CN115261067A - Residual oil hydrogenation method - Google Patents
Residual oil hydrogenation method Download PDFInfo
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- CN115261067A CN115261067A CN202110480780.4A CN202110480780A CN115261067A CN 115261067 A CN115261067 A CN 115261067A CN 202110480780 A CN202110480780 A CN 202110480780A CN 115261067 A CN115261067 A CN 115261067A
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 101
- 238000000034 method Methods 0.000 title claims abstract description 65
- 239000003054 catalyst Substances 0.000 claims abstract description 141
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 40
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 18
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- 229910052799 carbon Inorganic materials 0.000 claims description 4
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- 238000010438 heat treatment Methods 0.000 claims description 3
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- 229910052804 chromium Inorganic materials 0.000 claims description 2
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 2
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
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- 238000010306 acid treatment Methods 0.000 description 2
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- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
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Images
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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
- C10G67/0454—Solvent desasphalting
- C10G67/049—The hydrotreatment being a hydrocracking
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the field of residual oil processing, and discloses a residual oil hydrogenation method, which comprises the following steps: introducing a residual oil raw material, a dispersed catalyst and deasphalted oil into a fixed bed residual oil hydrogenation reaction zone filled with a residual oil hydrotreating catalyst for hydrogenation reaction to obtain hydrogenation generated oil, introducing the hydrogenation generated oil into a hot high-pressure separator for separation to obtain a gas phase material flow and a liquid phase material flow, wherein the content of toluene insoluble substances in the hydrogenation generated oil is not more than 0.1wt%, and the dosage of the dispersed catalyst is 0.01-2.0wt% based on the total weight of the residual oil raw material and the deasphalted oil; performing solvent deasphalting treatment on the liquid phase material flow to obtain deoiled asphalt and deasphalted oil which is recycled to the hydrogenation reaction; and carrying out hydrocracking reaction on the gas phase material flow to obtain heavy naphtha. The residual oil hydrogenation method provided by the invention ensures the stability of oil generated by hydrogenation, greatly improves the conversion rate of residual oil, and can realize the production of chemical raw materials and low-sulfur petroleum coke.
Description
Technical Field
The invention relates to the field of residual oil processing, in particular to a residual oil hydrogenation method.
Background
Under the conditions of increasing pressure, slowing down the increase of petroleum demand and aggravating the oscillation and fluctuation of oil price in the world economic development, the oil refining industry faces huge pressure of transformation. At present, the oil refining capacity in China is obviously surplus, but the demand of chemical raw materials and low-sulfur petroleum coke is still large, and oil refining enterprises need to accelerate the transformation from large-scale production of finished oil to multi-production of chemical raw materials and low-sulfur petroleum coke.
40-60% of crude oil is residual oil, and oil refining enterprises urgently need a high-efficiency residual oil conversion technology, while the residual oil hydrogenation technology is an important technical means for residual oil conversion and plays an important role in modern oil refining industry. Residual oil hydrogenation technologies are mainly divided into fixed bed, ebullated bed and slurry bed residual oil hydrogenation technologies according to different reactor forms.
The fixed bed residue hydrogenation technology is developed on the basis of the distillate oil hydrogenation technology in the 60 th of the 20 th century. The pressure of residual oil is increased by a pump until the pressure of a reaction system is mixed with new hydrogen and circulating hydrogen, and the mixture is heated by a heating furnace and then enters a reactor. The catalyst in the reactor is fixed, and hydrogen is pumped between catalyst beds to control the reaction temperature.
The boiling bed residual oil hydrogenation technology is successfully developed in the end of the 60's of the 20 th century, and the reactor is a three-phase fluidized bed system with back-mixed gas, liquid and catalyst particles. Hydrogen and raw oil enter from the bottom of the reactor, are mixed with circulating oil and then pass through a bubble cap distribution plate, and lift the catalyst upwards to expand the catalyst bed and keep the catalyst bed in a fluidized state. The height of the boiling catalyst bed can be controlled by the circulating oil flow.
The slurry bed residual oil hydrogenation technology is a gas/liquid/solid three-phase reaction process, and the catalyst is pushed by moving gas/liquid to be in a fluidized state. The catalyst used in the technology has small particle size, large outer surface, high catalyst particle number in unit volume of liquid medium and small space between catalyst particles, and is favorable for inhibiting the polymerization reaction of liquid.
At present, the fixed bed residual oil hydrogenation technology is the residual oil hydrogenation method which has the widest application range and the most mature process, and has the advantages of simple process and equipment, easy operation and lower device investment cost. The liquid in the fixed bed reactor is approximately plug flow, no back mixing exists, and the efficiency of impurities such as hydrodesulfurization, nitrogen and the like is high. However, the conversion rate of the fixed bed residual oil hydrogenation technology is low, generally only 10-20%, and high-value products such as LPG, gasoline, diesel oil and the like can be obtained after the hydrogenated residual oil is cracked by a subsequent catalytic cracking device.
