CN116478722A - Method for producing marine fuel oil through hydrogenation - Google Patents
Method for producing marine fuel oil through hydrogenation Download PDFInfo
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- CN116478722A CN116478722A CN202210038139.XA CN202210038139A CN116478722A CN 116478722 A CN116478722 A CN 116478722A CN 202210038139 A CN202210038139 A CN 202210038139A CN 116478722 A CN116478722 A CN 116478722A
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 143
- 239000010762 marine fuel oil Substances 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 239000003921 oil Substances 0.000 claims abstract description 170
- 238000000034 method Methods 0.000 claims abstract description 68
- 239000002994 raw material Substances 0.000 claims abstract description 66
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 48
- 239000001257 hydrogen Substances 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 238000002156 mixing Methods 0.000 claims abstract description 21
- 238000005194 fractionation Methods 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims description 141
- 229910052717 sulfur Inorganic materials 0.000 claims description 63
- 239000011593 sulfur Substances 0.000 claims description 63
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 52
- 238000011049 filling Methods 0.000 claims description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 150000002431 hydrogen Chemical class 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 7
- 229910001385 heavy metal Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000012856 packing Methods 0.000 claims 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 2
- 239000000047 product Substances 0.000 description 59
- 239000002283 diesel fuel Substances 0.000 description 14
- 239000000295 fuel oil Substances 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000008901 benefit Effects 0.000 description 10
- 239000007791 liquid phase Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- 239000000084 colloidal system Substances 0.000 description 8
- 239000002737 fuel gas Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000003223 protective agent Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229930195734 saturated hydrocarbon Natural products 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000001935 peptisation Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000003949 liquefied natural gas Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
- C10G2300/1007—Used oils
-
- 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
Abstract
The invention discloses a method for producing marine fuel oil by hydrogenation. The method comprises the following steps: mixing a residual oil raw material with relatively good properties, an effluent of the upflow hydrogenation reactor in the step (2) and hydrogen, and entering a fixed bed hydrogenation unit for a first hydrofining reaction to obtain hydrogenated oil; the hydrogenated oil is subjected to normal pressure fractionation to obtain hydrogenated normal pressure residual oil; performing vacuum fractionation on part of the hydrogenated atmospheric residuum to obtain hydrogenated vacuum residuum and hydrogenated vacuum wax oil; mixing the partial hydrogenation residue reduction obtained in the step (1) with residual oil raw materials with relatively inferior properties and hydrogen, and entering an up-flow hydrogenation reactor for a second hydrofining reaction to obtain an effluent of the up-flow hydrogenation reactor; mixing part of the hydrogenated atmospheric residuum obtained in the step (1) and part of the hydrogenated vacuum residuum obtained in the step (2) with at least part of hydrogenated vacuum wax oil to obtain a marine fuel oil product. The method can treat the poor residual oil raw material and can improve the comprehensive performance of the produced marine fuel oil.
Description
Technical Field
The invention relates to a process method for producing clean fuel oil by using inferior residual oil, in particular to a process method for producing low-sulfur marine fuel oil by using inferior high-sulfur residual oil as a raw material.
Background
Along with the stricter global environmental protection regulations, after the clean gasoline, diesel oil and other light oil products finish upgrading, the clean low-sulfur marine fuel oil becomes one of the oil products which pay attention to in the next few years. The international maritime organization (International Maritime Organization, IMO) provides that the sulfur mass fraction of marine fuel oil used for sailing in the general offshore area from the year 2020 on month 01 is reduced from no more than 3.5% to no more than 0.5%; the sulfur content of the marine fuel oil should not exceed 0.1% while the emission control zone is underway. In the marine fuel oil demand market, the high sulfur residue marine fuel oil is about 70% of the total market in price advantage, the fraction marine fuel oil is about 25%, and the rest is low sulfur fuel oil (sulfur mass fraction is less than 3.5%) and a small amount of liquefied natural gas. Thus, new environmental regulations will have a significant impact on the current marine fuel oil market, which is dominated by high sulfur fuel oils, and will also promote further development of marine fuel oil desulfurization technology.
At present, the main ways for producing the residue type marine fuel oil with the sulfur mass fraction of not more than 0.5 percent comprise: adopts low-sulfur straight-run residuum to carry out blending production. However, because low-sulfur crude oil resources are limited and the price is high, the production cost of the residue type marine fuel oil can be greatly increased, and the method is not suitable for producing the residue type marine fuel oil with low value; the technology is feasible for producing low-sulfur residue type marine fuel oil by hydrodesulfurization of high-sulfur residues, but the technology directly produces residue type marine fuel oil with the sulfur mass fraction lower than 0.5% by directly desulfurizing the residues with the sulfur content higher than 2.0% or even more than 3.0%, and has the advantages of high processing cost, large hydrogenation causticity scale, high operation cost and poor economy.
The main purpose of the residuum hydrotreatment process is to greatly reduce the impurity content in the residuum raw material through hydrotreatment, to hydrogenate and convert non-ideal components such as polycyclic aromatic hydrocarbon, colloid, asphaltene and the like, to reduce the viscosity and to obviously improve the physical properties of the residuum raw material.
In the existing fixed bed hydrogenation technology, the raw materials are subjected to hydrodesulphurization and other impurity removal reactions under the action of hydrogen and residual oil hydrogenation catalysts, and the product index requirements can be met under high temperature and high severity conditions. The residuum hydrogenation catalyst is generally filled in a grading manner and comprises a protective agent, a demetallization catalyst, a desulfurization catalyst and a high-activity denitrification and carbon residue removal catalyst. Along the liquid-phase material flow direction, the reaction temperature is gradually increased, the disadvantage of the route is that the hydrogen consumption is high and the hydrogenation amount is large in the hydrogenation process, generally, under the condition that the sulfur content meets the index, a higher reaction severity is required, under the condition of high temperature and high pressure, the sulfur content meets the index requirement, other indexes such as carbon residue are greatly reduced, the conversion rate is improved, and the processing cost is high. In addition, the adaptability to crude oil is poor, the problem of poor raw material adaptability of fixed bed hydrotreatment is not solved, and meanwhile, the device is short in operation period for processing inferior vacuum residuum and poor in economical efficiency.
