CN117070248A - Method for hydrotreating residual oil - Google Patents
Method for hydrotreating residual oil Download PDFInfo
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- CN117070248A CN117070248A CN202210506990.0A CN202210506990A CN117070248A CN 117070248 A CN117070248 A CN 117070248A CN 202210506990 A CN202210506990 A CN 202210506990A CN 117070248 A CN117070248 A CN 117070248A
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- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 200
- 239000003054 catalyst Substances 0.000 claims abstract description 155
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 43
- 239000001257 hydrogen Substances 0.000 claims abstract description 43
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- 238000004523 catalytic cracking Methods 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 2
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 2
- 238000006477 desulfuration reaction Methods 0.000 abstract description 17
- 230000023556 desulfurization Effects 0.000 abstract description 17
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000003921 oil Substances 0.000 description 170
- 230000000052 comparative effect Effects 0.000 description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- 229910052720 vanadium Inorganic materials 0.000 description 14
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 14
- 150000002431 hydrogen Chemical class 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000005262 decarbonization Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- -1 carbon olefins Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- 150000002830 nitrogen compounds Chemical class 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000002151 riboflavin Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004149 tartrazine Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000001179 sorption measurement Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the field of hydrotreating process, in particular to a method for hydrotreating residual oil, which comprises the following steps: (1) Introducing a wax oil raw material into a first hydrogenation reaction zone containing a wax oil hydrogenation catalyst in the presence of hydrogen to perform a first hydrogenation reaction to obtain hydrogenated wax oil; (2) Introducing a mixed stream containing vacuum residuum and hydrogenated wax oil into a second hydrogenation reaction zone in the presence of hydrogen to carry out a second hydrogenation reaction to obtain hydrogenated residuum; according to the flow direction of the liquid phase material flow, the second hydrogenation reaction zone is filled with a hydrogenation protecting catalyst, a hydrodemetallization catalyst and a hydrodesulphurization carbon residue catalyst in sequence. Compared with the prior art, the method adopts a method of partitioned hydrotreating and heat exchange treatment, improves the vacuum residue proportion, the residue denitrification rate, the desulfurization rate, the carbon removal rate, the demetallization rate and the hydrogen content of hydrogenated residue, reduces the energy consumption level of the device and improves the operation stability.
Description
Technical Field
The invention relates to the field of hydrotreating process, in particular to a method for hydrotreating residual oil.
Background
Residuum hydro-catalytic cracking (RHT-RFCC) combined technology is one of the most effective residuum conversion technologies. After the residuum is treated by hydrogenation-catalytic cracking, a light product with higher yield and better quality can be obtained. The slag oil can be efficiently converted and utilized, and simultaneously, the method can bring considerable economic benefit to refineries.
However, nitrogen compounds in resid, especially basic nitrogen compounds, will preferentially adsorb on the acid sites of the catalyst during catalytic cracking, reducing the density of the acid sites, thereby reducing the conversion of catalytic cracking and affecting the reaction selectivity. And the higher the level of nitrides in the residuum, the more pronounced the effect. However, the denitrification rate of the residual oil hydrogenation device in the field is only 40% -55% at present, so that the improvement of the denitrification rate of the residual oil hydrogenation device is beneficial to the improvement of the benefit of a refinery.
Wherein, the hydrogenation efficiency of wax oil component in residual oil hydrogenation device is very low, and the denitrification rate is low. On one hand, the intrinsic activity of the residual oil hydrogenation catalyst is far lower than that of the wax oil hydrogenation catalyst, and on the other hand, the residual oil contains a large amount of asphaltene and colloid macromolecules, and the adsorption performance of the macromolecules on the catalyst is far higher than that of wax oil molecules, so that the wax oil molecules are difficult to contact the catalyst to effectively react.
CN101747935a discloses a process for producing low carbon olefins and monocyclic aromatic hydrocarbons from heavy hydrocarbons. Wax oil raw materials, catalytic cracking light cycle oil and/or catalytic cracking heavy cycle oil are contacted with wax oil hydrogenation catalyst in a first hydrogenation reaction zone, and reaction effluent and residual oil are mixed and sequentially pass through a second hydrogenation reaction zone filled with residual oil hydrogenation catalyst. The method can realize the zonal hydrogenation of wax oil and residual oil. However, due to the limitations of the operating conditions, energy consumption, cost and the like, the vacuum residuum is low in doping amount, and is not suitable for the residuum hydrogenation-catalytic cracking (RHT-RFCC) combined technology which takes the residuum as a raw material.
CN105524655A and CN105586082a disclose a method for hydrodenitrogenation of heavy oil, which is to strip the material flow before the denitrification catalyst to improve the purity of hydrogen, and add sulfur-containing substances into the material flow to improve the content of hydrogen sulfide in the atmosphere of the denitrification catalyst bed, so as to achieve the goal of improving the overall denitrification rate. However, the process is complicated and is difficult to implement in industrial devices.
Disclosure of Invention
The invention aims to solve the problems of low hydrogenation efficiency and high energy consumption of a device of a residual oil hydrogenation catalyst in the prior art.
