CN109777518B - Refinery gas hydrogenation combination method - Google Patents
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Abstract
The invention discloses a refinery gas hydrogenation combination method, which comprises the following steps: (a) mixing wax oil raw oil and circulating oil, mixing the mixture with hydrogen in hydrogen dissolving equipment or mixing the mixture with hydrogen and refinery gas, and allowing the mixture to enter a hydrogenation catalyst bed layer to react under the hydrogenation operation condition, wherein the catalyst bed layer is provided with a plurality of layers, and the gas dissolving equipment is arranged between adjacent catalyst bed layers; (b) mixing refinery gas and/or hydrogen, entering a gas dissolving device arranged between any adjacent catalyst bed layers, mixing the refinery gas and/or hydrogen with a reactant flow from the previous catalyst bed layer, and entering the next catalyst bed layer for reaction; (c) separating the hydrogenation reaction effluent into a gas phase and a liquid phase, continuously separating the separated gas phase to obtain hydrogen and hydrotreated refinery gas, fractionating the separated liquid phase to obtain naphtha, diesel oil and hydrogenated wax oil, and returning part of the hydrogenation reaction effluent and/or the separated liquid phase as circulating oil to hydrogen dissolving equipment. The method can simultaneously carry out hydrotreatment on refinery gas and produce hydrogenated wax oil.
Description
Technical Field
The invention belongs to a hydrogenation process of an oil refining technology, and relates to a refinery gas hydrogenation combination method, in particular to a hydrogenation combination method for hydrotreating refinery gas and producing hydrogenated wax oil.
Background
Energy currently worldwide is derived primarily from fossil energy sources, with petroleum being the most prominent source of motor fuel. Petroleum belongs to non-renewable energy resources, resources are increasingly exhausted, the trend of heavy and poor petroleum is increased, the continuous development of world economy and the stricter environmental protection regulations require the production of a large amount of light clean fuel, and the improvement and improvement of the existing oil refining technology are required, and meanwhile, new petroleum substitutes are added, so that products meeting the requirements are produced at the lowest cost. Catalytic cracking is one of important means for the conversion of heavy oil into light oil, but with the deterioration and the heavy conversion of catalytic cracking processing raw materials, the operation conditions are more and more rigorous, the yield of light products and the properties of the products are poor, and the hydrotreating technology of the catalytic cracking raw materials can not only remove the contents of impurities such as sulfur, nitrogen, metals and the like, but also improve the cracking performance of feeding materials and reduce the severity of FCC operation; the product distribution is improved, and the selectivity of the target product is improved; the yield of dry gas and coke is reduced, and the economical efficiency of an FCC device is improved; the sulfur content of the target product is reduced; reduce the content of SOx and NOx in the regenerated flue gas, and the like.
The wax oil hydrogenation technology is the most important means for improving the quality of catalytic cracking products and realizing clean production, and the liquid phase wax oil hydrogenation technology can meet the requirement of clean diesel oil production 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 wax oil hydrotreating method, and CN104927902A discloses a wax oil hydrotreating method, which focuses more on dissolving hydrogen in the wax oil raw material, and these methods all dissolve hydrogen in the wax oil raw material to carry out hydrogenation reaction, and do not utilize the residual hydrogen, 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 wax oil hydrogenation is a liquid phase reaction, and the reaction types of the two are completely different, so the combined method of the hydrotreating process of refinery gas and the liquid phase hydrogenation of wax oil has been reported.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a hydrogenation combination method. The method can simultaneously carry out hydrotreatment on refinery gas and produce hydrogenated wax oil. The utilization efficiency of hydrogen is improved on the premise of not influencing the quality of wax oil products, the problem of temperature rise in the hydrotreating process of refinery gas is effectively solved, the equipment investment is reduced, and the operation energy consumption is reduced.