In the boiling bed and slurry bed residual oil hydrogenation technology, the catalyst can be replaced on line, the reaction temperature is high, higher residual oil conversion rate can be realized, but serious back mixing phenomenon exists in a reactor, the removal rate of impurities such as sulfur, nitrogen and the like is low, and under the condition of high conversion rate, the stability of hydrogenation generated oil is reduced, so that coking and blockage of a subsequent system are easily caused, and the long-period safe operation of the device is seriously influenced. In the industrial production process, in order to avoid coking and blockage, the residual oil hydrogenation devices in the fluidized bed and the slurry bed are designed with very complicated heat exchange and separation systems, so that the investment cost of the device is increased, and the operation difficulty is increased.
During residue conversion, the maximum conversion level is limited by the stability of the resulting residue. The residue conversion process changes the chemistry of the oils and asphaltenes, resulting in a gradual decrease in stability with increasing severity. Beyond a certain limit, the degree of phase separation (i.e., deposition) of asphaltenes in the feedstock increases and thus initiates the coke-forming process. The coke produced can be separated out at subsequent positions such as a heat exchanger, a fractionating tower and the like, and the long-period safe operation of the device is seriously influenced.
Research shows that the stability of the residual oil hydrogenation product oil is closely related to the conversion rate of the residual oil, and the stability of the hydrogenation product oil is represented by toluene insoluble substances, and the higher the toluene insoluble substances are, the more easily the hydrogenation product oil is precipitated and the more unstable the hydrogenation product oil is.
US4427535a discloses a process for achieving high conversion of heavy oil by hydrocracking. The method adopts the ebullated bed technology to process inferior heavy crude oil containing 10-28wt% of asphaltene and 12-35wt% of carbon residue, such as Canada cold lake crude oil and Lloydminster crude oil, at the reaction temperature of 404-446 ℃, the reaction pressure of 14.2-21.1MPa and the volume space velocity of 0.25-5.0h-1Under the conditions of (1), a conversion rate of 65-80% can be achieved.
CN101098949a discloses a process for the conversion of heavy feedstocks such as heavy crude oil and distillation residues. The method comprises the steps of firstly feeding residual oil into a deasphalting section, then mixing the deasphalted oil with a proper hydrogenation catalyst precursor, and then feeding the mixture into a hydrotreating reactor. The stream containing the hydrogenation product and the catalyst in the dispersed phase is fed to a fractionation column, where at least a portion of the residue obtained from the distillation and the liquid from the flash unit are recycled. The process is capable of achieving conversion rates in excess of 95%.
Disclosure of Invention
The invention aims to overcome the defect of low conversion rate of a fixed bed residual oil hydrogenation method in the prior art, and the existing fixed bed residual oil hydrogenation device is expected to be utilized, so that the conversion rate of residual oil is greatly improved while the stability of hydrogenation generated oil and the running period of the device are ensured, and chemical raw materials and low-sulfur petroleum coke are produced.
In order to achieve the above object, the present invention provides a residual oil processing method comprising:
(1) In the presence of hydrogen, introducing a residual oil raw material, a dispersion type catalyst and deasphalted oil into a fixed bed residual oil hydrogenation reaction zone filled with a residual oil hydrotreating catalyst for hydrogenation reaction to obtain hydrogenated oil, wherein the content of toluene insoluble substances in the hydrogenated oil is not more than 0.1wt%, and the dosage of the dispersion type catalyst is 0.01-2.0wt% based on the total weight of the residual oil raw material and the deasphalted oil;
(2) Introducing the hydrogenated oil into a hot high-pressure separator for separation to obtain a gas phase material flow and a liquid phase material flow containing hydrogenated residual oil;
(3) Performing solvent deasphalting treatment on the liquid phase material flow to obtain deasphalted asphalt and deasphalted oil which is circulated to the fixed bed residual oil hydrogenation reaction zone in the step (1) and is subjected to the hydrogenation reaction; and
and introducing the gas-phase material flow into a hydrocracking reaction zone filled with a hydrocracking catalyst for hydrocracking reaction to obtain heavy naphtha.
The technical scheme of the invention has the following advantages:
1. the invention gives consideration to the advantages of a fixed bed and a movable bed (a boiling bed and a slurry bed) residual oil hydrogenation device, and the high sulfur and nitrogen impurity removal rate of the fixed bed residual oil hydrogenation device is kept, the high conversion rate of the residual oil is realized, and the long-period safe operation of the device can be realized by adding a specific amount of dispersed catalyst into the feed.
2. The method realizes the high-efficiency utilization of hydrogen and carbon in the residual oil, wherein the hydrogen in the residual oil is mainly used for producing heavy naphtha with high hydrogen content, and the carbon is mainly used for producing low-sulfur petroleum coke.