In order to achieve the above object, the present invention provides a method for hydrotreating residuum, which is carried out in a fixed bed hydrogenation apparatus comprising a first hydrogenation reaction zone and a second hydrogenation reaction zone, comprising:
(1) Introducing a wax oil raw material into a first hydrogenation reaction zone containing a wax oil hydrogenation catalyst in the presence of hydrogen to perform a first hydrogenation reaction to obtain hydrogenated wax oil;
(2) Introducing a mixed stream containing vacuum residuum and hydrogenated wax oil into a second hydrogenation reaction zone in the presence of hydrogen to carry out a second hydrogenation reaction to obtain hydrogenated residuum; according to the flow direction of the liquid phase material flow, a hydrogenation protecting catalyst, a hydrodemetallization catalyst and a hydrodesulphurization carbon residue removing catalyst are sequentially filled in the second hydrogenation reaction zone;
optionally, the mixture flow also contains catalytic cracking light cycle oil;
taking the total mass flow of the wax oil raw material, the vacuum residue and the catalytic cracking light cycle oil entering the hydrogenation device as a reference, the mass flow of the wax oil raw material entering the hydrogenation device is 20-65%, the mass flow of the catalytic cracking light cycle oil entering the hydrogenation device is 0-30%, and the mass flow of the vacuum residue entering the hydrogenation device is 35-80%.
The method for the partitioned hydrotreatment of the residual oil provided by the invention can remove almost all nitrogen-containing compounds in the wax oil, so that the hydrodenitrogenation rate of the residual oil is effectively improved, the hydrogen content, the desulfurization rate, the decarbonization rate and the demetallization rate are also improved to different degrees, and high-quality raw materials are provided for a downstream catalytic cracking device, so that the production cost is saved.
Drawings
Only the critical equipment is indicated in the figures, equipment known to the person skilled in the art as pumps, heat exchangers, separators etc. are omitted and the person skilled in the art shall not be construed as limiting the invention.
FIG. 1 is a schematic flow diagram of a process for the partitioned hydroprocessing of residuum of this invention.
Description of the reference numerals
F101 Vacuum residuum of heating furnace 1
R101 first hydrogenation reaction zone 2 circulating hydrogen
R102 second hydrogenation reaction zone 3 catalytic cracking light cycle oil
E101 Hydrogenated residual oil-hydrogen mixing light cycle oil heat exchanger 4 wax oil raw material
E102 New hydrogen in hydrogenation residual oil-mixed hydrogen wax oil heat exchanger 5
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As previously described, the present invention provides a process for hydrotreating residuum carried out in a fixed bed hydrogenation unit comprising a first hydrogenation reaction zone and a second hydrogenation reaction zone comprising:
(1) Introducing a wax oil raw material into a first hydrogenation reaction zone containing a wax oil hydrogenation catalyst in the presence of hydrogen to perform a first hydrogenation reaction to obtain hydrogenated wax oil;
(2) Introducing a mixed stream containing vacuum residuum and hydrogenated wax oil into a second hydrogenation reaction zone in the presence of hydrogen to carry out a second hydrogenation reaction to obtain hydrogenated residuum; according to the flow direction of the liquid phase material flow, a hydrogenation protecting catalyst, a hydrodemetallization catalyst and a hydrodesulphurization carbon residue removing catalyst are sequentially filled in the second hydrogenation reaction zone;
optionally, the mixture flow also contains catalytic cracking light cycle oil;
taking the total mass flow of the wax oil raw material, the vacuum residue and the catalytic cracking light cycle oil entering the hydrogenation device as a reference, the mass flow of the wax oil raw material entering the hydrogenation device is 20-65%, the mass flow of the catalytic cracking light cycle oil entering the hydrogenation device is 0-30%, and the mass flow of the vacuum residue entering the hydrogenation device is 35-80%.
The inventor discovers that the method provided by the invention can effectively improve the denitrification rate, the hydrogen content, the desulfurization rate, the carbon residue removal rate and the demetallization rate of the residual oil hydrogenation. Preferably, the addition of the catalytic cracking light cycle oil can reduce the viscosity of the vacuum residuum, thereby being more beneficial to the hydrogenation reaction.
Preferably, in step (1), 1 to 2 fixed bed reactors are provided in the first hydrogenation reaction zone.
Preferably, in step (2), 2 to 5 fixed bed reactors are provided in the second hydrogenation reaction zone.
Preferably, in the present invention, the reactors in the first hydrogenation reaction zone and the second hydrogenation reaction zone are each independently connected in series.
In addition, the method of loading the catalyst in the fixed bed reactor in the second hydrogenation reaction zone is not particularly limited, and the various catalysts may be loaded in the same fixed bed reactor in the order required by the present invention, or may be loaded in a plurality of fixed bed reactors, respectively, as long as the loading order of the catalysts is the method required by the present invention.
Preferably, in step (1), the conditions of the first hydrogenation reaction at least satisfy: the temperature is 320-430 ℃, the reaction pressure is 6-20MPa, and the liquid hourly space velocity is 0.3-2.0h -1 The volume ratio of hydrogen to oil is 250-1500:1. more preferably, in step (1), the conditions of the first hydrogenation reaction at least satisfy: the temperature is 350-410 ℃, the reaction pressure is 10-18MPa, and the liquid hourly space velocity is 0.6-1.5h -1 The volume ratio of hydrogen to oil is 300-1000:1.
preferably, in step (1), the asphaltene content in the wax oil feedstock is 500ppm or less. More preferably, the wax oil feedstock is selected from at least one of a normal three-wire oil, a normal four-wire oil, a top oil reduction, a first wire oil reduction, a two wire oil reduction, a three wire oil reduction, a four wire oil reduction, a coker wax oil, a deasphalted oil, and a catalytic cracking heavy cycle oil.