CN107001959a discloses a low sulfur marine fuel composition and a method for preparing the same. The method comprises the following steps: hydrotreating a vacuum residuum feed stream with hydrogen in the presence of a hydrotreating catalyst to reduce sulfur to no more than 1500 parts per million (wppm) without substantial cracking of the vacuum residuum; blending the hydrotreated vacuum resid with no more than 10 vol% of a first diesel boiling range hydrocarbon stream and no more than 40 vol% of a second diesel boiling range hydrocarbon stream to form the low sulfur marine fuel composition, wherein the hydrotreated vacuum resid comprises at least 60 vol% of the low sulfur marine fuel composition, wherein the vacuum resid feed stream has from 1000wppm to 10000wppm sulfur, the first diesel boiling range hydrocarbon stream has no more than 20wppm sulfur, and the second diesel boiling range hydrocarbon stream has no more than 10wppm sulfur. The method needs to adopt the conventional residual oil hydrogenation technology to reduce the sulfur in the residual oil raw material to below 1500wppm, but the problems of short production period, increased product blending difficulty, complex process and poor economy of the conventional residual oil hydrogenation technology for processing the inferior vacuum residual oil raw material can not be overcome due to the fact that the production cost of adding a large proportion of diesel oil and other fractions is greatly increased.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for producing marine fuel oil by hydrogenation. The method can treat the inferior vacuum residue raw material, can meet the index requirements of sulfur content, viscosity and the like of the product, can also meet the control of hydrogenation depth and reduce processing cost, and simultaneously, the hydrogenated product is used as low-sulfur marine fuel oil, and the peptization system is stable.
The inventor finds that when the low-sulfur marine fuel oil is produced by using the fixed bed residual oil hydrogenation technology to treat the inferior residual oil raw material, a harsher reaction condition is generally required, besides the economical problem, under the reaction condition, the conversion rate is greatly improved, excessive hydrogenation of light components is caused, and a large amount of colloid is saturated by hydrogenation, so that the stability of an oil peptization system is easily damaged, on one hand, the stable operation of a device is not facilitated, on the other hand, various indexes on the surface of the produced marine fuel oil meet the requirements, but the problem of reduced stability of the oil also exists, and adverse effects are caused on the blending, storage and use of the low-sulfur marine fuel oil. The inventor also finds that when the low-sulfur marine fuel oil product is produced by facing to process residual oil raw materials with different properties, if the residual oil raw materials with relatively poor properties and the residual oil raw materials with relatively high properties are fed into a fixed bed residual oil hydrogenation device together, the poor raw materials need higher reaction severity, so that the performance and the service cycle of the catalyst are influenced, and the properties of the product are also influenced. Under the condition of higher reaction severity, under the condition of meeting key product indexes such as sulfur, viscosity and the like, carbon residue is greatly reduced, processing cost is increased, product usability is also influenced, and more importantly, the overall economic benefit is influenced due to the rapid increase of pressure drop easily caused by a fixed bed reactor. The method of the invention introduces two residual oil raw materials with different properties through different feed inlets, and optimizes the hydrogenation process route, thereby not only processing the inferior residual oil raw materials, but also improving the comprehensive performance of the produced marine fuel oil, and simultaneously having good economic and social benefits.
The invention provides a method for producing marine fuel oil by hydrogenation, which comprises the following steps:
(1) Mixing a residual oil raw material with relatively good properties, an effluent of an upflow hydrogenation reactor obtained in the step (2) and hydrogen, and entering a fixed bed hydrogenation unit for a first hydrofining reaction to obtain hydrogenated oil; the hydrogenation generated oil is subjected to normal pressure fractionation to obtain hydrogenation normal pressure residual oil; performing vacuum fractionation on part of the hydrogenated atmospheric residuum to obtain hydrogenated vacuum residuum and hydrogenated vacuum wax oil;
(2) Mixing the partial hydrogenation vacuum residuum obtained in the step (1) with residuum raw materials with relatively inferior properties and hydrogen, and entering an up-flow hydrogenation reactor for a second hydrofining reaction to obtain an effluent of the up-flow hydrogenation reactor;
(3) And (3) mixing the partially hydrogenated atmospheric residuum obtained in the step (1) and the partially hydrogenated vacuum residuum obtained in the step (2) with at least partially hydrogenated vacuum wax oil to obtain a marine fuel oil product.
In the method, the hydrogenated and decompressed wax oil obtained in the step (1) can be partially used as the feed of other devices such as a catalytic cracker and a hydrocracking device to produce other high-quality products.
In the method of the invention, the volume of the hydrogenated atmospheric residuum entering the vacuum fractionating unit in the step (1) accounts for 20% -90%, preferably 30% -80% of the total volume of the obtained hydrogenated atmospheric residuum; the volume of the hydrogenated atmospheric residuum as the marine fuel oil component in the step (3) accounts for 10% -80%, preferably 20% -70% of the total volume of the obtained hydrogenated atmospheric residuum.
In the method, the volume of the hydrogenated vacuum residue entering the up-flow hydrogenation reactor in the step (2) accounts for 10-80%, preferably 20-50% of the total volume of the hydrogenated vacuum residue obtained in the step (1); the volume of the hydrogenated vacuum residuum as the marine fuel oil component in the step (3) accounts for 20% -90%, preferably 50% -80% of the total volume of the hydrogenated vacuum residuum obtained in the step (1).
In the method of the present invention, the residual oil raw material in the step (1) includes at least one of atmospheric residual oil and vacuum residual oil, and the residual oil raw material may also contain one or more of coker gas oil, deasphalted oil and heavy distillate oil. The sulfur content in the residual oil raw material is not higher than 5.0% by mass and can be 2.0% -5.0%; the Kangshi carbon residue is not higher than 18 percent and can be 10 to 14 percent; the total content of the heavy metals nickel and vanadium is not higher than 200 mug/g and can be 50 mug/g to 200 mug/g; the total nitrogen content is not higher than 0.80% and can be 0.25% -0.45%.
In the method, the residual oil raw material with relatively poor properties has the sulfur content of more than 3.5 percent, further 3.5 to 5.0 percent, and the total content of heavy metal nickel and vanadium of more than 100 mug/g, further 100 mug/g to 200 mug/g based on the mass content. The residual oil raw material with relatively good property has the sulfur content of not more than 3.5 percent, further 1.0 to 3.5 percent, and the total content of heavy metal nickel and vanadium of not more than 100 mug/g, further 50 mug/g to 100 mug/g based on the mass content.
In the method of the invention, the residual oil raw materials with relatively poor properties and the residual oil raw materials with relatively good properties are taken as the reference, wherein the residual oil raw materials with relatively good properties account for 10% -90%, preferably 30% -70% of the total feeding volume, and the residual oil raw materials with relatively poor properties account for 10% -90%, preferably 30% -70% of the total feeding volume.
