CN112126465B - Hydrogenation catalyst composition and method for preparing lubricating oil base oil from Fischer-Tropsch synthetic wax - Google Patents
Hydrogenation catalyst composition and method for preparing lubricating oil base oil from Fischer-Tropsch synthetic wax Download PDFInfo
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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
- 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
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J29/00—Catalysts comprising molecular sieves
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- 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
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Abstract
The invention relates to the technical field of hydrogenation conversion of Fischer-Tropsch synthesis products, in particular to a hydrogenation catalyst composition and a method for preparing lubricating oil base oil from Fischer-Tropsch synthesis wax. The method can prepare the lubricating oil base oil with low pour point and high viscosity index with high yield by carrying out hydrogenation pretreatment, hydroisomerization, hydrofining and fractionation on fractions of Fischer-Tropsch synthetic wax at 320-540 ℃, and has the technical core that each component in the wide-distillation range raw material can be converted into an isomerate with high selectivity based on the hydroisomerization process of an aluminum silicate molecular sieve catalyst with a combined MEL structure and an MTW structure, so that the yield and the performance of the product are improved at the same time.
Description
Technical Field
The invention relates to the technical field of hydrogenation conversion of Fischer-Tropsch synthesis products, and discloses a method for processing lubricating oil base oil prepared from Fischer-Tropsch synthesis wax, a hydrogenation catalyst composition and application of the hydrogenation catalyst composition in improving the yield of the lubricating oil base oil with low pour point and high viscosity index prepared from Fischer-Tropsch synthesis wax.
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 ) The technological process of synthesizing liquid fuel and chemical with long chain alkane as main component in the presence of catalyst and proper reaction condition. In the product of the low temperature Fischer-Tropsch synthesis, the wax-containing component comprises a soft wax (C) 20 -C 30 ) And hard wax (>C 30 ) The main component is straight-chain alkane, almost no sulfur, nitrogen and aromatic hydrocarbon exist, and the lubricating oil is a high-quality high-grade lubricating oil base oil raw material. The technical key point of converting the Fischer-Tropsch synthetic wax product into the high-grade lubricating oil base oil is that the low-temperature flow property, namely the freezing point is reduced, of the oil product can be improved under the condition of keeping the high viscosity indexHydrocracking and hydroisomerization reactions.
Many patents have been published at home and abroad, for example, US5834522 discloses a process for producing lube base oil from a fischer-tropsch synthesis product as a feedstock, 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 oil and non-oil fractions. US5882505 discloses a process for producing lube base oil by converting fischer-tropsch wax having a boiling point of greater than 370 ℃ in a countercurrent reactor, wherein a feedstock is contacted with a hydroisomerization catalyst in a fixed bed reactor, and the product after the reaction is contacted with a hydrodewaxing catalyst in at least one fixed bed reactor to produce a target product, wherein the hydroisomerization reaction product and a hydrogen-containing gas flow in a countercurrent direction. CN1688674 discloses a multi-step process for producing a heavy lubricant base oil from fischer-tropsch wax, comprising hydrodewaxing the wax in a first hydrodewaxing step to produce an isomerate of a partially dewaxed heavy base oil fraction, and then hydrodewaxing said heavy lubricant fraction in one or more successive hydrodewaxing steps, removing hydrocarbons below the heavy lubricant fraction, to produce a heavy lubricant base oil. CN1703488 discloses a process for producing fuel and lubricant base oils from fischer-tropsch wax comprising (1) hydrodewaxing the fischer-tropsch wax to produce an isomerate comprising 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) further hydrodewaxing the lower boiling fraction and the heavy fraction, respectively, to produce lubricant base oils including heavy lubricant base stocks. CN101230290 discloses a method for producing solvent oil, lubricant base oil and heavy wax from Fischer-Tropsch synthetic wax, which comprises the steps of fractionating a full fraction product obtained by converting wax in a hydrofining area to obtain a solvent oil light fraction, separating a base oil fraction section product, performing hydroisomerization conversion, and directly performing hydrofining on the remaining heavy fraction to obtain the decolorized wax. US7198710 discloses a process for producing high viscosity index lube base oil from fischer-tropsch wax, wherein fischer-tropsch wax is fractionated to obtain light and heavy components, which are then subjected to hydroisomerization dewaxing to reduce the pour point of the feed stock, thereby obtaining a light lube base oil with a pour point meeting the requirements. When 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 heavy lubricating oil base oil product 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. In general, when the pour point of the heavy base oil component is acceptable, the loss of the viscosity index of the light base oil component is large, and it is difficult to produce API group III light lubricant base oil products with viscosity index > 120; while the viscosity index of the light base oil component is acceptable, the heavy component is not an acceptable lubricant base oil product. 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 existing production of light and heavy high-viscosity index lubricating oil base oil can be solved to a certain extent by fractionating raw materials and adopting 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 a hydrogenation catalyst composition and a method for preparing lubricating oil base oil from Fischer-Tropsch synthetic wax, which overcome the defects of the prior art, and enable all components in a wide distillation range raw material to be converted into an isomeric product with high selectivity based on a hydroisomerization process of an aluminum silicate molecular sieve catalyst with a combined MEL structure and MTW structure, thereby realizing the improvement of the product yield and performance.