Preferably, in step (2), the conditions of the second hydrogenation reaction at least satisfy: the temperature is 330-450 ℃, the reaction pressure is 6-25MPa, and the liquid hourly space velocity is 0.1-1h -1 The volume ratio of hydrogen to oil is 250-1500:1. more preferably, in step (2), the conditions of the second hydrogenation reaction at least satisfy: the temperature is 360-430 ℃, the reaction pressure is 12-20MPa, and the liquid hourly space velocity is 0.1-0.4h -1 The volume ratio of hydrogen to oil is 300-1000:1.
preferably, the mass flow rate of the wax oil raw material entering the hydrogenation device is 25-50%, the mass flow rate of the catalytic cracking light cycle oil entering the hydrogenation device is 0-20%, and the mass flow rate of the vacuum residuum entering the hydrogenation device is 50-75% based on the total mass flow rates of the wax oil raw material, the vacuum residuum and the catalytic cracking light cycle oil entering the hydrogenation device.
According to a preferred embodiment, the loading volume ratio of the wax oil hydrogenation catalyst is 2-25%, the loading volume ratio of the hydrogenation protecting catalyst is 1-20%, the loading volume ratio of the hydrodemetallization catalyst is 10-60%, and the loading volume ratio of the hydrodesulphurization carbon residue catalyst is 30-80%, based on the total volume of the loaded catalyst in the hydrogenation device. More preferably, the loading volume ratio of the wax oil hydrogenation catalyst is 4-20%, the loading volume ratio of the hydrogenation protecting catalyst is 2-15%, the loading volume ratio of the hydrodemetallization catalyst is 20-55%, and the loading volume ratio of the hydrodesulphurization carbon residue catalyst is 40-65% based on the total volume of the loaded catalyst in the hydrogenation device.
Preferably, each of the wax oil hydrogenation catalyst, the hydrodemetallization catalyst and the hydrodesulphurisation carbon residue removal catalyst independently comprises a carrier and an active metal component element supported on the carrier, wherein the active metal component element is at least one of a group VIB metal element and a group VIII metal element.
According to a particularly preferred embodiment, the hydrogenation protecting catalyst comprises a carrier and an active metal component element supported on the carrier, wherein the active metal component element is selected from at least one of a group VIB metal element and a group VIII metal element; in the hydrogenation protecting catalyst, the active metal component element on the carrier is selected from at least one of a group VIB metal element and a group VIII metal element.
Preferably, in the hydrogenation protecting catalyst, the wax oil hydrogenation catalyst, the hydrodemetallization catalyst, the hydrodesulfurization and carbon residue removal catalyst, the active metal component elements are each independently selected from at least one of the group consisting of nickel-tungsten, nickel-molybdenum, and cobalt-molybdenum.
Preferably, in the wax oil hydrogenation catalyst, the hydrogenation protecting catalyst, the hydrodemetallization catalyst and the hydrodesulphurisation carbon residue removal catalyst, the carriers are each independently selected from at least one of alumina, silica and titania.
Preferably, in the wax oil hydrogenation catalyst, the hydrogenation protection catalyst, the hydrodemetallization catalyst and the hydrodesulphurisation carbon residue removal catalyst, the carrier contains at least one modifying element selected from boron, germanium, zirconium, phosphorus, chlorine and fluorine independently.
Preferably, the total content of the modified elements germanium and zirconium in weight percent, calculated as metal oxides, is 0.1-15% and the total content of boron, phosphorus, chlorine and fluorine in weight percent, calculated as elements, is 0.1-15%, based on the total weight of the support.
Preferably, in the wax oil hydrogenation catalyst, the content of the active metal component element in terms of oxide is 20-38wt% based on the total weight of the wax oil hydrogenation catalyst.
Preferably, the wax oil hydrogenation catalyst has an average pore diameter of 3nm-20nm and an average particle diameter of 1.2mm-4mm.
Preferably, the bulk density of the wax oil hydrogenation catalyst is 0.5-1.6g/cm 3 A specific surface area of 80-500m 2 /g。
According to a preferred embodiment, in the present invention, the wax oil hydrogenation catalyst is at least one of the RN series of catalysts developed by the institute of petrochemical and petrochemical industries, china.
Preferably, in the hydrogenation protecting catalyst, the content of the active metal component element in terms of oxide is 1-12wt% based on the total weight of the hydrogenation protecting catalyst.
Preferably, the average pore diameter of the hydrogenation protecting catalyst is 18nm-30nm, and the average particle diameter is 1.3mm-50mm.
Preferably, in the hydrodemetallization catalyst, the content of the active metal component element in terms of oxide is 6-15wt% based on the total weight of the hydrodemetallization catalyst.
Preferably, the hydrodemetallization catalyst has an average pore diameter of 10nm-20nm and an average particle diameter of 0.8mm-5mm.
Preferably, in the hydrodesulfurization and carbon residue removal catalyst, the content of the active metal component element in terms of oxide is 8-25wt% based on the total weight of the hydrodesulfurization and carbon residue removal catalyst.
Preferably, the average pore diameter of the hydrodesulfurization and carbon residue removal catalyst is 8nm-15nm, and the average particle diameter is 0.6mm-2mm.
Preferably, the features of the hydro-protecting catalyst, the hydrodemetallization catalyst and the hydrodesulphurisation carbon residue removal catalyst are each independently selected from the group consisting of: bulk density of 0.3-1.2g/cm 3 A specific surface area of 50-400m 2 /g。
According to a preferred embodiment, in the present invention, the hydrogenation protecting catalyst is at least one of the RG series catalysts developed by the institute of petrochemical and petrochemical industries, china.