3. The product produced by the method has a flexible and reasonable structure, and can flexibly adjust the residual oil conversion rate of the fixed bed residual oil hydrogenation device by adjusting the addition proportion of the dispersed catalyst and controlling the hydrogenation severity of the hydrogenation device according to different market requirements.
4. The invention fully utilizes the heat and pressure of the hot high-pressure separator, realizes the further cracking of the hydrogenated diesel oil and the hydrogenated wax oil by adding the hydrocracking reactor behind the fixed bed residual oil hydrogenation device, obtains the chemical raw material heavy naphtha, and has simple whole processing flow, low energy consumption and low cost.
Drawings
FIG. 1 is a process flow diagram of a preferred embodiment of the process of the present invention.
Description of the reference numerals
1. Residual oil raw material 2, dispersed catalyst
3. Fixed bed residual oil hydrogenation reaction zone 4 and hydrogenation generated oil
5. Hot high pressure separator 6, gas phase stream
7. Hydrocracking reaction zone 8, heavy naphtha
9. Liquid phase material flow 10, solvent deasphalting device
11. Deoiled asphalt 12 and deasphalted oil
13. Delayed coking treatment device 14 and low-sulfur petroleum coke
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, unless otherwise specified, the pressures are expressed as hydrogen partial pressures and are gauge pressures.
In the present invention, the particle size of the catalyst means the maximum distance between two different points on the cross section of the particle, unless otherwise specified.
As previously mentioned, the present invention provides a process for hydrogenating a residue, comprising:
(1) In the presence of hydrogen, introducing a residual oil raw material, a dispersion type catalyst and deasphalted oil into a fixed bed residual oil hydrogenation reaction zone filled with a residual oil hydrotreating catalyst for hydrogenation reaction to obtain hydrogenated oil, wherein the content of toluene insoluble substances in the hydrogenated oil is not more than 0.1wt%, and the dosage of the dispersion type catalyst is 0.01-2.0wt% based on the total weight of the residual oil raw material and the deasphalted oil;
(2) Introducing the hydrogenated oil into a hot high-pressure separator for separation to obtain a gas phase material flow and a liquid phase material flow containing hydrogenated residual oil;
(3) Performing solvent deasphalting treatment on the liquid phase material flow to obtain deasphalted asphalt and deasphalted oil which is circulated to the fixed bed residual oil hydrogenation reaction zone in the step (1) and is subjected to the hydrogenation reaction; and
and introducing the gas-phase material flow into a hydrocracking reaction zone filled with a hydrocracking catalyst for hydrocracking reaction to obtain heavy naphtha.
Preferably, the dispersed catalyst is used in an amount of 0.02 to 1.5wt%, based on the total weight of the residuum feedstock and the deasphalted oil. The inventors have found that with this preferred embodiment, higher residue conversions can be achieved without shortening the run length.
Preferably, in step (1), the average particle diameter of the dispersed catalyst is 0.1 μm to 25 μm.
According to a preferred embodiment, in step (1), the dispersed catalyst is a granular catalyst containing a metallic element and a non-metallic element, the non-metallic element is selected from at least one of non-metallic elements of groups IVA and VIA, and the metallic element is selected from at least one of metallic elements of groups VB, VIB, IVA and VIII; based on the total weight of the dispersed catalyst, the content of the metal element is 5-20wt% and the content of the nonmetal element is 80-95wt% calculated by oxide.
Particularly preferably, the metal element is at least one selected from Cr, V, mo, W, ni, fe, co and Sn, and the nonmetal element is at least one selected from C, si and S.
In the present invention, the dispersed catalyst may be selected from commercial catalysts known in the art or prepared by a method known in the art, and the specific operations exemplified hereinafter in the present invention should not be construed as limiting the present invention by those skilled in the art.
According to a preferred embodiment, the conditions of the fixed bed residuum hydrogenation reaction zone are controlled such that the conversion of the residuum feedstock is no less than 30%.
Preferably, in the step (1), the conditions of the fixed bed residue hydrogenation reaction zone at least satisfy the following conditions: hydrogen partial pressure is 1.0-22.0MPa, reaction temperature is 330-470 ℃, volume space velocity is 0.1-3.0h-1The volume ratio of hydrogen to oil is 350-2000.
More preferably, the fixed bed residuum hydrogenation reaction zone conditions are at least: hydrogen partial pressure of 8.0-21.0MPa, reaction temperature of 360-460 deg.C, volume space velocity of 0.2-2.5h-1The volume ratio of hydrogen to oil is 400-1500. The inventors have found that with this preferred embodiment, higher conversion of the residue can be achieved.
Preferably, in step (1), the residue hydrotreating catalyst has a bulk density of 300 to 900kg/m3The average pore diameter is 5-20nm, the pore volume is not less than 0.45ml/g, and the specific surface area is not less than 90m2/g。
According to a particularly preferred embodiment, in step (1), the residue hydrotreating catalyst is selected from at least one of hydrodemetallization catalysts, hydrogenation protection catalysts, transition catalysts, hydrodesulphurization-denitrification catalysts.
