CN112126464A - Lubricating oil base oil prepared by hydrogenation of Fischer-Tropsch synthetic wax and preparation method thereof - Google Patents

Lubricating oil base oil prepared by hydrogenation of Fischer-Tropsch synthetic wax and preparation method thereof Download PDF

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CN112126464A
CN112126464A CN202010701247.1A CN202010701247A CN112126464A CN 112126464 A CN112126464 A CN 112126464A CN 202010701247 A CN202010701247 A CN 202010701247A CN 112126464 A CN112126464 A CN 112126464A
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catalyst
oil
hydrogenation
fischer
hydrogen
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CN112126464B (en
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王从新
田志坚
郭世清
潘振栋
郭棣
李鹏
徐刚
曲炜
张亚胜
崔军
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Karamay Huaao Special Oil Technology Development Co ltd
Xinjiang Huaao Energy Chemical Co ltd
Dalian Institute of Chemical Physics of CAS
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Karamay Huaao Special Oil Technology Development Co ltd
Xinjiang Huaao Energy Chemical Co ltd
Dalian Institute of Chemical Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/043—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a change in the structural skeleton
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Abstract

The invention relates to the technical field of preparation of lubricating oil base oil, in particular to lubricating oil base oil prepared by hydrogenation of Fischer-Tropsch synthetic wax and a preparation method thereof. The invention has strong adaptability of raw materials, does not need pre-fractionation of the raw materials, has simple preparation method and process conditions, does not need to circularly treat a hydroisomerized product, and has high yield and good performance of the lubricating oil base oil product prepared by hydrogenating the Fischer-Tropsch synthetic wax.

Description

Lubricating oil base oil prepared by hydrogenation of Fischer-Tropsch synthetic wax and preparation method thereof
Technical Field
The invention relates to the technical field of preparation of lubricating oil base oil, in particular to lubricating oil base oil prepared by hydrogenation of Fischer-Tropsch synthetic wax and a preparation method thereof.
Background
With the increasing trend of crude oil upgrading and deterioration and the increasing demand of markets for high-quality oil products and chemical raw materials, the preparation of liquid fuels and chemicals from coal through synthesis gas becomes a hot point of attention. Fischer-Tropsch synthesis (FT reaction), referred to as FT synthesis, is the synthesis of gases (CO and H)2) Synthesizing long chain with catalyst (such as iron series, cobalt series, etc.) and proper reaction conditionLiquid fuel and chemical process with alkane as main component. In the product of the low temperature Fischer-Tropsch synthesis, the wax-containing component comprises a soft wax (C)20To C30) And hard waxes (A), (B), (C), (>C30) The main component of the lubricating oil is straight-chain alkane, almost no sulfur, nitrogen and aromatic hydrocarbon exist, and the lubricating oil is a lubricating oil base oil raw material prepared by hydrogenation of high-quality high-grade Fischer-Tropsch synthetic wax. The technical key point of converting the Fischer-Tropsch synthetic wax product into the lubricating oil base oil prepared by hydrogenating the high-grade Fischer-Tropsch synthetic wax is that the low-temperature flow property of an oil product, namely the freezing point is reduced, can be improved under the condition of keeping a high viscosity index, and can be realized through hydrocracking and hydroisomerization reactions.
Many patents have been published at home and abroad, for example, US5834522 discloses a process for producing a lubricant base oil from hydrogenation of fischer-tropsch wax from a fischer-tropsch synthesis product, which is hydroisomerized in a hydroisomerization reaction zone, the resulting oil is separated by distillation, and the bottoms of the distillation column are dewaxed to obtain an oil fraction and a non-oil fraction. US5882505 discloses a process for producing a lubricant base oil by hydrogenation of fischer-tropsch wax by conversion of a fischer-tropsch wax having a boiling point greater than 370 ℃ in a countercurrent reactor, the feedstock being contacted with a hydroisomerization catalyst in a fixed bed reactor, the product of the reaction being contacted with a hydrodewaxing catalyst in at least one fixed bed reactor to produce the desired product, wherein the hydroisomerization product is in countercurrent flow to a hydrogen-containing gas. CN1688674 discloses a multi-step process for the preparation of a lubricant base oil from fischer-tropsch wax by hydrogenation, which comprises hydrodewaxing the wax in a first hydrodewaxing stage to produce an isomerate of a partially dewaxed heavy base oil fraction, and then hydrodewaxing the heavy lubricant fraction in one or more successive hydrodewaxing stages, removing hydrocarbons below the heavy lubricant fraction, to produce a lubricant base oil from hydrogenation of the heavy fischer-tropsch wax. CN1703488 discloses a process for producing a fuel from fischer-tropsch wax and a lubricant base oil produced by hydrogenating fischer-tropsch wax, comprising (1) hydrodewaxing the fischer-tropsch wax to produce an isomerate comprising the fuel and a partially hydrodewaxed base oil fraction; (2) separating the two fractions; (3) separating the partially hydrodewaxed base oil fraction into a heavy fraction and a lower boiling fraction; (4) the lower boiling fraction and the heavy fraction are each further hydrodewaxed to produce a lubricant base oil produced by hydrogenation of fischer-tropsch wax, including a heavy lubricant base stock. CN101230290 discloses a method for producing solvent oil from fischer-tropsch wax, and lubricating base oil and heavy wax from fischer-tropsch wax, wherein the method comprises the steps of fractionating a full fraction product obtained by wax conversion in a hydrorefining zone to obtain a solvent oil light fraction, separating a base oil fraction section product, performing hydroisomerization conversion, and directly performing hydrorefining on the remaining heavy fraction to obtain a decolorized wax. US7198710 discloses a process for producing lube base oil from fischer-tropsch wax by hydrogenation of high viscosity index fischer-tropsch wax, which comprises fractionating fischer-tropsch wax to obtain light and heavy fractions, and then respectively hydrodewaxing the light fraction and heavy fraction to reduce pour point of the feedstock, thereby obtaining lube base oil from fischer-tropsch wax having a pour point meeting the requirements. And when the heavy component is subjected to hydroisomerization dewaxing, the pour point of the heavy component is further reduced by adopting a solvent dewaxing method due to unqualified pour point, and finally the lubricating oil base oil product prepared by hydrogenation of the heavy Fischer-Tropsch synthetic wax with the pour point meeting the requirement is obtained.
In the above process, the conventional hydroisomerization dewaxing catalyst is used in its entirety in the hydrodewaxing unit, which has the following disadvantages: when using whole or wide-cut waxy oils as feed, it is difficult to have both light and heavy base components meet pour point and viscosity index requirements. Generally, when the pour point of the heavy base oil component is qualified, the viscosity index loss of the light base oil component is large, and it is difficult to produce a lubricating base oil product prepared by hydrogenation of API III light Fischer-Tropsch wax with the viscosity index of more than 120; and when the viscosity index of the light base oil component is qualified, the heavy component can not be used as a qualified lubricating oil base oil product prepared by hydrogenation of Fischer-Tropsch wax. When the traditional hydrocracking catalyst is adopted, no matter the full-fraction or wide-fraction waxy oil is used as a feed, most of light and heavy base oil products can simultaneously meet the requirements of pour points and viscosity indexes, but a large amount of cracking products are generated in the process, and the yield of the light and heavy base oil is too low, so that the process economy is seriously influenced.
The problems of low yield and poor product performance in the prior production of lubricating base oil prepared by hydrogenating light and heavy Fischer-Tropsch synthesis waxes with high viscosity indexes can be solved to a certain extent by fractionating raw materials and adopting a narrow-fraction Fischer-Tropsch wax as a feeding method for hydroisomerization dewaxing or a more complicated feeding method for circulating hydroisomerization dewaxing, but a plurality of raw material tanks and a plurality of separators are required to be arranged, so that the construction investment of the device is increased; in addition, in actual production, raw materials are frequently switched and technological parameters are frequently adjusted, so that the operation difficulty of the device is increased and a large amount of unqualified products are produced.
Disclosure of Invention
The invention provides lubricating oil base oil prepared by hydrogenation of Fischer-Tropsch wax and a preparation method thereof, overcomes the defects of the prior art, and can effectively solve the problems of frequent raw material switching, complex process parameters, low yield of the obtained product and poor performance of the lubricating oil base oil prepared by conversion of the Fischer-Tropsch wax.
One of the technical schemes of the invention is realized by the following measures: a lubricating oil base oil prepared by hydrogenation of Fischer-Tropsch wax is prepared by the following method: the first step, the fraction material of Fischer-Tropsch wax at 320-620 deg.c and hydrogen are mixed and fed into hydrogenation pre-treating reaction area, and the mixture is fed into the bed with hydrogenation pre-treating catalyst at 150-350 deg.c, hydrogen partial pressure of 1.0-20 MPa and material oil volume space velocity of 0.2 hr-1To 5h-1Under the condition that the hydrogen-oil ratio is 100-3000: 1, completing the hydrogenation saturation, hydrodesulfurization, hydrodenitrogenation and hydrodeoxygenation of non-alkane components in the raw materials to obtain hydrogenation pretreatment oil, wherein a hydrogenation pretreatment catalyst is composed of a heat-resistant inorganic oxide serving as a carrier, more than one metal of cobalt, nickel, molybdenum and tungsten with the mass loading of 15-45 wt% and more than one auxiliary agent of nitrogen, phosphorus, sulfur and boron with the mass loading of 2-8 wt% loaded on the carrier; secondly, the hydrogenation pretreatment oil enters a hydroisomerization reaction zone and is arranged on a bed layer added with a combined catalyst, the reaction temperature is 200 ℃ to 450 ℃, the hydrogen partial pressure is 1.0MPa to 20MPa,The volume space velocity of the raw oil is 0.2h-1To 5h-1Carrying out hydroisomerization reaction under the condition that the hydrogen-oil ratio is 100-3000: 1, and finishing hydroisomerization and hydrocracking reaction of hydrogenated pretreated oil to obtain hydroisomerization oil, wherein the combined catalyst is a catalyst formed by combining a catalyst A and a catalyst B according to the volume ratio of 1: 10-10: 1; thirdly, the hydroisomerized oil enters a hydrofining reaction zone and is arranged on a bed layer added with a hydrofining catalyst, the reaction temperature is 150-350 ℃, the hydrogen partial pressure is 1.0-20 MPa, and the volume space velocity of the raw oil is 0.2h-1To 5h-1And the hydrogen-oil ratio is 100-3000: 1, and the hydrogenation saturation of the hydroisomerization oil is completed to obtain a crude product, wherein the hydrofining catalyst is composed of a heat-resistant inorganic oxide as a carrier, more than one metal of platinum, palladium and iridium with the mass loading of 0.2-1.0 wt% and more than one auxiliary agent of cobalt, nickel, molybdenum and tungsten with the mass loading of 0.3-1.5 wt% which are loaded on the carrier; and fourthly, feeding the crude product into a normal pressure tower or a vacuum tower, and fractionating to obtain the lubricating oil base oil prepared by hydrogenation of the Fischer-Tropsch synthesis wax.
The following is a further optimization or/and improvement of one of the above-mentioned technical solutions of the invention:
the catalyst A is prepared by taking an aluminum phosphate molecular sieve with an AFO structure as a carrier and platinum, palladium and/or iridium loaded on the carrier with the mass loading amount of 0.1-0.5 wt% by adopting a conventional impregnation method; the catalyst B is prepared by taking an aluminum phosphate molecular sieve with an AFI structure as a carrier and platinum, palladium and/or iridium loaded on the carrier with the mass loading amount of 0.2-0.6 wt% by adopting a conventional impregnation method.
The aluminum phosphate molecular sieve with the AFO structure is more than one of SAPO-41 and MeAPO-41, wherein Me in the MeAPO-41 is more than one of Zn, Mg, Mn, Co, Cr, Cu, Cd and Ni; the aluminum phosphate molecular sieve with the AFI structure is more than one of SAPO-5 and MeAPO-5, wherein Me in the MeAPO-5 is more than one of Zn, Mg, Mn, Co, Cr, Cu, Cd and Ni.
The catalyst A and the catalyst B are positioned on the bed layer of the combined catalyst under the catalyst B on the catalyst A, the raw oil sequentially flows through the catalyst A and the catalyst B from top to bottom, and the volume ratio of the catalyst A to the catalyst B is 1: 5-5: 1.
The volume ratio of the catalyst A to the catalyst B is 1:5 to 2: 1.
The acid content of the catalyst A was 1.5mmol (NH)3) From/g to 2.0mmol (NH)3) (ii)/g; the acid content of catalyst B was 2.2mmol (NH)3) From/g to 3.2mmol (NH)3)/g。
The heat-resistant inorganic oxide carrier in the hydrogenation pretreatment catalyst is alumina and/or silicon oxide; the heat-resistant inorganic oxide carrier in the hydrofining catalyst is alumina and/or silica.
In the first step, the reaction conditions of the hydrogenation pretreatment are that the temperature is 200 ℃ to 320 ℃, the hydrogen partial pressure is 2.0MPa to 15MPa, and the volume space velocity of the raw oil is 0.5h-1To 3h-1The hydrogen-oil ratio is 200 to 1000: 1; in the second step, the hydroisomerization reaction conditions are that the temperature is 250 ℃ to 400 ℃, the hydrogen partial pressure is 5.0MPa to 15MPa, and the raw material oil volume space velocity is 0.5h-1To 2h-1The hydrogen-oil ratio is 200 to 1000: 1; in the third step, the hydrofining reaction conditions are that the temperature is 180 ℃ to 320 ℃, the hydrogen partial pressure is 2.0MPa to 15MPa, and the volume space velocity of the raw oil is 0.5h-1To 2h-1The hydrogen-oil ratio is 200 to 1000: 1.
In the second step, the hydroisomerization reaction conditions are that the temperature is 280-380 ℃, the hydrogen partial pressure is 8.0-15 MPa, and the raw material oil volume space velocity is 0.5h-1To 2h-1The hydrogen-oil ratio is 200 to 800: 1.
The second technical scheme of the invention is realized by the following measures: a preparation method of lubricating oil base oil prepared by hydrogenation of Fischer-Tropsch synthetic wax comprises the following steps: the first step, the fraction material of Fischer-Tropsch wax at 320-620 deg.c and hydrogen are mixed and fed into hydrogenation pre-treating reaction area, and the mixture is fed into the bed with hydrogenation pre-treating catalyst at 150-350 deg.c, hydrogen partial pressure of 1.0-20 MPa and material oil volume space velocity of 0.2 hr-1To 5h-1Under the condition that the hydrogen-oil ratio is 100-3000: 1, completing the hydrogenation saturation, hydrogenation desulfurization, hydrogenation denitrification and hydrogenation deoxidation of the non-alkane component in the raw material to obtain the catalystThe hydrogenation pretreatment catalyst consists of heat-resistant inorganic oxide serving as a carrier, more than one metal of cobalt, nickel, molybdenum and tungsten which is loaded on the carrier and has the mass load of 15-45 wt% and more than one auxiliary agent of nitrogen, phosphorus, sulfur and boron which has the mass load of 2-8 wt%; secondly, the hydrogenation pretreatment oil enters a hydroisomerization reaction zone, and is arranged on a bed layer added with a combined catalyst, the reaction temperature is 200 ℃ to 450 ℃, the hydrogen partial pressure is 1.0MPa to 20MPa, and the volume space velocity of the raw oil is 0.2h-1To 5h-1Carrying out hydroisomerization reaction under the condition that the hydrogen-oil ratio is 100-3000: 1, and finishing hydroisomerization and hydrocracking reaction of hydrogenated pretreated oil to obtain hydroisomerization oil, wherein the combined catalyst is a catalyst formed by combining a catalyst A and a catalyst B according to the volume ratio of 1: 10-10: 1; thirdly, the hydroisomerized oil enters a hydrofining reaction zone and is arranged on a bed layer added with a hydrofining catalyst, the reaction temperature is 150-350 ℃, the hydrogen partial pressure is 1.0-20 MPa, and the volume space velocity of the raw oil is 0.2h-1To 5h-1And the hydrogen-oil ratio is 100-3000: 1, and the hydrogenation saturation of the hydroisomerization oil is completed to obtain a crude product, wherein the hydrofining catalyst is composed of a heat-resistant inorganic oxide as a carrier, more than one metal of platinum, palladium and iridium with the mass loading of 0.2-1.0 wt% and more than one auxiliary agent of cobalt, nickel, molybdenum and tungsten with the mass loading of 0.3-1.5 wt% which are loaded on the carrier; and fourthly, feeding the crude product into a normal pressure tower or a vacuum tower, and fractionating to obtain the lubricating oil base oil prepared by hydrogenation of the Fischer-Tropsch synthesis wax.
The invention has strong adaptability of raw materials, does not need pre-fractionation of the raw materials, has simple preparation method and process conditions, does not need to circularly treat a hydroisomerized product, and has high yield and good performance of the lubricating oil base oil product prepared by hydrogenating the Fischer-Tropsch synthetic wax.
Drawings
FIG. 1 is a schematic process flow diagram of example 11 of the present invention.
Detailed Description
The present invention is not limited by the following examples, and specific embodiments may be determined according to the technical solutions and practical situations of the present invention. The various chemical reagents and chemical articles mentioned in the invention are all the chemical reagents and chemical articles which are well known and commonly used in the prior art, unless otherwise specified; the percentages in the invention are mass percentages unless otherwise specified; the solution in the present invention is an aqueous solution in which the solvent is water, for example, a hydrochloric acid solution is an aqueous hydrochloric acid solution, unless otherwise specified; the normal temperature and room temperature in the present invention generally mean a temperature of 15 ℃ to 25 ℃, and are generally defined as 25 ℃.
The invention is further described below with reference to the following examples:
example 1: the lubricating oil base oil prepared by hydrogenation of the Fischer-Tropsch synthetic wax is prepared by the following method: the first step, the fraction material of Fischer-Tropsch wax at 320-620 deg.c and hydrogen are mixed and fed into hydrogenation pre-treating reaction area, and the mixture is fed into the bed with hydrogenation pre-treating catalyst at 150-350 deg.c, hydrogen partial pressure of 1.0-20 MPa and material oil volume space velocity of 0.2 hr-1To 5h-1Under the condition that the hydrogen-oil ratio is 100-3000: 1, completing the hydrogenation saturation, hydrodesulfurization, hydrodenitrogenation and hydrodeoxygenation of non-alkane components in the raw materials to obtain hydrogenation pretreatment oil, wherein a hydrogenation pretreatment catalyst is composed of a heat-resistant inorganic oxide serving as a carrier, more than one metal of cobalt, nickel, molybdenum and tungsten with the mass loading of 15-45 wt% and more than one auxiliary agent of nitrogen, phosphorus, sulfur and boron with the mass loading of 2-8 wt% loaded on the carrier; secondly, the hydrogenation pretreatment oil enters a hydroisomerization reaction zone, and is arranged on a bed layer added with a combined catalyst, the reaction temperature is 200 ℃ to 450 ℃, the hydrogen partial pressure is 1.0MPa to 20MPa, and the volume space velocity of the raw oil is 0.2h-1To 5h-1Carrying out hydroisomerization reaction under the condition that the hydrogen-oil ratio is 100-3000: 1, and finishing hydroisomerization and hydrocracking reaction of hydrogenated pretreated oil to obtain hydroisomerization oil, wherein the combined catalyst is a catalyst formed by combining a catalyst A and a catalyst B according to the volume ratio of 1: 10-10: 1; thirdly, the hydroisomerized oil enters a hydrofining reaction zone and is arranged on a bed layer added with a hydrofining catalyst, the reaction temperature is 150 ℃ to 350 ℃, and the hydrogen partial pressure is 1.0MPa to 350 MPa20MPa and the volume airspeed of the raw oil is 0.2h-1To 5h-1And the hydrogen-oil ratio is 100-3000: 1, and the hydrogenation saturation of the hydroisomerization oil is completed to obtain a crude product, wherein the hydrofining catalyst is composed of a heat-resistant inorganic oxide as a carrier, more than one metal of platinum, palladium and iridium with the mass loading of 0.2-1.0 wt% and more than one auxiliary agent of cobalt, nickel, molybdenum and tungsten with the mass loading of 0.3-1.5 wt% which are loaded on the carrier; and fourthly, feeding the crude product into a normal pressure tower or a vacuum tower, and fractionating to obtain the lubricating oil base oil prepared by hydrogenation of the Fischer-Tropsch synthesis wax.
The lubricating oil base oil prepared by hydrogenating the Fischer-Tropsch synthetic wax with low pour point and high viscosity index can be prepared in high yield by carrying out simple hydrogenation pretreatment, hydroisomerization, hydrofining and fractionation on fractions of the Fischer-Tropsch synthetic wax at 320-620 ℃. The invention is based on the hydroisomerization process of the aluminum phosphate molecular sieve catalyst with the combined AFO structure and AFI structure, so that all components in the wide distillation range raw material can be converted into an isomeric product with high selectivity, thereby realizing the improvement of the product yield and performance at the same time.
Example 2: as optimization of the embodiment, the lubricant base oil prepared by hydrogenating the Fischer-Tropsch wax is prepared by the following method: the first step, the fraction material of Fischer-Tropsch wax at 320 deg.c or 620 deg.c and hydrogen are mixed in hydrogenation pre-treating reaction area in the bed with hydrogenation pre-treating catalyst at 150 deg.c or 350 deg.c, hydrogen partial pressure of 1.0MPa or 20MPa and material oil volume space velocity of 0.2 hr-1Or 5h-1Under the condition that the hydrogen-oil ratio is 100 or 3000:1, completing the hydrogenation saturation, hydrodesulfurization, hydrodenitrogenation and hydrodeoxygenation of non-alkane components in the raw materials to obtain hydrogenation pretreatment oil, wherein a hydrogenation pretreatment catalyst is composed of a heat-resistant inorganic oxide serving as a carrier, more than one metal of cobalt, nickel, molybdenum and tungsten with the mass loading of 15wt% or 45wt% and more than one auxiliary agent of nitrogen, phosphorus, sulfur and boron with the mass loading of 2wt% or 8wt% loaded on the carrier; secondly, the hydrogenation pretreatment oil enters a hydroisomerization reaction zone, and is arranged on a bed layer added with a combined catalyst, the reaction temperature is 200 ℃ or 450 ℃, the hydrogen partial pressure is 1.0MPa or 20MPa, and the raw materialsThe space velocity of oil volume is 0.2h-1Or 5h-1Carrying out hydroisomerization reaction under the condition that the hydrogen-oil ratio is 100 or 3000:1, and finishing hydroisomerization and hydrocracking reaction of hydrogenated pretreated oil to obtain hydroisomerization oil, wherein the combined catalyst is a catalyst formed by combining a catalyst A and a catalyst B according to the volume ratio of 1:10 or 10: 1; thirdly, the hydroisomerized oil enters a hydrofining reaction zone and is arranged on a bed layer added with a hydrofining catalyst, the reaction temperature is 150 ℃ or 350 ℃, the hydrogen partial pressure is 1.0MPa or 20MPa, and the volume space velocity of the raw oil is 0.2h-1Or 5h-1And the hydrogen-oil ratio is 100 or 3000:1, and the hydrogenation saturation of the hydroisomerization oil is completed to obtain a crude product, wherein the hydrofining catalyst is composed of a heat-resistant inorganic oxide as a carrier, more than one metal of platinum, palladium and iridium with the mass loading of 0.2wt% or 1.0wt% and more than one auxiliary agent of cobalt, nickel, molybdenum and tungsten with the mass loading of 0.3wt% or 1.5wt% which are loaded on the carrier; and fourthly, feeding the crude product into a normal pressure tower or a vacuum tower, and fractionating to obtain the lubricating oil base oil prepared by hydrogenation of the Fischer-Tropsch synthesis wax.
Example 3: as optimization of the above embodiment, the catalyst a is prepared by taking an aluminum phosphate molecular sieve with an AFO structure as a carrier, and platinum, palladium and/or iridium loaded on the carrier with a mass loading amount of 0.1wt% to 0.5wt%, and adopting a conventional impregnation method; the catalyst B is prepared by taking an aluminum phosphate molecular sieve with an AFI structure as a carrier and platinum, palladium and/or iridium loaded on the carrier with the mass loading amount of 0.2-0.6 wt% by adopting a conventional impregnation method.
Example 4: as the optimization of the embodiment, the aluminum phosphate molecular sieve with AFO structure is more than one of SAPO-41 and MeAPO-41, wherein Me in the MeAPO-41 is more than one of Zn, Mg, Mn, Co, Cr, Cu, Cd and Ni; the aluminum phosphate molecular sieve with the AFI structure is more than one of SAPO-5 and MeAPO-5, wherein Me in the MeAPO-5 is more than one of Zn, Mg, Mn, Co, Cr, Cu, Cd and Ni.
Example 5: as optimization of the above embodiment, the position of the catalyst A and the catalyst B on the bed of the combined catalyst is that the catalyst A is above the catalyst B, the raw oil sequentially flows through the catalyst A and the catalyst B from top to bottom, and the volume ratio of the catalyst A to the catalyst B is 1:5 to 5: 1.
Example 6: as an optimization of the above example, the volume ratio of catalyst a to catalyst B was 1:5 to 2: 1.
Example 7: as an optimization of the above example, the acid amount of catalyst A was 1.5mmol (NH)3) From/g to 2.0mmol (NH)3) (ii)/g; the acid content of catalyst B was 2.2mmol (NH)3) From/g to 3.2mmol (NH)3)/g。
Example 8: as optimization of the above embodiment, the refractory inorganic oxide carrier in the hydrogenation pretreatment catalyst is alumina and/or silica; the heat-resistant inorganic oxide carrier in the hydrofining catalyst is alumina and/or silica.
Example 9: as the optimization of the above embodiment, in the first step, the hydrogenation pretreatment reaction conditions are that the temperature is 200 ℃ to 320 ℃, the hydrogen partial pressure is 2.0MPa to 15MPa, and the volume space velocity of the raw oil is 0.5h-1To 3h-1The hydrogen-oil ratio is 200 to 1000: 1; in the second step, the hydroisomerization reaction conditions are that the temperature is 250 ℃ to 400 ℃, the hydrogen partial pressure is 5.0MPa to 15MPa, and the raw material oil volume space velocity is 0.5h-1To 2h-1The hydrogen-oil ratio is 200 to 1000: 1; in the third step, the hydrofining reaction conditions are that the temperature is 180 ℃ to 320 ℃, the hydrogen partial pressure is 2.0MPa to 15MPa, and the volume space velocity of the raw oil is 0.5h-1To 2h-1The hydrogen-oil ratio is 200 to 1000: 1.
Example 10: as the optimization of the above embodiment, in the second step, the hydroisomerization reaction conditions are that the temperature is 280 ℃ to 380 ℃, the hydrogen partial pressure is 8.0MPa to 15MPa, and the raw material oil volume space velocity is 0.5h-1To 2h-1The hydrogen-oil ratio is 200 to 800: 1.
Example 11: the preparation method of the lubricating oil base oil prepared by hydrogenation of the Fischer-Tropsch synthetic wax comprises the following steps: the first step, the fraction material of Fischer-Tropsch wax at 320-620 deg.c and hydrogen are mixed and fed into hydrogenation pre-treating reaction area, and the mixture is fed into the bed with hydrogenation pre-treating catalyst at 150-350 deg.c, hydrogen partial pressure of 1.0-20 MPa and material oil volume space velocity of 0.2 hr-1To 5h-1Under the condition that the hydrogen-oil ratio is 100-3000: 1, completing the hydrogenation saturation, hydrodesulfurization, hydrodenitrogenation and hydrodeoxygenation of non-alkane components in the raw materials to obtain hydrogenation pretreatment oil, wherein a hydrogenation pretreatment catalyst is composed of a heat-resistant inorganic oxide serving as a carrier, more than one metal of cobalt, nickel, molybdenum and tungsten with the mass loading of 15-45 wt% and more than one auxiliary agent of nitrogen, phosphorus, sulfur and boron with the mass loading of 2-8 wt% loaded on the carrier; secondly, the hydrogenation pretreatment oil enters a hydroisomerization reaction zone, and is arranged on a bed layer added with a combined catalyst, the reaction temperature is 200 ℃ to 450 ℃, the hydrogen partial pressure is 1.0MPa to 20MPa, and the volume space velocity of the raw oil is 0.2h-1To 5h-1Carrying out hydroisomerization reaction under the condition that the hydrogen-oil ratio is 100-3000: 1, and finishing hydroisomerization and hydrocracking reaction of hydrogenated pretreated oil to obtain hydroisomerization oil, wherein the combined catalyst is a catalyst formed by combining a catalyst A and a catalyst B according to the volume ratio of 1: 10-10: 1; thirdly, the hydroisomerized oil enters a hydrofining reaction zone and is arranged on a bed layer added with a hydrofining catalyst, the reaction temperature is 150-350 ℃, the hydrogen partial pressure is 1.0-20 MPa, and the volume space velocity of the raw oil is 0.2h-1To 5h-1And the hydrogen-oil ratio is 100-3000: 1, and the hydrogenation saturation of the hydroisomerization oil is completed to obtain a crude product, wherein the hydrofining catalyst is composed of a heat-resistant inorganic oxide as a carrier, more than one metal of platinum, palladium and iridium with the mass loading of 0.2-1.0 wt% and more than one auxiliary agent of cobalt, nickel, molybdenum and tungsten with the mass loading of 0.3-1.5 wt% which are loaded on the carrier; and fourthly, feeding the crude product into a normal pressure tower or a vacuum tower, and fractionating to obtain the lubricating oil base oil prepared by hydrogenation of the Fischer-Tropsch synthesis wax.
A simplified flow diagram of a preparation process of the lubricant base oil prepared by hydrogenation of the fischer-tropsch synthesis wax in example 11 of the present invention is shown in fig. 1, and in fig. 1, a hydrogenation pretreatment reactor, a hydroisomerization reactor, a hydrofining reactor, and a distillation tower are respectively a hydrogenation pretreatment reaction zone, a hydroisomerization reaction zone, a hydrofining reaction zone, an atmospheric tower, or a vacuum tower described in example 11 of the present invention.
Example 12: the hydrogenation pretreatment catalyst (which can be replaced by H1) was prepared using conventional impregnation methods.
The catalyst is composed of a heat-resistant inorganic oxide, namely alumina and/or silicon oxide, a carrier, more than one metal of cobalt, nickel, molybdenum and tungsten loaded on the carrier, and more than one auxiliary agent selected from nitrogen, phosphorus, sulfur or boron. The total content of cobalt, nickel, molybdenum and tungsten (the four element ratios in mass equal to each other are used in the following examples and comparative examples) was 40wt%, the total content of nitrogen, phosphorus, sulfur and boron (the four element ratios in mass equal to each other are used in the following examples and comparative examples) was 5wt%, and the balance was alumina and/or silica (the alumina and silica in mass ratio of 1:1 are used in the following examples and comparative examples), based on the weight percentage of H1.
Example 13: hydroisomerization catalysts a and B (i.e., catalyst a and catalyst B of the present invention) were prepared using conventional impregnation methods.
The catalyst A is composed of an aluminum phosphate molecular sieve SAPO-41 with an AFO structure as a carrier and more than one metal selected from platinum, palladium and/or iridium. Based on the weight percentage of the catalyst A, the total content of platinum, palladium and/or iridium (the three elements with the same mass are adopted in the following examples) is 0.4wt%, the rest is an aluminium phosphate molecular sieve SAPO-41 with an AFO structure, and the acid content of the catalyst A is 1.8mmol (NH)3)/g。
The catalyst B is composed of an aluminum phosphate molecular sieve SAPO-5 with an AFI structure as a carrier and more than one metal selected from platinum, palladium and/or iridium. Based on the weight percentage of the catalyst B, the total content of platinum, palladium and/or iridium (the three elements with the same mass are adopted in the following examples) is 0.5wt%, the rest is an aluminium phosphate molecular sieve SAPO-5 with an AFI structure, and the acid content of the catalyst B is 2.9mmol (NH)3)/g。
Example 14: the hydrofinishing catalyst (which can be replaced by H2) was prepared using conventional impregnation methods.
The catalyst is composed of a heat-resistant inorganic oxide alumina and/or silica as a carrier, more than one metal of platinum, palladium and iridium loaded on the carrier, and more than one auxiliary agent selected from cobalt, nickel, molybdenum and tungsten. Based on H2, the total content of platinum, palladium and/or iridium (in the following examples, these three elements are mixed by mass) is 0.4wt%, the total content of cobalt, nickel, molybdenum and tungsten (in the following examples, these four elements are mixed by mass) is 1.2wt%, and the balance is alumina and/or silica (in the following examples, alumina and silica are mixed by mass in a ratio of 1: 1)
Example 15: as shown in attached figure 1, a hydrogenation pretreatment catalyst H1 is adopted in a hydrogenation pretreatment reactor, and the reaction conditions are 300 ℃, 5MPa and space velocity of 2.0H-1Hydrogen-to-oil ratio of 500; the hydroisomerization reactor adopts hydroisomerization catalysts A and B, the filling mode of the hydroisomerization catalysts A and the hydroisomerization catalysts B is that A is above B, the filling volume ratio is 1:1, the reaction conditions are 360 ℃, 12MPa and the space velocity is 0.5h-1Hydrogen-to-oil ratio of 500; the hydrofining reactor adopts hydrofining catalyst H2, and the reaction conditions are 220 ℃, 12MPa and space velocity of 1.0H-1Hydrogen to oil ratio 500. The product yields of the raw materials shown in table 1 after conversion and fractionation through the reaction scheme are shown in table 2, and the properties of the base oil products are shown in table 3.
Example 16: as shown in attached figure 1, a hydrogenation pretreatment catalyst H1 is adopted in a hydrogenation pretreatment reactor, and the reaction conditions are 280 ℃, 5MPa and space velocity of 2.0H-1Hydrogen-to-oil ratio 600; the hydroisomerization reactor adopts hydroisomerization catalysts A and B, the filling mode of the hydroisomerization catalysts A and the hydroisomerization catalysts B is that A is above B, the filling volume ratio is 1:2, the reaction conditions are 355 ℃, 13MPa and the space velocity is 0.5h-1Hydrogen-to-oil ratio of 500; the hydrofining reactor adopts hydrofining catalyst H2, and the reaction conditions are 240 ℃, 10MPa and space velocity of 1.0H-1Hydrogen to oil ratio 500. The product yields of the raw materials shown in table 1 after conversion and fractionation through the reaction scheme are shown in table 2, and the properties of the base oil products are shown in table 3.
Example 17: as shown in attached figure 1, a hydrogenation pretreatment catalyst H1 is adopted in a hydrogenation pretreatment reactor, and the reaction conditions are 310 ℃, 6MPa and space velocity of 2.0H-1Hydrogen-to-oil ratio 600; the hydroisomerization reactor adopts hydroisomerization catalysts A and B, the filling mode of the hydroisomerization catalysts A and the hydroisomerization catalysts B is that A is above B, the filling volume ratio is 1:3, the reaction conditions are 350 ℃, 15MPa and the space velocity is 0.5h-1Hydrogen-to-oil ratio of 500; the hydrofining reactor adopts hydrofining catalyst H2, and the reaction conditions are 240 ℃, 10MPa and space velocity of 1.0H-1Hydrogen to oil ratio 500. The product yields of the raw materials shown in table 1 after conversion and fractionation through the reaction scheme are shown in table 2, and the properties of the base oil products are shown in table 3.
Example 18: as shown in attached figure 1, a hydrogenation pretreatment catalyst H1 is adopted in a hydrogenation pretreatment reactor, and the reaction conditions are 290 ℃, 4MPa and space velocity of 2.0H-1Hydrogen-to-oil ratio of 500; the hydroisomerization reactor adopts hydroisomerization catalysts A and B, the filling mode of the hydroisomerization catalysts A and the hydroisomerization catalysts B is that A is above B, the filling volume ratio is 1:5, the reaction conditions are 345 ℃, 15MPa and the space velocity is 0.5h-1Hydrogen-to-oil ratio of 500; the hydrofining reactor adopts hydrofining catalyst H2, and the reaction conditions are 270 ℃, 12MPa and space velocity of 1.0H-1Hydrogen to oil ratio 500. The product yields of the raw materials shown in table 1 after conversion and fractionation through the reaction scheme are shown in table 2, and the properties of the base oil products are shown in table 3.
Comparative example 1
A similar process flow as the present invention was used. A hydrogenation pretreatment catalyst H1 is adopted in the hydrogenation pretreatment reactor, the reaction conditions are 300 ℃, 5MPa and the space velocity is 2.0H-1Hydrogen-to-oil ratio of 500; the hydroisomerization reactor adopts a hydroisomerization catalyst A, and the reaction conditions are 360 ℃, 12MPa and 0.5h of space velocity-1Hydrogen-to-oil ratio of 500; the hydrofining reactor adopts hydrofining catalyst H2, and the reaction conditions are 220 ℃, 12MPa and space velocity of 1.0H-1Hydrogen to oil ratio 500. The product yields of the raw materials shown in table 1 after conversion and fractionation through the reaction scheme are shown in table 2, and the properties of the base oil products are shown in table 3.
Comparative example 2
A similar process flow as the present invention was used. A hydrogenation pretreatment catalyst H1 is adopted in the hydrogenation pretreatment reactor, the reaction conditions are 280 ℃, 5MPa and the space velocity is 2.0H-1Hydrogen-to-oil ratio 600; the hydroisomerization reactor adopts a hydroisomerization catalyst A, and the reaction conditions are 355 ℃, 13MPa and 0.5h of space velocity-1Hydrogen-to-oil ratio of 500; the hydrofining reactor adopts hydrofining catalyst H2, and the reaction conditions are 240 ℃, 10MPa and space velocity of 1.0H-1Hydrogen to oil ratio 500. Raw materials shown in Table 1The product yields obtained after conversion and fractionation of the reaction scheme are shown in table 2, and the properties of the base oil products are shown in table 3.
Comparative example 3
A similar process flow as the present invention was used. A hydrogenation pretreatment catalyst H1 is adopted in the hydrogenation pretreatment reactor, the reaction conditions are 310 ℃, 6MPa and the space velocity is 2.0H-1Hydrogen-to-oil ratio 600; the hydroisomerization reactor adopts a hydroisomerization catalyst B, and the reaction conditions are 350 ℃, 15MPa and 0.5h of space velocity-1Hydrogen-to-oil ratio of 500; the hydrofining reactor adopts hydrofining catalyst H2, and the reaction conditions are 240 ℃, 10MPa and space velocity of 1.0H-1Hydrogen to oil ratio 500. The product yields of the raw materials shown in table 1 after conversion and fractionation through the reaction scheme are shown in table 2, and the properties of the base oil products are shown in table 3.
Comparative example 4
A similar process flow was used as in the inventive examples. A hydrogenation pretreatment catalyst H1 is adopted in the hydrogenation pretreatment reactor, the reaction conditions are 290 ℃, 4MPa and the space velocity is 2.0H-1Hydrogen-to-oil ratio of 500; the hydroisomerization reactor adopts a hydroisomerization catalyst B, and the reaction conditions are 345 ℃, 15MPa and 0.5h of space velocity-1Hydrogen-to-oil ratio of 500; the hydrofining reactor adopts hydrofining catalyst H2, and the reaction conditions are 270 ℃, 12MPa and space velocity of 1.0H-1Hydrogen to oil ratio 500. The product yields of the raw materials shown in table 1 after conversion and fractionation through the reaction scheme are shown in table 2, and the properties of the base oil products are shown in table 3.
As can be seen from Table 2, compared with comparative examples 1, 2, 3 and 4, the preparation method of the lubricating base oil prepared by hydrogenation of Fischer-Tropsch wax provided by the invention has the advantages that the yield of medium and heavy base oil is remarkably improved, the yield of light hydrocarbon and diesel oil with lower values is remarkably reduced, and the content of unconverted heavy wax is remarkably reduced. Meanwhile, as can be seen from table 3, compared with comparative examples 1, 2, 3 and 4, the viscosity index of the medium base oil prepared by the preparation method of the lubricating oil base oil prepared by hydrogenation of fischer-tropsch wax is higher, and the pour point of the heavy base oil is lower.
In conclusion, the raw material adaptability of the invention is strong, the raw material pre-fractionation is not needed, the preparation method and the process conditions are simple, the hydroisomerized product is not needed to be circularly processed, and the lubricating oil base oil product prepared by hydrogenating the Fischer-Tropsch wax has high yield and good performance.
The technical characteristics form an embodiment of the invention, which has strong adaptability and implementation effect, and unnecessary technical characteristics can be increased or decreased according to actual needs to meet the requirements of different situations.
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Figure 737554DEST_PATH_IMAGE003

Claims (10)

1. A lubricating oil base oil prepared by hydrogenation of Fischer-Tropsch wax is characterized by being prepared by the following method: the first step, the fraction material of Fischer-Tropsch wax at 320-620 deg.c and hydrogen are mixed and fed into hydrogenation pre-treating reaction area, and the mixture is fed into the bed with hydrogenation pre-treating catalyst at 150-350 deg.c, hydrogen partial pressure of 1.0-20 MPa and material oil volume space velocity of 0.2 hr-1To 5h-1Under the condition that the hydrogen-oil ratio is 100-3000: 1, completing the hydrogenation saturation, hydrodesulfurization, hydrodenitrogenation and hydrodeoxygenation of non-alkane components in the raw materials to obtain hydrogenation pretreatment oil, wherein a hydrogenation pretreatment catalyst is composed of a heat-resistant inorganic oxide serving as a carrier, more than one metal of cobalt, nickel, molybdenum and tungsten with the mass loading of 15-45 wt% and more than one auxiliary agent of nitrogen, phosphorus, sulfur and boron with the mass loading of 2-8 wt% loaded on the carrier; secondly, the hydrogenation pretreatment oil enters a hydroisomerization reaction zone, and is arranged on a bed layer added with a combined catalyst, the reaction temperature is 200 ℃ to 450 ℃, the hydrogen partial pressure is 1.0MPa to 20MPa, and the volume space velocity of the raw oil is 0.2h-1To 5h-1Hydrogenation under the condition that the hydrogen-oil ratio is 100 to 3000:1Performing isomerization reaction, namely completing hydroisomerization and hydrocracking reaction of the hydrogenated pretreated oil to obtain the hydrogenated isomerized oil, wherein the combined catalyst is a catalyst formed by combining the catalyst A and the catalyst B according to the volume ratio of 1:10 to 10: 1; thirdly, the hydroisomerized oil enters a hydrofining reaction zone and is arranged on a bed layer added with a hydrofining catalyst, the reaction temperature is 150-350 ℃, the hydrogen partial pressure is 1.0-20 MPa, and the volume space velocity of the raw oil is 0.2h-1To 5h-1And the hydrogen-oil ratio is 100-3000: 1, and the hydrogenation saturation of the hydroisomerization oil is completed to obtain a crude product, wherein the hydrofining catalyst is composed of a heat-resistant inorganic oxide as a carrier, more than one metal of platinum, palladium and iridium with the mass loading of 0.2-1.0 wt% and more than one auxiliary agent of cobalt, nickel, molybdenum and tungsten with the mass loading of 0.3-1.5 wt% which are loaded on the carrier; and fourthly, feeding the crude product into a normal pressure tower or a vacuum tower, and fractionating to obtain the lubricating oil base oil prepared by hydrogenation of the Fischer-Tropsch synthesis wax.
2. The lubricant base oil prepared by hydrogenation of Fischer-Tropsch wax according to claim 1, wherein the catalyst A is prepared by taking an aluminum phosphate molecular sieve with an AFO structure as a carrier and platinum, palladium and/or iridium loaded on the carrier with the mass loading of 0.1-0.5 wt% by adopting a conventional impregnation method; the catalyst B is prepared by taking an aluminum phosphate molecular sieve with an AFI structure as a carrier and platinum, palladium and/or iridium loaded on the carrier with the mass loading amount of 0.2-0.6 wt% by adopting a conventional impregnation method.
3. The lubricant base oil prepared by hydrogenation of Fischer-Tropsch wax according to claim 2, wherein the aluminum phosphate molecular sieve with AFO structure is more than one of SAPO-41 and MeAPO-41, wherein Me in the MeAPO-41 is more than one of Zn, Mg, Mn, Co, Cr, Cu, Cd and Ni; the aluminum phosphate molecular sieve with the AFI structure is more than one of SAPO-5 and MeAPO-5, wherein Me in the MeAPO-5 is more than one of Zn, Mg, Mn, Co, Cr, Cu, Cd and Ni.
4. The lubricant base oil prepared by hydrogenation of Fischer-Tropsch wax according to claim 1, 2 or 3, wherein the catalyst A and the catalyst B are positioned on the combined catalyst bed layer under the catalyst A and the catalyst B, the raw oil flows through the catalyst A and the catalyst B from top to bottom in sequence, and the volume ratio of the catalyst A to the catalyst B is 1:5 to 5: 1.
5. The Fischer-Tropsch wax of claim 4, wherein the volume ratio of catalyst A to catalyst B is from 1:5 to 2: 1.
6. A lubricant base oil obtained by hydrogenation of Fischer-Tropsch wax according to claim 1 or 2 or 3 or 4 or 5, characterised in that the acid content of catalyst A is 1.5mmol (NH)3) From/g to 2.0mmol (NH)3) (ii)/g; the acid content of catalyst B was 2.2mmol (NH)3) From/g to 3.2mmol (NH)3)/g。
7. The Fischer-Tropsch wax of any one of claims 1 to 6, wherein the refractory inorganic oxide support in the hydroprocessing catalyst is alumina and/or silica; the heat-resistant inorganic oxide carrier in the hydrofining catalyst is alumina and/or silica.
8. The Fischer-Tropsch wax as claimed in any one of claims 1 to 7, wherein the hydrogenation pretreatment reaction conditions in the first step are 200 to 320 ℃, the hydrogen partial pressure of 2.0 to 15MPa, and the feedstock oil volume space velocity of 0.5h-1To 3h-1The hydrogen-oil ratio is 200 to 1000: 1; in the second step, the hydroisomerization reaction conditions are that the temperature is 250 ℃ to 400 ℃, the hydrogen partial pressure is 5.0MPa to 15MPa, and the raw material oil volume space velocity is 0.5h-1To 2h-1The hydrogen-oil ratio is 200 to 1000: 1; in the third step, the hydrofining reaction conditions are that the temperature is 180 ℃ to 320 ℃, the hydrogen partial pressure is 2.0MPa to 15MPa, and the volume space velocity of the raw oil is 0.5h-1To 2h-1The hydrogen-oil ratio is 200 to 1000: 1.
9. The Fischer-Tropsch wax as claimed in claim 8, wherein the hydroisomerization reaction is carried out at a temperature of 280 to 380 ℃, a hydrogen partial pressure of 8.0 to 15MPa, and a feedstock volumetric space velocity of 0.5h in the second step-1To 2h-1The hydrogen-oil ratio is 200 to 800: 1.
10. A process for the preparation of a lubricant base oil obtained by hydrogenation of a fischer-tropsch wax according to any one of claims 2 to 9, characterised in that it is carried out according to the following steps: the first step, the fraction material of Fischer-Tropsch wax at 320-620 deg.c and hydrogen are mixed and fed into hydrogenation pre-treating reaction area, and the mixture is fed into the bed with hydrogenation pre-treating catalyst at 150-350 deg.c, hydrogen partial pressure of 1.0-20 MPa and material oil volume space velocity of 0.2 hr-1To 5h-1Under the condition that the hydrogen-oil ratio is 100-3000: 1, completing the hydrogenation saturation, hydrodesulfurization, hydrodenitrogenation and hydrodeoxygenation of non-alkane components in the raw materials to obtain hydrogenation pretreatment oil, wherein a hydrogenation pretreatment catalyst is composed of a heat-resistant inorganic oxide serving as a carrier, more than one metal of cobalt, nickel, molybdenum and tungsten with the mass loading of 15-45 wt% and more than one auxiliary agent of nitrogen, phosphorus, sulfur and boron with the mass loading of 2-8 wt% loaded on the carrier; secondly, the hydrogenation pretreatment oil enters a hydroisomerization reaction zone, and is arranged on a bed layer added with a combined catalyst, the reaction temperature is 200 ℃ to 450 ℃, the hydrogen partial pressure is 1.0MPa to 20MPa, and the volume space velocity of the raw oil is 0.2h-1To 5h-1Carrying out hydroisomerization reaction under the condition that the hydrogen-oil ratio is 100-3000: 1, and finishing hydroisomerization and hydrocracking reaction of hydrogenated pretreated oil to obtain hydroisomerization oil, wherein the combined catalyst is a catalyst formed by combining a catalyst A and a catalyst B according to the volume ratio of 1: 10-10: 1; thirdly, the hydroisomerized oil enters a hydrofining reaction zone and is arranged on a bed layer added with a hydrofining catalyst, the reaction temperature is 150-350 ℃, the hydrogen partial pressure is 1.0-20 MPa, and the volume space velocity of the raw oil is 0.2h-1To 5h-1The hydrogen-oil ratio is 100 to 3000:1,the hydrogenation saturation of the hydroisomerization oil is completed to obtain a crude product, wherein the hydrofining catalyst is composed of a heat-resistant inorganic oxide serving as a carrier, more than one metal of platinum, palladium and iridium with the mass loading of 0.2wt% to 1.0wt% and more than one auxiliary agent of cobalt, nickel, molybdenum and tungsten with the mass loading of 0.3wt% to 1.5wt% which are loaded on the carrier; and fourthly, feeding the crude product into a normal pressure tower or a vacuum tower, and fractionating to obtain the lubricating oil base oil prepared by hydrogenation of the Fischer-Tropsch synthesis wax.
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