The refinery gas hydrogenation combination method comprises the following steps:
(a) mixing wax oil raw oil and circulating oil, mixing the mixture with hydrogen in a hydrogen dissolving device or mixing the mixture with hydrogen and refinery gas, and then entering a hydrogenation catalyst bed layer in a hydrogenation reactor to react under the condition of hydrogenation operation, wherein the catalyst bed layer is provided with a plurality of layers, preferably 2-8 layers, and the gas dissolving device is arranged between adjacent catalyst bed layers;
(b) mixing refinery gas and/or hydrogen, entering a gas dissolving device arranged between any adjacent catalyst bed layers, mixing the refinery gas and/or hydrogen with a reactant flow from the previous catalyst bed layer, and entering the next catalyst bed layer for reaction;
(c) separating the hydrogenation reaction effluent into a gas phase and a liquid phase, continuously separating the gas phase obtained by separation to obtain hydrogen and hydrotreated refinery gas, fractionating the liquid phase obtained by separation to obtain naphtha and wax oil products, and returning part of the hydrogenation reaction effluent and/or the liquid phase obtained by separation of the high-pressure separator as circulating oil to hydrogen dissolving equipment.
In the above method, the wax oil raw material oil used may include one or more of straight-run wax oil, coker wax oil, thermally cracked wax oil, visbreaker wax oil, synthetic wax oil, coal tar wax oil fraction, coal direct liquefaction wax oil, shale oil wax oil, and other wax oil fractions, or may be a portion of catalytically cracked light cycle oil, naphthenic straight-run diesel, coal tar diesel fraction, and other inferior diesel fractions mixed in the wax oil raw material oil.
In the method, the hydrogenation operation condition is generally 3.0MPa to 20.0MPa of reaction pressure, and the volume space velocity of the wax oil raw material oil is 0.2h-1~8.0h-1The average reaction temperature is 180-450 ℃, and the ratio of the circulating oil to the wax oil raw oil is 0.5: 1-10: 1; the preferable operation conditions are that the reaction pressure is 4.0 MPa-18.0 MPa, and the volume space velocity of the wax oil raw material oil is 0.5h-1~6.0h-1The average reaction temperature is 200-440 ℃, and the ratio of the circulating oil to the wax oil raw oil is 0.6: 1-8: 1.
In the method, the hydrogenation active component in the hydrogenation catalyst is one or more of Co, Mo, W and Ni, the weight content of the hydrogenation active component is 5-70% by weight calculated by oxide, the carrier of the hydrogenation 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 3926, 3936, CH-20, FF-14, FF-18, FF-24, FF-26, FF-36, FF-46, FF-56, FH-98, FH-UDS and FZC-41 developed by the Fushu petrochemical research institute (FRIPP), hydrogenation catalysts such as HR-406, HR-416 and HR-448 of IFP company, hydrogenation catalysts such as ICR154, ICR174, ICR178 and ICR179 of CLG company, hydrogenation catalysts such as HC-P, HC-K UF-210/220 newly developed by UOP company, hydrogenation catalysts such as TK-525, TK-555 and TK-557 of Topsor company, KF-752, KF-756, KF-757, KF-840, KF-848, KF-901, KF-907 and the like hydrogenation catalysts of AKZO corporation.
In the method, preferably, the wax oil raw oil and the circulating oil are mixed and then mixed with hydrogen in a hydrogen dissolving device, and then enter a hydrogenation catalyst bed layer to react under the hydrogenation operation condition, and the hydrogenation catalyst passing through the reaction material firstly accounts for 10-80% of the volume of all the hydrogenation catalysts, preferably 20-70%, and most preferably 30-60%, and then the refinery gas is introduced.
In the method, the wax oil raw oil and the circulating oil are mixed and then enter from the top of the hydrogenation reactor, the mixed material flow in which the hydrogen and/or the hydrogen-refinery gas is dissolved can pass through the catalyst bed layer from top to bottom in a downward mode, the wax oil raw oil and the circulating oil are mixed and then can also enter from the bottom of the hydrogenation reactor, and the mixed material flow in which the hydrogen and/or the hydrogen-refinery gas is dissolved can pass through the catalyst bed layer from bottom to top in an upward mode.
