CN116064115A - Process method for producing naphthenic rubber filling oil by hydrogenation - Google Patents
Process method for producing naphthenic rubber filling oil by hydrogenation Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 61
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 238000011049 filling Methods 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 18
- 238000007670 refining Methods 0.000 claims abstract description 17
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 12
- 239000003921 oil Substances 0.000 claims description 74
- 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 45
- 239000011148 porous material Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 230000000295 complement effect Effects 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- 239000002808 molecular sieve Substances 0.000 claims description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 239000011959 amorphous silica alumina Substances 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 239000004606 Fillers/Extenders Substances 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 10
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 30
- 238000005194 fractionation Methods 0.000 description 9
- 239000002199 base oil Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012071 phase Substances 0.000 description 6
- 239000010687 lubricating oil Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000010721 machine oil Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000008161 low-grade oil Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001502 supplementing effect Effects 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
- C10G65/08—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 hydrogenation of the aromatic hydrocarbons
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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 process method for producing naphthenic base rubber filling oil through hydrogenation. Cycloalkyl vacuum distillate is used as raw material, firstly, hydrotreating-hydrodewaxing reaction is carried out, and H influencing noble metal catalyst is removed from the effluent of the hydrotreating-hydrodewaxing reaction through high-pressure steam stripping 2 S and NH 3 After the impurities are removed, the oil enters a deep-replenishing refining reaction zone, so that the stability of the oil is improved. The method can obtain a high-quality naphthenic rubber filling oil product, and simultaneously produces a high-quality special oil product, greatly reduces energy consumption caused by two-stage method of boosting, reducing, boosting, heating, reducing and heating, and has the advantages of simple process and small occupied area.
Description
Technical Field
The invention relates to a process method for producing naphthenic base rubber filling oil through hydrogenation. In particular to a process method for producing cycloalkyl special oil products by using cycloalkyl vacuum distillate oil raw materials through two-stage process of hydrotreating, hydrodewaxing, high-pressure hydrogen stripping/supplementary refining.
Background
The naphthenic base crude oil has the characteristics of high density, high viscosity, low wax content, high aromatic hydrocarbon and naphthene content, low condensation point and the like, and is often used as a raw material for producing low-condensation lubricating oil base oil which has no requirement on viscosity-temperature performance, such as transformer oil, refrigerating machine oil, rubber filling oil and the like. The traditional production of the base oil of the lubricating oil adopts a solvent process, and the two main steps are the removal of non-ideal components such as aromatic hydrocarbon and the like by solvent refining and the dewaxing of the solvent so as to ensure the low-temperature flow property of the base oil. The hydrogenation method is a process method for producing lubricating oil base oil by adopting a hydrotreating or hydrocracking-hydrodewaxing or isomerization dewaxing-hydrofining combined process, and has the advantages of high product quality, no environmental problems, high base oil yield and the like, thereby gradually replacing the traditional solvent process.
In the prior art, various hydrogenation processes have been employed to produce naphthenic lube base oils. CN1990833a discloses a method for producing transformer oil from naphthenic oil as raw material by two-stage method of hydrotreating-hydrofining, which does not improve the condensation point, and the ideal product can be obtained by selecting proper raw material. CN1676585a reports a method for producing lubricating base oil by hydrotreating-hydrodewaxing-finishing, in which the hydrotreated product must be subjected to gas-liquid separation before the liquid product can enter the hydrodewaxing process. CN161376838A describes a method for producing lubricating base oils by two-stage hydroprocessing, hydrodewaxing and hydrofinishing, wherein the hydrotreated product is fed directly into the hydrodewaxing and hydrofinishing reaction zone without separation.
Shell discloses a method for directly removing H in hydrotreated products by adopting high-pressure steam stripping 2 S、NH 3 Then enters a noble metal hydrodewaxing and finishing reactor to produce naphthenic rubber filling oil, and has 3 sets of industrial applications in China but contains H 2 S and NH 3 Meanwhile, cold high-purity oil which is not subjected to deep dearomatization is directly integrated into a fractionation system, so that all products are poor in color and stability.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a process method for producing naphthenic base rubber filling oil through hydrogenation. In particular to a method for producing cycloalkyl special oil products by taking cycloalkyl vacuum distillate oil as a raw material through two-stage process of hydrotreating, hydrodewaxing, high-pressure hydrogen stripping/supplementary refining.
