CN111378495B - Fischer-Tropsch synthetic oil production API III+Hydrogenation method of base oil - Google Patents
Fischer-Tropsch synthetic oil production API III+Hydrogenation method of base oil Download PDFInfo
- Publication number
- CN111378495B CN111378495B CN201811652319.7A CN201811652319A CN111378495B CN 111378495 B CN111378495 B CN 111378495B CN 201811652319 A CN201811652319 A CN 201811652319A CN 111378495 B CN111378495 B CN 111378495B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- oil
- reaction
- oxide
- fischer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003921 oil Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 67
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 56
- 239000002199 base oil Substances 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 89
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims description 92
- 239000002808 molecular sieve Substances 0.000 claims description 32
- 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 32
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- 239000001257 hydrogen Substances 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 238000003786 synthesis reaction Methods 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 239000008186 active pharmaceutical agent Substances 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000010687 lubricating oil Substances 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 229910000510 noble metal Inorganic materials 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 239000011959 amorphous silica alumina Substances 0.000 claims description 5
- 239000012188 paraffin wax Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052773 Promethium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 230000000704 physical effect Effects 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 2
- -1 rare earth modified molecular sieve Chemical class 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 47
- 239000000314 lubricant Substances 0.000 abstract description 12
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 238000003672 processing method Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 41
- 150000001335 aliphatic alkanes Chemical class 0.000 description 11
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 10
- 150000001336 alkenes Chemical class 0.000 description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 9
- 238000004517 catalytic hydrocracking Methods 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000012668 chain scission Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 230000000881 depressing effect Effects 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001924 cycloalkanes Chemical class 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect 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
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 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
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1022—Fischer-Tropsch products
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
Landscapes
- 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 disclosesA processing method of Fischer-Tropsch synthetic oil is provided. The method uses Fischer-Tropsch synthetic oil as a raw material to produce API III by adopting a two-stage hydrogenation process of hydrofining, hydrogenation modification and isomerization dewaxing+A lubricant base oil. The oil obtained by separating the effluent of the hydrofining-hydroupgrading reaction enters an isomerization dewaxing reaction zone, and the effluent of the isomerization dewaxing reaction is separated and fractionated to obtain different types of API III+A lubricant base oil product. The method has the advantages of simple process flow and wide raw material adaptability, and can be suitable for the process of producing special oil products with good stability by hydrogenation of Fischer-Tropsch synthetic oil fractions.
Description
Technical Field
The invention relates to a Fischer-Tropsch synthetic oil production API III+A hydrogenation method of base oil, in particular to a method for producing API III by adopting hydrogenation combined process+A hydrogenation method of lubricant base oil.
Background
In a Fischer-Tropsch process, synthesis gas (CO + H)2) The catalytic conversion to essentially linear hydrocarbons and oxygenates can be in the form of a gas, liquid or solid. These fischer-tropsch synthesis products have a very low content of sulphur, nitrogen, aromatics and cyclics. The Fischer-Tropsch synthetic oil obtained by the Fischer-Tropsch synthesis technology has larger difference in hydrocarbon composition, main properties and other aspects compared with the conventional petroleum derivatives, is a substance with high wax content, mainly comprises paraffin and olefin, has extremely low sulfur and nitrogen content, and contains a certain amount of oxygen.
Since the introduction of oxygen during the synthesis gas production process determines the presence of certain amounts of oxygenates, such as alcohols, acids, etc., a certain amount of water is formed during subsequent processing, which adversely affects the use of the catalyst. The high olefin content is due to the reaction mechanism of the process to produce alkanes by forming olefin intermediates. The existence of a large amount of olefin not only is easy to generate oxidation, polymerization and other reactions, but also can promote the oxidation reaction of other hydrocarbons to generate products such as colloid which seriously influences the use performance of the oil product. Because the straight-chain hydrocarbon content in the products is high, the low-temperature performance of the products is poor, the products can not be directly used generally, and the products can be obtained after further hydrogenation modification.
EP-0515256 discloses a process for preparing a high viscosity index lubricant base oil from Fischer-Tropsch wax, which process comprises the steps of: (a) contacting a Fischer-Tropsch wax with hydrogen in the presence of an alumina-based hydroconversion catalyst; (b) contacting the effluent of step (a) with a hydroisomerization catalyst; (c) separating the effluent of step (b) into at least one light fraction and one heavy fraction; (d) dewaxing the heavy fraction to obtain a base oil and a wax fraction, which may be partly or fully recycled to step (b). The method mainly produces the lubricating oil base oil, and the yield of naphtha and diesel oil is low. And the effluent of step (a) is not separated and is subjected to hydroisomerization, which is burdened by the fact that the effluent contains a portion of light components, which do not substantially participate in the reaction during hydroisomerization.
US7,198,710 proposes a process for producing high viscosity index lubricant base oils from fischer-tropsch wax. Firstly, Fischer-Tropsch wax is fractionated to obtain a light component and a heavy component, and then hydrogenation isodewaxing is respectively carried out to reduce the pour point of the raw material, so that the light lubricating oil base oil with the pour point meeting the requirement can be obtained. And (3) because the pour point of the hydroisomerization dewaxing heavy component is unqualified, the pour point of the heavy component is further reduced by adopting a solvent dewaxing method, and finally the heavy lubricant base oil product with the pour point meeting the requirement is obtained.
US5378348 discloses a process for the production of middle distillates from fischer-tropsch synthesis products by hydrocracking and hydroisomerisation. The method divides the Fischer-Tropsch synthesis reaction products into naphtha (C5-160 ℃), light fraction (160-260 ℃) and heavy fraction (> 260 ℃), the heavy fraction (> 260 ℃) is subjected to hydrocracking reaction, and the unconverted heavy fraction (> 370 ℃) is recycled to the hydrocracking reactor to continue the cracking reaction. The catalyst is noble metal catalyst or Ni + Co/Mo catalyst, the conversion rate is controlled at 39-53 wt%; the light component products obtained by the light fraction hydrocracking reaction are mixed and then are subjected to hydrotreating, olefin saturation reaction and hydrodeoxygenation reaction mainly occur, and then kerosene is subjected to hydroisomerization reaction, so that the proportion of the heterogeneity in the hydrocarbon composition (the ratio of heterogeneous hydrocarbons to normal hydrocarbons) is improved. The method can increase the yield of distillate oil such as kerosene, diesel oil and the like, and the products have good low-temperature fluidity. The method adds an isomeric pour point depressing catalytic reaction process and a fractionating tower, so that the process flow is more complex; the dosage of the catalyst is greatly increased by increasing the isomerization and pour point depression section; water generated in the hydrofining process directly enters the isomerization pour point depressing reactor, and has certain influence on the isomerization pour point depressing catalyst; the yield of the middle distillate is not high.
The Fischer-Tropsch synthesis product is a raw material, and the fraction at the temperature of more than 350 ℃ is obtained by a hydrofining process and is subjected to direct hydroisomerization reaction, the used catalyst is a noble metal catalyst, the method can be used for producing API III + lubricating oil base oil, but the isomerization reaction of long-chain macromolecular alkane is severe, a large amount of naphtha components are generated, the total liquid yield is greatly reduced, and the base oil yield is not high.
In summary, the suitable process for producing the middle distillate oil by hydrogenating the Fischer-Tropsch synthetic oil is more, and the API III is produced+The technological process of the lubricant base oil is less. The prior art can not meet the requirement of producing special oil products by hydrogenation of Fischer-Tropsch synthetic oil.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the Fischer-Tropsch synthetic oil processing method which has strong raw material adaptability and simple and flexible process flow.
The invention relates to a Fischer-Tropsch synthetic oil production API III+The hydrogenation method of the lubricating oil base oil comprises the following steps:
(1) mixing raw material oil of Fischer-Tropsch synthetic oil with hydrogen, entering a hydrofining reaction zone, and contacting with a hydrofining catalyst for reaction;
(2) directly feeding the reaction effluent obtained in the step (1) into a hydro-upgrading reaction zone without separation, and contacting the reaction effluent with a hydro-upgrading catalyst containing a beta molecular sieve for reaction;
(3) separating and fractionating the reaction effluent obtained in the step (2), mixing the obtained generated oil with hydrogen, entering a hydroisomerization dewaxing reaction zone, and contacting and reacting with a hydroisomerization dewaxing catalyst containing a shape-selective molecular sieve;
(4) carrying out gas-liquid separation on the effluent of the isomerization dewaxing reaction obtained in the step (3), and fractionating the liquid to obtain API III+A lube base oil-like product fraction.
In the present invention, the obtained API III+The viscosity index of the lubricating oil base oil product is larger than 125, and is generally 130-170. API III+The pour points of the lubricant base oil products are all below-10 ℃, preferably below-15 ℃. API III+The pour point of the lubricant base oil product is-10 to-25 ℃, and the preferable pour point is-12 to-21 ℃.
In the invention, the Fischer-Tropsch synthetic oil raw material can be at least one of Fischer-Tropsch synthetic oil whole fraction and Fischer-Tropsch synthetic oil heavy fraction. The paraffin content of the Fischer-Tropsch synthesis oil raw material is generally more than 90 wt%, preferably 95-99 wt%; the density at 20 ℃ is generally 0.800 to 0.990 g/cm3. The initial boiling point of the Fischer-Tropsch synthesis oil raw material is generally 50-300 ℃, and the final boiling point is generally 500-750 ℃.
In step (1), the hydrofining catalyst is a conventional hydrofining catalyst in the field, and can be a conventional diesel hydrofining catalyst. The diesel oil hydrorefining catalyst has VIB group and/or VIII group metal as active component, alumina or silica-containing alumina as carrier, VIB group metal as Mo and/or W and VIII group metal as Co and/or Ni. Based on the weight of the catalyst, the content of the VIB group metal is 8-28 wt% calculated by oxide, and the content of the VIII group metal is 2-15 wt% calculated by oxide; the physical properties of the diesel hydrofining catalyst are as follows: the specific surface area is 100 to 650m2The pore volume is 0.15-0.8 mL/g.The commercial catalysts available for selection are various, such as hydrofining catalysts like FH-98 and FH-UDS series developed by the research and development institute of petrochemical industry (FRIPP).
The hydrofining catalyst in the step (1) can also be an oxidation state hydrotreating catalyst. The oxidation state hydrotreating catalyst comprises a carrier and a supported hydrogenation metal. The catalyst generally comprises a metal component of group VIB of the periodic table of elements, such as tungsten and/or molybdenum, in an amount of 10 to 35 wt%, preferably 15 to 30wt%, calculated as oxide; group VIII metals such as nickel and/or cobalt, in terms of oxides, are 1 to 7 wt.%, preferably 1.5 to 6 wt.%. The catalyst carrier is inorganic refractory oxide, and is one or several of alumina, amorphous silica-alumina, silica, titania, etc. Wherein the conventional hydrotreating catalyst can be selected from various existing commercial catalysts, such as hydrotreating catalysts developed by the Fushu petrochemical research institute (FRIPP), such as FF-14, FF-24, 3936, 3996, FF-16, FF-26, FF-36, FF-46, etc.; it can also be prepared according to the common knowledge in the field, if necessary.
The operation conditions of the hydrofining reaction zone in the step (1) are as follows: the reaction pressure is 4.0-20.0 MPa, the reaction temperature is 250-420 ℃, the volume ratio of hydrogen to oil is 200-2000, and the volume airspeed is 0.1-3.0 h-1(ii) a The preferred operating conditions are: the reaction pressure is 10.0-18.0 MPa, the volume ratio of hydrogen to oil is 500-1500, and the volume airspeed is 0.2-2.0 h-1And the reaction temperature is 300-380 ℃.
The hydro-upgrading catalyst in the step (2) is a hydro-upgrading catalyst containing a beta molecular sieve. The hydro-upgrading catalyst comprises an upgrading component and a hydrogenation component. The hydrogenation modification catalyst containing the beta molecular sieve comprises amorphous silica-alumina, a modified beta molecular sieve, a refractory porous oxide, and oxides of metals in families VIB and VIII. Based on the weight of the hydrogenation modified catalyst, the hydrogenation modified catalyst contains 1wt% -40 wt% of beta molecular sieve, preferably 1wt% -10 wt%, the weight ratio of silicon dioxide/aluminum oxide of the modified beta molecular sieve is 50-90, the average size of crystal grains is 0.1-0.5 micron, and the infrared acidity is 0.1-0.4 mmol/g; the VIB group metal is 15-30 wt% calculated by oxide, preferably 18-26 wt%; the amount of the group VIII metal is 1 to 10wt%, preferably 5 to 7wt%, calculated as oxide. The group VIB metal is typically W and/or Mo, and the group VIII metal is typically Ni and/or Co. The amorphous silica-alumina may be a product conventional in the art, and the weight of the amorphous silica-alumina in the hydro-upgrading catalyst is generally 10wt% to 60 wt%. The refractory porous oxide comprises one or more of alumina, titanium oxide, zirconium oxide, boron oxide, composite oxides of the elements and the like, and preferably alumina. The refractory porous oxide is generally present in the catalyst in an amount of from 0% to 45% by weight.
The operation conditions of the hydro-upgrading reaction zone are as follows: the reaction pressure is 10.0-20.0 MPa, the reaction temperature is 250-420 ℃, the volume ratio of hydrogen to oil is 200-2000, and the volume airspeed is 0.1-3.0 h-1(ii) a The preferred operating conditions are: the reaction pressure is 10.0-18.0 MPa, the volume ratio of hydrogen to oil is 500-1500, and the volume airspeed is 0.2-2.0 h-1And the reaction temperature is 270-380 ℃.
The hydroisomerization dewaxing catalyst in step (3) may be selected from lubricating oil hydroisomerization catalysts commonly used in the art. Commercial hydroisomerization catalysts may be used, or they may be prepared as is generally known in the art. Hydroisomerization dewaxing catalysts are typically comprised of rare earth modified shape selective molecular sieves and halogen modified inorganic refractory oxides and at least one group VIII noble metal. The shape-selective molecular sieve is a TON type NU-10 molecular sieve or a ZSM-22 molecular sieve and the like. Silicon-aluminum (i.e. SiO) of shape-selective molecular sieves2/Al2O3) The molar ratio is 50 to 200, preferably 70 to 150. The weight ratio of the rare earth modified shape-selective molecular sieve to the halogen modified inorganic refractory oxide is 10: 90-90: 10, preferably 30: 70-80: 20. in the catalyst, the VIII group noble metal component is one or more of Pt, Pd, Ru and Rh. The content of the group VIII noble metal is 0.1-10 wt%, preferably 0.2-5.0 wt% calculated by metal. Wherein, in the rare earth modified shape-selective molecular sieve, the mass content of the rare earth oxide is 0.5-60.0 percent, preferably 10.0-40.0 percent; in the halogen-modified inorganic refractory oxide, the halogen content is 0.5 to 20.0% by mass, preferably 1.0 to 10.0% by mass. The specific surface area of the hydroisomerization dewaxing catalyst is 200-350 m2The pore volume is 0.3 to 0.5 mL/g.
The rare earth elements are well known to those of ordinary skill in the art and include one or more mixtures of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, and the like, preferably lanthanum. The halogen is one or more of fluorine, chlorine and bromine, and is preferably chlorine. The hydroisomerization dewaxing catalyst needs to be subjected to a reduction treatment before use, so that the hydrogenation active metal is in a reduced state during the reaction. The preparation method of the hydroisomerization dewaxing catalyst is common knowledge in the field, for example, CN201010509390.7 discloses a paraffin hydrocarbon shape selective isomerization catalyst, and its preparation method and application.
The reaction conditions of the hydroisomerization dewaxing in the step (3) are as follows: the reaction temperature is 250-400 ℃, and preferably 280-360 ℃; the reaction pressure is 2.0-18.0 MPa, preferably 10.0-15.0 MPa; the hourly space velocity of the raw oil is 0.4 h-1～6.0h-1Preferably 0.8 h-1～1.8h-1(ii) a The volume ratio of the hydrogen to the oil is 200: 1-2000: 1, preferably 600: 1-1000: 1.
In the hydro-upgrading reaction zone in the step (2), the modified b molecular sieve in the used hydro-upgrading catalyst has higher silica-alumina ratio, weaker acidity, small crystal grains and more secondary pores, and has proper cracking action and good isomerization action on long-chain alkane, aromatic hydrocarbon and long-side chain alkyl of cycloalkane. The hydrogenation modification catalyst can properly reduce the condensation point of the product and ensure the product yield of the lubricating oil base oil.
Therefore, the hydro-upgrading-hydro-isomerization dewaxing process combination well achieves the purposes that long-chain alkane in Fischer-Tropsch synthetic oil is subjected to hydro-isomerization and is reserved in an ideal component, and chain scission or isomerization of the long-chain alkane reduces the pour point. Thereby leading the hydrogenation combined process to be used for directly producing the API III with good stability and high yield of target products+A lubricant base oil product.
In the present invention, the hydrorefining reaction zone and the hydroupgrading reaction zone may be provided in one reactor, or may be provided in two or more reactors, respectively.
In the present invention, since the Fischer-Tropsch synthesis oil feedstock contains substantially no sulfur, it is usually necessary to periodically perform a sulfur replenishment operation during the operation of the catalyst in order to maintain the activity of the catalyst. The sulfur replenishment operation is conventional in the art. For the mode needing sulfur supplement operation, a hydrogen circulation system is needed to be arranged in the hydrofining-hydroupgrading process section and the hydroisomerization dewaxing process section respectively. Of course, in some cases, such as those where a hydrofinishing-hydroupgrading process section employs a catalyst having a higher metal content, sulfur replenishment may not be performed. The hydrofining-hydroupgrading process section and the hydroisomerization dewaxing process section can share a set of hydrogen circulation system.
The invention adopts two-stage process flow, the produced oil obtained in the hydrofining-hydroupgrading reaction zone can be used as the feed of the isomerization dewaxing stage only by simple steam stripping, and the process flow is greatly simplified. By selecting a catalyst with proper performance, the hydrofining-hydro-upgrading process of paraffin distillate is simplified, and the product quality can be ensured. The process has strong adaptability to raw materials, different hydrofining, hydrogenation modification and hydrogenation isodewaxing process combination modes are adopted according to different characteristics of raw material fractions, different types of special oil products can be produced, and the process is flexible. And the reaction temperature gradient of the noble metal hydrogenation isodewaxing reaction zone is uniform, thereby being beneficial to reducing energy consumption, producing special oil products, greatly simplifying the process flow and saving investment.
One catalyst included in the hydrofinishing reaction zone is a hydrofinishing catalyst. The hydrorefining catalyst has the functions of desulfurization, denitrification and aromatic hydrocarbon saturation. When the raw material is Fischer-Tropsch synthetic oil full fraction, and special oil products such as light white oil and industrial white oil which have no requirement on viscosity-temperature performance are produced, the hydrotreating reaction zone can only be a hydrofining catalyst; the product of the hydrorefining reaction zone enters a reaction zone filled with a hydro-upgrading catalyst, the chain of the long-chain alkane part is broken, the isomerization reaction reduces the pour point of the produced oil, the produced oil enters a reaction zone filled with a hydro-isomerization dewaxing catalyst for further isomerization dewaxing reaction, and after the pour point of the product is reduced, the isomerization dewaxing product is subjected to a product separation process to obtain various API III with good stability+A lubricant base oil product.
Compared with the prior art, the Fischer-Tropsch synthesis oil raw material hydrogenation method has the following advantages:
1. the Fischer-Tropsch synthetic oil raw material containing olefin and oxygen firstly passes through a hydrofining reaction zone, olefin and oxygen are saturated and reduced to be within a proper content range, so that the coking speed of olefin and oxygen on a modifying catalyst in the hydro-modifying reaction zone is reduced, and the service cycle of hydro-modifying is prolonged. And (3) enabling the effluent of the hydrofining reaction to enter a hydro-upgrading reactor for hydro-upgrading reaction, and selectively carrying out isomerization dewaxing and cracking chain scission on long-chain alkane to reduce the condensation point of the Fischer-Tropsch synthetic oil. Light hydrocarbon components and moisture generated in the hydrogenation modified product are stripped through fractionation, so that the volume space velocity of the feeding material entering the hydrogenation isomerization dewaxing reaction zone can be reduced, the isomerization dewaxing reaction load is reduced, in other words, the feeding space velocity of the hydrogenation modified zone can be improved under the condition of maintaining the volume space velocity of the isomerization dewaxing reaction zone unchanged, and the processing capacity of the device can be increased. Therefore, the method can meet the requirement of long-period operation of the Fischer-Tropsch synthetic oil raw material and simultaneously improve the processing capacity of the device to the maximum extent.
2. When the effluent obtained by hydrofining passes through a hydro-upgrading catalyst bed, due to the special pore channel structure and proper acidity of the beta molecular sieve, the beta molecular sieve has proper cracking effect and good isomerization effect on long-chain alkane and long-side chain alkyl of cycloalkane. The long chain paraffins in the fischer-tropsch synthesis oil feedstock undergo cracking, isomerisation and partial cyclisation reactions over a beta zeolite. The applicant believes that the main action principle of the beta-molecular sieve-containing hydrogenation modification catalyst in the hydrogenation modification of Fischer-Tropsch synthetic oil is as follows: on one hand, compared with the existing hydrocracking catalyst containing the Y-type molecular sieve, the hydrocracking catalyst can greatly reduce the condensation point (pour point) of the Fischer-Tropsch synthetic oil; on the other hand, the beta molecular sieve has proper cracking activity, reduces the generation of light components and gas in the modification process, and maintains higher liquid yield; third, the upgrading process produces paraffins and naphthenes rich in branched chains, which have high viscosity indexes, are good raw materials for the downstream hydroisomerization dewaxing process, can perform further shape selective isomerization and proper chain scission on the hydroisomerization dewaxing catalyst, and cannot produce smaller hydrocarbon molecules, so that the reaction severity of the hydroisomerization dewaxing process is reduced to a certain extent, and the liquid yield of the hydroisomerization dewaxing process is improved, and the yield of target products is increased.
3. The method only needs to add a hydroisomerization dewaxing reaction system behind the conventional hydrocracking device. On the basis of improving the product quality, an ideal comprehensive processing effect is obtained. In the process flow, the method combines hydrofining, hydroupgrading and hydroisomerization dewaxing, has the advantages of equipment saving (a recycle hydrogen stabilizing tank, a recycle hydrogen compressor and the like), low operation cost and the like, and has wide application prospect. In addition, if the device aims to produce light white oil, white oil and other special oil products, the two parts of the fractionation and separation systems can be completely integrated, so that the overall investment of the device is greatly reduced.
Drawings
FIG. 1 is a schematic process flow diagram of the process of the present invention.
Detailed Description
The process of the present invention is described in more detail below with reference to specific examples. Many necessary devices (such as heating furnace, heat exchanger, pump, etc.) are omitted from the figure.
As shown in figure 1, raw Fischer-Tropsch synthetic oil passes through a pipeline 1, circulating hydrogen passes through a pipeline 2, and the raw Fischer-Tropsch synthetic oil and the circulating hydrogen are mixed and then enter a hydrofining reactor 3 for reactions such as olefin removal, oxygen removal, metal removal and the like. The effluent of the hydrorefining reaction enters a hydroupgrading reactor 5 through a pipeline 4 and contacts with a hydroupgrading catalyst to carry out a long-chain alkane hydroisomerization reaction; the effluent of the hydrogenation modification reaction enters a gas-liquid separator 9 through a pipeline 6 for gas-liquid separation, and the obtained hydrogen-rich gas passes through a pipeline 8 and is mixed with the make-up hydrogen introduced through a pipeline 7 to obtain circulating hydrogen; the obtained liquid product oil passes through a pipeline 10, is mixed with hydrogen passing through a pipeline 12, enters a hydroisomerization dewaxing reactor 11, is contacted with a hydroisomerization dewaxing catalyst, and is subjected to a deep long-chain alkane hydroisomerization reaction, and meanwhile, the yield of macromolecular alkanes is kept, so that the process is favorable for the purpose of improving the yield of the liquid product oilLow temperature fluidity of the product of (a). The effluent from the isomerization dewaxing reaction is passed via line 13 to a gas-liquid separator 14 (typically comprising a high pressure separator and a low pressure separator) to provide a hydrogen rich gas which is withdrawn via line 15. The liquid obtained from the gas-liquid separator 14 enters a fractionating tower 17 through a pipeline 16, the gas is discharged through a pipeline 18, and API III with different specifications is obtained+Special oils such as lube base oil products are discharged through lines 19, 20 and 21, respectively.
Unless otherwise specified, the following percentages are mass percentages. Wherein, the Saybolt color of the lubricating oil base oil adopts GB/T3555, and the distillation range adopts an analysis method or an analysis standard of GB/T9168-1997.
Example 1
As shown in FIG. 1, a conventional commercial catalyst is selected, a hydrotreating catalyst FF-26 is used in a hydrotreating reaction zone, a hydro-upgrading catalyst FC-14 is used in a hydro-upgrading reaction zone, and an isodewaxing catalyst FIW-12 is used in an isodewaxing reaction zone. The hydrogenation conditions and results are shown in tables 2-3.
Example 2
The process flow is shown in figure 1. The process parameters and the hydro-upgrading conversion rate are adjusted, and the hydrogenation process conditions and results are shown in tables 2-3.
Example 3
The process flow is shown in figure 1. The process parameters and the hydro-upgrading conversion rate are adjusted, and the hydrogenation process conditions and results are shown in tables 2-3.
Comparative example 1
The hydrotreating and hydroisomerization dewaxing portions were as in example 1, and the conventional Y-type molecular sieve containing hydrocracking FC-28 catalyst was used as the hydro-upgrading catalyst. The hydrogenation conditions and results are shown in tables 2-3.
Comparative example 2
In the same manner as in example 1, a conventional hydrofining-hydroisomerization dewaxing process was used without a hydroupgrading stage. The properties of the special oil fractions can likewise be obtained as shown in tables 2 to 3.
As can be seen from the data listed in tables 2-3, for the prior art scheme of raw material hydrogenation, the properties of the special oil products obtained under different conditions are different, and the hydrogenation combination process of example 1 is the best.
As can be seen from the data of the above examples and comparative examples, the Fischer-Tropsch synthetic oil raw material can obtain API III with qualified pour point by the processes of hydrotreating, hydro-upgrading and isodewaxing+A lubricant base oil product. And the hydrogenation modification reaction zone adopts a hydrogenation combination process scheme containing a modified beta molecular sieve catalyst, so that the obtained special oil product has higher target product yield and more ideal hydrogenation effect.
Table 1 properties of the feedstock.
Table 2 hydrofinishing-hydroupgrading conditions and results.
Table 3 isodewaxing conditions and results.
*: the yield is calculated on the basis of the isodewaxing feed (i.e. the hydro-upgraded whole fraction).
Claims (16)
1. Fischer-Tropsch synthetic oil production API III+The hydrogenation method of the lubricating oil base oil comprises the following steps:
(1) mixing the Fischer-Tropsch synthesis oil raw material with hydrogen, entering a hydrofining reaction zone, and contacting with a hydrofining catalyst for reaction;
(2) directly feeding the reaction effluent obtained in the step (1) into a hydro-upgrading reaction zone without separation, and contacting the reaction effluent with a hydro-upgrading catalyst containing a beta molecular sieve for reaction;
(3) separating and fractionating the reaction effluent obtained in the step (2), mixing the obtained generated oil with hydrogen, entering a hydroisomerization dewaxing reaction zone, and contacting and reacting with a hydroisomerization dewaxing catalyst containing a shape-selective molecular sieve;
(4) carrying out gas-liquid separation on the effluent of the isomerization dewaxing reaction obtained in the step (3), and fractionating the liquid to obtain API III+A lube base oil-like product fraction;
the Fischer-Tropsch synthetic oil has the paraffin content of 95-99 wt% and the density at 20 ℃ of 0.800-0.990 g/cm3；
The hydro-upgrading catalyst comprises amorphous silica-alumina, a modified beta molecular sieve, a refractory porous oxide, and metal oxides of families VIB and VIII; based on the weight percentage of the catalyst, the catalyst contains 1 to 40 weight percent of modified beta molecular sieve, the weight ratio of silicon dioxide to aluminum oxide of the modified beta molecular sieve is 50 to 90, the average size of crystal grains is 0.1 to 0.5 micron, and the infrared acidity is 0.1 to 0.4 mmol/g; the operation conditions of the hydro-upgrading reaction zone are as follows: the reaction pressure is 10.0-20.0 MPa, the reaction temperature is 250-420 ℃, the volume ratio of hydrogen to oil is 200-2000, and the volume airspeed is 0.1-3.0 h-1。
2. The hydrogenation process of claim 1, wherein the Fischer-Tropsch synthesis oil is at least one selected from the group consisting of a Fischer-Tropsch synthesis oil whole fraction and a Fischer-Tropsch synthesis oil heavy fraction.
3. The hydrogenation process of claim 1 wherein the hydrofinishing catalyst is a diesel hydrofinishing catalyst or a hydrotreating catalyst.
4. The hydrogenation method as claimed in claim 3, wherein the diesel hydrofining catalyst uses VIB group and/or VIII group metals as active components, and uses alumina or silicon-containing alumina as a carrier; based on the weight of the catalyst, the content of the VIB group metal is 8-28 wt% calculated by oxide, and the content of the VIII group metal is 2-15 wt% calculated by oxide; the physical properties of the hydrorefining catalyst were as follows: the specific surface area is 100 to 650m2The pore volume is 0.15-0.8 mL/g.
5. The hydrogenation process of claim 3, wherein said hydrotreating catalyst comprises a support and a supported hydrogenation metal; based on the weight of the catalyst, the catalyst comprises 10-35 percent of VIB group metal component in the periodic table of elements in terms of oxide, 1-7 percent of VIII group metal in terms of oxide, and inorganic refractory oxide as a carrier.
6. The hydrogenation process of claim 1, wherein the hydrofinishing reaction zone of step (1) is operated under the following conditions: the reaction pressure is 4.0-20.0 MPa, the reaction temperature is 250-420 ℃, the volume ratio of hydrogen to oil is 200-2000, and the volume airspeed is 0.1-3.0 h-1。
7. The hydrogenation process of claim 1 wherein the group VIB metal is present in an amount of 15 wt.% to 30 wt.% as oxide, the group VIII metal is present in an amount of 1 wt.% to 10 wt.% as oxide, and the refractory porous oxide is present in an amount of 0 wt.% to 45 wt.%, based on the weight of the hydro-upgrading catalyst.
8. The hydrogenation process of claim 1 wherein the hydroisomerization dewaxing catalyst is comprised of a rare earth-modified molecular sieve, a halogen-modified inorganic refractory oxide, and at least one group viii noble metal, said molecular sieve being a TON-type structure NU-10 molecular sieve or a ZSM-22 molecular sieve; the molecular sieve has a silica-alumina molar ratio of 50-200.
9. The hydrogenation process of claim 8, wherein the weight ratio of the rare earth-modified molecular sieve to the halogen-modified inorganic refractory oxide is 10: 90-90: 10, in the catalyst, the active metal component is one or more of Pt, Pd, Ru and Rh, and the content of the active metal component is 0.1-10% by weight of the metal.
10. The hydrogenation method according to claim 8, wherein the rare earth modified molecular sieve contains 0.5-60.0% by mass of rare earth oxide; in the halogen modified inorganic refractory oxide, the mass content of halogen is 0.5-20.0%.
11. The hydrogenation process according to any one of claims 8 to 10, wherein said rare earth element is selected from one or more of lanthanum, cerium, praseodymium, neodymium, promethium, samarium; the halogen is one or more of fluorine, chlorine and bromine.
12. The hydrogenation process of claim 1 wherein the hydroisomerization dewaxing reaction conditions are: the temperature is 250-400 ℃, the hydrogen partial pressure is 2.0-18.0 MPa, and the liquid hourly space velocity is 0.4 h-1～6.0h-1The volume ratio of hydrogen to oil is 200: 1-2000: 1.
13. The hydrogenation process of claim 1, wherein the hydrofinishing reaction zone and the hydro-upgrading reaction zone are disposed in one reactor or in two or more reactors, respectively.
14. The hydrogenation process of claim 1 wherein the group VIB metal is present in an amount of from 18 wt.% to 26 wt.% as oxide and the group VIII metal is present in an amount of from 5 wt.% to 7 wt.% as oxide, based on the weight of the hydro-upgrading catalyst.
15. The hydrogenation process according to claim 8, wherein the molecular sieve has a silica to alumina molar ratio of 70 to 150.
16. The hydrogenation process of claim 12 wherein said hydroisomerization dewaxing reaction is carried out under the following conditions: the temperature is 280-360 ℃, the hydrogen partial pressure is 10.0-15.0 MPa, and the liquid hourly space velocity is 0.8 h-1～1.8h-1The volume ratio of the hydrogen to the oil is 600: 1-1000: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811652319.7A CN111378495B (en) | 2018-12-31 | 2018-12-31 | Fischer-Tropsch synthetic oil production API III+Hydrogenation method of base oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811652319.7A CN111378495B (en) | 2018-12-31 | 2018-12-31 | Fischer-Tropsch synthetic oil production API III+Hydrogenation method of base oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111378495A CN111378495A (en) | 2020-07-07 |
| CN111378495B true CN111378495B (en) | 2021-12-07 |
Family
ID=71219570
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811652319.7A Active CN111378495B (en) | 2018-12-31 | 2018-12-31 | Fischer-Tropsch synthetic oil production API III+Hydrogenation method of base oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111378495B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111378494B (en) * | 2018-12-31 | 2021-12-07 | 中国石油化工股份有限公司 | Processing method of Fischer-Tropsch synthetic oil |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102533329A (en) * | 2010-12-31 | 2012-07-04 | 中国石油化工股份有限公司 | Method for producing base oil of lubricating oil by using Fischer-Tropsch synthesis wax |
| CN103805257A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Method for producing diesel oil with low condensation point by catalyst gradation technology |
| CN106675643A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Inferior diesel pour-point depressing modification method |
| CN111378494A (en) * | 2018-12-31 | 2020-07-07 | 中国石油化工股份有限公司 | Processing method of Fischer-Tropsch synthetic oil |
-
2018
- 2018-12-31 CN CN201811652319.7A patent/CN111378495B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102533329A (en) * | 2010-12-31 | 2012-07-04 | 中国石油化工股份有限公司 | Method for producing base oil of lubricating oil by using Fischer-Tropsch synthesis wax |
| CN103805257A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Method for producing diesel oil with low condensation point by catalyst gradation technology |
| CN106675643A (en) * | 2015-11-11 | 2017-05-17 | 中国石油化工股份有限公司 | Inferior diesel pour-point depressing modification method |
| CN111378494A (en) * | 2018-12-31 | 2020-07-07 | 中国石油化工股份有限公司 | Processing method of Fischer-Tropsch synthetic oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111378495A (en) | 2020-07-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2016127840A1 (en) | Hydrotreatment method for low-temperature fischer-tropsch synthesis product | |
| CN103059972B (en) | Combined hydrogenation method of producing chemical materials | |
| WO2017181813A1 (en) | Method and equipment thereof for producing high-quality diesel using low-temperature fischer-tropsch synthetic oil and low-grade oil feedstock | |
| CN102041029B (en) | Comprehensive utilization method of hydrocracking tail oil | |
| US10639618B2 (en) | Wax oil hydrocracking method and system | |
| CN102959054A (en) | Integrated hydrocracking and dewaxing of hydrocarbons | |
| US7507326B2 (en) | Process for the upgrading of the products of Fischer-Tropsch processes | |
| CN102899085B (en) | Method for producing synthetic naphtha | |
| CN103773476B (en) | Method for producing high-viscosity-index lubricant base oil by hydrocracking-isodewaxing combination | |
| CN103773466B (en) | Method for producing lubricant base oil by hydrocracking-isodewaxing combination | |
| CN111117701A (en) | Hydrogenation method for maximum production of heavy naphtha and jet fuel components | |
| CN101760236B (en) | Method for producing lube base oil | |
| CN102041081A (en) | Combined method of hydrocracking and producing lubricant oil base oil | |
| CN110540872B (en) | Naphthenic oil treatment process | |
| CN110540871B (en) | Processing method of naphthenic oil | |
| CN111378495B (en) | Fischer-Tropsch synthetic oil production API III+Hydrogenation method of base oil | |
| CN111378494B (en) | Processing method of Fischer-Tropsch synthetic oil | |
| CN111378493B (en) | Hydrogenation process for producing API III + base oil from Fischer-Tropsch synthetic oil | |
| CN103773497B (en) | A kind of method increasing production clean fuel oil | |
| CN110016363B (en) | Method and system for producing diesel oil and lubricant base oil by processing Fischer-Tropsch synthetic oil | |
| CN112126465B (en) | Hydrogenation catalyst composition and method for preparing lubricating oil base oil from Fischer-Tropsch synthetic wax | |
| CN110540873B (en) | Method for processing naphthenic oil | |
| CN103339231B (en) | Process for producing hydrocarbon oil | |
| CN109988625B (en) | Hydrofining and hydrocracking combined process | |
| CN106675648B (en) | A kind of method of hydrotreating for improving cetane number of inferior diesel oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231016 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |