sample PFO-1 of the silicon-aluminum-metal composite material.
Taking 500g of the prepared PFO-1 silicon-aluminum-metal composite material dry sample, adding 3.9g of hydroxypropyl methyl cellulose, 10.54g of citric acid and 470g of purified water, uniformly mixing, then forming a sphere, and roasting the sphere sample at 650 ℃ for 3h to obtain a carrier SF1 with the granularity of 0.3-0.8 mm.
Saturating and impregnating the carrier SF1 with the solution L2, drying at 110 ℃ for 2h, and carrying out reaction at the volume ratio of air to water vapor of 3:1, roasting for 5 hours at the roasting temperature of 480 ℃ to obtain the catalyst SF1, wherein the specific properties are shown in a table 2.
Comparative example 2
(1) Preparation of asphaltene conversion catalyst
The spherical alumina carrier is not coated, and the L-1 solution is directly impregnated into the spherical alumina carrier (the specific surface is 161 m) 2 Per g, pore volume 0.76mL/g, abrasion index 3.32%), drying at 120 deg.C for 6h, and then at a nitrogen gas volume space velocity of 300h -1 The calcination temperature of the catalyst is 450 ℃, the calcination time is 3 hours, the catalyst ASFC-1 is obtained, and the analysis result is shown in Table 1.
(2) Preparation of hydrodesulfurization catalyst
The preparation concentration is 40gAl 2 O 3 Aluminum sulfate solution/L and a concentration of 60gSiO 2 The first metal salt solution with the concentration of 50gNiO/L is prepared for standby. The caustic ratio is 1.20, the concentration is 150 gAl 2 O 3 and/L of sodium metaaluminate solution for later use.
1.5L of the solution with the concentration of 60gSiO is measured 2 Adding the/L silica sol solution into a container, and slowly adding 1L of 40gAl under stirring 2 O 3 Aluminum sulfate solution/L, during which aluminum hydroxide colloids are formed, but the solution is still in liquid form. And then adding a first metal salt solution with the concentration of 50gNiO/L to adjust the pH value to 3, wherein the dosage is 0.1L, and completing acidification treatment to obtain a mixed solution A.
Adding 1000mL of deionized water into a 5000mL reactor as bottom water, starting stirring and heating, heating the deionized water to 60 ℃, adding the mixed solution A into the reactor at a rate of 20mL/min, simultaneously adding the prepared sodium metaaluminate solution in a concurrent flow manner, controlling the pH value of the reaction to be 9.0 by adjusting the flow rate of the sodium metaaluminate, and keeping the temperature and the pH value of slurry in the reactor constant. After the reaction is finished, the using amount of sodium metaaluminate is 500mL. Washing the reacted slurry with hot water at 90 ℃ until the liquid is neutral, and drying at 120 ℃ for 6 hours to obtain a dried sample PFO-2 of the silicon-aluminum-metal composite material.
Taking 500g of the prepared PFO-2 silicon-aluminum-metal composite material dry sample, adding 3.9g of hydroxypropyl methyl cellulose, 10.54g of citric acid and 470g of purified water, uniformly mixing, then forming a sphere, and roasting the sphere sample at 650 ℃ for 3h to obtain a carrier SF2 with the granularity of 0.3-0.8 mm.
Saturating and impregnating the carrier SF2 with the solution L2, drying at 110 ℃ for 2h, and carrying out reaction at the volume ratio of air to water vapor of 3:1, roasting for 5 hours at the roasting temperature of 480 ℃ to obtain a catalyst SF2, wherein the specific properties are shown in a table 2.