According to a preferred embodiment, in the present invention, the hydrodemetallization catalyst is at least one of RDM series catalysts and RUF series catalysts developed by the institute of petrochemical and petrochemical industries, china.
According to a preferred embodiment, in the present invention, the hydrodesulfurization and carbon residue removal catalyst is at least one of an RMS series catalyst, an RCS series catalyst, and an RSN series catalyst developed by the institute of petrochemical and chemical industries, china.
According to a preferred embodiment, the method further comprises: in step (1), the wax oil raw material is subjected to heat exchange treatment with the hydrogenated residual oil in step (2) before being introduced into the first hydrogenation reaction zone, and the wax oil raw material is not heated by a heating furnace.
Preferably, in step (2), the vacuum residuum is subjected to a heating treatment by a furnace prior to entering the second hydrogenation reaction zone.
According to a preferred embodiment, in step (2), the mixture stream contains a catalytically cracked light cycle oil, and the catalytically cracked light cycle oil is heat exchanged with the hydrogenated residuum without heating in a furnace prior to the mixture stream entering the second hydrogenation reaction zone.
Preferably, the heat exchange treatment comprises the following two schemes:
in a first aspect, the present invention includes: and carrying out heat exchange treatment on the hydrogenated residual oil obtained in the second reaction zone, the wax oil raw material and hydrogen, and then carrying out heat exchange treatment on the hydrogenated residual oil, the catalytic cracking light cycle oil and the hydrogen.
In a second aspect, the present invention comprises: and carrying out heat exchange treatment on one part of the hydrogenated residual oil obtained in the second reaction zone, the wax oil raw material and hydrogen, and carrying out heat exchange treatment on the rest part of the hydrogenated residual oil, the catalytic cracking light cycle oil and the hydrogen.
The inventor finds that the heat exchange method can reduce the energy consumption of the device and the running cost of the device. And the temperature of residual oil raw materials at the inlet of the reactor, which is caused by direct hydrogen mixing after a furnace, is prevented from being unstable due to heat exchange and temperature rise of hydrogen in advance. The method provided by the invention ensures that the device is operated more stably, and the heat exchange efficiency of the high-pressure heat exchanger can be improved.
In the present invention, the average particle diameter refers to an average maximum linear distance between two different points on a cross section of a particle. When the particles of the wax oil hydrogenation catalyst, the hydrogenation protection catalyst, the hydrodemetallization catalyst and the hydrodesulphurization and carbon residue removal catalyst are spherical, the average particle size refers to the diameter of the catalyst particles.
A preferred embodiment of a resid hydrotreating process according to the present invention is described below in conjunction with fig. 1, in particular:
the process is carried out in a fixed bed hydrogenation unit comprising a first hydrogenation reaction zone R101 and a second hydrogenation reaction zone R102, comprising:
(1) Introducing a wax oil raw material 4 and new hydrogen 5 into a hydrogenation residual oil-hydrogen mixing wax oil heat exchanger E102 for heat exchange treatment, and then introducing a material flow into a first hydrogenation reaction zone R101 containing a wax oil hydrogenation catalyst for first hydrogenation reaction to obtain hydrogenated wax oil;
(2) Vacuum residuum 1 and recycle hydrogen 2 are introduced into a heating furnace F101 for heating treatment, catalytic cracking light cycle oil 3 or recycle hydrogen 2 is introduced into a hydrogenated residuum-hydrogen mixing light cycle oil heat exchanger E101 for heat exchange treatment, and then the heat exchanged material flow and the material flow from the heating furnace F101 are introduced into a second hydrogenation reaction zone R102 for second hydrogenation reaction, so as to obtain hydrogenated residuum.
The method provided by the invention can remove almost all nitrogen-containing compounds in wax oil, thereby effectively improving the hydrodenitrogenation rate of residual oil, improving the hydrogen content, the desulfurization rate, the decarbonization rate and the demetallization rate to different degrees, providing high-quality raw materials for downstream catalytic cracking devices, and further saving the production cost.
The invention will be described in detail below by way of examples, without thereby restricting the invention in any way.
In the examples below, unless otherwise specified, the catalysts used were all industrial agents developed by the institute of petrochemical and petrochemical industries, china.
The following examples were carried out using the process flow shown in fig. 1, unless otherwise specified.
Wax oil hydrofining catalyst (V1), with the brand of RN-32V;
a hydrogenation protecting catalyst (G1) with the brand RG-30B;
hydrodemetallization catalyst (M1), with the trademark RDM-202C;
hydrodemetallization catalyst (M2), with the trademark RDM-203B;
the hydrodesulfurization and carbon residue removal catalyst (S1) is named RCS-31B.
The following methods for calculating the carbon removal rate, desulfurization rate, denitrification rate, and removal rate of metallic nickel and vanadium are as follows (wherein the raw oil is a mixture of the wax oil raw material, vacuum residuum, and catalytic cracking light cycle oil (the amount is 0 if not used) practically used in each example):
carbon residue removal rate = (carbon residue content in raw oil used in example-carbon residue content in hydrogenated residue obtained in example)/carbon residue content in raw oil used in example 100%
Desulfurization rate = (sulfur content in raw oil used in example-sulfur content in hydrogenated residual oil obtained in example)/sulfur content in raw oil used in example is 100%
Denitrification rate = (nitrogen content in the raw oil used in the example-nitrogen content in the hydrogenated residual oil obtained in the example)/nitrogen content in the raw oil used in the example is 100%
The removal rate of metallic nickel and vanadium = (total content of nickel and vanadium in the feedstock used in the examples-total content of nickel and vanadium in the hydrogenated residuum obtained in the examples)/total content of nickel and vanadium in the feedstock used in the examples is 100%.