In the method, the hydrogenated atmospheric residuum in the step (3) is mixed with hydrogenated vacuum wax oil and hydrogenated vacuum residuum, and the mixing volume ratio is 0.1-100: 0.1 to 100:1, preferably 0.1 to 25:0.1 to 15:1.
in the process of the present invention, the hydrogen used in the fixed bed hydrogenation unit may be recycle hydrogen.
In the method of the invention, the hydrogen used in the upflow hydrogenation reactor is new hydrogen.
In the method of the present invention, the first hydrofining reaction in step (1) may employ a fixed bed residuum hydrotreating technique, and the fixed bed hydrogenation unit employs at least one hydrogenation reactor. More preferably, a plurality of hydrogenation reactors are arranged in series, and most preferably three to five hydrogenation reactors are arranged. The hydrogenation reactor is filled with a slag oil hydrotreating catalyst. Each reactor is preferably provided with a catalyst bed layer, so that the waste catalyst can be easily discharged and the fresh catalyst can be easily filled. The adopted residuum hydrotreating catalyst is a catalyst with at least one function of residuum hydrodemetallization, hydrodesulphurization, hydrodenitrogenation and the like. The residuum hydrotreating catalyst generally takes porous refractory inorganic oxide such as alumina as a carrier, and at least one of elements such as P, si, F, B and the like is selectively added by taking VIB and/or VIII metals (such as at least one of the oxides of W, mo, co, ni and the like) as active components.
In the process of the present invention, the fixed bed residuum hydrotreating catalyst used in the fixed bed hydrogenation unit in step (1) includes residuum hydrogenation protecting catalysts, residuum hydrodemetallization catalysts and residuum hydrodesulfurization catalysts. Wherein, the residual oil hydrogenation protection catalyst accounts for 3-20% of the total filling volume by taking the total filling volume of the fixed bed residual oil hydrogenation treatment catalyst as a reference; the residual oil hydrodemetallization catalyst accounts for 20-60% of the total filling volume, preferably 20-50%; the residual oil hydrodesulfurization catalyst accounts for 10-50% of the total filling volume, preferably 20-48%. After the hydrodesulfurization catalyst, a residual oil hydrodenitrogenation and carbon residue conversion catalyst can be optionally filled, wherein the filling volume of the residual oil hydrodenitrogenation and carbon residue conversion catalyst accounts for less than 28% of the total filling volume. The residuum hydrotreating catalyst may be packed in conventional grading sequence, which is to contact the material oil with the residuum hydrogenating protecting catalyst, the residuum hydrogenating demetallizing catalyst, the residuum hydrogenating desulfurizing catalyst, the residuum hydrogenating denitrogenating catalyst and the carbon residue converting catalyst successively. There are of course also techniques for mixing and loading two or more catalysts therein. The residuum hydrogenation protecting catalyst, residuum hydrodemetallization catalyst, residuum hydrodesulfurization catalyst, residuum hydrodenitrogenation, carbon residue conversion catalyst can be used as catalysts with corresponding functions commonly used in the art, such as CEN, FZC, ZTN, ZTS series residuum hydrotreating catalyst manufactured by catalyst division of China petrochemical Co., ltd.
In the method of the present invention, the conditions for the first hydrofining reaction in step (1) are as follows: the hydrogen partial pressure is 5 MPa-35 MPa, preferably 13 MPa-20 MPa, the reaction temperature is 300-420 ℃, preferably 330-400 ℃, and the total feed liquid hourly space velocity is generally 0.1h -1 ～5.0h -1 Preferably 0.15h -1 ～2.0h -1 The volume ratio of the total hydrogen oil is 100-5000, preferably 300-3000. Where the total feed refers to all feeds to the fixed bed hydrogenation unit.
In the method of the invention, the hydrogenated oil obtained in the step (1) can be subjected to gas-liquid separation and then atmospheric fractionation, wherein the gas-liquid separation is carried out under the condition of the same pressure level as the hydrogenation reaction, and the operation temperature is 300-400 ℃, preferably 330-370 ℃. The separated gas phase is mainly hydrogen, and is recycled to the fixed bed hydrogenation unit. And (3) the separated liquid phase enters an atmospheric fractionation system to obtain hydrogenated naphtha, hydrogenated diesel oil and hydrogenated atmospheric residuum. The hydrogenated atmospheric residuum enters a vacuum fractionation system to obtain hydrogenated vacuum wax oil and hydrogenated vacuum residuum. The initial boiling point of the hydrogenated atmospheric residuum is 330-370 ℃. The initial distillation point of the hydrogenated vacuum residuum is 520-540 ℃, the initial distillation point of the hydrogenated vacuum wax oil is 330-370 ℃, and the final distillation point is 520-540 ℃.
In the method, the step (2) adopts the residual oil hydrotreating technology of an up-flow hydrogenation reactor. The hydrogenated vacuum residuum obtained in the step (1) is circulated to an inlet of an up-flow hydrogenation reactor to be mixed with new hydrogen to enter the up-flow hydrogenation reactor, and a second hydrofining reaction is carried out under the action of an up-flow hydrotreating catalyst.
The upflow hydrogenation reactor (UFR) is technically characterized in that the reactant flows from bottom to top to slightly expand the catalyst bed, so that the pressure drop is small, and the upflow hydrogenation reactor is generally used for solving the problem of large initial and final pressure drop changes when a conventional fixed bed reactor processes inferior residuum, so as to protect a downstream fixed bed reactor and prolong the running period of the device. In the method, an up-flow hydrogenation reactor (UFR) is adopted to further hydrofining the hydrogenated vacuum residuum to remove sulfur and metals in the hydrogenated vacuum residuum. Because coking precursors and metals are also enriched in asphaltenes, namely slag reduction, the upflow hydrogenation reactor adopts high-temperature and high-hydrogen partial pressure operation conditions, the coking is restrained, the deep impurity removal reaction of the hydrogenated vacuum residuum is facilitated, the reactant flow state in the subsequent hydrofining process is more stable, and the long-period operation of the device is facilitated.
In the method, at least one hydrogenation reactor is adopted in the upflow hydrogenation reactor in the step (2). Each hydrogenation reactor is generally provided with a plurality of catalyst beds, and cold hydrogen or quenching oil is injected between the beds to control the reaction temperature. The upflow type residual oil hydrotreating catalyst is filled in the upflow type hydrogenation reactor. The upflow residuum hydrotreating catalysts used in the present invention include hydrodemetallization catalysts and hydrodesulfurization catalysts, and may optionally include a hydrogenation guard catalyst. The upflow type residuum hydrotreatment catalyst generally takes porous refractory inorganic oxide such as alumina as a carrier, takes VIB group and/or VIII group metal (such as at least one of W, mo, co, ni and the like) as an active component, and at least one of other various auxiliary agents such as P, si, F, B and the like is selectively added. As the hydrogenation protecting catalyst, the hydrodemetallization catalyst and the hydrodesulphurisation catalyst, catalysts having corresponding functions, which are generally used in the art, such as FZC series up-flow residuum hydrotreating catalysts manufactured by catalyst division of China petrochemical Co., ltd, can be used.
In the method, in the up-flow hydrogenation reactor, the total filling volume of the up-flow residual oil hydrotreating catalyst is taken as a reference, and the hydrogenation protecting catalyst accounts for less than 20 percent of the total filling volume and can be 3 to 20 percent, preferably 5 to 20 percent; the hydrodemetallization catalyst accounts for 20-80%, preferably 35-75% of the total filling volume; the hydrodesulfurization catalyst accounts for 5-70%, preferably 10-65% of the total packed volume.
In the method of the present invention, the reaction conditions of the second hydrofining reaction in the step (2) are as follows: the hydrogen partial pressure is 12 MPa-35 MPa, preferably 15 MPa-22 MPa, the reaction temperature is 350-500 ℃, preferably 380-420 ℃, and the total feed liquid hourly space velocity is generally 0.1h -1 ～5.0h -1 Preferably 0.15h -1 ～2.0h -1 The volume ratio of the total hydrogen oil is 200 to 400, preferably 210 to 350. Where the total feed refers to all feeds into the upflow reactor. The upflow reactor strictly controls the inlet temperature and the inlet hydrogen amount to keep the upflow reactor flow distribution state stable. The upflow reactor adopts new hydrogen, the purity of the hydrogen is more than 99 percent, and the upflow reactor has higher hydrogen partial pressure.
In the method, the mass content of aromatic hydrocarbon and colloid in the marine fuel oil product obtained in the step (3) is more than 35%, preferably 37% -50%, and more preferably 38% -45%.
In the method, the mass content of sulfur in the marine fuel oil product obtained in the step (3) is lower than 0.5%, and further lower than 0.4%. The method has the advantages that:
1. the method adopts a mode of combining an up-flow hydrogenation process and a fixed bed hydrogenation process, and residual oil raw materials with different properties are respectively fed into the up-flow hydrogenation process and the fixed bed hydrogenation process, so that the hydrogenation effect and the conversion depth can be better controlled, particularly under the condition that the sulfur content can meet the index, the conversion depth of carbon residue can be controlled, excessive hydrogenation conversion is prevented, low-sulfur marine fuel products with different viscosity indexes can be flexibly produced, and better economy is realized;
2. in the method, the residual oil raw materials with inferior properties enter an up-flow hydrogenation reactor to carry out hydrofining reaction, the advantage of the up-flow process is fully utilized, the higher partial pressure of reaction hydrogen and the lower pressure drop are achieved, and the prerefining reaction and the desulfurization target are realized; the residual oil raw material with better properties enters a fixed bed hydrogenation process, and the refining reaction is carried out under a milder condition, so that the rapid increase of the pressure drop of the reactor is avoided, and the advantage of deep hydrodesulfurization is achieved;
3. according to the method, the up-flow hydrogenation reactor is adopted to treat the hydrogenated vacuum residuum, so that the deep desulfurization is realized, meanwhile, the aromatic components and colloid in the oil product are prevented from being saturated by excessive hydrogenation due to fixed bed hydrogenation, the stability of an oil peptization system is improved, and the stability of marine fuel oil is further improved;
4. in the method, the upflow hydrogenation reactor can realize the deep desulfurization effect under the condition of lower hydrogen-oil volume ratio, improve the metal capacity and enhance the adaptability and the processing flexibility of raw materials; the fixed bed hydrogenation can meet the design requirement with or without adopting a high-activity denitrification and carbon residue removal catalyst in a small amount, can be carried out under mild reaction conditions, can produce marine fuel oil with good comprehensive performance, can produce hydrogenated naphtha and diesel oil, and has the advantages of low energy consumption of the device, long operation period of the device and good economic benefit;
5. in the method, the atmospheric and vacuum fractionation equipment of the product is flexible in processing mode, and the benefit maximization is realized.
Drawings
FIG. 1 is a schematic process flow diagram of one embodiment of the method of producing a low sulfur marine fuel oil of the present invention;
FIG. 2 is a schematic diagram of the process flow of comparative example 1 using a conventional upflow reactor with fixed bed hydrogenation.
Detailed Description
The method provided by the invention is further described below with reference to the accompanying drawings, but the scope of the invention is not limited thereby.
As shown in fig. 1, a residual oil raw material 1 with relatively good properties and an effluent 18 of an up-flow hydrogenation reactor 17 are mixed, boosted and then mixed with recycle hydrogen 5 to enter a fixed bed hydrogenation unit 2, and impurities such as metal, sulfur, nitrogen and the like in raw oil are removed by contacting with a fixed bed residual oil hydrotreating catalyst, and meanwhile, the viscosity and density of the raw material are reduced to meet the product requirements. The hydrogenation generated oil 3 of the fixed bed hydrogenation unit 2 enters a high-low pressure separator 4 for gas-liquid separation, the separated gas phase material flow is subjected to treatments such as hydrogen sulfide removal and the like, then enters a circulating compressor for boosting, and then circulates hydrogen 5 to an inlet of the fixed bed hydrogenation unit 2, the separated liquid phase material flow 6 is subjected to an atmospheric fractionating tower 7 to obtain fuel gas 8, hydrogenated naphtha 9, hydrogenated diesel oil 10 and hydrogenated atmospheric residuum 11, and the obtained partial hydrogenated atmospheric residuum 11 enters a vacuum fractionating tower 12 for vacuum fractionation to obtain hydrogenated vacuum residuum 14 and hydrogenated vacuum wax oil 13. The partially hydrogenated vacuum residuum 14 is mixed with a residuum raw material 16 with relatively inferior properties and new hydrogen 15 to enter an up-flow hydrogenation reactor 17, and impurities such as metal, sulfur and the like in the raw oil are further removed by contact with an up-flow residuum hydrotreating catalyst to obtain an up-flow hydrogenation reactor effluent 18. The obtained partially hydrogenated vacuum residuum 14, the obtained partially hydrogenated atmospheric residuum 11 and at least partially hydrogenated vacuum wax oil 13 are mixed to obtain a marine fuel oil product. The partial hydrogenation decompressed wax oil 13 can also be used as the feed of other devices such as a catalytic cracker and a hydrocracking device to produce other high-quality products.
