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. On the premise of further improving the quality of residual oil products, the utilization efficiency of hydrogen is improved, 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 entering a hydrogenation catalyst bed layer in a residual oil hydrogenation reactor to react under the condition of liquid-phase hydrogenation operation;
(b) mixing the reactant flow obtained in the step (a) with refinery gas and hydrogen in a gas dissolving device, and then allowing the mixture to enter a hydrogenation catalyst bed layer in a supplementary hydrogenation reactor to react under the liquid-phase hydrogenation operation condition;
(c) separating the hydrogenation reaction effluent in the step (b) into a gas phase and a liquid phase, continuously separating the gas phase obtained by separation after removing hydrogen sulfide to obtain hydrogen and hydrotreated refinery gas, fractionating the liquid phase obtained by separation to obtain naphtha, diesel oil and residual oil products, and returning part of the hydrogenation reaction effluent obtained in the step (a) and/or part of the hydrogenation reaction material flow obtained in the step (b) and/or part of the liquid phase obtained by separation of the high-pressure separator as circulating oil to hydrogen dissolving equipment.
In the 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, the catalyst bed layers of the hydrogenation reactor in the step (a) are arranged into a plurality of layers, preferably 2-8 layers, and a gas dissolving device is arranged between the adjacent catalyst bed layers; the introduced hydrogen is mixed with the reactant flow in the gas dissolving device and then enters the next catalyst bed layer for reaction.
In the above method, one or more catalyst beds, preferably 2 to 8 catalyst beds, may be provided in the make-up hydrogenation reactor. If only one catalyst bed layer is arranged in the supplementary hydrogenation reactor, the liquid-phase hydrogenation reaction material flow is mixed with the refinery gas in the gas dissolver and then enters the top of the supplementary hydrogenation reactor and passes through the catalyst bed layer; if a plurality of catalyst beds are arranged in the supplementary hydrogenation reactor, a gas dissolving device is arranged between the beds, refinery gas and hydrogen are mixed and then enter any gas dissolving device arranged between adjacent catalyst beds, and are mixed with reactant flow from the previous catalyst bed and then enter the next catalyst bed for reaction.
A preferred embodiment is as follows: the catalyst bed layers of the residual oil hydrogenation reactor are arranged into three layers, the catalyst bed layer of the supplementary hydrogenation reactor is arranged into two layers, hydrogen is introduced between the second catalyst and the third catalyst bed layer of the residual oil hydrogenation reactor, and hydrogen and refinery gas are introduced between the catalyst bed layers of the supplementary hydrogenation reactor.
In the method, the residual oil raw oil and the circulating oil are mixed and then enter from the top of the residual oil hydrogenation reactor, the mixture flow dissolved with the hydrogen can pass through the catalyst bed layer from top to bottom in a downward mode, the residual oil raw oil and the circulating oil can also enter from the bottom of the hydrogenation reactor after being mixed, and the mixture flow dissolved with the hydrogen can pass through the catalyst bed layer from bottom to top in an upward mode.
In the method, the mixed material flow of the residual oil hydrogenation reaction effluent dissolved with the refinery gas enters from the top of the supplementary hydrogenation reactor, the mixed material flow dissolved with the refinery gas can pass through the catalyst bed layer from top to bottom, the mixed material flow of the residual oil hydrogenation reaction effluent dissolved with the refinery gas can also enter from the bottom of the supplementary hydrogenation reactor, and the mixed material flow dissolved with the refinery gas can pass through the catalyst bed layer from bottom to top.
In the above method, the previous catalyst bed or the next catalyst bed is based on the flowing direction of the reactant flow, and whether the hydrogenation reaction is an upflow type or a downflow type, the bed in the adjacent beds which is contacted with the reactant flow first is an upper bed and then is a lower bed.
In the method, the refinery gas may comprise one or more of dry gas, liquefied gas and the like. The source of the gas can be one or more of coking, catalytic cracking, thermal cracking, visbreaking and the like.
In the method, if hydrogen and refinery gas are introduced simultaneously in any process, the volume ratio of the introduced hydrogen to the refinery gas is 1: 1-100: 1, preferably 1: 1-50: 1.
In the method, the hydrogenation reaction effluent is separated by a high-pressure separator and/or a low-pressure separator. The high-pressure separator is a conventional gas-liquid separator. The hydrogenation reaction flow is separated in a high-pressure separator to obtain gas and liquid. The low-pressure separator is a conventional gas-liquid separator. The liquid obtained by separation in the high-pressure separator is separated in the high-low pressure separator to obtain gas and liquid.
In the method, the fractionating system used for fractionating comprises a stripping tower and/or a fractionating tower. And the liquid obtained by separation in the low-pressure separator is subjected to stripping and/or fractionation in a fractionation system to obtain a naphtha product, a diesel product and a hydrogenated residual oil product.
In the above method, the gas separator used for gas separation is a conventional separator. The gas obtained by separation in the high-pressure separator and the gas obtained by separation in the low-pressure separator are mixed, hydrogen sulfide is removed, then hydrogen, dry gas, liquefied gas and the like are obtained by separation in the gas separator, and if liquid products exist, the gas directly enters a stripping tower and/or a fractionating tower.
In the process of gas hydrogenation, the temperature rise of a catalyst bed layer is large due to large reaction heat release, so that the temperature range of the hydrogenation reaction is large, the effect of the hydrogenation reaction is influenced, the generation of carbon deposition of the catalyst is accelerated, and the service cycle of the catalyst is shortened. In the residual oil liquid phase hydrogenation process, hydrogenation reaction is realized by hydrogen dissolved in oil, so that the purpose of producing clean residual oil products is achieved, however, the dissolved hydrogen is excessive and cannot be completely reacted, and the hydrogen dissolved in the hydrogenated oil after the reaction is completed can usually remain 20% -70% of the dissolved hydrogen, so that the hydrogen is inefficiently used, namely, the energy consumption is increased.
According to the invention, by fully utilizing the characteristic that a large amount of hydrogen is still dissolved in oil generated by a residual oil liquid-phase circulating hydrogenation process, a supplementary hydrogenation reactor is arranged in the subsequent stage of a residual oil hydrogenation reactor, a refinery gas raw material is dissolved in a residual oil hydrogenation reaction material flow and enters a catalyst bed layer of the supplementary hydrogenation reactor, and the hydrogenation reaction of gas is completed by utilizing the atmosphere of the dissolved hydrogen and the catalyst, so that the problem of large gas hydrogenation temperature rise is solved, and the hydrogen dissolved in the residual oil is used for the gas hydrogenation reaction, thereby reducing the hydrogen consumption; or a plurality of catalyst beds are arranged in a further supplementary hydrogenation reactor, part of dry gas or all dry gas raw materials in the mixed gas and 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 combined method is characterized in that the gas hydrogenation process is completed on the premise of not influencing the quality of the residual oil product or further improving the quality of the residual oil product to obtain the residual oil product and the gas product, and the two technologies are optimally combined to reduce the hydrogen dissolved in the residual oil product, namely reduce the hydrogen consumption and the energy consumption, save the equipment investment and reduce the operation cost.