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, the dry gas and the liquefied gas in the refinery gas in the step (b) are independently mixed with hydrogen and then respectively enter the gas dissolving equipment arranged between different adjacent catalyst bed layers, and the height of the catalyst bed layer through which the dry gas and the hydrogen are mixed is higher than that of the catalyst bed layer through which the liquefied gas and the hydrogen are mixed. One particularly preferred embodiment is as follows: three catalyst beds are arranged in the hydrogenation reactor, gas dissolving devices are arranged between adjacent catalyst beds, all dry gas or part of dry gas and hydrogen are mixed and then enter the gas dissolving devices between the first catalyst bed and the second catalyst bed, and liquefied gas, hydrogen and the rest dry gas are mixed and then enter the gas dissolving devices between the second catalyst bed and the third catalyst bed. The dry gas entering the space between the first catalyst bed layer and the second catalyst bed layer accounts for 50-100% of the volume of the whole dry gas raw material.
In the method, the volume ratio of the hydrogen introduced in the step (b) to the refinery gas is 2: 1-200: 1, preferably 5: 1-150: 1, and more preferably 10: 1-100: 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 naphtha, diesel oil and hydrogenated wax oil.
In the above method, the gas separator used for gas separation is a conventional separator. And the gas obtained by separation in the high-pressure separator and the gas obtained by separation in the low-pressure separator are mixed and then separated in the gas separator to obtain hydrogen, dry gas, liquefied gas and the like, and if a liquid product exists, the gas directly enters a stripping tower and/or a fractionating tower.
Hydrogen dissolved in the wax oil liquid phase hydrogenation process is excessive, and a large amount of hydrogen can be dissolved in hydrogenation generated oil after the reaction is finished, so that the hydrogen is not used effectively, namely, the energy consumption is increased; 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. Research results show that the refinery gas and the incompletely hydrotreated material of the wax oil have higher solubility and the refinery gas has higher saturation in a liquid phase, and the refinery gas can be effectively dissolved in the wax oil flow for hydrogenation reaction. In the wax oil liquid phase circulation hydrogenation device, a gas raw material and hydrogen are mixed and enter a plurality of catalyst bed layers behind the device, the aim of producing hydrogenation purified gas is achieved by utilizing higher reaction pressure, higher-activity hydrogenation catalyst and hydrogen atmosphere fused into a liquid phase, the utilization efficiency of the hydrogen is improved on the premise of not influencing the quality of wax oil products, the equipment investment is reduced overall, and the operation energy consumption is reduced.
In the prior art, wax oil raw materials can be used for producing hydrogenated wax oil by a liquid phase circulating hydrogenation method, dry gas raw materials are used for producing dry gas products by a fixed bed hydrogenation method, and liquefied gas raw materials are used for producing liquefied gas products by a fixed bed hydrogenation method. The gas has certain solubility in liquid, which is the principle of the development of wax oil liquid phase circulation hydrogenation technology, namely, the hydrogenation reaction is realized by utilizing hydrogen dissolved in wax oil, wherein the catalyst of the first bed layer plays the largest role, and a large amount of hydrodesulfurization reaction which easily occurs all occur in the bed layer. However, the dissolved hydrogen cannot be completely reacted, and a large amount of hydrogen can be remained in the reaction product, and usually 20% -70% of the dissolved hydrogen can be remained. The solubility of dry gas and liquefied gas as organic gas in wax oil is larger, and the dissolving amount of hydrogen can be increased in the presence of hydrogen. And the dissolved dry gas and liquefied gas are easy to generate hydrogenation reaction in the atmosphere of catalyst and hydrogen, thus realizing the purpose of producing clean gas. According to the invention, by fully utilizing the characteristic that the wax oil liquid phase circulation hydrogenation process needs to dissolve hydrogen, in order to reduce the influence of dissolved gas on the original wax oil hydrogenation as much as possible, the gas raw material mixed hydrogen enters the catalyst bed layer behind the first catalyst bed layer, the hydrogenation reaction of the gas is completed by utilizing the atmosphere of hydrogen and the catalyst, and the hydrogen can be more dissolved in the wax oil raw material to promote the hydrogenation reaction of the wax oil; or further mixing part of dry gas or all dry gas raw materials in the mixed gas with hydrogen to enter a second catalyst bed layer, and mixing the rest gas with the hydrogen to enter a subsequent catalyst bed layer, wherein the main characteristics are low olefin content in the dry gas, low hydrogen consumption, small quantity of required active centers, short reaction desorption process time and minimized influence on wax oil hydrogenation reaction, and the gas with relatively high hydrogen consumption is introduced into the subsequent catalyst bed layer with relatively low hydrogen consumption in wax oil hydrogenation, so that the influence on the wax oil hydrogenation effect is reduced. The combination method is generally characterized in that the gas hydrogenation process is completed on the premise of not influencing the quality of the hydrogenated wax oil to obtain a wax oil product and a gas product, and the two technologies are optimally combined to save equipment investment and operation cost.