One of the technical schemes of the invention is realized by the following measures: a hydroprocessing catalyst composition comprising a hydroprocessing pretreatment catalyst, a combined catalyst and a hydrofinishing catalyst; the combined catalyst is composed of a catalyst A and a catalyst B according to the volume ratio of 1; the hydrogenation pretreatment catalyst consists of a heat-resistant inorganic oxide as a carrier, one or more active metals of cobalt, nickel, molybdenum and tungsten loaded on the carrier, and one or more auxiliary agents selected from nitrogen, silicon, sulfur and boron; the hydrofining catalyst consists of refractory inorganic oxide as carrier, one or several active metals of Pt, pd and Ir and one or several assistants of Co, ni, mo and W.
The following is a further optimization or/and improvement of one of the above-mentioned technical solutions of the invention:
the molecular sieve with the MEL structure is a ZSM-11 molecular sieve; or/and the molecular sieve with the MTW structure is one or more of ZSM-12, NU-13, CZH-5, TPZ-12, VS-12 and Theta-3; or/and in the hydrogenation pretreatment catalyst, the mass loading of the active metal is 18wt% to 38wt%, and the mass loading of the auxiliary agent is 2wt% to 12wt%; or/and in the hydrofining catalyst, the mass loading of the active metal is 0.2wt% to 1.0wt%, and the mass loading of the auxiliary agent is 0.3wt% to 1.5wt%; or/and catalyst A and catalyst B are mixed according to the volume ratio of 1:5 to 5:1.
The acid content of the catalyst A was 2.2mmol (NH) 3 ) From/g to 2.7mmol (NH) 3 ) Acid quantity of catalyst B1.2 mmol (NH)/g 3 ) From/g to 2.2mmol (NH) 3 ) (ii)/g; the mass loading of the active metal in catalyst a is 0.1wt% to 0.5wt%, and the mass loading of the active metal in catalyst B is 0.2wt% to 0.7wt%.
The second technical scheme of the invention is realized by the following measures: the application of the hydrogenation catalyst composition in the technical scheme in improving the yield of the lubricant base oil with low pour point and high viscosity index prepared from Fischer-Tropsch synthetic wax.
The third technical scheme of the invention is realized by the following measures: a method for processing Fischer-Tropsch synthesis wax to prepare lubricating oil base oil by using the hydrogenation catalyst composition in one of the technical schemes comprises the following steps: 1) Mixing the fraction raw oil of Fischer-Tropsch wax at 320-540 deg.C and hydrogen gas, feeding them into hydrogenation pretreatment reaction zone, and making them pass through hydrogenation pretreatment catalyst, and making its temperature be 150-350 deg.C, hydrogen partial pressure be 1.0-20 MPa and raw oil volume space velocity be 0.2h -1 To 5h -1 Under the condition that the hydrogen-oil ratio is 100 to 3000;
2) The hydrogenation pretreatment oil obtained in the step 1) enters a hydroisomerization reaction zone, the reaction temperature is 200-450 ℃, the hydrogen partial pressure is 1.0-20 MPa, and the volume space velocity of the raw oil is 0.2h on a combined catalyst -1 To 5h -1 Carrying out a hydroisomerization reaction under the condition that the hydrogen-oil ratio is between 100 and 3000;
3) The hydroisomerized oil obtained in the step 2) enters a hydrofining reaction zone, the reaction temperature is 150-350 ℃, the hydrogen partial pressure is 1.0-20 MPa, and the raw oil volume space velocity is 0.2h on a hydrofining catalyst -1 To 5h -1 And the hydrogen-oil ratio is 100;
4) And (3) feeding the crude product obtained in the step 3) into an atmospheric tower or a vacuum tower, and fractionating to obtain gasoline, diesel oil and base oil.
The third technical scheme of the invention is further optimized or/and improved as follows:
the position of the combined catalyst in the catalyst bed layer is that the catalyst A is arranged above the catalyst B, and the raw oil sequentially flows through the catalyst A and the catalyst B.
The hydrogenation pretreatment reaction conditions are as follows: 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 to 2h -1 The hydrogen-oil ratio is 200.
The hydroisomerization reaction conditions are as follows: the temperature is 250 ℃ to 400 ℃, the hydrogen partial pressure is 5.0MPa to 15MPa, and the volume space velocity of the raw oil is 0.5h to 2h -1 The hydrogen-oil ratio is 200.
The hydrorefining reaction conditions are as follows: 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 to 2h -1 The hydrogen-oil ratio is 200.
And 3) sequentially feeding the crude product obtained in the step 3) into a normal pressure tower and a vacuum tower for fractionation to obtain gasoline, kerosene, diesel oil and base oil.
The method can prepare the lubricating oil base oil with low pour point and high viscosity index with high yield by carrying out hydrogenation pretreatment, hydroisomerization, hydrofining and fractionation on fractions of Fischer-Tropsch synthetic wax at 320-540 ℃, and has the technical core that each component in the wide-distillation range raw material can be converted into an isomerate with high selectivity based on the hydroisomerization process of an aluminum silicate molecular sieve catalyst with a combined MEL structure and an MTW structure, so that the yield and the performance of the product are improved at the same time.
Drawings
FIG. 1 is a process flow diagram of the method for processing Fischer-Tropsch wax to produce lube base oil 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 hydrogenation catalyst composition comprises a hydrogenation pretreatment catalyst, a combined catalyst and a hydrofining catalyst; the combined catalyst is composed of a catalyst A and a catalyst B according to the volume ratio of 1; the hydrogenation pretreatment catalyst consists of a heat-resistant inorganic oxide as a carrier, one or more active metals of cobalt, nickel, molybdenum and tungsten loaded on the carrier, and one or more auxiliary agents selected from nitrogen, silicon, sulfur and boron; the hydrofining catalyst consists of refractory inorganic oxide as carrier, one or several active metals of Pt, pd and Ir and one or several assistants of Co, ni, mo and W.
Example 2: the hydrogenation catalyst composition comprises a hydrogenation pretreatment catalyst, a combined catalyst and a hydrofining catalyst; the combined catalyst is composed of a catalyst A and a catalyst B according to the volume ratio of 1; the hydrogenation pretreatment catalyst consists of a heat-resistant inorganic oxide as a carrier, one or more active metals of cobalt, nickel, molybdenum and tungsten loaded on the carrier, and one or more auxiliary agents selected from nitrogen, silicon, sulfur and boron; the hydrofining catalyst consists of refractory inorganic oxide as carrier, one or several active metals of Pt, pd and Ir and one or several assistants of Co, ni, mo and W.
The combined catalyst is applied to hydroisomerization reaction, and all components in the wide distillation range raw material can be converted into an isomeric product with high selectivity by combining molecular sieve catalysts (catalyst A and catalyst B) with MEL structures and MTW structures and combining a subsequent recorded hydroisomerization process, so that the yield and the performance of the product are improved at the same time.
The refractory inorganic oxide in both the hydrotreating catalyst and the hydrofinishing catalyst may be alumina and/or silica.
Example 3: as optimization of the above embodiment, the molecular sieve with MEL structure is ZSM-11 molecular sieve; or/and the molecular sieve with the MTW structure is one or more of ZSM-12, NU-13, CZH-5, TPZ-12, VS-12 and Theta-3; or/and in the hydrogenation pretreatment catalyst, the mass loading of the active metal is 18wt% to 38wt%, and the mass loading of the auxiliary agent is 2wt% to 12wt%; or/and in the hydrofining catalyst, the mass loading of the active metal is 0.2wt% to 1.0wt%, and the mass loading of the auxiliary agent is 0.3wt% to 1.5wt%; or/and catalyst A and catalyst B are mixed according to the volume ratio of 1:5 to 5:1.
Preferably, catalyst a and catalyst B are in a volume ratio of 1:5 to 2:1.
Example 4: as an optimization of the above example, the acid amount of catalyst A was 2.2mmol (NH) 3 ) From/g to 2.7mmol (NH) 3 ) Acid amount of catalyst B1.2 mmol (NH)/g 3 ) From/g to 2.2mmol (NH) 3 ) (ii)/g; the mass loading of the active metal in catalyst a is 0.1wt% to 0.5wt%, and the mass loading of the active metal in catalyst B is 0.2wt% to 0.7wt%.
Example 5: the hydrogenation catalyst composition described in the above embodiment is applied to the improvement of the yield of the lubricant base oil with low pour point and high viscosity index prepared from Fischer-Tropsch wax.
Example 6: the method for processing the base oil of the Fischer-Tropsch synthesis wax by using the hydrogenation catalyst composition in the embodiment comprises the following steps: 1) The method comprises the steps of mixing raw oil of fractions of Fischer-Tropsch synthetic wax at 320-540 ℃ with hydrogen, feeding the mixture into a hydrogenation pretreatment reaction zone, and reacting on a hydrogenation pretreatment catalyst at 150-350 ℃ under the conditions of hydrogen partial pressure of 1.0-20 MPa and raw oil volume space velocity of 0.2h -1 To 5h -1 And the addition of non-alkane components in the raw oil is completed under the condition that the hydrogen-oil ratio is 100Hydrogen saturation, hydrodesulfurization, hydrodenitrogenation and hydrodeoxygenation to obtain hydrogenated pretreated oil;
2) The hydrogenation pretreatment oil obtained in the step 1) enters a hydroisomerization reaction zone, the reaction temperature is 200-450 ℃, the hydrogen partial pressure is 1.0-20 MPa, and the volume space velocity of the raw oil is 0.2h on a combined catalyst -1 To 5h -1 Carrying out a hydroisomerization reaction under the condition that the hydrogen-oil ratio is 100 to 3000;
3) The hydroisomerized oil obtained in the step 2) enters a hydrofining reaction zone, the reaction temperature is 150-350 ℃, the hydrogen partial pressure is 1.0-20 MPa, and the raw oil volume space velocity is 0.2h on a hydrofining catalyst -1 To 5h -1 And the hydrogen-oil ratio is 100;
4) And (3) feeding the crude product obtained in the step 3) into an atmospheric tower or a vacuum tower, and fractionating to obtain products such as gasoline, diesel oil and base oil.
From the content of the embodiment 6, the fraction of the fischer-tropsch wax at 320 to 540 ℃ first enters a hydrogenation pretreatment reaction zone to complete the hydrogenation saturation, the hydrogenation desulfurization, the hydrogenation denitrification and the hydrogenation deoxidation of the non-alkane components in the raw material; the obtained hydrogenation pretreatment oil enters a hydroisomerization reaction zone, and the hydroisomerization of the hydrogenation pretreatment oil is completed on the combined catalyst; the obtained hydrogenation isomeric oil enters a hydrogenation refining reaction zone for further treatment to obtain a crude product; and fractionating the crude product by an atmospheric tower or a vacuum tower to obtain base oil, diesel oil, gasoline and other products.
Example 7: as an optimization of example 6, the position of the combined catalyst in the catalyst bed layer is that the combined catalyst is arranged on the catalyst A and under the catalyst B, and the raw oil flows through the catalyst A and the catalyst B in sequence.