Example 1
This example was conducted using a fixed bed hydrogenation unit comprising a first hydrogenation reaction zone and a second hydrogenation reaction zone.
Wherein the first hydrogenation reaction zone comprises 2 fixed bed hydrogenation reactors connected in series; the second hydrogenation reaction zone contains 2 fixed bed hydrogenation reactors connected in series.
The wax oil hydrofining catalyst V1 is filled in both an upstream fixed bed hydrogenation reactor and a downstream fixed bed hydrogenation reactor in the first hydrogenation reaction zone, and the filling volume ratio is 1:1 (20 ml and 20ml respectively);
the upper stream of the fixed bed hydrogenation reactor in the second hydrogenation reaction zone is sequentially filled with a protecting catalyst G1, a hydrodemetallization catalyst M1 and a hydrodemetallization catalyst M2, and the lower stream of the fixed bed hydrogenation reactor is filled with a hydrodesulphurization and carbon residue removal catalyst S1; and the filling volume ratio of G1, M2 and S1 is 1:4.8:3.2:11 (25 ml, 120ml, 80ml, 275ml, respectively).
The wax oil raw material used in this example is wax oil a of the properties shown in table 1; the vacuum residuum used in this example was vacuum residuum a of the nature shown in table 2. The weight ratio of the wax oil A to the vacuum residue A is 4:6.
the specific reaction conditions of this example are:
after heat exchange treatment, the temperature of the wax oil raw material is 365 ℃;
in the first hydrogenation reaction zone, R101, the reaction pressure is 15.5MPa, and the hydrogen-oil volume ratio is 600:1, the reaction temperature is 385 ℃, and the liquid hourly space velocity is 1.0h -1 ；
In the second hydrogenation reaction zone, R102, the reaction pressure is 16.0MPa, and the hydrogen-oil volume ratio is 700:1, a step of; the reaction temperature of the reactor where the hydrogenation protecting catalyst and the hydrodemetallization catalyst are positioned is 385 ℃, the reaction temperature of the reactor where the hydrodesulphurization and carbon residue removal catalyst is positioned is 395 ℃, the second oneThe liquid hourly space velocity of the hydrogenation reaction zone is 0.18h -1 。
The total liquid hourly space velocity of the two hydrogenation reaction zones is 0.17h -1 。
The properties of the hydrogenated residuum obtained by the method of this example are shown in Table 5, wherein the carbon removal rate, desulfurization rate, denitrification rate, and removal rate of metallic nickel and vanadium are shown in Table 6.
Comparative example 1
This comparative example uses a similar process flow as in example 1, except that:
in this comparative example, only the second hydrogenation reaction zone R102 was used, and the first hydrogenation reaction zone R101 was not used. Namely, the residual oil A shown in the table 4 obtained after the wax oil raw material and the vacuum residual oil are mixed directly enters a second hydrogenation reaction zone to be contacted with a hydrogenation protecting catalyst, hydrogenation demetallization catalysts (M1 and M2) and a hydrogenation desulfurization and carbon residue removal catalyst in sequence in the presence of hydrogen to obtain hydrogenated residual oil.
And the catalyst loading in the second hydrogenation reaction zone R102 is: the upstream fixed bed hydrogenation reactor is sequentially filled with a protecting catalyst G1, a hydrodemetallization catalyst M1 and a hydrodemetallization catalyst M2, and the downstream fixed bed hydrogenation reactor is filled with a hydrodesulphurization and carbon residue removal catalyst S1; and the filling volume ratio of G1, M2 and S1 is 1:4.8:3.2:11 (25 ml, 120ml, 80ml, 275ml, respectively).
The raw oil used in this comparative example was the same as that in example 1, namely, wax oil a and vacuum residue a, and the ratio of the amounts used was the same as that in example 1.
The specific reaction conditions of this comparative example are:
a first hydrogenation reaction zone, absent;
in the second hydrogenation reaction zone, R102, the reaction pressure is 16.0MPa, and the hydrogen-oil volume ratio is 700:1, a step of; the reaction temperature of the reactor where the hydrogenation protecting catalyst and the hydrodemetallization catalyst are positioned is 385 ℃, the reaction temperature of the reactor where the hydrodesulphurization and carbon residue removal catalyst is positioned is 395 ℃, and the liquid hourly space velocity of the second hydrogenation reaction zone is 0.17h -1 。
The properties of the hydrogenated residuum obtained by the method of this comparative example are shown in Table 5, wherein the carbon removal rate, desulfurization rate, denitrification rate, and removal rate of metallic nickel and vanadium are shown in Table 6.
Example 2
This example was conducted in a similar manner to example 1 except that:
in this example, the wax oil feedstock used was wax oil B of the properties shown in table 1, the vacuum residuum used was vacuum residuum B of the properties shown in table 2, both at 4:6 (wax oil B: vacuum residue B) was used.
The properties of the hydrogenated residuum obtained by the method of this example are shown in Table 5, wherein the carbon removal rate, desulfurization rate, denitrification rate, and removal rate of metallic nickel and vanadium are shown in Table 6.
Comparative example 2
This comparative example was conducted using a similar process to comparative example 1, except that:
in this comparative example, the wax oil feedstock used was wax oil B of the properties shown in table 1, and the vacuum residue used was vacuum residue B of the properties shown in table 2, both at 4:6 (wax oil B: vacuum residuum B) by weight ratio (properties of residuum B obtained after mixing are shown in Table 4).
