CN113088328B - Hydrogenation method - Google Patents
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- CN113088328B CN113088328B CN201911335609.3A CN201911335609A CN113088328B CN 113088328 B CN113088328 B CN 113088328B CN 201911335609 A CN201911335609 A CN 201911335609A CN 113088328 B CN113088328 B CN 113088328B
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000003921 oil Substances 0.000 claims abstract description 99
- 239000003054 catalyst Substances 0.000 claims abstract description 77
- 239000010687 lubricating oil Substances 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000007791 liquid phase Substances 0.000 claims abstract description 34
- 239000002199 base oil Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims description 50
- 229910052739 hydrogen Inorganic materials 0.000 claims description 50
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 150000002431 hydrogen Chemical class 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 15
- 230000002829 reductive effect Effects 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000011280 coal tar Substances 0.000 claims description 2
- 238000004939 coking Methods 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000003079 shale oil Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 2
- 239000007788 liquid Substances 0.000 description 20
- 239000002994 raw material Substances 0.000 description 19
- 239000007789 gas Substances 0.000 description 16
- 238000005194 fractionation Methods 0.000 description 9
- 239000000376 reactant Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003223 protective agent Substances 0.000 description 7
- 239000010724 circulating oil Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005504 petroleum refining Methods 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000001174 ascending effect Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
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- 239000002904 solvent Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
- C10G65/043—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a hydrogenation method, which comprises the following steps: (1) the raw oil of the lubricating oil is contacted with a hydrotreating catalyst to carry out hydrotreating reaction; (2) shunting the material subjected to the hydrotreating reaction in the step (1) to obtain hydrotreated light distillate oil and hydrotreated heavy distillate oil; (3) contacting the hydrotreated heavy distillate with a hydroisomerization catalyst to perform a liquid-phase hydroisomerization reaction, and separating the hydroisomerization product to obtain various lubricating oil base oils. The method can improve the reaction efficiency and the quality of the lubricating oil base oil.
Description
Technical Field
The invention relates to a hydrogenation method, in particular to a hydrogenation method for producing high-quality lubricating oil base oil by a liquid phase hydrogenation mode.
Background
The lubricating oil plays an important role in various fields of national economy, is a non-volatile oily lubricant and is prepared by blending base oil and additives, wherein 70-99 wt% of the finished lubricating oil is the base oil, and the quality of the base oil determines the evaporation performance, low-temperature fluidity, high-temperature thermal oxidation stability, viscosity-temperature performance and the like of the lubricating oil product. The base oil is a carrier of the lubricating oil additive and also a main body of the lubricating oil. Hydrogenation is an important means for producing the base of lubricating oils and plays an increasing role. Through a chemical reaction mode, the original molecular composition structure is changed, and cyclic substances, saturated hydrocarbon, aromatic hydrocarbon and the like in the raw materials are converted into components meeting performance requirements, so that the raw material sources are greatly widened, and the base oil obtained by a hydrogenation method has the characteristics of low sulfur, low nitrogen, low aromatic hydrocarbon content, low toxicity, higher viscosity index and the like, and has excellent thermal stability and oxidation stability, good viscosity-temperature performance and additive sensitivity.
The hydrogenation technology for producing lubricating oil usually adopts a two-stage process, namely a two-stage process combining the hydrogenation pretreatment of raw oil and the hydrogenation isomerization dewaxing of hydrogenated raw material. In the hydrotreating process, raw oil passes through a hydrotreating catalyst bed under hydrotreating conditions to undergo hydrodesulfurization, hydrodenitrogenation, hydrodeoxygenation and other reactions to remove impurities, aromatic hydrocarbons are subjected to hydrogenation saturation to obtain hydrotreated product oil with low impurity content and high aromatic hydrocarbon saturation, the product oil continues to pass through a hydroisomerization catalyst under hydroisomerization conditions to obtain different types of high-quality lubricant base oil after isomerization and dewaxing, and in general, the hydrotreating adopts a trickle bed hydrogenation process and requires a recycle hydrogen compressor to recycle hydrogen. The liquid phase lubricating oil hydrogenation technology can meet the production requirement of clean lubricating oil base oil under the condition of greatly reducing energy consumption.
CN109777481A, CN109777489A and CN109777495A disclose a combined processing method of refinery gas, refinery gas is introduced in a liquid phase hydrotreating section, the used cycle oil is hydrotreating whole fraction, the hydroisomerization section uses a conventional trickle bed operation mode, and a recycle hydrogen compressor is still used. CN107267198A discloses a method for preparing lubricating oil base oil by liquid phase hydrogenation of waste lubricating oil, which comprises the steps of mixing a waste lubricating oil raw material with hydrogen and then feeding the mixture into a liquid phase hydrogenation reactor for hydrogenation reaction, separating the hydrogenation product by a heat low-pressure separator to obtain a liquid phase product, and uniformly mixing 10-60 wt% of the material in the liquid phase product obtained by the separation of the heat low-pressure separator and the hydrogen and refluxing the mixture to the liquid phase hydrogenation reactor. US6213835, US6428686 and CN103797093B disclose a hydrogenation process in which hydrogen is dissolved in a raw material to carry out hydrogenation reaction, and one part of the hydrogenation resultant flow is directly recycled and the other part is separated and then is directly treated additionally, but there is no clear operation mode of hydroisomerization.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a hydrogenation method. The process can improve the reaction efficiency and the quality of the lubricating oil base oil.
The invention relates to a hydrogenation method, which comprises the following steps:
(1) the raw oil of the lubricating oil is contacted with a hydrotreating catalyst to carry out hydrotreating reaction;
(2) shunting the material after the hydrotreating reaction in the step (1) to obtain hydrotreated light distillate oil and hydrotreated heavy distillate oil;
(3) contacting the hydrotreated heavy distillate with a hydroisomerization catalyst to perform a liquid-phase hydroisomerization reaction, and separating the hydroisomerization product to obtain various lubricating oil base oils.
In the method, the raw oil of the lubricating oil in the step (1) is contacted with a hydrotreating catalyst to carry out liquid-phase hydrotreating reaction.
In the method, the light distillate oil in the step (2) is recycled to the hydrotreating reactor to contact with the hydrotreating catalyst for liquid phase hydrotreating reaction.
In the method, the hydroisomerization product in the step (3) is separated to obtain hydroisomerization heavy fraction oil, and part or all of the hydroisomerization heavy fraction oil is recycled to the hydroisomerization reactor to contact with a hydroisomerization catalyst to perform a liquid-phase hydroisomerization reaction. The initial boiling point temperature of the hydroisomerized heavy distillate oil is more than 450 ℃, and preferably the initial boiling point temperature is more than 480 ℃.
In the method, part of the hydroisomerization products in the step (3) are recycled to the hydroisomerization reactor, preferably to the hydroisomerization hydrogen dissolving equipment and are mixed with the hydrotreated heavy distillate oil and then recycled to the hydroisomerization reactor.
In the method, the raw oil of the lubricating oil and the hydrotreated light distillate oil are optionally mixed with hydrogen in a hydrogen dissolving device, the mixed material enters a hydrotreating reactor under the condition of liquid-phase hydrogenation operation, passes through a hydrotreating catalyst bed layer and undergoes hydrogenation reaction, and then the reaction effluent of a hydrotreating section is obtained.
In the method, the effluent of the hydrotreating reaction is separated to obtain a liquid phase and a gas phase, wherein the liquid phase can be fractionated to obtain light distillate oil and heavy distillate oil, and the light distillate oil is recycled and directly enters the hydrotreating hydrogen dissolving equipment.
In the method, the hydrotreated heavy distillate oil and optionally hydroisomerized heavy distillate oil are mixed with hydrogen in a hydrogen dissolving device, the mixed material enters a hydroisomerizing reactor under the liquid-phase hydroisomerizing operation condition, passes through a hydroisomerizing catalyst bed layer and is subjected to hydrogenation reaction, and then the reaction effluent of a hydroisomerizing section is obtained.
In the method, the effluent of the hydroisomerization reaction is separated to obtain a liquid phase and a gas phase, the liquid phase obtained by separation is continuously fractionated in a fractionating tower to obtain a plurality of lubricating oil base oils, wherein all or part of the heaviest fraction (hydroisomerization heavy fraction oil) is returned to the hydroisomerization hydrogen dissolving equipment as heavy cycle oil.
The raw oil of the lubricating oil used in the above process may include various vacuum distillates such as second-cut distillate, third-cut distillate, fourth-cut distillate, coker gas oil, light deasphalted oil and the like obtained by petroleum refining, or vacuum distillates such as coal tar, shale oil, synthetic oil and the like, or mixed vacuum distillates of the above distillates, or solvent refined oil of the above raw materials, and solvent refining may be carried out by a conventional method.
In the method, the range of the fraction of the light cycle oil is 35-260 ℃, and preferably 45-260 ℃. In the initial stage of use, the external light raw material which is similar to the range of light cycle oil fraction can be considered to be mixed with the raw oil and enter the hydrogen dissolving equipment, and the external light raw material can be replaced after the device is subjected to hydrotreating reaction to obtain light distillate oil. If no proper external raw material is available, the circulating oil is not used in the initial stage of the device start-up, the raw oil directly enters the hydrogen dissolving equipment to dissolve hydrogen and then enters the reactor, and light fraction is obtained after hydrogenation reaction and fractionation and then is gradually introduced into the reaction system. The light fraction obtained in the hydroisomerization part may also be used as light cycle oil.
In the method, the light raw material with the same fraction as the light cycle oil can be gasoline (naphtha) fraction, kerosene fraction and light diesel oil fraction obtained in the petroleum refining process, the petroleum refining process comprises atmospheric and vacuum distillation, coking, catalytic cracking, hydrofining, hydrotreating, hydrocracking, thermal cracking, catalytic reforming and the like, and the light raw material oil can be one or more mixed raw material oils obtained in the petroleum refining process
In the method, the operation conditions of the hydrotreating part are that the total reaction pressure is 3.0MPa to 20.0MPa and the total volume space velocity of the raw oil of the lubricating oil is 0.2h-1～8.0h-1The average reaction temperature of the catalyst bed layer is 180-450 ℃, and the ratio of the light cycle oil to the raw oil of the lubricating oil is 0.4: 1-10: 1; the optimized operation conditions of the hydrotreating part are that the total reaction pressure is 4.0MPa to 18.0MPa, and the total volume space velocity of the raw oil of the lubricating oil is 0.5h-1～6.0h-1The average reaction temperature of the catalyst bed layer is 200-440 ℃, and the ratio of the light cycle oil to the raw oil of the lubricating oil is 0.5: 1-8: 1.
In the above method, the hydrogenation active component in the hydrogenation catalyst used in the hydrogenation part is one or more of Co, Ni, Mo and W, and the content thereof is in the range of 5% to 68% by weight of all hydrogenation active metal oxides, the carrier of the hydrogenation catalyst is generally alumina, titania, silica, amorphous silica-alumina, etc., and other additives, such as Zr, B, P, Ti, Si, etc., may also be added during the preparation process, or two or more thereof may also be used. Can be prepared according to the existing method in the field, and can also adopt a commercial catalyst. The hydrogenation active component is usually an oxidation state catalyst, and the conventional presulfurization treatment needs to be carried out in a reactor before the catalyst is used, so that the hydrogenation active component on the catalyst is converted into a sulfuration state, and a better hydrogenation effect is achieved. A presulfiding catalyst may also be used. The commercial hydrogenation catalysts mainly include hydrogenation pretreatment catalysts such as 3936, FF-14, FF-16, FF-18, FF-20, FF-24, FF-26, FF-36, FF-46, FF-56, FF-66, FZC-41, FZC-42, etc., developed by the Dop petrochemical research institute (FRIPP), hydrogenation catalysts such as HC-P, HC-K, HC-T, UF-210/220, etc., hydrogenation catalysts such as HR-406, HR-416, HR-448, etc., of the IFP company, hydrogenation catalysts such as ICR154, ICR174, ICR178, ICR179, etc., of the Topsor company, hydrogenation catalysts such as TK-525, TK-555, TK-ZO, etc., KF-756, KF-757, KF-557 840, KF-848, KF-901, KF-757, KF-557-18, KF-901, FzC-16, FF-26, FZC, etc., developed by the AK company, KF-907 and the like. One grade of catalyst may be used, or multiple catalyst grades may be used.
In the above method, in order to protect the main hydrogenation catalyst and to extend the operation period of the apparatus, it is considered to fill a certain amount of the protecting agent. The protective agent is a conventional protective agent, only one protective agent can be used, and two or more protective agents can be selected according to the sequence of the particle size from large to small, the hydrogenation metal content from small to large and the hydrogenation performance from weak to strong to form a protective agent system. Such as the three protectant systems FZC-100/FZC-105/FZC-106 developed using FRIPP. The volume space velocity of the protective agent is 6.0h-1～20.0h-1。
In the method, the raw lubricating oil and the light cycle oil are mixed, hydrogen is dissolved by the hydrogen dissolving equipment and then enters from the top of the hydrogenation reactor, and the mixture flow with the dissolved hydrogen can pass through the catalyst bed layer from top to bottom, namely descending. The raw oil of lubricating oil is mixed with circulating oil, and can enter from the bottom of a hydrogenation reactor after hydrogen is dissolved by a hydrogen dissolving device, and the mixture flow dissolved with hydrogen can pass through a catalyst bed layer from bottom to top, namely, the mixture flow moves upwards.
In the above method, the catalyst bed may be one catalyst bed or a plurality of catalyst beds. If a plurality of catalyst bed layers exist, hydrogen dissolving equipment is arranged between the adjacent catalyst bed layers.
In the method, the previous catalyst bed layer or the next catalyst bed layer takes the flowing direction of reactant flow as a reference, and no matter the hydrogenation reaction is carried out in an ascending manner or a descending manner, the bed layer which is firstly contacted with the reactant flow in the adjacent bed layers is arranged upwards and then contacted downwards.
In the above method, the separation of the hydrogenation effluent is carried out by using a high-pressure separator and/or a low-pressure separator, preferably without using a high-pressure separator. The high-pressure separator is a conventional gas-liquid separator. The hydroprocessing reactant stream is separated in a high pressure separator to yield a gas and a 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 low-pressure separator to obtain gas and liquid. The hydroprocessing reactant stream is separated in a low pressure separator to obtain a gas and a liquid.
In the above method, the fractionation system used for the hydrotreating fractionation includes a stripping column and/or a fractionation column. The liquid obtained by separation in the low-pressure separator is stripped and/or fractionated in a fractionation system to obtain a light fraction and a hydrogenated heavy fraction.
In the method, the hydroisomerized raw oil is hydrogenated heavy fraction obtained by fractionating hydrogenated reactant flow, and the sulfur content of the hydrogenated heavy fraction is required to be less than 5 mu g/g, the nitrogen content is required to be less than 5 mu g/g, preferably the sulfur content is less than 3 mu g/g, and the nitrogen content is required to be less than 3 mu g/g.
In the method, the operation conditions of the hydroisomerization part are generally 3.0-18.0 MPa of reaction pressure and 0.2h of raw material oil volume space velocity-1～6.0h-1The average reaction temperature is 180-450 ℃, and the volume ratio of hydrogen to oil is 300: 1-1500: 1; the preferable operating conditions are that the reaction pressure is 4.0MPa to 16.0MPa, and the volume space velocity of the raw oil is 0.4h-1～5.0h-1The average reaction temperature is 200-440 ℃, and the volume ratio of hydrogen to oil is 400: 1-1200: 1.
In the method, the hydroisomerization catalyst is various suitable lubricating oil hydroisomerization catalysts, the carrier is an NU-10 molecular sieve or ZSM-22 molecular sieve with an alumina and TON structure, an SAPO-11 molecular sieve, beta zeolite and the like, the content of the molecular sieve in the catalyst is 5-70 wt%, preferably 10-60 wt%, and partial silica, amorphous silicon-aluminum and the like can also be added into the carrier; the active metal component is one or more of Pt, Pd, Ru, Rh and Mo, Ni, and the content in the catalyst is 0.1 wt% -30.0 wt%. The optional auxiliary agent component is one or more of boron, fluorine, chlorine and phosphorus, and the content of the optional auxiliary agent component in the catalyst is 0.1 wt% -5.0 wt%; the specific surface of the catalyst is 150-500 m2The pore volume is 0.15-0.60 ml/g. Before use, the catalyst is reduced to make the hydrogenation active metal in a reduction state in the reaction process. The commercial hydrogenation catalysts mainly comprise hydroisomerization catalysts such as FIW-1, FRIC-1 and FEIC-2 developed by the Fushun petrochemical research institute (FRIPP), hydroisomerization catalysts such as ICR-418 and ICR-422 developed by Chevron, and hydroisomerization catalysts such as MSDW-1 and MSDW-2 developed by Mobil.
In the method, the heavy fraction after the hydrotreating is mixed with the heavy cycle oil, hydrogen is dissolved by a hydrogen dissolving device and then enters from the top of a hydrogenation reactor, and the mixture flow with the dissolved hydrogen can pass through a catalyst bed layer from top to bottom, namely, a descending manner. The heavy fraction after hydrogenation treatment is mixed with heavy cycle oil, and the mixture can enter from the bottom of the hydrogenation reactor after hydrogen is dissolved by a hydrogen dissolving device, and the mixture flow dissolved with the hydrogen can pass through the catalyst bed layer from bottom to top, namely, the mixture flow moves upwards.
In the above method, the catalyst bed may be one catalyst bed or a plurality of catalyst beds. If a plurality of catalyst bed layers exist, hydrogen dissolving equipment is arranged between the adjacent catalyst bed layers.
In the method, the previous catalyst bed layer or the next catalyst bed layer takes the flowing direction of reactant flow as a reference, and no matter the hydrogenation reaction is carried out in an ascending manner or a descending manner, the bed layer which is firstly contacted with the reactant flow in the adjacent bed layers is arranged upwards and then contacted downwards.
In the above method, the hydrogenation reaction effluent is separated by using a high-pressure separator and/or a low-pressure separator, preferably without using a high-pressure separator. The high-pressure separator is a conventional gas-liquid separator. The hydroprocessing reactant stream is separated in a high pressure separator to yield a gas and a 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 low-pressure separator to obtain gas and liquid. The hydroprocessing reactant stream is separated in a low pressure separator to obtain a gas and a liquid.
In the method, the fractionation system adopted by the hydroisomerization fractionation comprises a fractionation tower. And the liquid obtained by separation in the low-pressure separator is fractionated in a fractionating system to obtain light products such as naphtha, diesel oil and the like and various lubricating oil base oil products.
In the method, the heavy cycle oil used in the hydroisomerization part is a heavy fraction with an initial boiling point temperature of more than 450 ℃ obtained by fractionation, and preferably a heavy fraction with an initial boiling point temperature of more than 480 ℃.
In the prior art, the lubricating oil raw material can be used for producing hydrogenated lubricating oil base oil by a liquid-phase circulating hydrogenation method, but the circulating oil used for hydrogenation pretreatment in the method is usually a hydrogenation product stream, namely the range of fractions is equivalent to that of the lubricating oil raw material. Research results also show that when light distillate oil is used as circulating oil, the light distillate oil can also dissolve hydrogen and can meet the requirement of the reaction required in the liquid phase hydrogenation reaction process of lubricating oil on the quantity of hydrogen, when macromolecules of heavier distillate preferentially carry out hydrogenation reaction, the fraction molecules contained in the light circulating oil are smaller, the influence on competitive adsorption during the summary macromolecule reaction of raw oil is smaller, and the influence on internal diffusion is smaller particularly, so that the hydrogenation reaction of the macromolecules of the heavy distillate in the raw oil is greatly facilitated, and the reaction efficiency is improved while the hydrogenation purpose requirement is met.
In the prior art, a plurality of high-quality lube base oils are obtained by continuously carrying out hydroisomerization on a hydrotreated heavy fraction, raw oil passes through once, the product selectivity is poor, particularly the pour point of a heavy fraction lube base oil product is high, even if a liquid phase circulation method is used, the pour point of a lighter fraction can be further reduced, although the pour point of the heavy fraction is also reduced correspondingly, the reduction range is not large.
The liquid phase hydrogenation method for the lubricating oil generally shows that the operation severity of the lubricating oil hydrotreating is reduced on the premise of not influencing the quality of the hydrogenated lubricating oil, the reaction efficiency is improved, and the quality of the hydrogenated lubricating oil base oil product can be further improved by using heavy fraction circulation in a hydrogenation isomerization section.
Drawings
FIG. 1 is a flow diagram of a liquid phase hydrogenation process of the present invention.
FIG. 2 is another flow diagram of the liquid phase hydrogenation process of the present invention.
Wherein: 1-raw oil, 2-raw oil pump, 3-hydrotreated cycle oil, 4-hydrotreatment hydrogen dissolving device, 5-1-hydrotreatment fresh hydrogen, 5-2-hydroisomerization fresh hydrogen, 6-hydrotreatment reactor, 7-hydrotreatment product stream, 8-vent valve, 9-hydrotreatment low-pressure separator, 10-hydrotreatment low-pressure separator gas stream, 11-hydrotreatment low-pressure separator liquid stream, 12-stripping/fractionating system, 13-stripping gas, 14-hydrotreatment light distillate oil, 15-hydrotreatment heavy distillate oil, 16-hydroisomerization raw oil, 17-hydroisomerization hydrogen dissolving device, 18-hydroisomerization reactor, 19-hydroisomerization reaction stream, 20-hydroisomerization low-pressure separator, 21-hydroisomerization low pressure separator gas stream, 22-hydroisomerization low pressure separator liquid stream, 23-hydroisomerization fractionator, 24-hydroisomerization light product, 25-lube base oil product 1, 26-lube base oil product 2.
Detailed Description
The flow and effect of the liquid phase hydrogenation process 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 liquid phase hydrogenation method for the lubricating oil has the following specific implementation mode: raw oil 1 and hydrotreating cycle oil 3 are mixed, the mixed material and hydrogen 5-1 are mixed in a hydrogen dissolving device 4 and then enter a hydrotreating reactor 6, the mixture passes through a first catalyst bed layer, hydrogen is dissolved in the effluent of the first catalyst bed layer, the mixture passes through a second catalyst bed layer, a hydrogen raw material is dissolved in the effluent of the second catalyst bed layer, the effluent 7 of the third catalyst bed layer passes through a third catalyst bed layer, the effluent enters a low-pressure separator 9, a gas 10 and a liquid 11 are obtained by separation in the low-pressure separator 9, the liquid 11 enters a stripping/fractionating system 12, a hydrotreating light fraction 14 and a hydrotreating heavy oil 15 are obtained by fractionating in the fractionating system, 90% of the hydrotreating light fraction 14 is recycled as the cycle oil 3, all of the hydrotreating heavy fraction 15 is mixed with hydroisomerization cycle oil 27 and hydrogen 5-2 in a hydrogen dissolving device 17, then the mixture enters a hydroisomerization reactor 18 and passes through a hydroisomerization first catalyst bed, hydrogen is dissolved in the effluent of the first catalyst bed, the mixture passes through a second catalyst bed, and optionally 75% of the reaction stream 19 of the second catalyst bed is recycled as hydroisomerization cycle oil 27, the rest 19 is subjected to gas-liquid separation in a hydroisomerization low-pressure separator 20 to obtain a gas product 21, and the separated liquid 22 continuously enters a fractionating tower 23 to be fractionated to obtain a light oil product 24, a lubricating oil base oil product 25 and a lubricating oil base oil product 26.
The following examples further illustrate specific aspects of the present invention. Experimental studies were conducted using FF-66 hydrotreating catalyst and FIW-1 hydroisomerization catalyst developed and produced by FRIPP development.
TABLE 1 Primary Properties of the raw materials
| Raw materials | Lubricating oil stock oil 1 | Lubricating oil stock oil 2 | Light distillate oil |
| Density, g/cm3 | 0.868 | 0.936 | 0.796 |
| Sulfur content, wt.% | 0.21 | 2.68 | 0.25 |
| Nitrogen content, wt% | 0.04 | 0.11 | 0.01 |
| Freezing point, deg.C | 38 | 32 | -10 |
| Viscosity (100 ℃ C.), mm2/s | 5.65 | 11.69 | — |
Table 2 examples process conditions and main product properties
As can be seen from the examples, the lubricating oil raw material can be directly used for producing various high-quality lubricating oil base oils by the liquid-phase hydrogenation method of the technology.
Claims (7)
1. A hydrogenation process characterized by: the method comprises the following steps:
(1) the raw oil of the lubricating oil is contacted with a hydrotreating catalyst to carry out liquid phase hydrotreating reaction;
(2) shunting the material subjected to the hydrotreating reaction in the step (1) to obtain hydrotreated light distillate oil and hydrotreated heavy distillate oil;
(3) contacting the hydrotreated heavy distillate with a hydroisomerization catalyst to perform a liquid-phase hydroisomerization reaction, and separating a hydroisomerization product to obtain various lubricating oil base oils;
in the step (2), the light distillate oil is recycled to the hydrotreating reactor to contact with a hydrotreating catalyst to carry out liquid phase hydrotreating reaction;
separating the hydroisomerization product in the step (3) to obtain hydroisomerization heavy distillate oil, and recycling part or all of the hydroisomerization heavy distillate oil to the hydroisomerization reactor to contact with a hydroisomerization catalyst to perform a liquid-phase hydroisomerization reaction;
the initial boiling point temperature of the hydroisomerized heavy distillate oil is more than 450 ℃; the range of the fraction of the light distillate oil is 35-260 ℃.
2. The method of claim 1, wherein: and (4) recycling part of the hydroisomerization products in the step (3) to the hydroisomerization reactor.
3. The method of claim 2, wherein: part of the hydroisomerized products are recycled to the hydroisomerized hydrogen dissolving equipment and are mixed with the hydrotreated heavy fraction oil, and then the mixture is recycled to the hydroisomerizing reactor.
4. The method of claim 1, wherein: the raw oil of lubricating oil and the hydrotreated light distillate oil are mixed with hydrogen in a hydrogen dissolving device, the mixed material enters a hydrotreating reactor under the condition of liquid-phase hydrogenation operation, passes through a hydrotreating catalyst bed layer and generates a hydrogenation reaction, and then a hydrotreating reaction effluent is obtained.
5. The method of claim 1, wherein: mixing the hydrotreated heavy distillate oil and the hydroisomerized heavy distillate oil with hydrogen in a hydrogen dissolving device, feeding the mixed material into a hydroisomerizing reactor under the liquid-phase hydroisomerizing operation condition, passing through a hydroisomerizing catalyst bed layer, carrying out hydrogenation reaction, and then obtaining a hydroisomerizing reaction effluent.
6. The method of claim 1, wherein: the raw oil of the lubricating oil is one or more of reduced second-line distillate oil, reduced third-line distillate oil, reduced fourth-line distillate oil, coking wax oil, light deasphalted oil, coal tar, shale oil and synthetic oil.
7. The method of claim 1, wherein the step of removing the metal oxide is performed in a batch processThe method comprises the following steps: the hydrotreating operation conditions include total reaction pressure of 3.0-20.0 MPa and total volume airspeed of the raw oil of the lubricating oil of 0.2h-1~8.0h-1The average reaction temperature of the catalyst bed layer is 180-450 ℃, and the ratio of the light distillate oil to the raw oil of the lubricating oil is 0.4: 1-10: 1.
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| CN109777488A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of refinery gas Combined machining technique |
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| CN109777488A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of refinery gas Combined machining technique |
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