As shown in fig. 2, the residual oil raw material 1 with relatively good properties, the residual oil raw material 16 with relatively bad properties and the recycle hydrogen 5 are mixed and enter an up-flow hydrogenation reactor 17 to carry out hydrogenation reaction, the up-flow hydrogenation reactor effluent 18 is pressurized and then mixed with new hydrogen 15 (and/or the recycle hydrogen 5) and enter a fixed bed hydrogenation unit 2, and impurities such as metal, sulfur, nitrogen and the like in the raw oil are removed by contacting with a fixed bed residual oil hydrotreating catalyst, and meanwhile, the viscosity and the density of the raw material are reduced to meet the product requirements. The hydrogenation generated oil 3 of the fixed bed hydrogenation unit 2 enters a high-low pressure separator 4 for gas-liquid separation, the separated gas phase material flow is subjected to treatments such as hydrogen sulfide removal and the like, then enters a circulating compressor for boosting, and then circulates hydrogen 5 to an inlet of the fixed bed hydrogenation unit 2, and the separated liquid phase material flow 6 is subjected to an atmospheric fractionating tower 7 to obtain fuel gas 8, hydrogenated naphtha 9, hydrogenated diesel oil 10 and hydrogenated atmospheric residuum 11.
The method provided by the present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The feedstock used in the examples was a middle eastern high sulfur residuum, whose properties are listed in table 1. The fixed bed hydrotreating catalyst and the up-flow type residuum hydrotreating catalyst used in the examples are FZC series residuum hydrotreating catalysts produced by catalyst division of petrochemical company, inc. The fixed bed residuum hydrotreatment catalyst specifically comprises a hydrogenation protecting agent, a hydrodemetallization catalyst, a hydrodesulphurization catalyst, a hydrodenitrogenation and carbon residue removal catalyst, and the filling sequence is that raw oil is sequentially contacted with the hydrogenation protecting agent, the hydrodemetallization catalyst, the hydrodesulphurization catalyst, the hydrodenitrogenation and the carbon residue removal catalyst. Wherein the upflow residuum hydrotreating catalyst specifically comprises a hydrodemetallization catalyst, a hydrodesulphurisation catalyst.
Example 1
This example adopts the production method of low sulfur marine fuel oil (see figure 1) provided by the invention, and adopts the residual oil raw material A with relatively good property and the residual oil raw material B with relatively bad property, the residual oil raw material property is shown in table 1, and it can be seen that the residual oil raw material A with relatively good property has sulfur content of 1.55wt%, carbon residue content of 9.75wt%, metal (Ni+V) content of 62 mug/g and total nitrogen content of 4326 mug/g. The residual oil raw material B with relatively inferior properties shows that the residual oil sulfur content is up to 3.84wt%, the carbon residue content is 13.58wt%, and the metal (Ni+V) content is 121 mug/g, which belongs to the high sulfur type bad residual oil. Both feedstocks must be hydrotreated to produce a low sulfur marine combustion product. The ratio of the feed volume of the residual oil feed A with relatively good properties to the feed volume of the residual oil feed B with relatively poor properties is 1:1.
the device fixed bed reactor adopts three reactors connected in series, wherein one reactor is reversely filled with three residual oil hydrogenation protective agents, and the filling volumes are 20mL of FZC-12B catalyst, 20mL of FZC-103D catalyst and 60mL of FZC-103E catalyst respectively; the two residual oil hydrodemetallization catalysts are reversely filled, the filling volume is 100mL of FZC-28A catalyst, and the FZC-204 catalyst is 200mL; the three-way filling of the residual oil hydrodesulfurization catalyst FZC-34A has a filling volume of 210mL, and the denitrification and carbon residue removal catalyst FZC-41A has a filling volume of 90mL. The catalyst properties are shown in Table 2.
The device up-flow reactor adopts one reactor, and is provided with two beds, wherein the first bed is filled with 300mL of FZC-10U up-flow residual oil hydrodemetallization catalyst, and the second bed is filled with 350mL of FZC-11U up-flow residual oil hydrodemetallization catalyst. The catalyst properties are shown in Table 3.
Further hydrogenation treatment is carried out to obtain fixed bed hydrogenation reaction generated oil. The main operating conditions are shown in Table 4, and the properties of the reaction products are shown in Table 5.
The method comprises the steps of mixing a raw material A with an effluent of an up-flow hydrogenation reactor and circulating hydrogen, performing hydrogenation treatment by a fixed bed hydrogenation reactor, and performing gas-liquid separation to obtain a gas phase product and a liquid phase product, wherein the liquid phase product is subjected to normal pressure fractionation to obtain fuel gas, hydrogenated naphtha, hydrogenated diesel oil and hydrogenated atmospheric residuum. Fractionating 70% hydrogenated atmospheric residuum by a vacuum fractionating system to obtain hydrogenated vacuum wax oil and hydrogenated vacuum residuum. The obtained 50% hydrogenated vacuum residuum is mixed with 30% hydrogenated atmospheric residuum and partial hydrogenated vacuum wax oil to be used as low sulfur marine fuel oil product. The 50% hydrogenated vacuum residuum is returned to the upflow reactor to be mixed with new hydrogen for further hydrofining.
Example 2
Example 2 the production method of the low sulfur marine fuel provided by the invention (see figure 1) adopts a residual oil raw material A with relatively good properties and a residual oil raw material B with relatively poor properties, and the properties of the residual oil raw materials are shown in table 1. Both feedstocks must be hydrotreated to produce a low sulfur marine combustion product. The feed volume ratio of the residue feed a with relatively good properties to the residue feed B with relatively bad properties was 1:2.
the hydrogenation device adopts four serially connected fixed bed reactors, wherein one reactor is reversely filled with three residual oil hydrogenation protective agents, the filling volume is 30mL of FZC-12B catalyst, 40mL of FZC-103D catalyst and 80mL of FZC-103E catalyst respectively; the two residual oil hydrodemetallization catalysts are reversely filled, the filling volume is 200mL of FZC-28A catalyst, and the FZC-204 catalyst is 230mL; filling a residual oil hydrodesulfurization catalyst FZC-34A in three-reaction mode, wherein the filling volume is 200mL; four-reverse filling of a residual oil hydrodenitrogenation carbon residue removal catalyst FZC-41A with a filling volume of 100mL, and specific catalyst properties are shown in Table 2.
The device up-flow reactor adopts a reactor and is provided with three beds, wherein the first bed is filled with 260mL of FZC-10U up-flow residual oil hydrodemetallization catalyst, the second bed is filled with 190mL of FZC-10U catalyst at the lower part, 110mL of FZC-11U up-flow residual oil hydrodemetallization catalyst is filled at the upper part, and the third bed is filled with 240mL of FZC-11U up-flow residual oil hydrodemetallization catalyst. The catalyst properties are shown in Table 3.