TABLE 1 Properties of asphaltene conversion catalysts
| Catalyst numbering | ASC-1 | ASC-2 | ASC-3 | ASC-4 | ASC-5 | ASFC-1 |
| The volume of the holes is the same as the volume of the holes,mL/g | 0.71 | 0.70 | 0.71 | 0.68 | 0.68 | 0.74 |
| specific surface area, m 2 /g | 138 | 131 | 125 | 127 | 123 | 153 |
| Catalyst composition in wt% | ||||||
| MoO 3 | 5.89 | 5.91 | 5.86 | 7.93 | 7.91 | 5.87 |
| NiO | 1.39 | 1.42 | 1.36 | 1.94 | 1.92 | 1.41 |
| P | 0.41 | 0.40 | 0.43 | 0.95 | 0.93 | 0.40 |
| Carbon (C) | 6.68 | 6.01 | 8.31 | 6.50 | 6.52 | - |
| Silicon dioxide | 6.20 | 7.60 | 5.99 | 6.01 | 6.03 | - |
| Wear index% | 0.38 | 0.40 | 0.36 | 0.37 | 0.38 | 3.14 |
TABLE 2 Properties of the hydrodesulfurization catalyst
| Numbering | SC-1 | SC-2 | SC-3 | SC-4 | SC-5 | SF-1 | SF-2 |
| Specific surface area, m 2 /g | 189 | 198 | 154 | 205 | 162 | 141 | 116 |
| Pore volume, mL/g | 0.56 | 0.57 | 0.52 | 0.59 | 0.56 | 0.40 | 0.31 |
| Total acid, mmol/g | 0.402 | 0.418 | 0.394 | 0.411 | 0.390 | 0.278 | 0.245 |
| Catalyst composition in wt% | |||||||
| MoO 3 | 12.85 | 12.87 | 12.81 | 9.87 | 9.81 | 12.87 | 12.86 |
| NiO/CoO | 4.83 | 3.91 | 5.01 | 2.15 | 2.09 | 2.95 | 2.89 |
| ZrO 2 ，% | - | - | - | 0.60 | 0.57 | - | - |
| P | 0.95 | 0.91 | 0.91 | 0.94 | 0.91 | 0.92 | 0.91 |
| Wear index% | 0.60 | 0.62 | 0.61 | 0.63 | 0.64 | 0.83 | 1.15 |
The activity evaluation was carried out on a two-stage series continuous tank reactor (CSTR) unit, in which the asphaltene conversion catalyst was packed in one reaction and the hydrodesulfurization catalyst was packed in the other reaction, and the evaluation was carried out using high-sulfur vacuum residue, and the properties and evaluation conditions thereof are shown in Table 3. The oil produced after 1000h running was sampled and analyzed, and the activity of comparative example 2 was taken as 100, and the results of other evaluations compared with the activity of comparative example 2 are shown in Table 4.
TABLE 3 high-sulfur vacuum residue Properties and evaluation conditions
| Item | Numerical value |
| Properties of crude oil | |
| Density, g/cm 3 | 1.0359 |
| Sulfur content% | 5.72 |
| Residual carbon content% | 23.34 |
| Ni+V/µg·g -1 | 210.86 |
| >Yield of 540 ℃ residual oil | 87.4 |
| Content of deposits% | 0.32 |
| Viscosity of the residue, (100 ℃ C.) mm 2 /s | 4125 |
| Saturated fraction of% | 9.85 |
| Aromatic fraction% | 55.08 |
| Gelatine% | 30.19 |
| Asphaltene,% of | 4.89 |
| Process conditions | |
| Reaction temperature/. Degree.C | 410/410 |
| Reaction pressure/MPa | 15 |
| Space velocity/h -1 | 0.3 |
| Volume ratio of hydrogen to oil | 600:1 |
TABLE 4 evaluation results of catalyst grading
| Catalyst and process for preparing same | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 |
| Relative hydrogenation activity | |||||||
| HDS | 131 | 135 | 127 | 129 | 120 | 104 | 100 |
| HD（Ni+V） | 135 | 131 | 142 | 138 | 146 | 102 | 100 |
| HDAs | 120 | 129 | 138 | 131 | 140 | 100 | 100 |
| >Residual oil relative conversion rate at 540 deg.C | 122 | 124 | 118 | 121 | 115 | 102 | 100 |
| >Relative fraction deposit content at 350 DEG C | 80 | 75 | 68 | 71 | 65 | 100 | 100 |
As can be seen from the data in the tables: compared with the catalyst prepared by a comparative example, the catalyst prepared by the method has the advantages that the asphaltene conversion is improved, the desulfurization activity is improved, the sediment content of the fraction with the temperature of more than 350 ℃ is obviously reduced, and a foundation is laid for directly producing low-sulfur ship fuel from atmospheric residue.