The properties of the hydrogenated residuum obtained by the method of this comparative example are shown in Table 5, wherein the carbon removal rate, desulfurization rate, denitrification rate, and removal rate of metallic nickel and vanadium are shown in Table 6.
Example 3
This example was conducted in a similar manner to example 1 except that:
in this example, the catalytic cracking light cycle oil feedstock used was catalytic cracking light cycle oil a in table 3, the wax oil feedstock used was wax oil a of the properties shown in table 1, and the vacuum residuum used was vacuum residuum a of the properties shown in table 2, the three components were as follows: 4:5 (catalytic cracking light cycle oil A: wax oil A: vacuum residuum A) were used.
In the embodiment, the hydrogenated residual oil obtained in the second hydrogenation reaction zone is subjected to heat exchange treatment with wax oil raw materials and hydrogen, and then is subjected to heat exchange treatment with catalytic cracking light cycle oil and hydrogen.
The remainder was the same as in example 1.
The properties of the hydrogenated residuum obtained by the method of this example are shown in Table 5, wherein the carbon removal rate, desulfurization rate, denitrification rate, and removal rate of metallic nickel and vanadium are shown in Table 6.
Example 4
This example was conducted in a similar manner to example 2 except that:
in this example, the catalytic cracking light cycle oil feedstock used was catalytic cracking light cycle oil B in table 3, the wax oil feedstock used was wax oil B of the properties shown in table 1, and the vacuum residue used was vacuum residue B of the properties shown in table 2, all three of which were used in a 1:4:5 (catalytic cracking light cycle oil B: wax oil B: vacuum residuum B) weight ratio was used.
In the embodiment, the hydrogenated residual oil obtained in the second hydrogenation reaction zone is subjected to heat exchange treatment with wax oil raw materials and hydrogen, and then is subjected to heat exchange treatment with catalytic cracking light cycle oil and hydrogen.
The remainder was the same as in example 2.
The properties of the hydrogenated residuum obtained by the method of this example are shown in Table 5, wherein the carbon removal rate, desulfurization rate, denitrification rate, and removal rate of metallic nickel and vanadium are shown in Table 6.
Example 5
This example was conducted in a similar manner to example 1 except that:
in this example, the wax oil feedstock used was wax oil a of the properties shown in table 1, the vacuum residuum applied was vacuum residuum a of the properties shown in table 2, both at 5:5 (wax oil A: vacuum residuum A) were used.
The wax oil hydrofining catalyst V1 is filled in both an upstream fixed bed hydrogenation reactor and a downstream fixed bed hydrogenation reactor in the first hydrogenation reaction zone, and the filling volume ratio is 1:1 (25 ml and 25ml respectively);
in the second hydrogenation reaction zone, R102, the reaction pressure is 16.0MPa, and the hydrogen-oil volume ratio is 700:1, a step of; the reaction temperature of the reactor where the hydrogenation protecting catalyst and the hydrodemetallization catalyst are positioned is 380 ℃, the reaction temperature of the reactor where the hydrodesulphurization and carbon residue removal catalyst is positioned is 390 ℃,the liquid hourly space velocity of the second hydrogenation reaction zone is 0.19h -1 . The total liquid hourly space velocity of the two hydrogenation reaction zones is 0.17h -1 。
The remainder was the same as in example 1.
The properties of the hydrogenated residuum obtained by the method of this example are shown in Table 5, wherein the carbon removal rate, desulfurization rate, denitrification rate, and removal rate of metallic nickel and vanadium are shown in Table 6.
Comparative example 3
This comparative example was conducted in a similar manner to example 5 except that:
in this comparative example, the wax oil feedstock used was wax oil a of the properties shown in table 1, the vacuum residuum applied was vacuum residuum a of the properties shown in table 2, both at 5:5 (wax oil A: vacuum residuum A) was used, the feed after mixing being residuum C of the nature indicated in Table 4.
In this comparative example, only the second hydrogenation reaction zone R102 was used, and the first hydrogenation reaction zone R101 was not used. The wax oil raw material is mixed with vacuum residuum and then directly enters a second hydrogenation reaction zone in the presence of hydrogen to be sequentially contacted with a hydrogenation protecting catalyst, hydrodemetallization catalysts (M1 and M2) and a hydrodesulphurization carbon residue catalyst, so that hydrogenated residuum is obtained.
The remainder was the same as in example 5.
The properties of the hydrogenated residuum obtained by the method of this comparative example are shown in Table 5, wherein the carbon removal rate, desulfurization rate, denitrification rate, and removal rate of metallic nickel and vanadium are shown in Table 6.
Comparative example 4
This comparative example was conducted using a similar process to that of example 1, except that:
in this comparative example, the wax oil feedstock used was wax oil a of the properties shown in table 1, the vacuum residuum applied was vacuum residuum a of the properties shown in table 2, both at 1.5:8.5 (wax oil A: vacuum residuum A) weight ratio was used.
The first hydrogenation reaction zone contains 1 fixed bed hydrogenation reactor; the second hydrogenation reaction zone contains 2 fixed bed hydrogenation reactors connected in series. The fixed bed hydrogenation reactor in the first hydrogenation reaction zone was filled with wax oil hydrofining catalyst V1 in a filling volume of 15ml.
The loading in the second hydrogenation reaction zone was the same as in example 1.