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-gas raw material, 6-1-dry gas raw material, 6-2-liquefied gas raw material, 7-reactor, 8-exhaust valve, 9-hydrogenation reaction flow, 10-high pressure separator, 11-low pressure separator, 12-stripping/fractionating system, 13-stripping gas, 14-naphtha, 15-diesel oil, 16-hydrogenation wax oil, 17-high pressure separator gas, 18-low pressure separator gas, 19-gas separator, 20-hydrogen, 21-dry gas and 22-liquefied gas.
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 and cycle oil 3 are mixed, the mixed material and hydrogen are mixed in a hydrogen dissolver 4 and then enter a reactor 7, and pass through a first catalyst bed layer, the hydrogen and gas raw materials are dissolved in the effluent of the first catalyst bed layer and pass through a second catalyst bed layer, the hydrogen and gas raw materials are dissolved in the effluent of the second catalyst bed layer, pass through a third catalyst bed layer, the hydrogenation reaction material flow 9 of the third catalyst bed layer enters a high-pressure separator 10, high-pressure separator gas 17 and liquid are obtained by separation in the high-pressure separator 10, the liquid enters a low-pressure separator 11, low-pressure separator gas 18 and liquid are obtained by separation in the low-pressure separator 11, the liquid and liquid components obtained by separation in a gas separator 19 are mixed and then enter a stripping/fractionating system 12, naphtha 14, diesel 15 and hydrogenation wax oil 16 are obtained by fractionation under the action of stripping gas 13 in the fractionating system, the high pressure separator gas 17 and the low pressure separator gas 18 are mixed and then enter a gas separator 19, and hydrogen, dry gas and liquefied gas products are obtained through separation in the gas separator 19. The recycle oil 3 may be obtained directly from the hydrogenation reaction stream 9 or may be obtained by separating the resulting liquid in the high pressure separator 10.
The following examples further illustrate specific aspects of the present invention. Experimental studies were conducted using FF-24 catalyst developed and produced by FRIPP.
