CN109777502B - Oil refinery gas hydrogenation combined processing method - Google Patents
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Abstract
The invention discloses a combined processing method for hydrogenation of refinery gas, which comprises the following steps: (a) mixing the raw diesel oil and the circulating oil with hydrogen in a hydrogen dissolving device, and then adding the mixture into a hydrofining catalyst and a hydro-upgrading catalyst bed in a hydrogenation reactor to react under the condition of liquid-phase hydrogenation operation; (b) mixing the reactant flow obtained in the step (a) with refinery gas and hydrogen in a gas dissolving device, and then allowing the mixture to enter a hydrogenation catalyst bed layer in a supplementary hydrogenation reactor to react under the liquid-phase hydrogenation operation condition; (c) separating the hydrogenation reaction effluent in the step (b) into a gas phase and a liquid phase, continuously separating the gas phase obtained by separation after removing hydrogen sulfide to obtain hydrogen and hydrotreated refinery gas, fractionating the liquid phase obtained by separation to obtain naphtha and clean diesel oil, and returning part of the hydrogenation reaction effluent obtained in the step (a) and/or part of the hydrogenation reaction material flow obtained in the step (b) and/or part of the liquid phase obtained by separation of the high-pressure separator as circulating oil to hydrogen dissolving equipment. The method can simultaneously hydrotreat refinery gas and produce clean diesel.
Description
Technical Field
The invention belongs to a hydrogenation process of an oil refining technology, and relates to a combined hydrogenation processing method for refinery gas, in particular to a combined hydrogenation method for hydrotreating the refinery gas and producing clean diesel oil.
Background
Energy currently worldwide is derived primarily from fossil energy sources, with petroleum being the most prominent source of motor fuel. As the world economy continues to evolve, environmental regulations become more stringent requiring the production of large quantities of light, clean motor fuels, which require improvements and modifications to existing refinery technologies. The quality requirement of diesel oil as important motor fuel is higher and higher, and especially the content of sulfur, density, polycyclic aromatic hydrocarbon and the like is strictly limited, and the hydrogenation modification technology of inferior diesel oil can greatly reduce the sulfur content and the aromatic hydrocarbon content of diesel oil products, and reduce the density, reduce the condensation point and improve the cetane number.
The diesel oil hydrogenation modification technology is the most important means for improving the quality of poor-quality diesel oil fractions and producing clean diesel oil, and the liquid-phase diesel oil hydrogenation technology can meet the requirement of producing clean diesel oil under the condition of greatly reducing energy consumption. US6213835 and US6428686 disclose a hydrogenation process of pre-dissolved hydrogen, CN104560132A discloses a continuous liquid phase diesel oil hydrotreating method, and CN104927902A discloses a diesel oil hydrotreating method, which focuses more on dissolving hydrogen in the diesel oil raw material, and these methods all dissolve hydrogen in the diesel oil raw material to carry out hydrogenation reaction, and do not utilize the residual hydrogen of the reaction, and directly treat it additionally after separation.
Refinery gases generally include dry gases, liquefied gases, and the like, and have various paths for their use. The main application comprises that dry gas is hydrogenated and then used as a raw material for preparing ethylene by steam cracking, liquefied gas is hydrogenated and then used as a raw material for preparing ethylene by steam cracking, a raw material for synthesizing maleic anhydride, liquefied gas for vehicles and the like. In the existing refinery gas hydrogenation technology, CN201410271572.3 discloses a coking dry gas hydrogenation catalyst and a catalyst grading method. The method only solves the problem of controlling the reaction temperature during the hydrogenation of the coking dry gas, but the temperature rise in the reaction process is large. CN201010221244.4 discloses a method for preparing ethylene cracking material by hydrogenation of liquefied petroleum gas, which comprises two reactors, a cooling facility is arranged between the reactors, and CN201310628425.2 discloses a high-temperature hydrogenation purification process of liquefied petroleum gas, wherein olefin saturation and hydrogenation are performed by hydrogenation to remove impurities. As is well known, the hydrogenation reaction of unsaturated hydrocarbons such as olefin, diene, alkyne and the like is a strong exothermic reaction, the temperature rise in the gas hydrogenation process is very large, generally 100-200 ℃, the balance of the hydrogenation reaction is damaged along with the temperature rise, and the generation of carbon deposition is seriously increased, so that the service cycle of the catalyst is reduced.