According to another particularly preferred embodiment, the fixed bed residue hydrogenation reaction zone is sequentially packed with the hydrogenation protection catalyst, the hydrodemetallization catalyst and the hydrodesulfurization and denitrogenation catalyst in the direction of flow.
Preferably, the loading volume ratio of the hydrogenation protection catalyst, the hydrodemetallization catalyst and the hydrodesulfurization and denitrogenation catalyst is 1: (2-10): (5-12).
Preferably, in the step (1), the residue hydrotreating catalyst contains a carrier selected from at least one of alumina, silica and titania, and an active metal element selected from group vib and/or group viii metal elements supported on the carrier.
More preferably, in the residue hydrotreating catalyst, the active metal element is selected from at least one of a nickel-tungsten combination, a nickel-tungsten-cobalt combination, a nickel-molybdenum combination, and a cobalt-molybdenum combination.
Particularly preferably, the content of the active metal element in terms of oxide is 0.05 to 25wt%, preferably 1 to 20wt%, based on the total weight of the residue hydrotreating catalyst.
Preferably, the residue hydrotreating catalyst further contains at least one auxiliary element selected from boron, germanium, zirconium, phosphorus, chlorine and fluorine.
More preferably, the total content of the promoter element, calculated as element, in the residuum hydroprocessing catalyst is from 0.01 to 10 wt.%.
In the present invention, the residual oil hydrotreating catalyst may be selected from commercial catalysts known in the art or prepared by a method known in the art, and illustratively, the residual oil hydrotreating catalyst may be selected from commercial catalysts of RG series, RDM series, RMS series, RCS series, and RSN series developed by the institute of petrochemical engineering science, china.
According to a particularly preferred embodiment, the residue hydrotreating catalyst is selected from at least one of the designations RG-30B, RDM-202 and RCS-31 produced by ChangLing catalyst works, china petrochemical catalyst division.
Preferably, in the step (1), the fixed bed residual oil hydrogenation reaction zone contains at least 2 fixed bed reactors which are connected in series in sequence.
Preferably, the fixed bed residual oil hydrogenation reaction zone contains 2-6 fixed bed reactors connected in series in sequence.
The temperature of the fixed bed residuum hydrogenation reaction zone is the average temperature of each fixed bed reactor bed, unless otherwise specified.
Preferably, in step (1), the residual oil hydrotreating catalyst has a bed void ratio e of greater than 0.40, the bed void ratio e = (bed volume-bed packing volume)/bed volume of the catalyst, and the unit of the bed volume and the bed packing volume is the same (for example, both mL), and the bed packing is the residual oil hydrotreating catalyst.
Preferably, in the step (1), the residue feedstock is selected from at least one of atmospheric residue, vacuum residue, and heavy oil.
Preferably, the resid feed has a density (20 ℃) of greater than 950kg/m3。
According to a particularly preferred embodiment, the conditions of the hot high-pressure separator are controlled such that the density (20 ℃) of the gas-phase stream is in the range from 500 to 1000kg/m3Hydrogen content of not less than 5wt%; the density (20 ℃) of the liquid phase stream is 800-1200kg/m3The sulfur content is less than 5wt%, and the carbon residue content is less than 45wt%.
Preferably, in step (2), the conditions of the hot high-pressure separator at least satisfy: the temperature is 330-450 deg.C, and the pressure is 5-22Mpa.
According to a particularly preferred embodiment, the conditions of the solvent deasphalting treatment are controlled so that the deasphalted asphalt has a sulphur content of less than 2% by weight, the deasphalted oil has a carbon residue value of less than 50% by weight and a sulphur content of less than 3% by weight.
According to a preferred embodiment, in step (3), the solvent deasphalting treatment is carried out under conditions at least satisfying: the extraction temperature is 100-300 ℃, the pressure is 0.5-5MPa, and the volume ratio of the solvent to the oil is (5-10): 1, wherein the volume ratio of the solvent to the liquid phase material flow is the ratio of the solvent to the liquid phase material flow.
More preferably, the solvent involved in the solvent deasphalting is selected from C5-C8Alkane, C5-C8At least one of olefins, condensate and naphtha of。
The specific operation method of the solvent deasphalting treatment of the present invention is not particularly limited, and may be an operation method known in the art.
According to another preferred embodiment, in step (3), the conditions of the hydrocracking reaction zone at least satisfy: hydrogen partial pressure of 5.0-22.0MPa, reaction temperature of 300-450 deg.C, volume space velocity of 0.1-2.0h-1The volume ratio of hydrogen to oil is 350-2000.
