CN109777498B - Refinery gas hydrogenation combined process - Google Patents
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- CN109777498B CN109777498B CN201711118800.3A CN201711118800A CN109777498B CN 109777498 B CN109777498 B CN 109777498B CN 201711118800 A CN201711118800 A CN 201711118800A CN 109777498 B CN109777498 B CN 109777498B
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Abstract
The invention discloses a refinery gas hydrogenation combined process, which comprises the following contents: (a) mixing wax oil raw oil and circulating oil with hydrogen in hydrogen dissolving equipment, then adding the mixture into a hydrogenation catalyst bed in a hydrogenation reactor to react under the condition of hydrogenation operation, and arranging gas dissolving equipment between adjacent catalyst beds; (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) mixing the hydrogenation reaction material flow obtained in the step (b) 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; (d) and (c) separating the hydrogenation reaction effluent obtained in the step (c) into a gas phase and a liquid phase, removing hydrogen sulfide from the separated gas phase, and continuously separating to obtain hydrogen and hydrotreated refinery gas. 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, relates to a refinery gas hydrogenation combined process, and particularly relates to a hydrogenation combined 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 combined process. 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 the hydrogenated wax oil product and even improving the quality of the hydrogenated wax oil product, 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 process, which comprises the following steps:
(a) mixing wax oil raw oil and circulating oil with hydrogen in hydrogen dissolving equipment, and then adding the mixture into a hydrogenation catalyst bed in a hydrogenation reactor to react under the condition of hydrogenation operation, wherein the catalyst bed is provided with a plurality of layers, preferably 2-8 layers, and gas dissolving equipment is arranged between adjacent catalyst beds;
(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) mixing the hydrogenation reaction material flow obtained in the step (b) 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;
(d) separating the hydrogenation reaction effluent obtained in the step (c) 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, diesel oil and hydrogenated wax oil products, and returning part of the liquid phase obtained by separation of the high-pressure separator and/or part of the hydrogenation reaction effluent obtained in the step (b) and/or part of the hydrogenation reaction material flow obtained in the step (c) 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 supplementary 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 0.3h-1~40.0h-1The average reaction temperature is 180-450 ℃; 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-1~30.0h-1The average reaction temperature is 200-440 ℃.
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 30-80% of the volume of all the hydrogenation catalysts, preferably 35-75%, and most preferably 40-65%, and then is introduced into the refinery gas.
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) and the step (c) are independently mixed with hydrogen and then respectively enter gas dissolving equipment arranged between different adjacent catalyst bed layers.
One particularly preferred embodiment is as follows: the hydrogenation reactor is internally provided with three catalyst beds, gas dissolving equipment is arranged between adjacent catalyst beds, dry gas and hydrogen are mixed and then enter the gas dissolving equipment between the second catalyst bed and the third catalyst bed, liquefied gas and hydrogen are mixed and then enter the gas dissolving equipment between the beds of the supplementary hydrogenation reactor, and the dry gas entering the hydrogenation reactor accounts for 50-100% of the volume of all dry gas raw materials.
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 products.
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, the wax oil raw material can be used for producing clean wax oil by a liquid phase circulating hydrogenation method, the dry gas raw material is used for producing a dry gas product by a fixed bed hydrogenation method, and the liquefied gas raw material is used for producing a liquefied gas product 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, wherein the main points are that the olefin content in the dry gas is low, the hydrogen consumption is low, the number of required active centers is small, the time of a reaction desorption process is short, the influence on the wax oil hydrogenation reaction is reduced to the minimum, and the gas with relatively high hydrogen consumption is introduced into a 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 method further makes full use of the characteristic that a large amount of hydrogen is still dissolved in the oil generated by the wax oil liquid phase circulation hydrogenation process, and a supplementary hydrogenation reactor is arranged in the subsequent stage of the wax oil hydrogenation reactor, so that the refinery gas raw material is dissolved in the wax oil hydrogenation reaction material flow and enters a 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, thereby not only solving the problem of large temperature rise of the gas hydrogenation, but also using the hydrogen dissolved in the wax oil for the gas hydrogenation reaction and 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 wax oil hydrogenation generated oil are mixed to enter the first catalyst bed, and the rest gas and/or hydrogen mixed mixture enters the subsequent catalyst bed. The combination method is characterized in that the gas hydrogenation process is completed on the premise of not influencing the quality of the wax oil product to obtain the wax oil product and the 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, 7-hydrogenation reactor, 8-vent valve, 9-hydrofining reaction flow, 10-high pressure separator, 11-low pressure separator, 12-stripping/fractionating system, 13-stripping gas, 14-naphtha product, 15-diesel product, 16-hydrogenation wax oil product, 17-high pressure separator gas, 18-low pressure separator gas, 19-gas separator, 20-hydrogen, 21-dry gas product, 22-liquefied gas product, 23-gas dissolver, 24-supplementary reactor, 25-hydrogenation reaction flow.
