CN109777491B - Refinery gas hydrogenation combined processing technology - Google Patents
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- CN109777491B CN109777491B CN201711118828.7A CN201711118828A CN109777491B CN 109777491 B CN109777491 B CN 109777491B CN 201711118828 A CN201711118828 A CN 201711118828A CN 109777491 B CN109777491 B CN 109777491B
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Abstract
The invention discloses a refinery gas hydrogenation combined process, which comprises the following contents: (a) mixing residual oil raw oil and circulating oil with hydrogen in a hydrogen dissolving device, then adding the mixture into a hydrogenation catalyst bed in a hydrogenation reactor to react under the condition of hydrogenation operation, and arranging a gas dissolving device 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 process enables simultaneous hydrotreating of refinery gases and production of hydrogenated residue.
Description
Technical Field
The invention belongs to a hydrogenation process of an oil refining technology, relates to a refinery gas hydrogenation combined processing process, and particularly relates to a hydrogenation combined method for hydrotreating refinery gas and producing hydrogenated residual 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 residue oil hydrogenation technology is the most important means for improving the quality of catalytic cracking products and realizing clean production, and the liquid phase residue 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, CN104927903A discloses a residual oil hydrotreating method, CN105316037A discloses a residual oil hydrotreating method, which mainly employs a gas-liquid-solid three-phase hydrogenation and a liquid-solid two-phase hydrogenation for hydrotreating in an upflow and a fixed bed respectively, and different methods are all that hydrogen is dissolved in residual oil raw material for hydrogenation reaction, and the residual hydrogen is not utilized, and is directly treated 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 refinery gas hydrotreating process is a gas phase reaction, the residual oil hydrogenation is a liquid phase reaction, and the reaction types of the two reactions are completely different, so the refinery gas hydrotreating and residual oil liquid phase hydrogenation combined method is rarely reported.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a hydrogenation combination method. The process enables simultaneous hydrotreating of refinery gases and production of hydrogenated residue. The utilization efficiency of hydrogen is improved on the premise of not influencing the quality of the hydrogenated residual oil product and even improving the quality of the hydrogenated residual 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 refinery gas hydrogenation combination method comprises the following steps:
(a) mixing residual oil raw oil and circulating oil with hydrogen in a hydrogen dissolving device, and then adding the mixture into a hydrogenation catalyst bed layer in a hydrogenation reactor to react under the hydrogenation operation condition, wherein the catalyst bed layer is provided with a plurality of layers, preferably 2-12 layers, and a 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) 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 residual 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 residual oil feedstock used may include one or more of residue fractions such as atmospheric residue, vacuum residue, coker heavy oil, thermally cracked heavy oil, visbreaker heavy oil, coal tar heavy oil fraction, coal direct liquefaction heavy oil, and shale oil heavy oil, and a part of light fractions such as catalytically cracked light cycle oil, catalytically cracked heavy cycle oil, and virgin wax oil, which reduce the viscosity of the feedstock oil, may be mixed with the residual oil feedstock.
In the method, the hydrogenation operation condition is generally that the reaction pressure is 4.0-20.0 MPa, and the volume space velocity of the residual oil raw oil is 0.1h-1~6.0h-1The average reaction temperature is 180-470 ℃, and the ratio of the circulating oil to the residual oil raw oil is 0.3: 1-10: 1; the preferable operation conditions are that the reaction pressure is 5.0 MPa-19.0 MPa, and the volume space velocity of the residual oil raw oil is 0.15h-1~5.0h-1The average reaction temperature is 200-460 ℃, and the ratio of the circulating oil to the residual oil raw oil is 0.4: 1-8: 1.
In the method, the supplementary hydrogenation operation condition is generally that the reaction pressure is 4.0-20.0 MPa, and the volume space velocity of the residual oil raw oil is 0.2h-1~30.0h-1The average reaction temperature is 180-470 ℃; the preferable operation conditions are that the reaction pressure is 5.0 MPa-19.0 MPa, and the volume space velocity of the residual oil raw oil is 0.3h-1~25.0h-1The average reaction temperature is 200-460 ℃.
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 include hydrogenation catalysts such as FZC-1 series protective agents, FZC-2 series demetallization catalysts, FZC-3 series desulfurization catalysts, and FZC-4 series decarbonization catalysts developed by the fushu petrochemical research institute (FRIPP), hydrogenation catalysts such as HMC945 and HMC841 from the IFP company, RF series catalysts and R series catalysts developed by the UOP company, KFR series participation from the AKZO company, HT series catalysts developed by the Axen company, and TK series catalysts developed by the Haldor Topsoe company.
In the method, preferably, the residual 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 residual 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, the residual 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 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 stripping and/or fractionation in a fractionation system to obtain naphtha, diesel oil and hydrogenated residual 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 residual 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 ineffective use of the hydrogen is caused, 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 residual oil material have high solubility, the saturation of the refinery gas in a liquid phase is high, and the refinery gas can be effectively dissolved in the residual oil stream for hydrogenation reaction. In the liquid phase circulation hydrogenation device for residual oil, a gas raw material and hydrogen are mixed and enter a plurality of catalyst beds behind the device, the aim of producing hydrogenation purified gas is achieved by utilizing a hydrogenation catalyst with higher reaction pressure and higher activity and a hydrogen atmosphere fused into a liquid phase, the utilization efficiency of the hydrogen is improved on the premise of not influencing the quality of the residual oil product, the equipment investment is reduced overall, and the operation energy consumption is reduced.
In the prior art, hydrogenated residual oil can be produced from a residual oil raw material by a liquid phase circulating hydrogenation method, a dry gas product is produced from a dry gas raw material by a fixed bed hydrogenation method, and a liquefied gas product is produced from a liquefied gas raw material by a fixed bed hydrogenation method. The gas has a certain solubility in liquid, which is the principle of residual oil liquid phase circulation hydrogenation technology development, namely, the hydrogenation reaction is realized by utilizing hydrogen dissolved in residual oil, wherein the first bed layer catalyst plays the most 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 residual oil is higher, 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. The method fully utilizes the characteristic that hydrogen needs to be dissolved in the liquid-phase circulating hydrogenation process of the residual oil, and in order to reduce the influence of the dissolved gas on the original residual oil hydrogenation as much as possible, the mixed hydrogen of the gas raw material enters the catalyst bed layer behind the first catalyst bed layer, the hydrogenation reaction of the gas is completed by utilizing the atmosphere of the hydrogen and the catalyst, and the hydrogen can be dissolved in the residual oil raw material more, so that the hydrogenation reaction of the residual oil is promoted; 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, which mainly has the advantages of low olefin content in the dry gas, low hydrogen consumption, small quantity of required active centers, short reaction desorption process time, minimized influence on the residual oil hydrogenation reaction, introduction of gas with relatively high hydrogen consumption into a subsequent catalyst bed layer with relatively low residual oil hydrogenation hydrogen consumption, and overall reduced influence on the residual oil hydrogenation effect.
The invention further makes full use of the characteristic that a large amount of hydrogen is still dissolved in the oil generated by the residual oil liquid phase circulation hydrogenation process, and a supplementary hydrogenation reactor is arranged in the subsequent part of the residual oil hydrogenation reactor, so that the refinery gas raw material is dissolved in the residual oil hydrogenation reaction material flow and enters the catalyst bed layer of the supplementary hydrogenation reactor, and the hydrogenation reaction of the gas is completed by utilizing the atmosphere of the dissolved hydrogen and the catalyst, thereby not only solving the problem of large gas hydrogenation temperature rise, but also using the hydrogen dissolved in the residual 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 the residual oil hydrogenation generated oil are mixed and 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 residual oil product, the hydrogenated residual oil product and the gas product are obtained, and the two technologies are optimally combined, so that the equipment investment and the operation cost are saved.
Drawings
FIG. 1 is a flow diagram of a hydroprocessing combined process of the present invention.
FIG. 2 is another flow diagram of the hydroprocessmg 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-hydrogenation reactor, 8-exhaust valve, 9-hydrofining reaction material flow, 10-high pressure separator, 11-low pressure separator, 12-stripping/fractionating system, 13-stripping gas, 14-naphtha product, 15-diesel product, 16-hydrogenation residual 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 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 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 residual 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. The experimental research is carried out on the FZC series catalyst system which is developed and produced by using FRIPP and combines a protective agent, a demetallization catalyst, a desulfurization catalyst and a carbon residue removal catalyst.
TABLE 1 Main Properties of the residua feedstock
| Residual oil feedstock | |
Raw oil 2 |
| Sulfur content, wt.% | 3.5 | 3.0 |
| Nitrogen content, wt% | 0.27 | 0.21 |
| Carbon residue in wt% | 12.0 | 10.1 |
| Ni + V content, microgram/g | 105 | 88 |
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 |
| Residual oil hydrogenation reactor operating conditions | |||||
| Reaction pressure, MPa | 18.0 | 17.0 | 17.0 | 14.0 | 16.0 |
| Average reaction temperature,. degree.C | 390 | 385 | 385 | 380 | 385 |
| Volume space velocity of fresh raw oil, h-1 | 0.25 | 0.35 | 0.35 | 0.30 | 0.4 |
| 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 | |||||
| Reactor with a reactor shellInlet refinery gas feedstock | Dry gas | Mixed gas | Dry gas | Liquefied gas | Mixed gas |
| Reaction pressure, MPa | 18.0 | 17.0 | 17.0 | 14.0 | 16.0 |
| Average reaction temperature,. degree.C | 390 | 385 | 385 | 380 | 385 |
| Volume space velocity of fresh raw oil, h-1 | 15.0 | 8.0 | 8.0 | 4.0 | 10.0 |
| 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 | 0.5 | 0.5 | 0.5 | 0.4 | 0.3 |
| Diesel oil product | |||||
| Density, g/cm3 | 0.835 | 0.836 | 0.836 | 0.832 | 0.831 |
| Sulphur content, μ g/g | 85 | 91 | 90 | 70 | 45 |
| Hydrogenated residue oil product | |||||
| Sulphur content, μ g/g | 2000 | 2520 | 2500 | 1800 | 2200 |
| Nitrogen content, microgram/g | 1200 | 1150 | 1150 | 700 | 750 |
| Ni + V content, microgram/g | 12.0 | 9.7 | 9.6 | 8.5 | 10.2 |
It can be seen from the examples that a residuum feedstock and a gaseous feedstock can be directly produced into a hydrogenated residuum product and a clean gaseous product by the hydrocombinatorial process of the present technology.
Claims (13)
1. The refinery gas hydrogenation combined process comprises the following steps:
(a) mixing residual oil raw oil and circulating oil with hydrogen in a hydrogen dissolving device, 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 arranged into a plurality of layers, and a gas dissolving device 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 residual 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.
2. The process according to claim 1, characterized in that: in the step (a), the catalyst bed layer is arranged into 2-12 layers.
3. The process according to claim 1, characterized in that: the residual oil raw oil is one or more of atmospheric residue, vacuum residue, coking heavy oil, thermal cracking heavy oil, coal tar heavy oil fraction, direct coal liquefaction heavy oil and shale oil heavy oil, or part of catalytic cracking light cycle oil, catalytic cracking heavy cycle oil and/or straight-run wax oil is mixed in the residual oil raw oil.
4. The process according to claim 1, characterized in that: the residual oil hydrogenation operation condition is that the reaction pressure is 4.0-20.0 MPa, and the volume airspeed of the residual oil raw material oil is 0.1h-1~6.0h-1The average reaction temperature is 180-470 ℃, and the ratio of the circulating oil to the residual oil raw oil is 0.3: 1-10: 1.
5. The process according to claim 4, characterized in that: the residual oil hydrogenation operation conditions are that the reaction pressure is 5.0-19.0 MPa, and the volume space velocity of the residual oil raw material oil is 0.15h-1~5.0h-1The average reaction temperature is 200-460 ℃, and the ratio of the circulating oil to the residual oil raw oil is 0.4: 1-8: 1.
6. The process according to claim 1, characterized in that: the supplementary hydrogenation operation conditions are that the reaction pressure is 4.0MPa to 20.0MPa, and the volume airspeed of the residual oil raw oil is 0.2h-1~30.0h-1The average reaction temperature is 180-470 ℃.
7. The process according to claim 6, characterized in that: the supplementary hydrogenation operation conditions comprise the reaction pressure of 5.0-19.0 MPa and the volume of the residual oil raw oilThe space velocity is 0.3h-1~25.0h-1The average reaction temperature is 200-460 ℃.
8. The process according to claim 1, characterized in that: the hydrogenation active components of the hydrogenation catalyst used in the residual 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 residual 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 a hydrogenation catalyst passing through a reaction material is 30-80% of that of all hydrogenation catalysts in a 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 at least adding liquefied gas into the mixture of the dry gas and the hydrogen, 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: and (c) the dry gas entering the hydrogenation reactor in the step (a) 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)
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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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Patent 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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