Preferably, the hydrocracking catalyst has a bulk density of 500 to 1200g/cm3The average pore diameter is 5-20nm, the pore volume is not less than 0.2ml/g, and the specific surface area is not less than 190m2/g。
More preferably, the hydrocracking catalyst comprises a carrier and an active metal element loaded on the carrier, wherein the carrier is selected from at least one of alumina, silica and titania, and the active metal element is selected from at least one of nickel, cobalt, molybdenum and tungsten.
Particularly preferably, in the hydrocracking catalyst, the content of nickel and/or cobalt in terms of oxide is 0 to 30wt%, the content of molybdenum and/or tungsten in terms of oxide is 0 to 35wt%, and the sum of the contents of nickel, cobalt, molybdenum and tungsten in terms of oxide is greater than 0, based on the total weight of the hydrocracking catalyst.
In the present invention, the hydrocracking reaction zone may use a known hydrocracking system, and exemplarily, may include a reactor, a fractionation system, a combination employing a fixed bed reactor and/or a slurry bed reactor.
Preferably, the shape of the residual oil hydrotreating catalyst or the hydrocracking catalyst in the present invention is raschig ring or butterfly bar.
The subsequent treatment of the deoiled asphalt is not particularly required, and can be performed by those skilled in the art using operations known in the art, for example, the deoiled asphalt of the present invention can be introduced into a delayed coking treatment unit for a delayed coking reaction, etc.
According to a particularly preferred embodiment, the process further comprises subjecting said deoiled asphalt to a delayed coking treatment to obtain petroleum coke.
Preferably, the conditions of the delayed coking process are at least: the outlet temperature of the heating furnace is 450-600 ℃, the pressure is 0.1-0.5MPa, and the circulation ratio is 0.1-1, wherein the circulation ratio is the ratio of the amount of the circulating oil to the amount of the fresh oil (the circulating oil can be coker gas oil generally).
The process flow of a preferred embodiment of the fixed bed resid hydrogenation process of the present invention is provided below in conjunction with FIG. 1:
(1) In the presence of hydrogen, introducing a residual oil raw material 1, a dispersed catalyst 2 and deasphalted oil 12 into a fixed bed residual oil hydrogenation reaction zone 3 for hydrogenation reaction to obtain hydrogenated oil 4;
(2) Introducing the hydrogenated oil 4 into a hot high-pressure separator 5 for separation to obtain a gas-phase material flow 6 and a liquid-phase material flow 9;
(3) Introducing the liquid phase material flow 9 into a solvent deasphalting device 10 for solvent deasphalting treatment to obtain deoiled asphalt 11 and deasphalted oil 12 which is circulated back to the fixed bed residual oil hydrogenation reaction zone of the step (1) for hydrogenation reaction, and introducing the deoiled asphalt 11 into a delayed coking treatment device 13 for delayed coking treatment to obtain low-sulfur petroleum coke 14; and introducing the gas phase material flow 6 into a hydrocracking reaction zone 7 for hydrocracking reaction to obtain heavy naphtha 8.
The present invention will be described in detail below by way of examples. In the following examples, various raw materials used unless otherwise specified are commercially available.
In the following examples, without corresponding indications:
the hydrogenation reaction is carried out in a medium-sized device for hydrotreating residual oil in a fixed bed;
the solvent deasphalting treatment is carried out in a solvent deasphalting treatment device;
the hydrocracking reaction is carried out in a pilot plant;
the delayed coking process is carried out in a delayed coking process unit;
the residual feedstock properties are shown in table 1;
the amount of the dispersed catalyst is based on the total weight of the residuum feedstock and the deasphalted oil;
in a fixed bed residual oil hydrotreating reaction zone, a catalyst A, a catalyst B and a catalyst C are sequentially filled along a material flow direction, wherein the filling volume ratio of the catalyst A to the catalyst B to the catalyst C is 9:41:50;
the catalyst A, the catalyst B and the catalyst C are all produced by Changling catalyst factories of China petrochemical catalyst division, and the types and the properties of the catalysts are shown in Table 2;
wherein, the catalyst A is a hydrogenation protection catalyst, the catalyst B is a hydrogenation demetalization catalyst, and the catalyst C is a hydrogenation desulfurization denitrification catalyst;
the hydrocracking catalysts are all RIC-3, are produced by Changling catalyst factories of China petrochemical catalyst division, and have specific properties shown in Table 2.
The dispersed catalyst FS-1 and the dispersed catalyst FS-2 in the following examples are prepared by the method of the preparation example 1 or the preparation example 2;
preparation example 1
The dispersed catalyst FS-1 is prepared by the following method:
5.89g of ammonium molybdate ((NH)4)6Mo7O24·4H2O) and 300mL of water are uniformly stirred, 83g of activated carbon subjected to acid treatment (sequentially subjected to hydrochloric acid with the concentration of 2mol/L and nitric acid with the concentration of 2 mol/L) and 7.2g of vulcanizing agent (sublimed sulfur) are added, the mixture is vulcanized for 60min under the conditions of 300 ℃, 7.0MPa (initial hydrogen pressure) and high-speed stirring (300 rpm), and the dispersed residual oil hydrogenation catalyst FS-1 is obtained after filtration and drying, wherein the specific properties are shown in Table 2.