Example 8: as an optimization of examples 6 to 7, the hydrogenation pretreatment reaction conditions were: 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 to 2h -1 The hydrogen-oil ratio is 200.
Example 9:as an optimization of examples 6 to 8, the hydroisomerization reaction conditions were: the temperature is 250 ℃ to 400 ℃, the hydrogen partial pressure is 5.0MPa to 15MPa, and the volume space velocity of the raw oil is 0.5h to 2h -1 The hydrogen-oil ratio is 200.
Example 10: as an optimization of examples 6 to 9, the hydrofinishing reaction conditions were: 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 to 2h -1 The hydrogen-oil ratio is 200.
Example 11: as optimization of examples 6 to 10, the crude product obtained in step 3) enters an atmospheric tower and a vacuum tower in sequence for fractionation to obtain products such as gasoline, kerosene, diesel oil, base oil and the like.
Such atmospheric and vacuum column fractionation is well known in the art and typically comprises one or more operating units of flash, atmospheric and vacuum distillation columns to effect separation of the products of the different distillation ranges.
(1) Hydrogenation pretreatment catalyst H1
The hydrogenation pretreatment catalyst H1 (which can be replaced by H1) is prepared by a conventional impregnation method. The catalyst is composed of a heat-resistant inorganic oxide alumina and/or silica serving as a carrier, one or more metals of cobalt, nickel, molybdenum and tungsten loaded on the carrier, and one or more auxiliary agents selected from nitrogen, silicon, sulfur or boron. The total content of cobalt, nickel, molybdenum and tungsten (in the following examples, these four element ratios are equal in mass) was 37wt%, the total content of nitrogen, silicon, sulfur and boron (in the following examples and comparative examples, these four element ratios are equal in mass) was 9wt%, and the balance was alumina and/or silica (in the following examples and comparative examples, alumina and silica in a mass ratio of 1:1).
(2) Hydroisomerization catalysts A and B
The catalyst A (namely the hydroisomerization catalyst A) is prepared by a conventional impregnation method. The hydroisomerization catalyst A is composed of an aluminum silicate molecular sieve ZSM-11 with an MEL structure as a carrier and one or more metals selected from platinum, palladium and iridium. Based on the weight percentage of the hydroisomerization catalyst A, platinum and palladiumAnd iridium (the same mass ratios of these three elements are used in the following examples and comparative examples) in a total amount of 0.3wt%, with the remainder being an aluminosilicate molecular sieve ZSM-11 having a MEL structure, and the acid amount of catalyst A being 2.4mmol (NH) 3 )/g。
The catalyst B (namely the hydroisomerization catalyst B) is prepared by a conventional impregnation method. The hydroisomerization catalyst B is composed of an aluminum silicate molecular sieve ZSM-12 with an MTW structure as a carrier and one or more metals selected from platinum, palladium and iridium. Based on the weight percentage of the hydroisomerization catalyst B, the total content of platinum, palladium and iridium (the three elements in the following examples and comparative examples are equal in mass) is 0.6wt%, the balance is an aluminum silicate molecular sieve ZSM-12 having an MTW structure, and the acid content of the catalyst A is 2.0mmol (NH) 3 )/g。
(3) Hydrofining catalyst H2
The hydrogenation pretreatment catalyst (which can be replaced by H2) is prepared by a conventional impregnation method. The H2 is composed of a carrier, one or more metals of platinum, palladium and iridium and one or more auxiliary agents selected from cobalt, nickel, molybdenum and tungsten, wherein the carrier is made of heat-resistant inorganic oxide alumina and/or silica. The total content of platinum, palladium and iridium (the three element ratios in mass equal in the following examples and comparative examples) was 0.3wt%, the total content of cobalt, nickel, molybdenum and tungsten (the four element ratios in mass equal in the following examples and comparative examples) was 1wt%, and the balance was alumina and/or silica (the alumina and silica in mass ratio 1:1 were used in the following examples and comparative examples), based on the weight percentage of H2.
The following examples were prepared using Fischer-Tropsch wax as the feedstock and the lubricant base oil prepared according to the method of the present invention described in the above examples, and the properties of the Fischer-Tropsch wax are shown in Table 1. The comparative example also uses Fischer-Tropsch wax as raw material to prepare lubricant base oil.
Example 12: as shown in attached figure 1, a hydrogenation pretreatment catalyst H1 is adopted in a hydrogenation pretreatment reactor, the reaction conditions are 290 ℃,7MPa and the space velocity is 2.0H -1 Hydrogen to oil ratio of 500; the hydroisomerization reactor employs hydroisomerizationThe catalyst A and the catalyst B are loaded in a mode that the catalyst A is loaded on the catalyst B, the loading volume ratio is 1:1, the reaction condition is 340 ℃,12MPa and the airspeed is 0.5h -1 Hydrogen to oil ratio of 500; the hydrofining reactor adopts hydrofining catalyst H2, and the reaction conditions are 220 deg.C, 5MPa and airspeed of 1.0H -1 Hydrogen to oil ratio of 500. The product yields of the raw materials shown in table 1 after conversion and fractionation by the reaction scheme are shown in table 2, and the properties of the lubricant base oil products are shown in table 3.
Example 13: as shown in attached figure 1, a hydrogenation pretreatment catalyst H1 is adopted in a hydrogenation pretreatment reactor, the reaction conditions are 280 ℃,7MPa and the space velocity is 2.0H -1 Hydrogen to oil ratio 600; the hydroisomerization reactor adopts hydroisomerization catalysts A and B, the filling mode of the hydroisomerization catalysts A and the catalyst B is that the catalyst A is arranged under the catalyst B, the filling volume ratio is 1:2, the reaction conditions are 335 ℃,13MPa and the airspeed is 0.5h -1 Hydrogen to oil ratio of 500; the hydrofining reactor adopts hydrofining catalyst H2, and the reaction conditions are 240 ℃,6MPa and airspeed of 1.0H -1 Hydrogen to oil ratio of 500. The product yields of the raw materials shown in table 1 after conversion and fractionation by the reaction process are shown in table 2, and the properties of the lubricating base oil products are shown in table 3.
Example 14: as shown in attached figure 1, a hydrogenation pretreatment catalyst H1 is adopted in a hydrogenation pretreatment reactor, the reaction conditions are 300 ℃,8MPa and the space velocity is 2.0H -1 Hydrogen to oil ratio of 600; the hydroisomerization reactor adopts hydroisomerization catalysts A and B, the filling mode of the hydroisomerization catalysts A and the catalyst B is that the catalyst A is arranged under the catalyst B, the filling volume ratio is 1:3, the reaction conditions are 330 ℃,15MPa and the airspeed is 0.5h -1 Hydrogen to oil ratio of 500; the hydrofining reactor adopts hydrofining catalyst H2, and the reaction conditions are 240 ℃,6MPa and airspeed of 1.0H -1 Hydrogen to oil ratio of 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 15: as shown in attached figure 1, a hydrogenation pretreatment catalyst H1 is adopted in a hydrogenation pretreatment reactor, the reaction conditions are 310 ℃,8MPa and the space velocity is 2.0H -1 Hydrogen to oil ratio of 500; the hydroisomerization reactor adopts hydroisomerization catalysts A and B, the filling mode of the hydroisomerization catalysts A and the catalyst B is that the catalyst A is arranged under the catalyst B, the filling volume ratio is 1:5, the reaction conditions are 325 ℃, and the reaction temperature is 15MPa, space velocity of 0.5h -1 Hydrogen to oil ratio of 500; the hydrofining reactor adopts hydrofining catalyst H2, and the reaction conditions are 270 ℃,5MPa and airspeed of 1.0H -1 Hydrogen to oil ratio of 500. The product yields of the raw materials shown in table 1 after conversion and fractionation by the reaction process are shown in table 2, and the properties of the lubricating 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 290 ℃,7MPa and the space velocity is 2.0H -1 Hydrogen to oil ratio of 500; the hydroisomerization reactor adopts a hydroisomerization catalyst A, the reaction conditions are 340 ℃,12MPa and the space velocity is 0.5h -1 Hydrogen to oil ratio of 500; the hydrofining reactor adopts hydrofining catalyst H2, and the reaction conditions are 220 deg.C, 5MPa and airspeed of 1.0H -1 Hydrogen to oil ratio of 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 ℃,7MPa and the airspeed is 2.0H -1 Hydrogen to oil ratio of 600; the hydroisomerization reactor adopts a hydroisomerization catalyst A, and the reaction conditions are 335 ℃,13MPa and 0.5h of airspeed -1 Hydrogen to oil ratio of 500; the hydrofining reactor adopts hydrofining catalyst H2, the reaction conditions are 240 ℃,6MPa and the airspeed is 1.0H -1 Hydrogen to oil ratio of 500. The product yields of the raw materials shown in table 1 after conversion and fractionation by 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 300 ℃,8MPa and the airspeed of 2.0H -1 Hydrogen to oil ratio of 600; the hydroisomerization reactor adopts a hydroisomerization catalyst B, and the reaction conditions are 330 ℃,15MPa and 0.5h of space velocity -1 Hydrogen to oil ratio of 500; the hydrofining reactor adopts hydrofining catalyst H2, the reaction conditions are 240 ℃,6MPa and the airspeed is 1.0H -1 Hydrogen to oil ratio of 500. The product yields of the raw materials shown in Table 1 after conversion and fractionation by the reaction scheme are shown in Table 2, and the base oilsThe product properties are shown in Table 3.
Comparative example 4: a similar process flow as the present invention was used. A hydrogenation pretreatment catalyst H1 is adopted in a hydrogenation pretreatment reactor, the reaction conditions are 310 ℃,8MPa and the space velocity is 2.0H -1 Hydrogen to oil ratio of 500; the hydroisomerization reactor adopts a hydroisomerization catalyst B, and the reaction conditions are 325 ℃,15MPa and 0.5h of airspeed -1 Hydrogen to oil ratio of 500; the hydrofining reactor adopts hydrofining catalyst H2, the reaction conditions are 250 ℃,5MPa and the airspeed is 1.0H -1 Hydrogen to oil ratio of 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, the yield of base oil is significantly increased and the yields of light hydrocarbons and diesel, which are of lower value, are significantly reduced by the process of the present invention compared to the comparative examples. Meanwhile, as can be seen from table 3, the base oil prepared by the method of the present invention has a higher viscosity index and a lower pour point than the comparative example.
Compared with the existing method for preparing the base oil of the lubricating oil by using the Fischer-Tropsch synthetic wax, the method for processing the Fischer-Tropsch synthetic wax by the hydro-conversion method has the following advantages: the method has the advantages of strong raw material adaptability, simple process conditions, no need of circularly treating the hydroisomerized product, and capability of obtaining the target product by one-time passing.
In conclusion, the method can prepare the lubricating oil base oil with low pour point and high viscosity index in high yield by carrying out hydrogenation pretreatment, hydroisomerization, hydrofining and fractionation on fractions of Fischer-Tropsch wax at 320-540 ℃, and the technical core of the method is that each component in the wide distillation range raw material can be converted into an isomeric product with high selectivity based on the hydroisomerization process of an aluminum silicate molecular sieve catalyst with a combined MEL structure and an MTW structure, so that the yield and the performance of the product are improved at the same time.
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.