CN201010221263.7 discloses a liquefied petroleum gas-coker gasoline hydrogenation combination process method, which is a combination method, but not a liquid phase hydrogenation method, the coker gasoline is firstly mixed with hydrogen to carry out fixed bed hydrogenation reaction, and a hydrogenation product and liquefied gas are mixed and enter another reactor, so that the problem of hydrogenation temperature rise of the liquefied gas is only solved.
In summary, in the prior art, the hydrotreating process of refinery gas is a gas phase reaction, the diesel hydrogenation is a liquid phase reaction, and the reaction types of the two are completely different, so the combined method of the refinery gas hydrotreating and the diesel liquid phase hydrogenation modification is rarely reported.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a hydrogenation combination processing method. The method can simultaneously hydrotreat refinery gas and produce clean diesel. The utilization efficiency of hydrogen is improved on the premise of further improving the quality of diesel oil products, the problem of temperature rise in the hydrotreating process of refinery gas is effectively solved, the equipment investment is reduced overall, and the operation energy consumption is reduced.
The invention relates to a refinery gas hydrogenation combined processing method, which comprises the following steps:
(a) mixing the raw diesel oil and the circulating oil with hydrogen in a hydrogen dissolving device, and then sequentially entering a hydrofining catalyst bed and a hydro-upgrading catalyst bed in a diesel hydrogenation reactor to react under the condition of liquid-phase hydrogenation operation;
(b) mixing the reactant flow obtained in the step (a) with refinery gas and hydrogen in a gas dissolving device, and then allowing the mixture to enter a hydrogenation catalyst bed layer in a supplementary hydrogenation reactor to react under the liquid-phase hydrogenation operation condition;
(c) separating the hydrogenation reaction effluent in the step (b) into a gas phase and a liquid phase, continuously separating the gas phase obtained by separation after removing hydrogen sulfide to obtain hydrogen and hydrotreated refinery gas, fractionating the liquid phase obtained by separation to obtain naphtha and diesel oil products, and returning part of the hydrogenation reaction effluent obtained in the step (a) and/or part of the hydrogenation reaction material flow obtained in the step (b) and/or part of the liquid phase obtained by separation of the high-pressure separator as circulating oil to hydrogen dissolving equipment.
In the method, the used diesel raw oil can comprise one or more of straight-run diesel, catalytic diesel, coking diesel, thermal cracking diesel, visbreaking diesel, synthetic diesel, coal tar diesel fraction, coal direct liquefaction diesel, shale oil diesel and other diesel fractions.
In the method, the diesel hydrogenation operation condition is generally 3.0-16.0 MPa of reaction pressure, and the volume airspeed of the diesel raw oil is 0.1h-1~6.0h-1The average reaction temperature is 180-450 ℃, and the ratio of the circulating oil to the diesel raw oil is 0.2: 1-10: 1; the preferable operation conditions are that the reaction pressure is 4.0 MPa-15.0 MPa, and the volume airspeed of the diesel raw oil is 0.2h-1~5.0h-1The average reaction temperature is 200-440 ℃, and the ratio of the circulating oil to the diesel raw oil is 0.5: 1-8: 1.