The reaction conditions in the first reaction zone were the same as in example 1. The liquid hourly space velocity of the second hydrogenation reaction zone is 0.174h -1 The remaining reaction conditions were the same as in example 1. The total liquid hourly space velocity of the two reaction zones was 0.17h -1 。
The properties of the hydrogenated residuum obtained by the method of this comparative example are shown in Table 5, wherein the carbon removal rate, desulfurization rate, denitrification rate, and removal rate of metallic nickel and vanadium are shown in Table 6.
TABLE 1
| Analysis item | Wax oil A | Wax oil B |
| H,wt％ | 11.94 | 12.37 |
| MCR,wt％ | 0.60 | 0.36 |
| S,wt％ | 3.07 | 0.66 |
| N,wt％ | 0.091 | 0.160 |
TABLE 2
| Analysis item | Vacuum residuum A | Vacuum residuum B |
| H,wt％ | 10.25 | 11.56 |
| MCR,wt％ | 20.30 | 19.16 |
| S,wt％ | 4.93 | 2.19 |
| N,wt％ | 0.43 | 0.70 |
| Ni+V，ppm | 204 | 125 |
TABLE 3 Table 3
| Analysis item | Catalytic cracking light cycle oil A | Catalytic cracking light cycle oil B |
| H,wt％ | 8.75 | 9.20 |
| MCR,wt％ | 0 | 0 |
| S,wt％ | 0.89 | 1.25 |
| N，ppm | 471 | 644 |
| Ni+V，ppm | 0 | 0 |
TABLE 4 Table 4
| Analysis item | H，wt％ | Carbon residue, wt% | S，wt％ | N，wt％ | Ni+V，wt％ |
| Residuum A | 11.00 | 12.31 | 4.22 | 0.28 | 117.0 |
| Residuum B | 11.34 | 12.08 | 1.51 | 0.48 | 75.0 |
| Residuum C | 11.11 | 10.35 | 4.05 | 0.24 | 99.0 |
TABLE 5
| Analysis item | H，wt％ | Carbon residue, wt% | S，wt％ | N，wt％ | Ni+V，wt％ |
| Example 1 | 12.64 | 2.90 | 0.15 | 0.09 | 1.6 |
| Comparative example 1 | 12.45 | 3.11 | 0.22 | 0.10 | 4.1 |
| Example 2 | 12.53 | 4.47 | 0.14 | 0.21 | 8.7 |
| Comparative example 2 | 12.34 | 4.89 | 0.15 | 0.24 | 9.1 |
| Example 3 | 12.36 | 2.39 | 0.11 | 0.08 | 1.1 |
| Example 4 | 12.28 | 3.52 | 0.12 | 0.18 | 5.2 |
| Example 5 | 12.68 | 2.35 | 0.13 | 0.08 | 1.3 |
| Comparative example 3 | 12.51 | 2.55 | 0.20 | 0.09 | 3.1 |
| Comparative example 4 | 12.13 | 4.38 | 0.33 | 0.14 | 8.69 |
TABLE 6
From the above results, it can be seen that the hydrotreating process of the present invention is excellent in hydrogen content, desulfurization rate, decarbonization rate and demetallization ability. The hydrogenation generated oil obtained by the invention provides high-quality raw materials for a downstream catalytic cracking device, thereby saving the production cost.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (14)
1. A process for hydrotreating residuum, wherein the process is carried out in a fixed bed hydrogenation unit comprising a first hydrogenation reaction zone and a second hydrogenation reaction zone, comprising:
(1) Introducing a wax oil raw material into a first hydrogenation reaction zone containing a wax oil hydrogenation catalyst in the presence of hydrogen to perform a first hydrogenation reaction to obtain hydrogenated wax oil;
(2) Introducing a mixed stream containing vacuum residuum and hydrogenated wax oil into a second hydrogenation reaction zone in the presence of hydrogen to carry out a second hydrogenation reaction to obtain hydrogenated residuum; according to the flow direction of the liquid phase material flow, a hydrogenation protecting catalyst, a hydrodemetallization catalyst and a hydrodesulphurization carbon residue removing catalyst are sequentially filled in the second hydrogenation reaction zone;
optionally, the mixture flow also contains catalytic cracking light cycle oil;
taking the total mass flow of the wax oil raw material, the vacuum residue and the catalytic cracking light cycle oil entering the hydrogenation device as a reference, the mass flow of the wax oil raw material entering the hydrogenation device is 20-65%, the mass flow of the catalytic cracking light cycle oil entering the hydrogenation device is 0-30%, and the mass flow of the vacuum residue entering the hydrogenation device is 35-80%.
2. The process of claim 1, wherein in step (1), 1-2 fixed bed reactors are disposed in the first hydrogenation reaction zone;
preferably, in step (2), 2 to 5 fixed bed reactors are provided in the second hydrogenation reaction zone.
3. The process according to claim 1 or 2, wherein in step (1) the conditions of the first hydrogenation reaction at least satisfy: the temperature is 320-430 ℃, the reaction pressure is 6-20MPa, and the liquid hourly space velocity is 0.3-2.0h -1 The volume ratio of hydrogen to oil is 250-1500:1, a step of;
preferably, in step (1), the conditions of the first hydrogenation reaction at least satisfy: the temperature is 350-410 ℃, the reaction pressure is 10-18MPa, and the liquid hourly space velocity is 0.6-1.5h -1 The volume ratio of hydrogen to oil is 300-1000:1.
4. a process according to any one of claims 1 to 3, wherein in step (1) the asphaltene content in the wax oil feedstock is 500ppm or less;
preferably, the wax oil raw material is at least one selected from the group consisting of normal three-wire oil, normal four-wire oil, top oil reduction, first-wire oil reduction, two-wire oil reduction, three-wire oil reduction, four-wire oil reduction, coker wax oil, deasphalted oil and catalytic cracking heavy cycle oil.
5. The process according to any one of claims 1-4, wherein in step (2), the conditions of the second hydrogenation reaction at least satisfy: the temperature is 330-450 ℃, the reaction pressure is 6-25MPa, and the liquid hourly space velocity is 0.1-1h -1 The volume ratio of hydrogen to oil is 250-1500:1；
preferably, in step (2), the conditions of the second hydrogenation reaction at least satisfy: the temperature is 360-430 ℃, the reaction pressure is 12-20MPa, and the liquid hourly space velocity is 0.1-0.4h -1 The volume ratio of hydrogen to oil is 300-1000:1.
6. the process of any of claims 1-5, wherein the mass flow of the waxy oil feedstock to the hydrogenation unit is 25-50%, the mass flow of the catalytically cracked light cycle oil to the hydrogenation unit is 0-20%, and the mass flow of the vacuum resid to the hydrogenation unit is 50-75%, based on the total mass flow of the waxy oil feedstock, the vacuum resid, and the catalytically cracked light cycle oil to the hydrogenation unit.
7. The process of any of claims 1-6, wherein the loading volume ratio of the wax oil hydrogenation catalyst is 2-25%, the loading volume ratio of the hydro-guard catalyst is 1-20%, the loading volume ratio of the hydrodemetallization catalyst is 10-60%, and the loading volume ratio of the hydrodesulphurisation carbon residue catalyst is 30-80%, based on the total volume of the loaded catalyst in the hydrogenation unit;
preferably, the loading volume ratio of the wax oil hydrogenation catalyst is 4-20%, the loading volume ratio of the hydrogenation protection catalyst is 2-15%, the loading volume ratio of the hydrodemetallization catalyst is 20-55%, and the loading volume ratio of the hydrodesulphurization carbon residue removal catalyst is 40-65% based on the total volume of the loaded catalyst in the hydrogenation device.
8. The method according to any one of claims 1 to 7, wherein each of the wax oil hydrogenation catalyst, the hydrodemetallization catalyst, and the hydrodesulphurisation carbon residue removal catalyst independently comprises a support and an active metal component element supported on the support, the active metal component element being selected from at least one of a group VIB metal element and a group VIII metal element;
preferably, the active metal component element is selected from at least one of the group consisting of nickel-tungsten, nickel-molybdenum and cobalt-molybdenum.
9. The process according to claim 8, wherein the content of active metal component elements in oxide is 20-38wt% in the wax oil hydrogenation catalyst, based on the total weight of the wax oil hydrogenation catalyst; and/or
In the hydrogenation protecting catalyst, the content of active metal component elements calculated by oxide is 1-12wt% based on the total weight of the hydrogenation protecting catalyst; and/or
In the hydrodemetallization catalyst, the content of active metal component elements calculated by oxide is 6-15wt% based on the total weight of the hydrodemetallization catalyst; and/or
In the hydrodesulfurization carbon residue removal catalyst, the content of active metal component elements in terms of oxide is 8-25wt% based on the total weight of the hydrodesulfurization carbon residue removal catalyst.
10. The process according to any one of claims 1 to 9, wherein the wax oil hydrogenation catalyst has an average pore size of 3nm to 20nm and an average particle size of 1.2mm to 4mm; and/or
The average pore diameter of the hydrogenation protecting catalyst is 18nm-30nm, and the average particle diameter is 1.3mm-50mm; and/or
The average pore diameter of the hydrodemetallization catalyst is 10nm-20nm, and the average particle diameter is 0.8mm-5mm; and/or
The average pore diameter of the hydrodesulphurization and carbon residue removal catalyst is 8nm-15nm, and the average particle diameter is 0.6mm-2mm.
11. The process according to any one of claims 1 to 10, wherein the wax oil hydrogenation catalyst has a bulk density of 0.5 to 1.6g/cm 3 A specific surface area of 80-500m 2 /g; and/or
The hydrogenation protecting catalyst, the hydrodemetallization catalyst and the hydrodesulfurizationThe carbon removal catalyst is characterized by being each independently selected from the group consisting of: bulk density of 0.3-1.2g/cm 3 A specific surface area of 50-400m 2 /g。
12. The method of any of claims 8-11, wherein in the wax oil hydrogenation catalyst, the hydroprotection catalyst, the hydrodemetallization catalyst, and the hydrodesulphurisation carbon residue catalyst, the supports are each independently selected from at least one of alumina, silica, and titania;
preferably, the carrier contains at least one modifying element selected from boron, germanium, zirconium, phosphorus, chlorine and fluorine;
preferably, the total content of germanium and zirconium in weight percent, calculated as metal oxide, is 0.1-15% and the total content of boron, phosphorus, chlorine and fluorine in weight percent, calculated as element, is 0.1-15%, based on the total weight of the support.
13. The process of any one of claims 1-12, wherein in step (1), the waxy oil feedstock and hydrogen are heat exchanged with the hydrogenated residuum in step (2) without heating by a furnace prior to introduction into the first hydrogenation reaction zone; and
in step (2), the vacuum residuum and hydrogen are heated in a furnace prior to entering the second hydrogenation reaction zone.
14. The process of any one of claims 1-13, wherein in step (2) the mixture stream contains a catalytically cracked light cycle oil and the catalytically cracked light cycle oil is heat exchanged with the hydrogenated residuum without heating by a furnace prior to the mixture stream entering the second hydrogenation reaction zone.
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