Further hydrogenation treatment is carried out to obtain fixed bed hydrogenation reaction generated oil. The main operating conditions are shown in Table 3, and the distribution of the reaction products is shown in Table 5.
The method comprises the steps of mixing a raw material A with an effluent of an up-flow hydrogenation reactor and circulating hydrogen, performing hydrogenation treatment by a fixed bed hydrogenation reactor, and performing gas-liquid separation to obtain a gas phase product and a liquid phase product, wherein the liquid phase product is subjected to normal pressure fractionation to obtain fuel gas, hydrogenated naphtha, hydrogenated diesel oil and hydrogenated atmospheric residuum. The obtained 40% hydrogenated atmospheric residuum is fractionated by a vacuum fractionating system to obtain hydrogenated vacuum wax oil and hydrogenated vacuum residuum. The 30% hydrogenated vacuum residuum is mixed with 60% hydrogenated atmospheric residuum and partial hydrogenated vacuum wax oil to be used as low sulfur marine fuel oil product. 70% of the hydrogenated vacuum residuum is returned to the upflow reactor to be mixed with new hydrogen for further hydrofining.
Example 3
This example uses the production method of low sulfur marine fuel oil (see figure 1) provided by the present invention, and uses a residual oil raw material a with relatively good properties and a residual oil raw material B with relatively bad properties, and the properties of the residual oil raw materials are shown in table 1. The feed volume ratio of the residue feed a with relatively good properties to the residue feed B with relatively bad properties was 3:1.
the device fixed bed reactor adopts three reactors connected in series, wherein one reactor is reversely filled with two residual oil hydrogenation protective agents, the filling volume is 50mL of FZC-12B catalyst and 100mL of FZC-103E catalyst respectively; the two residual oil hydrodemetallization catalysts are reversely filled, the filling volume is 120mL of FZC-28A catalyst, and the FZC-204 catalyst is 180mL; the three-way filling of the residual oil hydrodesulfurization catalyst FZC-34A has a filling volume of 300mL. The catalyst properties are shown in Table 2.
The device up-flow reactor adopts a reactor, and is provided with two beds, wherein the first bed is filled with 200mL of FZC-10U up-flow residual oil hydrodemetallization catalyst, and the second bed is filled with 220mL of FZC-11U up-flow residual oil hydrodemetallization catalyst. The catalyst properties are shown in Table 3.
Further hydrogenation treatment is carried out to obtain fixed bed hydrogenation reaction generated oil. The main operating conditions are shown in Table 4, and the properties of the reaction products are shown in Table 5.
The method comprises the steps of mixing a raw material A with an effluent of an up-flow hydrogenation reactor and circulating hydrogen, performing hydrogenation treatment by a fixed bed hydrogenation reactor, and performing gas-liquid separation to obtain a gas phase product and a liquid phase product, wherein the liquid phase product is subjected to normal pressure fractionation to obtain fuel gas, hydrogenated naphtha, hydrogenated diesel oil and hydrogenated atmospheric residuum. And fractionating the obtained 50% hydrogenated atmospheric residuum by a vacuum fractionating system to obtain hydrogenated vacuum wax oil and hydrogenated vacuum residuum. The 65% hydrogenated vacuum residuum is mixed with 50% hydrogenated atmospheric residuum and partial hydrogenated vacuum wax oil to be used as low sulfur marine fuel oil product. And returning 35% of hydrogenated vacuum residuum to the upflow reactor for mixing with new hydrogen and then further hydrofining.
TABLE 1 residuum feedstock Properties
| Project | Raw material A | Raw material B |
| S，wt％ | 1.55 | 3.84 |
| N，μg/g | 4326 | 3288 |
| Carbon Residue (CCR), wt% | 9.75 | 13.58 |
| Density (20 ℃ C.) kg/m 3 | 980.1 | 996.2 |
| Viscosity (100 ℃ C.) mm 2 /s | 67 | 254 |
| Ni+V，μg/g | 62 | 121 |
| Saturated hydrocarbon, wt% | 40.67 | 38.45 |
| Aromatic hydrocarbon, wt% | 38.96 | 37.75 |
| Colloid, wt% | 18.1 | 20.02 |
| Asphaltenes, wt% | 2.27 | 3.78 |
TABLE 2 Properties of fixed bed residuum hydroprocessing catalyst
TABLE 3 Properties of the upflow hydroprocessing catalyst
Table 4 example major operating conditions
TABLE 5 distribution of hydrogenation reaction products
TABLE 6 example 1 Main product Properties
| Hydrogenation product | Hydrogenated naphtha | Hydrogenated diesel oil | Hydrogenated atmospheric residuum | Hydrogenation decompression wax oil | Hydrogenated vacuum residuum |
| Density (20 ℃), g/cm 3 | 0.731 | 0.842 | 0.928 | 0.882 | 0.965 |
| Viscosity (100 ℃ C.) mm 2 /s | - | - | 30 | 12 | 230 |
| Viscosity (50 ℃ C.) mm 2 /s | - | - | - | 77 | - |
| Carbon residue value, wt% | - | - | 5.10 | 0.20 | 8.82 |
| S，μg/g | 55 | 210 | 4343 | 2230 | 6513 |
| N，μg/g | 22 | 163 | 2260 | 1200 | 4877 |
| Ni+V，μg/g | - | - | 9.8 | - | 19.3 |
TABLE 7 example 2 Main product Properties
| Hydrogenation product | Hydrogenated naphtha | Hydrogenated diesel oil | Hydrogenated atmospheric residuum | Hydrogenation decompression wax oil | Hydrogenated vacuum residuum |
| Density (20 ℃), g/cm 3 | 0.730 | 0.843 | 0.933 | 0.882 | 0.976 |
| Viscosity (100 ℃ C.) mm 2 /s | - | - | 31 | 22 | 283 |
| Viscosity (50 ℃ C.) mm 2 /s | - | - | - | 86 | - |
| Carbon residue value, wt% | - | - | 5.73 | 0.26 | 8.80 |
| S，μg/g | 50 | 271 | 4270 | 2170 | 7520 |
| N，μg/g | 43 | 213 | 2110 | 1452 | 5320 |
| Ni+V，μg/g | - | - | 12.6 | - | 25.2 |
TABLE 8 example 3 Main product Properties
TABLE 9 Properties of Low Sulfur Marine Fuel Main product
| Project | Example 1 | Example 2 | Example 3 |
| Hydrogenated atmospheric residuum, wt% | 11.14 | 36.34 | 20.31 |
| Hydrogenated vacuum residuum, wt% | 11.91 | 1.89 | 11.88 |
| Hydrogenated vacuum wax oil, wt% | 15.01 | 3.84 | 8.26 |
| Density (20 ℃), g/cm 3 | 0.921 | 0.935 | 0.930 |
| Viscosity (50 ℃ C.) mm 2 /s | 210 | 202 | 238 |
| S，μg/g | 4189 | 4424 | 4341 |
| Carbon residue, wt% | 4.78 | 6.40 | 5.66 |
| Acid number (in terms of KOH), mg/g | 0.020 | 0.021 | 0.022 |
| Ash, wt% | 0.03 | 0.02 | 0.03 |
| Carbon aromatic index CCAI | 855 | 854 | 852 |
| Ni+V，μg/g | 8.908 | 13.184 | 12.876 |
| Saturated hydrocarbon, wt% | 60.75 | 59.77 | 58.86 |
| Aromatic hydrocarbon, wt% | 28.72 | 29.68 | 29.11 |
| Colloid, wt% | 9.95 | 9.98 | 11.32 |
| Asphaltenes, wt% | 0.58 | 0.57 | 0.71 |
TABLE 10 Properties of Low Sulfur Marine Fuel Main product
It can be seen from tables 9 and 10 that examples 1-3 demonstrate that blending hydrogenated wax oil in different proportions can achieve different viscosity requirements while meeting sulfur levels of less than 0.5% and other criteria can meet fuel oil quality requirements. The hydrogenated wax oil has good properties, can be used as a raw material for hydrocracking and catalytic cracking to produce high added value products, and can be used for flexibly producing ship combustion products with different viscosities by adjusting and adding the hydrogenated wax oil with different proportions. The method of the invention flexibly produces the low-sulfur marine fuel product, and can well meet the enterprises hopeing to increase the yield of the light oil.
In addition, the saturated mass fraction of the low-sulfur marine fuel prepared by the method is 58-61%; the aroma is about 28-30%, and the colloid content is 9-12%. The sum of the two reaches more than 38.5 percent. The inventors found that fixed bed hydrogenation, such that the sum of aromatic components and gum in the oil is less than 35% by excessive hydrogenation, affects the stability of the oil system. Therefore, the invention can meet the conditions of various product indexes and improve the stability of the marine fuel oil.
Comparative example 1
This comparative example uses the same feed stock feed as in example 1 and the same feed amount, the ratio by volume of the feed amount of residuum feed a of relatively good properties to the feed amount of residuum feed B of relatively poor properties is 1:1. the residuum feedstock properties are shown in table 1. Different from the two feeding modes of the embodiment 1, the residual oil raw material A with relatively good properties and the residual oil raw material B with relatively bad properties in the comparative example both enter an up-flow reactor for hydrogenation reaction, then enter a fixed bed reactor for hydrogenation reaction, and the hydrogenated oil is fractionated to obtain fuel gas, hydrogenated naphtha, hydrogenated diesel oil and hydrogenated atmospheric residual oil. The hydrogenated atmospheric residuum is used as low sulfur ship combustion product.
The device up-flow reactor adopts one reactor, and is provided with two beds, wherein the first bed is filled with 300mL of FZC-10U up-flow residual oil hydrodemetallization catalyst, and the second bed is filled with 350mL of FZC-11U up-flow residual oil hydrodemetallization catalyst. The catalyst properties are shown in Table 3.
The device fixed bed reactor adopts three reactors connected in series, wherein one reactor is reversely filled with three residual oil hydrogenation protective agents, and the filling volumes are 20mL of FZC-12B catalyst, 20mL of FZC-103D catalyst and 60mL of FZC-103E catalyst respectively; the two residual oil hydrodemetallization catalysts are reversely filled, the filling volume is 100mL of FZC-28A catalyst, and the FZC-204 catalyst is 200mL; the three-way filling of the residual oil hydrodesulfurization catalyst FZC-34A has a filling volume of 210mL, and the denitrification and carbon residue removal catalyst FZC-41A has a filling volume of 90mL. The catalyst properties were the same as in example 1. Table 11 shows the main operating conditions, table 12 shows the distribution of the hydrogenation reaction products, and Table 13 shows the main product properties.
Table 11 comparative example 1 major operating conditions
TABLE 12 distribution of hydrogenation reaction products
| Project | Comparative example 1 |
| Hydrogenation reaction part | |
| Fuel gas, wt% | 3.81 |
| Hydrogenated naphtha wt% | 2.66 |
| Hydrogenated diesel oil, wt% | 11.35 |
| Hydrogenated atmospheric residuum, wt% | 82.18 |
TABLE 13 Main product Properties of comparative example 1
| Hydrogenation product | Hydrogenated naphtha | Hydrogenated diesel oil | Hydrogenated atmospheric residuum |
| Density (20 ℃), g/cm 3 | 0.733 | 0.842 | 0.923 |
| Viscosity (100 ℃ C.) mm 2 /s | / | / | 42 |
| Viscosity (50 ℃ C.) mm 2 /s | / | / | 342 |
| Carbon residue value, wt% | / | / | 4.52 |
| S，μg/g | 62 | 263 | 4722 |
| N，μg/g | 24 | 211 | 2325 |
| Ni+V，μg/g | / | / | 11.23 |
| Saturated hydrocarbon, wt% | / | / | 65.69 |
| Aromatic hydrocarbon, wt% | / | / | 22.73 |
| Colloid, wt% | / | / | 10.35 |
| Asphaltenes, wt% | / | / | 1.23 |
As can be seen from Table 13, in comparative example 1, the conventional upflow and fixed bed combined process is adopted, and in order to meet the index requirements of the contents of impurities such as sulfur, nitrogen, carbon residue and the like in the hydrogenated residual oil, a higher reaction temperature is adopted, the upflow reaction temperature is 387 ℃, the fixed bed reaction temperature is 384 ℃, and the hydrogen consumption is far higher than that in example 1. In addition, it can be seen that in order to meet the impurity content, in particular the sulfur content, of the productThe index requirement is that under higher reaction temperature, the yield of the light oil product of the hydrogenation product is increased, especially the yield of fuel gas is increased, the processing cost is increased, the yield of the hydrogenation residual oil of the target product is reduced, and the product yield is influenced. The sulfur content of the hydrogenated slag is 0.47%, but the viscosity (50 ℃) is 342mm 2 And/s can only be used as a high viscosity marine product, if other low viscosity products are produced, other products need to be blended.
In addition, in the hydrogenated product obtained in comparative example 1, the aromatic hydrocarbon yield was 22.73%, the gum content was 10.35%, and the total content was less than 35%. It can be seen that the depth of hydrogenation is high and the saturated hydrocarbon content reaches 65.69% in order to achieve the required impurity content and viscosity. However, the excessively high saturated hydrocarbon content and the relatively low gum and aromatic hydrocarbon content affect the system stability of the oil product, which is not beneficial to the storage and transportation of the marine fuel oil, and further affects the service performance of the marine fuel oil.
Claims (14)
1. A method for producing marine fuel oil by hydrogenation, comprising:
(1) Mixing a residual oil raw material with relatively good properties, an effluent of an upflow hydrogenation reactor obtained in the step (2) and hydrogen, and entering a fixed bed hydrogenation unit for a first hydrofining reaction to obtain hydrogenated oil; the hydrogenation generated oil is subjected to normal pressure fractionation to obtain hydrogenation normal pressure residual oil; performing vacuum fractionation on part of the hydrogenated atmospheric residuum to obtain hydrogenated vacuum residuum and hydrogenated vacuum wax oil;
(2) Mixing the partial hydrogenation vacuum residuum obtained in the step (1) with residuum raw materials with relatively inferior properties and hydrogen, and entering an up-flow hydrogenation reactor for a second hydrofining reaction to obtain an effluent of the up-flow hydrogenation reactor;
(3) And (3) mixing the partially hydrogenated atmospheric residuum obtained in the step (1) and the partially hydrogenated vacuum residuum obtained in the step (2) with at least partially hydrogenated vacuum wax oil to obtain a marine fuel oil product.
2. A method according to claim 1, characterized in that: the volume of the hydrogenated atmospheric residuum entering the vacuum fractionating unit in the step (1) accounts for 20% -90%, preferably 30% -80% of the total volume of the obtained hydrogenated atmospheric residuum; the volume of the hydrogenated atmospheric residuum as the marine fuel oil component in the step (3) accounts for 10% -80%, preferably 20% -70% of the total volume of the obtained hydrogenated atmospheric residuum.
3. A method according to claim 1, characterized in that: the volume of the hydrogenated vacuum residue entering the up-flow hydrogenation reactor in the step (2) accounts for 10-80%, preferably 20-50% of the total volume of the hydrogenated vacuum residue obtained in the step (1); the volume of the hydrogenated vacuum residuum as the marine fuel oil component in the step (3) accounts for 20% -90%, preferably 50% -80% of the total volume of the hydrogenated vacuum residuum obtained in the step (1).
4. A method according to claim 1, characterized in that: residual oil raw materials with relatively poor properties have sulfur content of more than 3.5 percent and total content of heavy metals nickel and vanadium of more than 100 mug/g based on mass content; the residual oil raw material with relatively good property contains no more than 3.5% of sulfur and no more than 100 mug/g of total content of heavy metals nickel and vanadium.
5. A method according to claim 1, characterized in that: the residual oil raw materials with relatively poor properties account for 10% -90%, preferably 30% -70% and the residual oil raw materials with relatively poor properties account for 10% -90%, preferably 30% -70% of the total feeding volume based on the total feeding volume of the residual oil raw materials with relatively poor properties and the residual oil raw materials with relatively good properties.
6. A method according to claim 1, characterized in that: in the step (3), the hydrogenated atmospheric residuum is mixed with hydrogenated vacuum wax oil and hydrogenated vacuum residuum, and the mixing volume ratio is 0.1-100: 0.1 to 100:1, preferably 0.1 to 25:0.1 to 15:1.
7. a method according to claim 1, characterized in that: the hydrogen used in the fixed bed hydrogenation unit may be recycle hydrogen; the hydrogen used in the upflow hydrogenation reactor is new hydrogen.
8. A method according to claim 1, characterized in that: the first hydrofining reaction in step (1) uses fixed bed residuum hydrotreating technology.
9. A method according to claim 1, characterized in that: the fixed bed residuum hydrotreating catalyst used in the fixed bed hydrotreating unit in the step (1) comprises a residuum hydrotreating catalyst, a residuum hydrodemetallization catalyst and a residuum hydrodesulfurization catalyst, wherein the residuum hydrotreating catalyst accounts for 3% -20% of the total packing volume based on the total packing volume of the fixed bed residuum hydrotreating catalyst; the residual oil hydrodemetallization catalyst accounts for 20-60% of the total filling volume, preferably 20-50%; the residual oil hydrodesulfurization catalyst accounts for 10-50% of the total filling volume, preferably 20-48%; after the hydrodesulfurization catalyst, a residual oil hydrodenitrogenation and carbon residue conversion catalyst is selectively filled, wherein the filling volume of the catalyst accounts for less than 28% of the total filling volume.
10. A method according to claim 1, 8 or 9, characterized in that: the conditions for the first hydrofining reaction of step (1) are as follows: the hydrogen partial pressure is 5 MPa-35 MPa, preferably 13 MPa-20 MPa, the reaction temperature is 300-420 ℃, preferably 330-400 ℃, and the total feed liquid hourly space velocity is 0.1h -1 ～5.0h -1 Preferably 0.15h -1 ～2.0h -1 The volume ratio of the total hydrogen oil is 100-5000, preferably 300-3000.
11. A method according to claim 1, characterized in that: the initial distillation point of the hydrogenated atmospheric residuum is 330-370 ℃, the initial distillation point of the hydrogenated vacuum residuum is 520-540 ℃, the initial distillation point of the hydrogenated vacuum wax oil is 330-370 ℃ and the final distillation point is 520-540 ℃.
12. A method according to claim 1, characterized in that: and (2) adopting an upflow hydrogenation reactor residual oil hydrotreating technology.
13. A method according to claim 1, characterized in that: in the up-flow hydrogenation reactor, the hydrogenation protecting catalyst accounts for less than 20 percent, preferably 5 to 20 percent of the total filling volume based on the total filling volume of the up-flow residual oil hydrotreating catalyst; the hydrodemetallization catalyst accounts for 20-80%, preferably 35-75% of the total filling volume; the hydrodesulfurization catalyst accounts for 5-70%, preferably 10-65% of the total packed volume.
14. A method according to claim 1, 12 or 13, characterized in that: the reaction conditions of the second hydrofining reaction in the step (2) are as follows: the hydrogen partial pressure is 12 MPa-35 MPa, preferably 15 MPa-22 MPa, the reaction temperature is 350-500 ℃, preferably 380-420 ℃, and the total feed liquid hourly space velocity is 0.1h -1 ～5.0h -1 Preferably 0.15h -1 ～2.0h -1 The volume ratio of the total hydrogen oil is 200 to 400, preferably 210 to 350.
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