Claims (12)
1. A method for producing low-sulfur marine fuel oil comprises the following steps: under the condition of hydrogen, residual oil raw materials enter a hydrogenation reaction zone to be sequentially contacted with an asphaltene conversion catalyst and a hydrodesulfurization catalyst for reaction, and fractions with the temperature of more than 350 ℃ obtained after reaction effluent is separated are directly used as low-sulfur marine fuel oil components or used as blending components for producing marine fuel oil;
the asphaltene conversion catalyst comprises a carrier and active metal, wherein the carrier comprises a carrier substrate and a coating, the coating is a composite material containing carbon and silicon oxide, and a space network structure is formed between the coating and the carrier substrate in an sp3 hybridization mode; the carrier matrix is one or more of a metal oxide carrier and a carbon carrier; in the asphaltene conversion catalyst, the total weight content of the carrier is taken as a reference, the content of the carrier matrix is 80-99 wt%, and the content of the coating is 1-20%; in the coating, the weight ratio of carbon to silicon oxide is 1:0.1 to 1:1.5; the metal oxide carrier is one or any combination of more of alumina, titanium oxide, zirconium oxide and ferric oxide; the specific surface area of the carrier is 140-220 m 2 The pore volume is 0.6-0.9 mL/g, the carbon content is 0.5-10%, the silicon oxide content is 0.5-10%, and the abrasion index is less than 0.5%; the active metal component is one or more of VIB group metals and VIII group metals; the content of VIB group metal is 4-25 wt%; the content of the VIII group metal is 1wt% -10 wt%; the metal of group VIB is Mo and/or W, theThe VIII group metal is Ni and/or Co; the properties of the asphaltene conversion catalyst were as follows: the specific surface area is 120 to 200m 2 Per gram, the pore volume is 0.5-0.8 mL/g, the carbon content is 0.3-9%, the silicon oxide content is 0.3-9%, and the abrasion index is less than 0.5%;
the hydrodesulfurization catalyst comprises a silicon-aluminum material and a first metal and a second metal which are loaded on the silicon-aluminum material; wherein the first metal is selected from at least one of IVB group metals, VIB group metals and VIII group metals; the second metal is selected from at least one of VIB group metals and VIII group metals; the specific surface area of the hydrodesulfurization catalyst is 160-250 m 2 The pore volume is 0.4 to 0.7mL/g, the total acid number of the catalyst is 0.3 to 0.6mol/g, and the ratio of the B acid to the L acid is 0.3 to 1.0; based on the weight of the catalyst, the content of the VIB group metal is 6 to 15 percent calculated by oxide, the content of the VIII group metal is 2 to 10 percent calculated by oxide, and the content of the IVB group metal is 0.1 to 4.0 percent calculated by oxide;
the reaction conditions in the hydrogenation reaction zone were as follows: the reaction pressure is 13-18 MPaG, the reaction temperature is 380-430 ℃, and the liquid hourly space velocity is 0.1-0.6 h -1 The volume ratio of hydrogen to oil is 400-800.
2. The method for producing low-sulfur bunker fuel oil according to claim 1, wherein said asphaltene conversion catalyst has a carrier matrix content of 85 to 95wt% and a coating content of 5 to 15%, based on the total weight content of the carrier; in the coating, the weight ratio of carbon to silicon oxide is 1:0.5 to 1:1.
3. the process for producing low sulfur bunker fuel oil of claim 1, wherein said metal oxide support is alumina.
4. The method for producing low-sulfur bunker fuel oil according to claim 1, wherein said metal oxide support is modified alumina, and said modification is one or more of substances capable of adjusting surface properties of alumina.
5. The method for producing low-sulfur bunker fuel oil according to claim 4, wherein the substance capable of adjusting the surface properties of alumina is one or more of silicon, phosphorus, boron, fluorine, silicon, titanium, zirconium and magnesium.
6. The method for producing low-sulfur bunker fuel oil according to claim 1, wherein the hydrodesulfurization catalyst has a specific surface area of 160 to 230m 2 The pore volume is 0.45 to 0.65mL/g, the total acid value of the catalyst is 0.35 to 0.6mol/g, and the ratio of the B acid to the L acid is 0.3 to 0.8.
7. The method for producing low-sulfur bunker fuel oil according to claim 1, wherein the content of group VIB metal in the hydrodesulfurization catalyst is 8 to 15% in terms of oxide, based on the weight of the catalyst; the content of the VIII group metal is 2 to 6 percent calculated by oxide, and the content of the IVB group metal is 0.5 to 4.0 percent calculated by oxide.
8. The process for the production of low sulfur bunker fuel oil of claim 1 wherein the resid feed has the following properties: the metal Ni + V is not less than 180 mu g/g, the sulfur content is not less than 4wt%, and the carbon residue is not less than 18wt%.
9. The process for the production of low sulfur bunker fuel oil of claim 1 wherein the resid feed has the following properties: the metal Ni + V is not less than 200 mu g/g, the sulfur content is not less than 4.5wt%, and the carbon residue is not less than 20wt%.
10. The method for producing low-sulfur bunker fuel oil according to claim 1, wherein the hydrogenation reaction zone is provided with more than one reactor, and the reactors are one or more of a fixed bed hydrogenation reactor, a boiling bed hydrogenation reactor and a suspension bed hydrogenation reactor.
11. The method for producing low-sulfur bunker fuel oil according to claim 1, wherein 2 to 3 reactors are provided in the hydrogenation reaction zone.
12. The method for producing low-sulfur bunker fuel oil of claim 10, wherein the reactor is an ebullated bed hydrogenation reactor.
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