Preparation example 2
The dispersed catalyst FS-2 is prepared by the following method:
6.79g of ammonium molybdate ((NH)4)6Mo7O24·4H2O) and 300mL of water are stirred uniformly, and 90g of activated carbon subjected to acid treatment (hydrochloric acid with the concentration of 2mol/L and nitric acid with the concentration of 2mol/L are added, and 8.5g of vulcanizing agent (sublimation is carried out)Sulfur), sulfurizing for 80min at 350 deg.C and 9.0MPa (hydrogen initial pressure) under high-speed stirring (300 rpm), filtering, and drying to obtain dispersed residue hydrogenation catalyst FS-2, the specific properties of which are shown in Table 2.
Table 1: residual oil feedstock properties
| Item | Residual oil A | Residual oil B |
| Density (20 ℃), kg/m3 | 985.0 | 1012.5 |
| Kinematic viscosity (100 ℃ C.), mm2/s | 300 | 3000 |
| Carbon residue content, wt% | 12.3 | 22.4 |
| Nitrogen content, wt% | 0.26 | 0.40 |
| Sulfur content, wt.% | 4.1 | 5.5 |
| The contents of the four components are in percentage by weight | ||
| Saturated hydrocarbons | 20.5 | 7.6 |
| Aromatic hydrocarbons | 50.1 | 54.4 |
| Glue | 23.6 | 23.4 |
| Asphaltenes (C)7Insoluble matter) | 5.8 | 11.6 |
| Metal content, ppm | ||
| Nickel (II) | 85 | 110 |
| |
8 | 256 |
Table 2: types and properties of residuum hydrotreating catalysts and dispersive catalysts
Example 1
The present example was carried out by using the process flow shown in fig. 1, specifically:
(1) In the presence of hydrogen, introducing the residual oil A, the dispersed catalyst FS-1 and the deasphalted oil from the step (2) into a fixed bed residual oil hydrogenation reaction zone filled with a residual oil hydrotreating catalyst for hydrogenation reaction, and separating hydrogenation generated oil obtained after the hydrogenation reaction in a hot high-pressure separator to obtain a gas-phase material flow and a liquid-phase material flow; wherein the amount of the dispersed catalyst is 0.03wt% based on the total weight of the residuum feedstock and the deasphalted oil;
(2) Performing solvent deasphalting treatment on the liquid phase material flow, separating to obtain deoiled asphalt and deasphalted oil, circulating the deasphalted oil to the fixed bed residual oil hydrogenation reaction zone in the step (1) for hydrogenation reaction, and performing delayed coking treatment on the deoiled asphalt to obtain low-sulfur petroleum coke; and introducing the gas-phase material flow into a hydrocracking reaction zone filled with a hydrocracking catalyst for hydrocracking reaction to obtain heavy naphtha.
The reaction conditions and product distribution and yield of the fixed bed resid hydrogenation reaction zone, the hydrocracking reaction zone, the solvent deasphalting treatment, and the delayed coking treatment are shown in table 3.
Example 2
This example is similar to the method of operation of example 1, except that:
the residual oil raw material is residual oil B, and the dosage of the dispersed catalyst is 0.3wt%;
the reaction conditions and product distribution and yield of the fixed bed resid hydrogenation reaction zone, the hydrocracking reaction zone, the solvent deasphalting treatment, and the delayed coking treatment are shown in table 3.
Example 3
This example is similar to the method of operation of example 1, except that:
the residual oil raw material is residual oil B, and the dosage of the dispersed catalyst is 0.8wt%;
the reaction conditions and product distribution and yield of the fixed bed resid hydrogenation reaction zone, the hydrocracking reaction zone, the solvent deasphalting treatment, and the delayed coking treatment are shown in table 3.
Example 4
This example is similar to the method of operation of example 1, except that:
the dispersed catalyst is a dispersed catalyst FS-2;
the reaction conditions and product distribution and yield of the fixed bed resid hydrogenation reaction zone, the hydrocracking reaction zone, the solvent deasphalting treatment, and the delayed coking treatment are shown in table 3.
Comparative example 1
This comparative example is similar to the procedure of example 1, except that:
the method for hydrogenating the residual oil in the prior art is adopted, and specifically comprises the following steps:
in the presence of hydrogen, introducing the residual oil B into a fixed bed residual oil hydrogenation reaction zone filled with a residual oil hydrotreating catalyst for hydrogenation reaction, and separating hydrogenation generated oil obtained after the hydrogenation reaction in a hot high-pressure separator to obtain atmospheric residual oil (350 ℃), wherein the atmospheric residual oil is used as a raw material of a catalytic cracking device to obtain catalytic cracking gasoline.
The reaction conditions and product distribution and yield of the fixed bed resid hydrogenation reaction zone, the hydrocracking reaction zone, the solvent deasphalting treatment, and the delayed coking treatment are shown in table 3.
Comparative example 2
This comparative example is similar to the procedure of example 1, except that:
the dosage of the dispersion type catalyst is 3wt%;
the reaction conditions and product distribution and yield of the fixed bed resid hydrogenation reaction zone, the hydrocracking reaction zone, the solvent deasphalting treatment, and the delayed coking treatment are shown in table 3.
Comparative example 3
This comparative example is similar to the procedure of example 1, except that:
the dosage of the dispersed catalyst is 0.005wt%;
the reaction conditions and product distribution and yield of the fixed bed resid hydrogenation reaction zone, the hydrocracking reaction zone, the solvent deasphalting treatment, and the delayed coking treatment are shown in table 3.
TABLE 3
As can be seen from table 3, when the amount of the dispersed catalyst added is too low, both the residual oil conversion and the yield of the heavy naphtha are not good, and when the amount of the dispersed catalyst added is too high, the residual oil conversion and the yield of the heavy naphtha are equivalent, but on one hand, the catalyst cost is greatly increased, and on the other hand, the excessive addition of the dispersed catalyst causes the blockage of the fixed bed residual oil hydrogenation apparatus, and the operation cycle is greatly shortened.
When the method is used for residual oil hydrogenation, the stability of oil generated by hydrogenation is ensured, the yield of heavy naphtha is higher, low-sulfur petroleum coke with the sulfur content lower than 3.0wt% can be produced, the conversion rate of residual oil is greatly improved, and the transformation utilization of the existing fixed bed residual oil hydrogenation device can be realized under the condition of ensuring that the operation period is not shortened.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (20)
1. A process for hydrogenating a residuum, comprising:
(1) In the presence of hydrogen, introducing a residual oil raw material, a dispersion type catalyst and deasphalted oil into a fixed bed residual oil hydrogenation reaction zone filled with a residual oil hydrotreating catalyst for hydrogenation reaction to obtain hydrogenated oil, wherein the content of toluene insoluble substances in the hydrogenated oil is not more than 0.1wt%, and the dosage of the dispersion type catalyst is 0.01-2.0wt% based on the total weight of the residual oil raw material and the deasphalted oil;
(2) Introducing the hydrogenated oil into a hot high-pressure separator for separation to obtain a gas phase material flow and a liquid phase material flow containing hydrogenated residual oil;
(3) Performing solvent deasphalting treatment on the liquid phase material flow to obtain deasphalted asphalt and deasphalted oil which is circulated to the fixed bed residual oil hydrogenation reaction zone in the step (1) and is subjected to the hydrogenation reaction; and
and introducing the gas phase material flow into a hydrocracking reaction zone filled with a hydrocracking catalyst to carry out hydrocracking reaction, thereby obtaining heavy naphtha.
2. The process of claim 1, wherein the dispersed catalyst is used in an amount of 0.02 to 1.5wt% based on the total weight of the residuum feedstock and deasphalted oil in step (1).
3. The process according to claim 1 or 2, wherein in step (1), the dispersed catalyst has an average particle diameter of 0.1 μm to 25 μm.
4. The process according to any one of claims 1 to 3, wherein, in step (1), the dispersed catalyst is a particulate catalyst containing a metallic element selected from at least one of non-metallic elements of groups IVA and VIA and a non-metallic element selected from at least one of metallic elements of groups VB, VIB, IVA and VIII; based on the total weight of the dispersion catalyst, the content of the metal element is 5-20wt% and the content of the nonmetal element is 80-95wt% calculated by oxide.
5. The method according to claim 4, wherein in step (1), in the dispersed catalyst, the metallic element is selected from at least one of Cr, V, mo, W, ni, fe, co and Sn, and the non-metallic element is selected from at least one of C, si and S.
6. The process of any one of claims 1 to 5, wherein in step (1), the fixed bed residuum hydrogenation reaction zone conditions are at least: hydrogen partial pressure is 1.0-22.0MPa, reaction temperature is 330-470 ℃, volume space velocity is 0.1-3.0h-1The volume ratio of hydrogen to oil is 350-2000;
preferably, the fixed bed residuum hydrogenation reaction zone conditions are at least: hydrogen partial pressure of 8.0-21.0MPa, reaction temperature of 360-460 deg.C, volume space velocity of 0.2-2.5h-1The volume ratio of hydrogen to oil is 400-1500.
7. The method as claimed in any one of claims 1 to 6, wherein the residue hydrotreating catalyst has a bulk density of 300 to 900kg/m in step (1)3Average pore diameter of 5-20nm, pore volume of not less than 0.45ml/g, specific surface area of not less than 90m2/g。
8. The process of any one of claims 1 to 7, wherein in step (1), the residue hydrotreating catalyst is selected from at least one of hydrodemetallization catalysts, hydrogenation protection catalysts, transition catalysts, hydrodesulphurization-denitrification catalysts;
preferably, in the step (1), the residue hydrotreating catalyst contains a carrier selected from at least one of alumina, silica and titania, and an active metal element selected from group vib and/or group viii metal elements supported on the carrier.
9. The process of claim 8, wherein in the residuum hydroprocessing catalyst, the active metal element is selected from at least one of a nickel-tungsten combination, a nickel-tungsten-cobalt combination, a nickel-molybdenum combination, a cobalt-molybdenum combination;
preferably, the active metal element is present in an amount of 0.05 to 25wt% in terms of oxide, based on the total weight of the residuum hydrotreating catalyst.
10. The process according to any one of claims 7 to 9, wherein the residue hydrotreating catalyst further contains at least one auxiliary element selected from boron, germanium, zirconium, phosphorus, chlorine and fluorine;
preferably, the total content of the promoter element, calculated as element, in the residuum hydroprocessing catalyst is from 0.01 to 10 wt.%.
11. The process of any one of claims 1-10, wherein in step (1), the fixed bed residuum hydrogenation reaction zone contains at least 2 fixed bed reactors connected in series;
preferably, the fixed bed residual oil hydrogenation reaction zone contains 2-6 fixed bed reactors which are connected in series in sequence.
12. The process as in any one of claims 1-11, wherein in step (1), the residual hydrotreating catalyst has a bed void fraction e of greater than 0.40, the catalyst has a bed void fraction e = (bed volume-bed packing volume)/bed volume, and the units of bed volume and bed packing volume are the same.
13. The process according to any one of claims 1 to 12, wherein, in step (1), the residue feedstock is selected from at least one of atmospheric residue, vacuum residue, heavy oil;
preferably, the resid feedstock has a density (20 ℃) of greater than 950kg/m3。
14. The process according to any one of claims 1 to 13, wherein in step (2) the conditions of the hot high pressure separator are at least such that: the temperature is 330-450 deg.C, and the pressure is 5-22Mpa.
15. The process according to any one of claims 1 to 14, wherein in step (3), the solvent deasphalting treatment is carried out under conditions at least satisfying: the extraction temperature is 100-300 ℃, the pressure is 0.5-5MPa, and the volume ratio of the solvent to the oil is (5-10): 1;
preferably, the solvent involved in the solvent deasphalting treatment is selected from C5-C8Alkane, C5-C8At least one of olefins, condensate and naphtha.
16. The process of any one of claims 1 to 15, wherein in step (3), the conditions of the hydrocracking reaction zone are at least: hydrogen partial pressure of 5.0-22.0MPa, reaction temperature of 300-450 deg.C, and volume space velocity of 0.1-2.0h-1The volume ratio of hydrogen to oil is 350-2000.
17. The process of any of claims 1-16, wherein the hydrocracking catalyst has a bulk density of 500-1200kg/m3The average pore diameter is 5-20nm, the pore volume is not less than 0.2ml/g, and the specific surface area is not less than 190m2/g。
18. The process as claimed in any one of claims 1 to 17, wherein the hydrocracking catalyst contains a carrier selected from at least one of alumina, silica and titania and an active metal element selected from at least one of nickel, cobalt, molybdenum and tungsten supported on the carrier.
19. The process according to claim 18, wherein in the hydrocracking catalyst, the content of nickel and/or cobalt in terms of oxide is 0 to 30wt%, the content of molybdenum and/or tungsten in terms of oxide is 0 to 35wt%, and the sum of the contents of nickel, cobalt, molybdenum, tungsten in terms of oxide is more than 0, based on the total weight of the hydrocracking catalyst.
20. The process of any one of claims 1-19, further comprising subjecting the deoiled asphalt to a delayed coking process to obtain petroleum coke;
preferably, the conditions of the delayed coking process are at least: the outlet temperature of the heating furnace is 450-600 ℃, the pressure is 0.1-0.5MPa, and the circulation ratio is 0.1-1.
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| CN103102980A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Combined process for in-depth conversion of residual oil |
| CN103789036A (en) * | 2012-10-26 | 2014-05-14 | 中国石油化工股份有限公司 | Combination processing method of inferior heavy oil |
| CN106544055A (en) * | 2015-09-16 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of processing method of inferior heavy oil and/or poor residuum |
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| CN103102980A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Combined process for in-depth conversion of residual oil |
| CN103789036A (en) * | 2012-10-26 | 2014-05-14 | 中国石油化工股份有限公司 | Combination processing method of inferior heavy oil |
| CN106544055A (en) * | 2015-09-16 | 2017-03-29 | 中国石油化工股份有限公司 | A kind of processing method of inferior heavy oil and/or poor residuum |
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