The invention relates to a process method for producing naphthenic rubber filling oil by hydrogenation, which comprises the following steps:
(1) The naphthenic base vacuum distillate oil and hydrogen are mixed and then enter a hydrotreating reaction zone, and are sequentially contacted with a hydrogenation protecting catalyst, a hydrofining catalyst and a hydrogenation modifying catalyst for hydrogenation reaction, wherein the hydrogenation modifying catalyst contains amorphous silicon-aluminum and a modified Y molecular sieve;
(2) The hydrotreated effluent obtained in the step (1) enters a hydrodewaxing reaction zone and is contacted and reacted with a hydrodewaxing catalyst, so that the linear alkane with the greatest influence on the pour point of the product is cracked in a shape-selective manner, and the pour point of the product is reduced;
(3) Feeding the hydrodewaxing effluent obtained in the step (2) into a high-pressure stripping tower from the upper part, injecting hydrogen at the bottom of the tower as a stripping medium, and stripping to obtain the H-removed product 2 S and NH 3 And (b) a bottom oil containing H 2 S、NH 3 An overhead of hydrogen and a portion of the light oil;
(4) Step (3) to obtain a catalyst containing H 2 S、NH 3 The tower top effluent of hydrogen and part of light oil enters a cold high-pressure separator after heat exchange, and contains H 2 S and NH 3 Cold high-fraction oil enters cold low-fraction to separate low-fraction gas, and then cold low-fraction oil enters H removal 2 S stripping tower for removing H 2 S and NH 3 After pressure boosting and heat exchange, the waste water enters a complementary refining reaction zone;
(5) Mixing the high-pressure stripping tower bottom oil obtained in the step (3) with hydrogen, and removing H 2 S and NH 3 The cold low-fraction oil enters a complementary refining reaction zone together for deep dearomatization reaction, so that the product stability is improved;
(6) And (3) introducing the reaction effluent obtained in the step (5) into a separation system to obtain a cycloalkyl special oil product with pour point meeting requirements and good stability and a series of light white oil meeting the technical index requirements of the light white oil (II) in NB/SH/T0913-2015.
Further, the high pressure stripper of step (3) includes a packing therein, such as may include calendaring Konghuan packing. The choice of the filler is a matter of routine for a person skilled in the art. Preferably, a ZnO bed layer is also arranged at the lower part of the filling zone, and can be used for removing a small amount of H which is not stripped cleanly due to operation fluctuation 2 S, S. The operating conditions of the high pressure stripper are well known to those skilled in the art. The operating conditions of the high pressure stripper include: the stripping temperature is 150-400 ℃, preferably the outlet temperature of the hydrodewaxing reaction zone, the stripping pressure is the same as the pressure of the hydrodewaxing reaction zone, the hydrogen consumption is higher than the chemical hydrogen consumption of the hydrotreating and hydrodewaxing reaction, preferably the sum of the chemical hydrogen consumption of the hydrotreating and hydrodewaxing reaction and the dissolved hydrogen of a first-stage hydrogenation system.
Further, the cold high-molecular gas phase obtained in the step (4) is subjected to selective H removal 2 S is re-entered into the hydrotreating reactor as recycle hydrogen.
Further, the naphthenic base distillate oil can be at least one of naphthenic base distillate oil, coal tar hydrocracking tail oil or catalytic cracking diesel oil distillate. The aromatic hydrocarbon content of the cycloalkyl fraction is generally 30-99 wt%, and the density at 20 ℃ is generally 0.923-0.955 g/cm 3 . The distillation range of the naphthenic base distillate oil raw material is any range formed by any two values within the range of 140-600 ℃; preferably, the initial distillation point of the naphthenic base distillate oil is 140-350 ℃, and the final distillation point is 400-600 ℃.
Further, the hydrofining catalyst in step (1) is a conventional hydrofining catalyst in the art, such as a diesel hydrofining catalyst or a hydrocracking pretreatment catalyst. The hydrofining catalyst generally takes VIB group and/or VIII group metal as an active component, alumina or silicon-containing alumina as a carrier, VIB group metal is generally Mo and/or W, and VIII group metal is generally Co and/or Ni. The content of the metal in the VIB group is 10 to 50 weight percent based on oxide, and the content of the metal in the VIII group is 3 to 15wt percent based on oxide; the properties are as follows: the specific surface area is 100-350 m 2 Per g, the pore volume is 0.15-0.6 mL/g. The selected commercial catalyst is 3936, 3996, FF-16, FF-26, FF-36, FF-46, FF-56, FF-66 and other hydrofining catalysts which are developed by China petrochemical industry Co., ltd. It can also be a similar function catalyst developed by foreign catalyst companies, such as HC-K, HC-P catalyst from UOP company, TK-555 and TK-565 catalyst from Topsoe company, KF-847 and KF-848 from AKZO company, etc.
Further, the hydro-upgrading catalyst contains amorphous silica-alumina and a modified Y molecular sieve. The catalyst for hydrogenation modification contains 20-60 wt% of amorphous silica-alumina, 5-25 wt% of modified Y zeolite, 10-30 wt% of VIB metal calculated by oxide and 4-15 wt% of VIII metal calculated by oxide. The specific surface area of the hydro-upgrading catalyst is generally 220-300 m 2 The pore volume per gram is 0.3-0.6 mL/g, the pore volume with the pore diameter of 3-10nm accounts for 75-95 percent of the total pore volume, preferably 85-95 percent, and the infrared acidity is 0.30-0.5 mmol/g. Wherein, the properties of the amorphous silica-alumina used are as follows: 10 to 60 weight percent of silicon oxide and the specific surface is 400 to 650m 2 Per gram, the pore volume is 1.0-1.8 mL/g, the infrared acidity is 0.34-0.50 mmol/g, the pore volume with the pore diameter of 4-10 nm accounts for 85-95% of the total pore volume,>the pore volume of 15nm accounts for less than 5% of the total pore volume; the preferred properties are as follows: 10 to 35 weight percent of silicon oxide with a specific surface of 530 to 650m 2 Per gram, the pore volume is 1.2-1.5 mL/g. The modified Y zeolite has the following properties: siO (SiO) 2 /Al 2 O 3 The molar ratio is 40-60, the unit cell constant is 2.425-2.440 nm, the relative crystallinity is 80-100%, the infrared acidity is 0.1-0.5 mmol/g, wherein the distribution of the medium and strong acid at 250-550 ℃ is concentrated, the medium and strong acid accounts for 60-70% of the total acid, and the specific surface area is 600-900 m 2 And/g, the pore volume is 0.3-0.6 mL/g, wherein the pore volume of the secondary mesopores with the diameter of 4-15 nm accounts for 40-50% of the total pore volume. The hydro-upgrading catalyst can also contain one or more of alumina, zirconia, titania and other components.
Further, the hydrodewaxing catalyst in the step (2) can be selected from hydrodewaxing catalysts commonly used in the field, such as 3881 and FDW-3 catalysts developed by China petrochemical and smooth petrochemical institute, and can be prepared according to common knowledge in the field. The hydrogenation pour point depressing catalyst contains ZSM-5 molecular sieve. Based on the weight of the catalyst, the ZSM-5 molecular sieve content is 50-85 wt%, the NiO and/or CoO is 1.0-1.0 wt.0-wt%, and the balance is a binder.
Further, the supplementary refining catalyst filled in the supplementary refining reaction zone is a conventional reduction type hydrofining catalyst, and the active metal of the supplementary refining catalyst is one or two of Pt and Pd or nickel. The weight content of active metal in the noble metal catalyst is generally 0.05-1%, and the weight content of nickel in the reduced nickel catalyst is 30-80% in terms of oxide; the catalyst support is typically Al 2 O 3 Or Al 2 O 3 -SiO 2 One or more of P, ti, B, zr can be optionally contained as an auxiliary agent. The catalyst needs to be reduced conventionally before use, so that the hydrogenation active metal is ensured to be in a reduced state in the reaction process. The catalyst can be selected from common commercial catalysts in the field or prepared according to common methods in the field.
Further, the operating conditions of the hydrotreating reaction zone are: the hydrogen partial pressure is 5.0-18.0 MPa, preferably 10.0-16.0 MPa; the reaction temperature is 230-430 ℃, preferably 350-410 ℃; the volume ratio of hydrogen to oil is 200-1500, preferably 600:1-1000:1; volume space velocity is 0.1-10.0 h -1 Preferably 0.3. 0.3h -1 ～0.5h -1 . Hydrofining catalyst and hydro-upgrading catalyst filling ratio of the hydrotreating reaction zone 1:9~9:1, preferably 4:6~6:4.
further, the operation conditions of the hydrodewaxing reaction zone are as follows: the hydrogen partial pressure is 5.0-18.0 MPa, preferably 10.0-16.0 MPa; the reaction temperature is 230-430 ℃, preferably 300-410 ℃; the volume ratio of the hydrogen to the oil is 200-1500, preferably 500:1-1000:1; volume space velocity is 0.1-10.0 h -1 Preferably 0.3. 0.3h -1 ～1.0h -1 ；
Further, the reaction conditions of the complementary refining reaction zone are as follows: the reaction temperature is 200-300 ℃, preferably 210-280 ℃, the hydrogen partial pressure is 6.0-18.0 MPa, preferably 10.0-15.0 MPa, and the volume space velocity is 0.2h -1 ～3.0h -1 Preferably 0.3h -1 ～0.6h -1 The volume ratio of hydrogen oil is 400:1-1500:1, preferably 600:1-800:1.
Further, the hydrotreating reaction zone and the hydrodewaxing reaction zone may be provided in one reactor, or in two reactors, respectively.
Further, the cycloalkyl special oil product obtained in the step (6) comprises one or more of transformer oil, refrigerating machine oil and series rubber filling oil.
Compared with the prior art, the method has the following beneficial effects:
1. the two-stage hydrogenation process adopting high-pressure hydrogen stripping hydrogenation treatment-hydrodewaxing/deep supplementary refining avoids the conventional two-stage hydrogenation process to avoid H 2 S and NH 3 The influence on noble metal catalyst needs to set two sets of fractionating systems, and the reaction feed of the two-stage hydrogenation process of high-pressure hydrogen stripping hydrotreating-hydrodewaxing-deep replenishing refining is mostly equal to that of the reaction feed of the two-stage hydrogenation process>85 w%) is a one-step boosting process, so that the processes of boosting, reducing pressure and re-boosting of all raw oil between two sections of reaction areas of a traditional two-section process device are avoided, the power consumption is saved, and meanwhile, the stripping hydrogen injected into the bottom of a high-pressure stripping tower is part of the supplementing hydrogen and enters a hydrogen circulating system of a hydrotreatment device; the operation temperature of the high-pressure stripping tower is regulated, the bottom effluent can directly enter the complementary refining reactor, an isomerism dewaxing feeding heating furnace is not required to be arranged, the energy loss in the heating, cooling and reheating processes of all reaction products in the traditional two-stage process is avoided, the electricity consumption and the fuel gas consumption are saved, and meanwhile, the occupied area is saved.
2. The effluent from the top of the high-pressure stripping tower enters a cold high-pressure separator after heat exchange, and after the gas-phase recycle hydrogen is separated, the effluent contains H 2 S and NH 3 The cold high-pressure oil is depressurized and then enters a cold low-pressure separator to separate low-pressure gas, and the cold low-pressure oil enters a conventional H removal device 2 S stripping tower for removing H 2 S and NH 3 After heat exchange, the oil enters a complementary refining reactor, so that the problem of influence on the color and stability of the product caused by direct entry of cold high-fraction oil of the shell process into a fractionation system is solved.
Drawings
FIG. 1 is a schematic process flow diagram of the method of the present invention.
Detailed Description
The method of the present invention will be described in more detail below with reference to the accompanying drawings and specific examples.
Referring to fig. 1, the method for producing naphthenic rubber extender oil by hydrogenation according to the present invention is as follows: after being mixed with recycle hydrogen of a pipeline 2 through a pipeline 1, naphthenic base vacuum distillate firstly enters a hydrotreating reaction zone 3 to carry out desulfurization, denitrification, deoxidation and arene saturation reactions; then the hydrotreated product 4 enters a hydrodewaxing reaction zone 5, and linear alkane with the greatest influence on the pour point of the product in the product is cracked in a shape-selective manner; then the hydrodewaxing product 6 enters a high-pressure hydrogen stripping tower 7, stripping hydrogen 8 is blown into the bottom of the tower, and H is removed 2 S and NH 3 The top of the high pressure stripping column enters a separation system 10 of a hydrotreating-hydrodewaxing section, the separation system 10 generally comprising a high pressure separator and a low pressure separator; the separated gas phase is used as recycle hydrogen to be returned to the hydrotreating reaction system through a pipeline 2, and the liquid phase product 11 enters into the H removal 2 S stripping column 12, removing H 2 S and NH 3 After pressure boosting and heat exchange, the bottom oil 13 of the (a) is mixed with recycle hydrogen 15, new hydrogen 14 and high-pressure stripping bottom oil 9 of a finishing section and directly enters a finishing reactor 16 to carry out deep dearomatization reaction, so that the photo-thermal stability of the product is improved, a finishing reaction product 17 enters a separation system 18, the separation system 18 generally comprises a high-pressure separator and a low-pressure separator, low-fraction oil enters a fractionation system 19, and the fractionation system comprises an atmospheric fractionation tower and a vacuum fractionation tower to obtain light naphtha, light white oil and naphthenic base products (comprising transformer oil, refrigerating machine oil and series naphthenic base rubber filling oil).
The details and effects of the method according to the invention are described below by means of specific examples.
The following examples further illustrate the methods provided by the present invention, but are not intended to limit the scope of the invention. The properties of the raw materials treated by the method are shown in Table 1, and the physicochemical properties of the catalyst used are shown in Table 2.
TABLE 1 Properties of the feedstock
TABLE 2 catalyst physicochemical Properties
Example 1
The raw materials are naphthenic base two-wire oil listed in table 1, and the physical and chemical properties of the catalyst are shown in table 2, wherein a hydrotreating zone is filled with a series of hydrogenation protecting agents, a hydrofining catalyst and a hydro-upgrading catalyst, and the series of hydrogenation protecting agents are as follows: hydrofining catalyst: hydro-upgrading catalyst = 1:5.5:3.5 (volume). The principle flow chart is shown in fig. 1. The process conditions and test results are shown in tables 3-4.
Example 2
The feedstock was cycloalkyl minus three-wire oil as listed in table 1 using the same catalyst as in example 1. The principle flow chart is shown in fig. 1. The process conditions and tests are shown in tables 3-4.
Comparative example 1
Comparative example 1 used a conventional two-stage hydrogenation process. The process flow is as follows: the hydrotreating-hydrodewaxing product firstly enters a hot high-pressure separator, after gas phase heat exchange, enters a cold high-pressure separator, cold high-fraction gas phase enters a circulating hydrogen system, cold high-fraction oil is depressurized, and then enters cold low-fraction gas, and the top of the separator is low-fraction gas; the hot high-pressure oil is decompressed and enters into hot low-pressure gas; the hot low-pressure oil (the vast majority of the product) and the cold low-pressure oil are mixed and then all enter a hydrogen sulfide stripping tower (the pressure is about 1 MPa), a small amount of gasoline containing hydrogen sulfide is discharged from the top of the tower and the whole tower bottom liquid (sulfur content<10µg.g -1 Nitrogen content of<2µg.g -1 ) After heating and boosting, the mixture enters a two-stage complementary refining reactor; the supplementary refined product is separated from gas and liquid and fractionated to obtain various products.
Comparative example 1 the same starting material as in example 1 was used, and the same catalyst as in example 1 was used. The process conditions and tests are shown in tables 3-4.
Comparative example 2
Comparative example 2 employed the shell process ("application study of high pressure hydrogen stripping in full hydrogenation lube oil production flow", xue Nan, petroleum refining and chemical industry, 2019, 10 months).
Comparative example 2 the same feed as in example 1 was used, and the same catalyst as in example 1 was used, the flow was that the hydrotreated-hydrodewaxed product was subjected to high pressure stripping and then directly fed to the finishing stage, the hot high-pressure gas phase was fed to the cold low-pressure separator, the cold low-pressure gas was returned as recycle hydrogen to the reaction system, and the cold low-pressure oil was directly fed to the following fractionation system, followed by fractionation to obtain various products. The process conditions and test results are shown in tables 3-4.
TABLE 3 Process conditions
* Fresh feed was made.
Table 4 test results
* Fresh feed.
As can be seen from the data in tables 3-4, the cycloalkyl vacuum distillate is used as a raw material, and the two-stage process of hydrotreating-hydrodewaxing-high pressure hydrogen stripping/hydrofinishing is adopted, so that the product with the quality equivalent to that of the two-stage process of conventional hydrotreating-hydrodewaxing/hydrofinishing can be produced, meanwhile, the energy consumption of the whole feeding pressure increasing, pressure decreasing, pressure increasing, temperature decreasing and temperature increasing processes of the conventional two-stage process is avoided, the occupied area of the device is reduced, and the energy consumption of the device is reduced by about 12%. In comparative example 2, a shell process flow is adopted, and although the energy consumption is lower, aromatic hydrocarbon in cold low-grade oil is directly fed into a fractionation system without hydrofining, so that the light stability and the heat stability of all-line products are unqualified.
Claims (15)
1. A process method for producing naphthenic rubber filling oil by hydrogenation comprises the following steps:
(1) The naphthenic base vacuum distillate oil and hydrogen are mixed and then enter a hydrotreating reaction zone, and are sequentially contacted with a hydrogenation protecting catalyst, a hydrofining catalyst and a hydrogenation modifying catalyst for hydrogenation reaction, wherein the hydrogenation modifying catalyst contains amorphous silicon-aluminum and a modified Y molecular sieve;
(2) The hydrotreated effluent obtained in the step (1) enters a hydrodewaxing reaction zone and is contacted and reacted with a hydrodewaxing catalyst;
(3) Feeding the hydrodewaxing effluent obtained in the step (2) into a high-pressure stripping tower from the upper part, injecting hydrogen at the bottom of the tower as a stripping medium, and stripping to obtain the H-removed product 2 S and NH 3 And (b) a bottom oil containing H 2 S、NH 3 An overhead of hydrogen and a portion of the light oil;
(4) Step (3) to obtain a catalyst containing H 2 S、NH 3 The tower top effluent of hydrogen and part of light oil enters a cold high-pressure separator after heat exchange, and contains H 2 S and NH 3 Cold high-fraction oil enters cold low-fraction to separate low-fraction gas, and then cold low-fraction oil enters H removal 2 S stripping tower for removing H 2 S and NH 3 After pressure boosting and heat exchange, the waste water enters a complementary refining reaction zone;
5) Mixing the high-pressure stripping tower bottom oil obtained in the step (3) with hydrogen, and removing H 2 S and NH 3 Cold low-fraction oil of (2) enters a complementary refining reaction zone together for deep dearomatization reaction;
(6) And (3) introducing the reaction effluent obtained in the step (5) into a separation system to obtain a cycloalkyl special oil product with pour point meeting requirements and good stability and a series of light white oil meeting the technical index requirements of the light white oil (II) in NB/SH/T0913-2015.
2. The process of claim 1 wherein the ZnO bed is disposed in the lower portion of the packing region in the high pressure stripper.
3. The process of claim 1, wherein the operating conditions of the high pressure stripper comprise: the stripping temperature is 150-400 ℃, preferably the outlet temperature of the hydrodewaxing reaction zone, the stripping pressure is the same as the pressure of the hydrodewaxing reaction zone, the hydrogen consumption is higher than the chemical hydrogen consumption of the hydrotreating and hydrodewaxing reaction, preferably the sum of the chemical hydrogen consumption of the hydrotreating and hydrodewaxing reaction and the dissolved hydrogen of a first-stage hydrogenation system.
4. The process according to claim 1, wherein the cold high-molecular gas phase obtained in step (4) is subjected to selective H removal 2 S is re-entered into the hydrotreating reactor as recycle hydrogen.
5. The process according to claim 1, wherein the naphthenic distillate has an aromatic hydrocarbon content of 30-99 wt% and a 20 ℃ density of 0.923-0.955 g/cm 3 。
6. The process according to claim 1, wherein the initial point of the cycloalkyl fraction is 140 to 350 ℃ and the final point is 400 to 600 ℃.
7. The process according to claim 1, wherein the hydro-upgrading catalyst comprises 20 to 60wt% of amorphous silica-alumina, 5 to 25wt% of modified Y zeolite, 10 to 30wt% of group vi B metal in terms of oxide and 4 to 15wt% of group viii metal in terms of oxide, based on the weight of the catalyst.
8. The process according to claim 7, wherein the specific surface area of the hydro-upgrading catalyst is 220-300 m 2 And/g, wherein the pore volume is 0.3-0.6 mL/g, the pore volume with the pore diameter of 3-10nm accounts for 75-95% of the total pore volume, and the infrared acidity is 0.30-0.5 mmol/g.
9. The process of claim 1, wherein the hydrodewaxing catalyst comprises a ZSM-5 molecular sieve, the ZSM-5 molecular sieve content being 50-85 wt%, niO and/or CoO being 1.0 wt% -8.0 wt%, the remainder being binder, based on the weight of the catalyst.
10. The process according to claim 1, wherein the finishing catalyst packed in the finishing reaction zone is a reduced hydrofining catalyst, the active metal is one or both of Pt and Pd, or nickel, and the catalyst carrier is Al 2 O 3 Or Al 2 O 3 -SiO 2 Optionally one or more of P, ti, B, zr as an auxiliary agent.
11. The process of claim 1 wherein the operating conditions of the hydrotreating reaction zone are: the hydrogen partial pressure is 5.0-18.0 MPa, preferably 10.0-16.0 MPa; the reaction temperature is 230-430 ℃, preferably 350-410 ℃; the volume ratio of hydrogen to oil is 200-1500, preferably 600:1-1000:1; volume space velocity is 0.1-10.0 h -1 Preferably 0.3. 0.3h -1 ～0.5h -1 。
12. The process of claim 1 wherein the hydrofinishing catalyst and hydrofinishing catalyst loading ratio 1:9~9:1.
13. the process of claim 1 wherein the operating conditions of the hydrodewaxing reaction zone are: the hydrogen partial pressure is 5.0-18.0 MPa, preferably 10.0-16.0 MPa; the reaction temperature is 230-430 ℃, preferably 300-410 ℃; the volume ratio of the hydrogen to the oil is 200-1500, preferably 500:1-1000:1; volume space velocity is 0.1-10.0 h -1 Preferably 0.3. 0.3h -1 ～1.0h -1 。
14. The process of claim 1 wherein the reaction conditions of the finishing reaction zone are: the reaction temperature is 200-300 ℃, preferably 210-280 ℃, the hydrogen partial pressure is 6.0-18.0 MPa, preferably 10.0-15.0 MPa, and the volume space velocity is 0.2h -1 ～3.0h -1 Preferably 0.3h -1 ～0.6h -1 The volume ratio of hydrogen oil is 400:1-1500:1, preferably 600:1-800:1.
15. The process of claim 1, wherein the naphthenic specialty oil obtained in step (6) comprises one or more of transformer oil, refrigerator oil, and series rubber extender oil.
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| US20050109673A1 (en) * | 2003-11-10 | 2005-05-26 | Schleicher Gary P. | Process for making lube oil basestocks |
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| CN113122325A (en) * | 2019-12-31 | 2021-07-16 | 中国石油化工股份有限公司 | Method for producing rubber filling oil by catalytic cracking slurry oil |
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- 2021-10-31 CN CN202111278635.4A patent/CN116064115A/en active Pending
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| US20050109673A1 (en) * | 2003-11-10 | 2005-05-26 | Schleicher Gary P. | Process for making lube oil basestocks |
| CN103627430A (en) * | 2012-08-23 | 2014-03-12 | 中国石油化工股份有限公司 | Hydrogenation method used for direct production of low-condensation point lubricant base oil |
| CN108559545A (en) * | 2018-04-09 | 2018-09-21 | 华南理工大学 | A kind of residual hydrogenation rectification flow for stopping fractionating column system and change cold low point oily whereabouts |
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