TABLE 1 wax oil feedstock Primary Properties
| Wax oil feedstock | Raw oil 1 | Raw oil 2 |
| Density, g/cm3 | 0.923 | 0.945 |
| Range of distillation range, deg.C | 345~540 | 300~600 |
| Sulfur content, wt.% | 1.5 | 2.3 |
TABLE 2 gas feed principal Properties
| Gaseous 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 | Example 2 | Example 3 | Example 4 | Example 5 |
| Reaction pressure, MPa | 12.0 | 8.0 | 8.0 | 10.0 | 16.0 |
| Raw oil | Raw oil 1 | Raw oil 1 | Raw oil 1 | Raw oil 2 | Raw oil 2 |
| Circulation ratio | 3:1 | 2.5:1 | 2.5:1 | 4:1 | 3:1 |
| Gaseous feedstock | Dry gas | Mixed gas | Dry gas and liquefied gas | Liquefied gas | Mixed gas |
| Volume ratio of dissolved hydrogen to gas feed | 90:10 | 95:5 | 95:5 | 97:3 | 93:7 |
| Volume space velocity of fresh raw oil, h-1 | 2.0 | 1.0 | 1.0 | 0.8 | 1.5 |
| Average reaction temperature,. degree.C | 370 | 360 | 360 | 375 | 385 |
| Gas raw material at inlet of two bed layers | — | — | Dry gas | — | — |
| Volume ratio of hydrogen and gas raw material dissolved into inlet of two bed layers | — | — | 80:20 | — | — |
| Three-bed inlet gas feedstock | — | — | Liquefied gas | — | — |
| Volume ratio of hydrogen and gas raw material dissolved in three-bed layer inlet | — | — | 90:10 | — | — |
| 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 | 0.3 | 0.4 | 0.3 | 0.3 | 0.4 |
| Diesel oil product | |||||
| Density, g/cm3 | 0.864 | 0.867 | 0.867 | 0.886 | 0.873 |
| Sulphur content, μ g/g | 150 | 240 | 230 | 400 | 130 |
| Hydrogenated wax oil | |||||
| Density, g/cm3 | 0.885 | 0.889 | 0.889 | 0.912 | 0.899 |
| Sulphur content, μ g/g | 400 | 1500 | 1470 | 2000 | 300 |
It can be seen from the examples that wax oil feedstock and gas feedstock can be directly produced into hydrogenated wax oil product and clean gas product by the hydrogenation combination process of the present technology.
Claims (16)
1. A refinery gas hydrogenation combination method is characterized in that: the method comprises the following steps:
(a) mixing wax oil raw oil and circulating oil, mixing the mixture with hydrogen in hydrogen dissolving equipment or mixing the mixture with hydrogen and refinery gas, and allowing the mixture to enter a hydrogenation catalyst bed layer to react under the hydrogenation operation condition, wherein the catalyst bed layer is provided with a plurality of layers, and the gas dissolving equipment is arranged between adjacent catalyst bed layers;
(b) mixing refinery gas and/or hydrogen, entering a gas dissolving device arranged between any adjacent catalyst bed layers, mixing the refinery gas and/or hydrogen with a reactant flow from the previous catalyst bed layer, and entering the next catalyst bed layer for reaction;
(c) separating the hydrogenation reaction effluent into a gas phase and a liquid phase, continuously separating the gas phase obtained by separation to obtain hydrogen and hydrotreated refinery gas, fractionating the liquid phase obtained by separation to obtain naphtha, diesel oil and hydrogenated wax oil, and returning part of the hydrogenation reaction effluent and/or the liquid phase obtained by separation of the high-pressure separator as circulating oil to the hydrogen dissolving equipment.
2. The method of claim 1, wherein: the catalyst bed layer is arranged into 2-8 layers.
3. The method of claim 1, wherein: the wax oil raw material oil is one or more of straight-run wax oil, coked wax oil, thermal cracking wax oil, visbreaking wax oil, synthetic wax oil, coal tar wax oil fraction, coal direct liquefaction wax oil and shale oil wax oil, or one or more of part of catalytic cracking light cycle oil, naphthenic straight-run diesel oil and coal tar diesel oil fraction is mixed in the wax oil raw material oil.
4. The method of claim 1, wherein: the hydrogenation operation conditions are that the reaction pressure is 3.0MPa to 20.0MPa, and the volume airspeed of the wax oil raw material oil is 0.2h-1~8.0h-1The average reaction temperature is 180-450 ℃, and the ratio of the circulating oil to the wax oil raw oil is 0.5: 1-10: 1.
5. The method of claim 4, wherein: the hydrogenation operation condition is that the reaction pressure is 4.0The pressure is between MPa and 18.0MPa, and the volume space velocity of the wax oil raw material oil is 0.5h-1~6.0h-1The average reaction temperature is 200-440 ℃, and the ratio of the circulating oil to the wax oil raw oil is 0.6: 1-8: 1.
6. The method of claim 1, wherein: the hydrogenation catalyst comprises one or more of Co, Mo, W and Ni as hydrogenation active components, the weight content of the hydrogenation active components is 5-70% by weight calculated by oxides, and the carrier of the hydrogenation catalyst is at least one of alumina, amorphous silicon aluminum, silicon oxide and titanium oxide.
7. The method of claim 1, wherein: mixing the wax oil raw oil and the circulating oil, mixing the mixture with hydrogen in a hydrogen dissolving device, then entering a hydrogenation catalyst bed layer to react under the hydrogenation operation condition, and introducing refinery gas after the reaction material firstly passes through a hydrogenation catalyst accounting for 10-80% of the volume of all the hydrogenation catalysts.
8. The method of claim 1, wherein: the wax oil raw oil and the circulating oil are mixed and then enter from the top of the hydrogenation reactor, the mixed material flow in which the hydrogen and/or the refinery gas are dissolved passes through the catalyst bed layer from top to bottom in a downward mode, or the wax oil raw oil and the circulating oil are mixed and then enter from the bottom of the hydrogenation reactor, and the mixed material flow in which the hydrogen and/or the refinery gas are dissolved passes through the catalyst bed layer from bottom to top in an upward mode.
9. The method of claim 1, wherein: the refinery gas is at least one of dry gas and liquefied gas, and the source of the gas is one or more of coking, catalytic cracking and thermal cracking reactions.
10. The method of claim 1, wherein: the volume ratio of the hydrogen introduced in the step (b) to the refinery gas is 2: 1-200: 1.
11. The method of claim 1, wherein: the hydrogenation reaction effluent is separated by a high-pressure separator and/or a low-pressure separator, the hydrogenation reaction material flow is separated in the high-pressure separator to obtain gas and liquid, and the liquid separated in the high-pressure separator is separated in the low-pressure separator to obtain gas and liquid.
12. The method of claim 11, wherein: the fractionating system adopted by the fractionation is a stripping tower and/or a fractionating tower, and the liquid obtained by the separation in the low-pressure separator is stripped and/or fractionated in the fractionating system to obtain naphtha products, diesel oil products and hydrogenated wax oil.
13. The method of claim 11, wherein: and the gas obtained by separation in the high-pressure separator and the gas obtained by separation in the low-pressure separator are mixed and then separated in the gas separator to obtain hydrogen, dry gas, liquefied gas and liquid, and the liquid product directly enters a stripping tower and/or a fractionating tower.
14. The method of claim 9, wherein: and (b) independently mixing dry gas and liquefied gas in the refinery gas with hydrogen, and then respectively entering gas dissolving equipment arranged between different adjacent catalyst bed layers, wherein the height of the catalyst bed layer through which the dry gas and the hydrogen are mixed is higher than that of the catalyst bed layer through which the liquefied gas and the hydrogen are mixed.
15. The method of claim 14, wherein: three catalyst beds are arranged in the hydrogenation reactor, gas dissolving equipment is arranged between adjacent catalyst beds, dry gas and hydrogen gas are mixed and then enter the gas dissolving equipment between the first catalyst bed and the second catalyst bed, and liquefied gas and hydrogen gas are mixed and then enter the gas dissolving equipment between the second catalyst bed and the third catalyst bed.
16. The method of claim 1, wherein: three catalyst beds are arranged in the hydrogenation reactor, gas dissolving equipment is arranged between adjacent catalyst beds, part of dry gas and hydrogen gas are mixed and then enter the gas dissolving equipment between the first catalyst bed and the second catalyst bed, and liquefied gas, hydrogen gas and the rest of dry gas are mixed and then enter the gas dissolving equipment between the second catalyst bed and the third catalyst bed.
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Citations (3)
| 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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Effective date of registration: 20230908 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |