Background
Paraffin is a solid petroleum product obtained by solvent dewaxing and deoiling vacuum distillate oil, and is an important raw material for medicine, daily chemical industry and other fine chemical industries. The paraffin wax can be roughly classified into paraffin wax, high-melting-point petroleum wax, microcrystalline wax, vaseline, and the like. The paraffin wax for the applications needs to be deeply refined to remove sulfur, nitrogen compounds and polycyclic aromatic hydrocarbon contained in the paraffin wax so as to be harmless to human bodies. The paraffin refining includes clay refining and hydrorefining, wherein the hydrorefining technology is a process of hydro-converting non-ideal components in raw materials under certain temperature, pressure, hydrogen and the presence of a catalyst. Compared with clay refining, hydrorefining has the characteristics of high product yield, good quality, no waste residue and the like, and is a main method for refining paraffin.
The paraffin hydrofining is to deeply refine a paraffin raw material under mild reaction conditions to effectively remove heteroatoms such as sulfur, nitrogen and the like and saturated polycyclic aromatic hydrocarbons. The mild reaction condition means that cracking and isomerization reaction of carbon-carbon bond is not allowed to occur in the paraffin hydrogenation process, the oil content in the paraffin is prevented from rising, and the physical properties such as penetration degree, melting point and the like are prevented from changing. The hydrogenation technology of microcrystalline wax and mixed crystal wax is to process the high-quality microcrystalline wax and mixed crystal wax produced by refining deasphalted oil or heavy oil with solvent and dewaxing and deoiling, and even can reach the quality requirements of food grade and medicine grade. The liquid phase hydrogenation technology can meet the requirement of producing clean paraffin under the condition of greatly reducing energy consumption. US6213835 and US6428686 disclose a hydrogenation process in which hydrogen is pre-dissolved. In the methods, hydrogen is dissolved in raw materials to carry out hydrogenation reaction, the residual hydrogen in the reaction is not utilized, and the hydrogen 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 paraffin hydrogenation is a liquid phase reaction, and the reaction types of the two reactions are completely different, so the refinery gas hydrotreating and paraffin 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 method can simultaneously hydrotreat refinery gas and produce clean paraffin. The utilization efficiency of hydrogen is improved on the premise of further improving the quality of paraffin products, the problem of temperature rise in the hydrotreating process of refinery gas is effectively solved, the equipment investment is reduced overall, and the operation energy consumption is reduced.
The invention relates to a refinery gas hydrogenation combination method, which comprises the following steps:
(a) mixing the paraffin raw oil and the circulating oil with hydrogen in hydrogen dissolving equipment, and then entering a hydrogenation catalyst bed layer in a paraffin 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 refinery gas after hydrogenation treatment, fractionating the liquid phase obtained by separation to obtain naphtha and paraffin 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 raw paraffin oil used may include one or more of liquid paraffin, high melting point petroleum wax, microcrystalline wax, mixed microcrystalline wax, vaseline, synthetic wax, and other paraffin fractions.
In the method, the hydrogenation operation condition is generally that the reaction pressure is 3.0-15.0 MPa, and the volume space velocity of the paraffin raw oil is 0.2h-1~6.0h-1The average reaction temperature is 180-450 ℃, and the ratio of the circulating oil to the paraffin raw oil is 0.2: 1-10: 1; the preferable operation conditions are that the reaction pressure is 4.0 MPa-14.0 MPa, and the volume airspeed of the paraffin raw oil is 0.3h-1~5.0h-1The average reaction temperature is 200-430 ℃, and the ratio of the circulating oil to the paraffin raw oil is 0.5: 1-8: 1.
In the method, the supplementary hydrogenation operation condition is generally that the reaction pressure is 3.0-15.0 MPa, and the volume space velocity of the paraffin raw oil is 0.3h-1~40.0h-1The average reaction temperature is 180-450 ℃; the preferable operation conditions are that the reaction pressure is 4.0 MPa-14.0 MPa, and the volume airspeed of the paraffin raw oil is 0.5h-1~30.0h-1The average reaction temperature is 200-430 ℃.
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 481-2B, FV-1, FV-10, FV-20, FV-30 and the like developed by Fushun petrochemical research institute (FRIPP).
In the method, the catalyst bed layers of the hydrogenation reactor in the step (a) are arranged into a plurality of layers, preferably 2-6 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 6 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 paraffin 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 paraffin hydrogenation reactor, and hydrogen and refinery gas are introduced between the catalyst bed layers of the supplementary hydrogenation reactor.
In the method, the paraffin raw oil and the circulating oil are mixed and then enter from the top of the paraffin 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 paraffin 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 paraffin hydrogenation reaction effluent dissolved with the refinery gas enters from the top of the supplementary hydrogenation reactor, the mixed material flow of the paraffin hydrogenation reaction effluent dissolved with the refinery gas can pass through the catalyst bed layer from top to bottom in a downward mode, the mixed material flow of the paraffin hydrogenation reaction effluent dissolved with the refinery gas can also enter from the bottom of the supplementary hydrogenation reactor, and the mixed material flow of the paraffin hydrogenation reaction effluent dissolved with the refinery gas 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, if hydrogen and refinery gas are introduced simultaneously in any process, the volume ratio of the introduced hydrogen to the refinery gas is 1: 1-100: 1, preferably 1: 1-50: 1.
In the method, the hydrogenation reaction effluent is separated by a high-pressure separator and/or a low-pressure separator. The high-pressure separator is a conventional gas-liquid separator. The hydrogenation reaction flow is separated in a high-pressure separator to obtain gas and liquid. The low-pressure separator is a conventional gas-liquid separator. The liquid obtained by separation in the high-pressure separator is separated in the high-low pressure separator to obtain gas and liquid.
In the method, the fractionating system used for fractionating comprises a stripping tower and/or a fractionating tower. And the liquid obtained by separation in the low-pressure separator is subjected to steam stripping and/or fractionation in a fractionation system to obtain a naphtha product and a paraffin 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 paraffin liquid-phase hydrogenation process, hydrogenation reaction is realized by hydrogen dissolved in oil, so that the aim of producing a clean paraffin product is fulfilled, however, the dissolved hydrogen is excessive and cannot be completely reacted, and the hydrogen dissolved in the oil generated by hydrogenation after the reaction is finished can usually remain 20% -70% of the dissolved hydrogen, so that the hydrogen is ineffectively 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 paraffin liquid-phase circulating hydrogenation process, a supplementary hydrogenation reactor is arranged in the subsequent stage of the paraffin hydrogenation reactor, refinery gas raw materials are dissolved in paraffin hydrogenation reaction material flow and enter a catalyst bed layer of the supplementary hydrogenation reactor, and the hydrogenation reaction of gas is completed by utilizing the dissolved hydrogen and the catalyst atmosphere, so that the problem of large gas hydrogenation temperature rise is solved, and the hydrogen dissolved in paraffin 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 paraffin hydrogenation 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 generally characterized in that the gas hydrogenation process is completed on the premise of not influencing the quality of the paraffin product or further improving the quality of the paraffin product to obtain the paraffin product and the gas product, and the two technologies are optimally combined to reduce the hydrogen dissolved in the paraffin product, namely reduce the hydrogen consumption and the energy consumption, save the equipment investment and reduce the operation cost.