In the method, the supplementary hydrogenation operation condition is generally that the reaction pressure is 3.0-16.0 MPa, and the volume airspeed of the diesel raw oil is 0.3h-1~40.0h-1The average reaction temperature is 180-450 ℃; the preferable operation conditions are that the reaction pressure is 4.0 MPa-15.0 MPa, and the volume airspeed of the diesel raw oil is 0.5h-1~35.0h-1The average reaction temperature is 200-440 ℃,
in the method, the hydrogenation active component of the hydrofining catalyst is one or more of Co, Mo, W and Ni, the weight content of the hydrogenation active component is 5-70% in terms of oxide, the carrier of the hydrofining catalyst is generally alumina, amorphous silicon aluminum, silicon oxide, titanium oxide and the like, and other auxiliary agents such as P, Si, B, Ti, Zr and the like can be simultaneously contained. The catalyst may be used commercially or may be prepared by methods known in the art. The hydrogenation active component is a catalyst in an oxidation state, and is subjected to conventional vulcanization treatment before use, so that the hydrogenation active component is converted into a vulcanization state. The commercial hydrogenation catalysts mainly comprise hydrogenation catalysts such as 3936, CH-20, FF-14, FF-26, FH-5A, FH-98, FH-DS, FH-UDS series and FZC-41 developed by the Fushu petrochemical research institute (FRIPP), hydrogenation catalysts such as HR-416 and HR-448 of IFP company, and hydrogenation catalysts such as HC-P, HC-K UF-210/220, KF-752, KF-840, KF-848, KF-901 and KF-907 of AKZO company. The hydro-upgrading catalyst is a conventional diesel hydro-upgrading catalyst, and is generally a VIB-group and/or VIII-group catalystThe group VIB metal is Mo and/or W, and the group VIII metal is Co and/or Ni. The carrier of the catalyst is one or more of alumina, silicon-containing alumina and molecular sieve, preferably molecular sieve, and the molecular sieve can be Y-type and/or beta-type molecular sieve. Based on the weight of the catalyst, the content of the VIB group metal is 10 to 35 weight percent calculated by oxide, the content of the VIII group metal is 3 to 15 weight percent calculated by oxide, the content of the molecular sieve is 5 to 40 weight percent, the content of the alumina is 10 to 80 weight percent, and the specific surface area is 100m2/g～650m2The pore volume is 0.15mL/g to 0.50 mL/g. The main catalysts comprise 3963, FC-18, FC-32, FC-14, FC-20 catalysts and the like which are developed by the petrochemical research institute. For the hydrogenation modification catalyst, certain hydrogenation activity and certain cracking activity are required, and both hydrogenation saturation of olefin and aromatic hydrocarbon in diesel oil fraction and ring-opening reaction of saturated aromatic hydrocarbon are required. The hydrogenation catalyst can be placed in one reactor or multiple reactors, and the hydrofining catalyst is placed in the front portion of the hydroupgrading catalyst. The volume ratio of the hydrorefining catalyst to the hydroupgrading catalyst is 20: 80-80: 20, preferably 25: 75-75: 25.
In the method, the catalyst bed layers (including a hydrofining catalyst bed layer and a hydrofining catalyst bed layer) of the hydrogenation reactor in the step (a) are arranged into a plurality of layers, preferably 2-10 layers, and a gas dissolving device is arranged between the adjacent catalyst bed layers; the introduced hydrogen is mixed with the reactant flow in the gas dissolving device and then enters the next catalyst bed layer for reaction.
In the above method, one or more catalyst beds, preferably 2 to 8 catalyst beds, may be provided in the make-up hydrogenation reactor. If only one catalyst bed layer is arranged in the supplementary hydrogenation reactor, the liquid-phase hydrogenation reaction material flow is mixed with the refinery gas in the gas dissolver and then enters the top of the supplementary hydrogenation reactor and passes through the catalyst bed layer; if a plurality of catalyst beds are arranged in the supplementary hydrogenation reactor, a gas dissolving device is arranged between the beds, refinery gas and hydrogen are mixed and then enter any gas dissolving device arranged between adjacent catalyst beds, and are mixed with reactant flow from the previous catalyst bed and then enter the next catalyst bed for reaction.
A preferred embodiment is as follows: the catalyst bed layers of the diesel hydrogenation reactor are arranged into three layers, the catalyst bed layer of the supplementary hydrogenation reactor is arranged into two layers, hydrogen is introduced between the second catalyst and the third catalyst bed layer of the diesel hydrogenation reactor, and hydrogen and refinery gas are introduced between the catalyst bed layers of the supplementary hydrogenation reactor.
In the method, the raw diesel oil and the circulating oil are mixed and then enter from the top of the diesel hydrogenation reactor, the mixture flow dissolved with the hydrogen can pass through the catalyst bed layer from top to bottom in a downward mode, the raw diesel oil and the circulating oil can also enter from the bottom of the hydrogenation reactor after being mixed, and the mixture flow dissolved with the hydrogen can pass through the catalyst bed layer from bottom to top in an upward mode.