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 hydrogenation reactor 7, and pass through a first catalyst bed layer, the hydrogen is dissolved in the effluent of the first catalyst bed layer, and pass through a second catalyst bed layer, the hydrogen and a gas raw material 6 are dissolved in the effluent of the second catalyst bed layer, and pass through a third catalyst bed layer, a hydrofining reaction material flow 9 and the gas raw material 6 are mixed in a gas dissolver 23 and then enter a supplementary reactor 24, and pass through the first catalyst bed layer, the gas raw material 6 is dissolved in the effluent of the first catalyst bed layer, and pass through the second catalyst bed layer, a hydrogenation reaction material flow 25 enters a high-pressure separator 10, a high-pressure separator gas 17 and a liquid are obtained by separation in the high-pressure separator 10, the liquid enters a low-pressure separator 11, and a low-pressure separator gas 18 and a liquid are obtained by separation in the low-pressure separator 11, the liquid and the liquid component separated by the gas separator 19 enter the stripping/fractionating system 12 after being mixed, and are fractionated in the fractionating system under the action of the stripping gas 13 to obtain a naphtha product 14, a diesel product 15 and a hydrogenated wax oil product 16, the gas 17 of the high-pressure separator and the gas 18 of the low-pressure separator enter the gas separator 19 after being mixed, and hydrogen, dry gas and liquefied gas products are separated in the gas separator 19. The cycle oil 3 can be obtained directly from 9 or can be obtained from the liquid separated 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 | |
| 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 |
| Hydrogenation reactor operating conditions | |||||
| Raw oil | Raw oil 1 | Raw oil 1 | Raw oil 1 | Raw oil 2 | Raw oil 2 |
| Wax oil hydrogenation reactionReactor operating conditions | |||||
| Reaction pressure, MPa | 12.0 | 8.0 | 8.0 | 10.0 | 16.0 |
| Average reaction temperature,. degree.C | 370 | 360 | 360 | 375 | 385 |
| Volume space velocity of fresh raw oil, h-1 | 2.0 | 1.0 | 1.0 | 0.8 | 1.5 |
| Circulation ratio | 3:1 | 2.5:1 | 2.5:1 | 4:1 | 3:1 |
| Three-bed inlet gas feedstock | Dry gas | Dry gas | Dry gas | Liquefied gas | Mixed gas |
| Volume ratio of hydrogen and gas raw material dissolved in three-bed layer inlet | 80:20 | 80:20 | 80:20 | 95:5 | 80:20 |
| 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 | 12.0 | 8.0 | 8.0 | 10.0 | 16.0 |
| Average reaction temperature,. degree.C | 370 | 360 | 360 | 375 | 385 |
| Volume space velocity of fresh raw oil, h-1 | 20.0 | 15.0 | 15.0 | 25.0 | 18.0 |
| Two-bed inlet refinery gas raw material | — | Liquefied gas | Liquefied gas | Liquefied gas | Mixed gas |
| Volume ratio of hydrogen dissolved in inlet of two-bed layer to raw material of refinery gas | — | 95:5 | 95:5 | 100:0 | 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 | 0.3 | 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 | 145 | 235 | 227 | 380 | 120 |
| Hydrogenated wax oil product | |||||
| Density, g/cm3 | 0.885 | 0.889 | 0.889 | 0.912 | 0.899 |
| Sulphur content, μ g/g | 390 | 1450 | 1420 | 1950 | 290 |
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 (13)
1. The refinery gas hydrogenation combined process comprises the following steps:
(a) mixing wax oil raw oil and circulating oil with hydrogen in hydrogen dissolving equipment, and then adding the mixture into a hydrogenation catalyst bed in a hydrogenation reactor to react under the condition of hydrogenation operation, wherein the catalyst bed is provided with a plurality of layers, and gas dissolving equipment is arranged between adjacent catalyst beds;
(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) mixing the hydrogenation reaction material flow obtained in the step (b) 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;
(d) separating the hydrogenation reaction effluent obtained in the step (c) 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, diesel oil and hydrogenated wax oil, and returning part of the liquid phase obtained by separation of the high-pressure separator and/or part of the hydrogenation reaction effluent obtained in the step (b) and/or part of the hydrogenation reaction material flow obtained in the step (c) as circulating oil to hydrogen dissolving equipment.
2. The process according to claim 1, characterized in that: in the step (a), the catalyst bed layer is arranged into 2-8 layers.
3. The process according to claim 1, characterized in that: the wax oil raw material oil is one or more of straight-run wax oil, coked wax oil, thermal cracking wax oil, synthetic wax oil, coal tar wax oil fraction, coal direct liquefaction wax oil and shale oil wax oil, or at least one 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 process according to claim 1, characterized in that: the wax oil hydrogenation operation conditions are that the reaction pressure is 3.0MPa to 20.0MPa, 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.
5. The process according to claim 4, characterized in that: the wax oil hydrogenation operation conditions are that the reaction pressure is 4.0MPa to 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 process according to claim 1, characterized in that: the supplementary 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 0.3h-1~40.0h-1The average reaction temperature is 180-450 ℃.
7. The process according to claim 6, characterized in that: the supplementary hydrogenation operation conditions are that the reaction pressure is 4.0MPa to 18.0MPa, and the volume airspeed of the wax oil raw material oil is 0.5h-1~30.0h-1The average reaction temperature is 200-440 ℃.
8. The process according to claim 1, characterized in that: the hydrogenation active components of the hydrogenation catalyst used in the wax oil hydrogenation reactor and the hydrogenation active components of 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 percent calculated by oxides, and the carrier of the hydrogenation catalyst is one or more of alumina, amorphous silicon aluminum, silicon oxide and titanium oxide.
9. The process according to claim 1, characterized in that: mixing wax oil raw oil and circulating oil, mixing the mixture with hydrogen in a hydrogen dissolving device, then entering a hydrogenation catalyst bed layer in the step (a) to react under the hydrogenation operation condition, and introducing refinery gas after the volume of hydrogenation catalyst passing through the reaction material is 30-80% of that of the hydrogenation catalyst in the hydrogenation reactor in the step (a).
10. The process according to claim 1, characterized in that: 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.
11. The process according to claim 10, characterized in that: and (b) arranging three catalyst beds in the hydrogenation reactor in the step (a), arranging gas dissolving equipment between adjacent catalyst beds, mixing dry gas and hydrogen, then feeding the mixture into the gas dissolving equipment between the second catalyst bed and the third catalyst bed, arranging two catalyst beds in the supplementary hydrogenation reactor, and mixing the dry gas at least containing liquefied gas and the hydrogen, and then feeding the mixture into the gas dissolving equipment between the beds of the supplementary hydrogenation reactor.
12. The process according to claim 11, characterized in that: the volume of the dry gas entering the hydrogenation reactor accounts for 50-100% of the volume of the whole dry gas raw material.
13. The process according to claim 1, characterized in that: when hydrogen and refinery gas are introduced simultaneously in the step (b) or the step (c), the volume ratio of the introduced hydrogen to the refinery gas is 2: 1-200: 1.
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Citations (3)
| 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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| 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: 20230909 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. |