In the method, the mixed material flow of the diesel hydrogenation reaction effluent dissolved with the refinery gas enters from the top of the supplementary hydrogenation reactor, the mixed material flow dissolved with the refinery gas can pass through the catalyst bed layer from top to bottom, the mixed material flow of the diesel hydrogenation reaction effluent dissolved with the refinery gas can also enter from the bottom of the supplementary hydrogenation reactor, and the mixed material flow dissolved with the refinery gas can pass through the catalyst bed layer from bottom to top.
In the above method, the previous catalyst bed or the next catalyst bed is based on the flowing direction of the reactant flow, and whether the hydrogenation reaction is an upflow type or a downflow type, the bed in the adjacent beds which is contacted with the reactant flow first is an upper bed and then is a lower bed.
In the method, the refinery gas may comprise one or more of dry gas, liquefied gas and the like. The source of the gas can be one or more of coking, catalytic cracking, thermal cracking, visbreaking and the like.
In the method, if hydrogen and refinery gas are introduced simultaneously in any process, the volume ratio of the introduced hydrogen to the refinery gas is 1: 1-100: 1, preferably 1: 1-50: 1.
In the method, the hydrogenation reaction effluent is separated by a high-pressure separator and/or a low-pressure separator. The high-pressure separator is a conventional gas-liquid separator. The hydrogenation reaction flow is separated in a high-pressure separator to obtain gas and liquid. The low-pressure separator is a conventional gas-liquid separator. The liquid obtained by separation in the high-pressure separator is separated in the high-low pressure separator to obtain gas and liquid.
In the method, the fractionating system used for fractionating comprises a stripping tower and/or a fractionating tower. And the liquid obtained by separation in the low-pressure separator is subjected to steam stripping and/or fractionation in a fractionation system to obtain a naphtha product and a diesel product.
In the above method, the gas separator used for gas separation is a conventional separator. The gas obtained by separation in the high-pressure separator and the gas obtained by separation in the low-pressure separator are mixed, hydrogen sulfide is removed, then hydrogen, dry gas, liquefied gas and the like are obtained by separation in the gas separator, and if liquid products exist, the gas directly enters a stripping tower and/or a fractionating tower.
In the process of gas hydrogenation, the temperature rise of a catalyst bed layer is large due to large reaction heat release, so that the temperature range of the hydrogenation reaction is large, the effect of the hydrogenation reaction is influenced, the generation of carbon deposition of the catalyst is accelerated, and the service cycle of the catalyst is shortened. In the diesel oil liquid phase hydrogenation modification process, hydrogenation reaction is realized through hydrogen dissolved in oil, and the purpose of producing clean diesel oil products is achieved, but the dissolved hydrogen is excessive and cannot be completely reacted, and the hydrogen dissolved in the hydrogenated oil after the reaction is completed can usually remain 20% -70% of the dissolved hydrogen, so that the hydrogen is not used effectively, namely, the energy consumption is increased.
According to the invention, by fully utilizing the characteristic that a large amount of hydrogen is still dissolved in the oil generated by the diesel liquid-phase circulation hydrogenation modification process, a supplementary hydrogenation reactor is arranged in the subsequent stage of the diesel hydrogenation reactor, the refinery gas raw material is dissolved in the diesel hydrogenation reactant flow and enters the catalyst bed layer of the supplementary hydrogenation reactor, and the hydrogenation reaction of the gas is completed by utilizing the dissolved hydrogen and the catalyst atmosphere, so that the problem of large gas hydrogenation temperature rise is solved, and the hydrogen dissolved in the diesel is used for the gas hydrogenation reaction, thereby reducing the hydrogen consumption; or a plurality of catalyst beds are arranged in a further supplementary hydrogenation reactor, part of dry gas or all dry gas raw materials in the mixed gas and diesel oil hydrogenation generated oil are mixed and enter the first catalyst bed, and the rest gas and/or hydrogen gas mixed mixture enters the subsequent catalyst bed, so that the hydrogen consumption is low, the dry gas which is easiest to react firstly carries out hydrogenation reaction, then liquefied gas with slightly higher hydrogen consumption enters the subsequent catalyst bed for reaction, and the liquefied gas is supplemented and enters the inlet of the subsequent catalyst bed when the hydrogen gas is required to be supplemented; the hydroupgrading reactant flow continuously passes through the supplementary hydrorefining catalyst bed layer, so that the unsaturated hydrocarbon generated by hydroupgrading can be subjected to supplementary hydrorefining reaction, the post-refining catalyst in the hydroupgrading reactor can be saved, or the quality of diesel oil is further improved. The combination method is characterized in that the gas hydrogenation process is completed on the premise of not influencing the quality of the diesel oil product or further improving the quality of the diesel oil product to obtain the diesel oil product and the gas product, and the two technologies are optimally combined, so that the hydrogen dissolved in the diesel oil product is reduced, namely, the hydrogen consumption and the energy consumption are reduced, the equipment investment is saved, and the operation cost is reduced.
Drawings
FIG. 1 is a flow diagram of a hydrogenation combination process of the present invention.
Wherein: 1-raw oil, 2-raw oil pump, 3-cycle oil, 4-hydrogen dissolver, 5-new hydrogen, 6-refinery gas raw material, 7-diesel hydrogenation reactor, 8-vent valve, 9-diesel hydrogenation reaction stream, 10-high pressure separator, 11-low pressure separator, 12-stripping/fractionating system, 13-stripping gas, 14-naphtha, 15-diesel, 16-high pressure separator gas, 17-low pressure separator gas, 18-gas separator, 19-hydrogen, 20-dry gas, 21-liquefied gas, 22-gas dissolver, 23-supplementary hydrogenation reactor, 24-supplementary hydrogenation reaction stream.
Detailed Description
The flow and effect of the hydrogenation combination method of the present invention will be further illustrated with reference to the following examples, which should not be construed as limiting the process of the present invention.
The specific implementation mode of the hydrogenation combination method is as follows: raw oil 1 is mixed with cycle oil 3, the mixed material and hydrogen are mixed in a hydrogen dissolver 4 and then enter a diesel hydrogenation reactor 7, a diesel hydrogenation reactant stream 9 and a refinery gas raw material are mixed in a gas dissolver 22 and then enter a supplementary hydrogenation reactor 23, a supplementary hydrogenation reactant stream 24 enters a high-pressure separator 10, a high-pressure separator gas 16 and liquid are obtained by separation in the high-pressure separator 10, the liquid enters a low-pressure separator 11 and is separated in the low-pressure separator 11 to obtain a low-pressure separator gas 17 and liquid, the liquid and a liquid component obtained by separation in the gas separator 18 are mixed and then enter a stripping/fractionating system 12, naphtha 14 and diesel 15 are obtained by fractionation in the fractionating system under the action of a stripping gas 13, the high-pressure separator gas 16 and the low-pressure separator gas 17 are mixed and then enter the gas separator 18, and hydrogen is obtained by separation in the gas separator 18, Dry gas and liquefied gas products. The recycle oil 3 can be obtained directly from the diesel hydrogenation reaction material flow 9, and can also be obtained from the liquid obtained by the separation in the high-pressure separator 10.
The following examples further illustrate specific aspects of the present invention. Experimental studies were performed using FH-UDS-6/FC-32 catalyst (volume ratio 60: 40) developed and produced by FRIPP development.
TABLE 1 Main Properties of Diesel feedstocks
| Diesel fuel feedstock | |
Raw oil 2 |
| Density, g/cm3 | 0.935 | 0.883 |
| Range of distillation range, deg.C | 135~360 | 140~376 |
| Sulfur content, wt.% | 1.0 | 1.5 |
| Cetane number | 32 | 45 |
TABLE 2 refinery gas feedstock key properties
| Refinery gas feedstock | Dry gas | Liquefied gas | Mixed gas |
| Gas composition | |||
| H2 | 7.0 | 0 | 3.5 |
| CH4 | 12.6 | 0 | 2.9 |
| C2H6 | 55.3 | 0 | 27.1 |
| C2H4 | 5.6 | 0.1 | 4.6 |
| C3 H8 | 10.8 | 16.0 | 13.6 |
| C3 H6 | 2.7 | 6.5 | 4.5 |
| C3 H4 | 0 | 0 | 0 |
| C4 H10 | 5.3 | 34.5 | 20.5 |
| C4 H8 | 0.5 | 33.1 | 19.1 |
| C4 H6 | 0 | 1.2 | 0.5 |
| C5 + | 0.1 | 8.6 | 3.6 |
| CO | 0.005 | 0 | 0.002 |
| CO2 | 0.01 | 0 | 0.008 |
Table 3 examples process conditions and main product properties
| Process conditions | Example 1 | Examples2 | Example 3 | Example 4 | Example 5 |
| Hydrogenation reactor operating conditions | |||||
| Raw oil | Raw oil 1 | Raw oil 1 | Raw oil 1 | Raw oil 2 | Raw oil 2 |
| Operating conditions of diesel hydrogenation reactor | |||||
| Reaction pressure, MPa | 13.0 | 10.0 | 10.0 | 8.0 | 12.0 |
| Average reaction temperature,. degree.C | 380 | 350 | 350 | 355 | 375 |
| Volume space velocity of fresh raw oil, h-1 | 0.6 | 1.0 | 1.0 | 0.8 | 1.5 |
| Circulation ratio | 3:1 | 2.5:1 | 2.5:1 | 4:1 | 3:1 |
| Make-up of hydrogenation reactor operating conditions | |||||
| Refinery gas feedstock at reactor inlet | Dry gas | Mixed gas | Dry gas | Liquefied gas | Mixed gas |
| Reaction pressure, MPa | 13.0 | 10.0 | 10.0 | 8.0 | 12.0 |
| Average reaction temperature,. degree.C | 380 | 350 | 350 | 355 | 375 |
| Volume space velocity of fresh raw oil, h-1 | 15 | 20 | 20 | 10 | 30 |
| Two-bed inlet refinery gas raw material | — | — | Liquefied gas | — | — |
| Hydrogen dissolved in the inlet of the two-bed layer and refinery gas sourceVolume ratio of materials | — | — | 95:5 | — | — |
| Dry gas product | |||||
| Olefin content, v% | 0 | 0 | 0 | 0 | 0 |
| Liquefied gas product | |||||
| Olefin content, v% | 0 | 0 | 0 | 0 | 0 |
| CO+CO2，µg/g | 0 | 0 | 0 | 0 | 0 |
| Naphtha product | |||||
| Sulphur content, μ g/g | 0.2 | 0.4 | 0.4 | 0.3 | 0.2 |
| Diesel oil product | |||||
| Density, g/cm3 | 0.845 | 0.850 | 0.850 | 0.845 | 0.842 |
| Sulphur content, μ g/g | 6.6 | 4.5 | 4.5 | 3.5 | 1.6 |
| Cetane number | 46 | 45 | 45 | 51 | 52 |
It can be seen from the examples that diesel feedstock and refinery gas feedstock can be directly produced into clean diesel product and clean gas product by the hydrogenation combination process of the present technology.
Claims (11)
1. The refinery gas hydrogenation combination method is characterized in that: the method comprises the following steps:
(a) mixing the raw diesel oil and the circulating oil with hydrogen in a hydrogen dissolving device, and then sequentially entering a hydrofining catalyst bed and a hydro-upgrading catalyst bed in a diesel hydrogenation reactor to react under the condition of liquid-phase hydrogenation operation;
(b) mixing the reactant flow obtained in the step (a) with refinery gas and hydrogen in a gas dissolving device, and then allowing the mixture to enter a hydrogenation catalyst bed layer in a supplementary hydrogenation reactor to react under the liquid-phase hydrogenation operation condition;
(c) separating the hydrogenation reaction effluent in the step (b) into a gas phase and a liquid phase, continuously separating the gas phase obtained by separation after removing hydrogen sulfide to obtain hydrogen and hydrotreated refinery gas, fractionating the liquid phase obtained by separation to obtain naphtha and diesel oil products, and returning part of the hydrogenation reaction effluent obtained in the step (a) and/or part of the hydrogenation reaction material flow obtained in the step (b) and/or part of the liquid phase obtained by separation of a high-pressure separator as circulating oil to hydrogen dissolving equipment;
the method comprises the steps that three catalyst beds are arranged in a diesel hydrogenation reactor, two catalyst beds are arranged in a supplementary hydrogenation reactor, gas dissolving equipment is arranged between the beds, hydrogen enters the gas dissolving equipment between the beds of the diesel hydrogenation reactor, hydrogen and refinery gas enter the gas dissolving equipment between the beds of the supplementary hydrogenation reactor, and when the hydrogen and the refinery gas are introduced at the same time, the volume ratio of the introduced hydrogen to the refinery gas is 1: 1-100: 1.
2. The method of claim 1, wherein: the diesel raw oil is one or more of straight-run diesel, catalytic diesel, coking diesel, thermal cracking diesel, synthetic diesel, coal tar diesel fraction, coal direct liquefaction diesel and shale oil diesel.
3. The method of claim 1, wherein: the diesel hydrogenation operation conditions are that the reaction pressure is 3.0MPa to 16.0MPa, and the volume airspeed of the diesel raw oil is 0.1h-1~6.0h-1The average reaction temperature is 180-450 ℃, and the ratio of the circulating oil to the diesel raw oil is 0.2: 1-10: 1.
4. The method of claim 3, wherein: the diesel hydrogenation operation conditions are that the reaction pressure is 4.0 MPa-15.0 MPa, and the volume airspeed of the diesel raw oil is 0.2h-1~5.0h-1The average reaction temperature is 200-440 ℃, and the ratio of the circulating oil to the diesel raw oil is 0.5: 1-8: 1.
5. The method of claim 1, wherein: the supplementary hydrogenation operation conditions are that the reaction pressure is 3.0MPa to 16.0MPa, and the volume airspeed of the diesel raw oil is 0.3h-1~40.0h-1The average reaction temperature is 180-450 ℃.
6. The method of claim 5, wherein: the supplementary hydrogenation operation conditions are that the reaction pressure is 4.0MPa to 15.0MPa, and the volume airspeed of the diesel raw oil is 0.5h-1~30.0h-1The average reaction temperature is 200-440 ℃.
7. The method of claim 1, wherein: the hydrogenation active components of the hydrofining catalyst used in the diesel hydrogenation reactor and the hydrogenation catalyst used in the supplementary hydrogenation reactor are one or more of Co, Mo, W and Ni, the weight content of the hydrogenation active components is 5-70% by weight calculated by oxides, and the carrier of the hydrogenation catalyst is one or more of alumina, amorphous silicon aluminum, silicon oxide and titanium oxide.
8. The method of claim 1, wherein: the hydro-upgrading catalyst used in the diesel hydrogenation reactor takes VIB group and/or VIII group metals as active components, the carrier is alumina containing Y type and/or beta type molecular sieves, the VIB group metal content is 10wt% -35 wt% calculated by oxides, the VIII group metal content is 3wt% -15 wt% calculated by oxides, and the molecular sieve content is 5wt% -40 wt%.
9. The method of claim 1, wherein: the volume ratio of the hydrofining catalyst to the hydro-upgrading catalyst is 20: 80-80: 20.
10. The method of claim 9, wherein: the volume ratio of the hydrofining catalyst to the hydro-upgrading catalyst is 25: 75-75: 25.
11. The method of claim 1, wherein: the refinery gas is one or more of dry gas and liquefied gas, and the gas is one or more of coking, catalytic cracking and thermal cracking reaction.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101880549A (en) * | 2009-05-06 | 2010-11-10 | 中国石油化工股份有限公司 | Hydrogenation method for liquefied gas fraction |
| CN102268293A (en) * | 2010-06-07 | 2011-12-07 | 中国石油化工集团公司 | Hydrogenation combined process |
| CN104560132A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for hydrotreatment of continuous liquid-phase wax oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101880549A (en) * | 2009-05-06 | 2010-11-10 | 中国石油化工股份有限公司 | Hydrogenation method for liquefied gas fraction |
| CN102268293A (en) * | 2010-06-07 | 2011-12-07 | 中国石油化工集团公司 | Hydrogenation combined process |
| CN104560132A (en) * | 2013-10-29 | 2015-04-29 | 中国石油化工股份有限公司 | Method for hydrotreatment of continuous liquid-phase wax oil |
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