Claims (8)
1. A method for processing Fischer-Tropsch synthetic wax to prepare lube base oil by using a hydrogenation catalyst composition is characterized in that the hydrogenation catalyst composition comprises a hydrogenation pretreatment catalyst, a combined catalyst and a hydrofining catalyst; the combined catalyst is composed of a catalyst A and a catalyst B according to a volume ratio of 1 to 10, wherein the catalyst A is composed of a molecular sieve with an MEL structure as a carrier and supported active metal platinum and/or palladium and/or iridium, the molecular sieve with the MEL structure is a ZSM-11 molecular sieve, and the catalyst B is composed of a molecular sieve with an MTW structure as a carrier and supported active metal platinum and/or palladium and/or iridium; the molecular sieve with MTW structure is ZSM-12 hydrogenation pretreatment catalyst; the catalyst consists of a heat-resistant inorganic oxide as a carrier, one or more active metals of cobalt, nickel, molybdenum and tungsten loaded on the carrier, and one or more auxiliary agents selected from nitrogen, silicon, sulfur and boron; the hydrofining catalyst consists of a heat-resistant inorganic oxide as a carrier, one or more active metals of platinum, palladium and iridium loaded on the carrier, and one or more auxiliary agents selected from cobalt, nickel, molybdenum and tungsten;
wherein, in the hydrogenation pretreatment catalyst, the mass loading of the active metal is 18wt% to 38wt%, and the mass loading of the auxiliary agent is 2wt% to 12wt%; in the hydrofining catalyst, the mass loading of the active metal is 0.2wt% to 1.0wt%, and the mass loading of the auxiliary agent is 0.3wt% to 1.5wt%; catalyst A and catalyst B are mixed according to the volume ratio of 1:5 to 5:1;
the acid content of catalyst A was 2.2mmol (NH) 3 ) G to 2.7mmol(NH 3 ) Acid amount of catalyst B1.2 mmol (NH)/g 3 ) From/g to 2.2mmol (NH) 3 ) (ii)/g; the mass loading of the active metal in catalyst A is 0.1wt% to 0.5wt%, and the mass loading of the active metal in catalyst B is 0.2wt% to 0.7wt%;
the method for processing the Fischer-Tropsch synthetic wax to prepare the lubricating oil base oil comprises the following steps: 1) Mixing the fraction raw oil of Fischer-Tropsch wax at 320-540 deg.C and hydrogen gas, feeding them into hydrogenation pretreatment reaction zone, and making them pass through hydrogenation pretreatment catalyst, and making its temperature be 150-350 deg.C, hydrogen partial pressure be 1.0-20 MPa and raw oil volume space velocity be 0.2h -1 To 5h -1 Under the condition that the hydrogen-oil ratio is 100 to 3000;
2) The hydrogenation pretreatment oil obtained in the step 1) enters a hydroisomerization reaction zone, the reaction temperature is 200-450 ℃, the hydrogen partial pressure is 1.0-20 MPa, and the volume space velocity of the raw oil is 0.2h on a combined catalyst -1 To 5h -1 Carrying out a hydroisomerization reaction under the condition that the hydrogen-oil ratio is 100 to 3000;
3) The hydroisomerized oil obtained in the step 2) enters a hydrofining reaction zone, the reaction temperature is 150-350 ℃, the hydrogen partial pressure is 1.0-20 MPa, and the raw oil volume space velocity is 0.2h on a hydrofining catalyst -1 To 5h -1 And the hydrogen-oil ratio is 100;
4) Feeding the crude product obtained in the step 3) into an atmospheric tower or a vacuum tower, and fractionating to obtain gasoline, diesel oil and base oil;
the position of the combined catalyst in the catalyst bed layer is that the catalyst A is arranged under the catalyst B, and the raw oil flows through the catalyst A and the catalyst B in sequence.
2. The method of processing Fischer-Tropsch wax lubricant base oil according to claim 1, wherein the hydrogenation pretreatment reaction conditions areComprises the following steps: 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 to 2h -1 The hydrogen-oil ratio is 200.
3. The method for processing Fischer-Tropsch wax to make lube base oil according to claim 1 or 2, wherein the hydroisomerization reaction conditions are: the temperature is 250 ℃ to 400 ℃, the hydrogen partial pressure is 5.0MPa to 15MPa, and the volume space velocity of the raw oil is 0.5h to 2h -1 The hydrogen-oil ratio is 200.
4. The method for processing the Fischer-Tropsch wax lubricant base oil according to claim 1 or 2, wherein the hydrofining reaction conditions are as follows: 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 to 2h -1 The hydrogen-oil ratio is 200.
5. The method for processing the Fischer-Tropsch synthesis wax lubricating oil base oil according to claim 3, wherein the hydrofining reaction conditions are as follows: 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 to 2h -1 The hydrogen-oil ratio is 200.
6. The method for processing the Fischer-Tropsch synthesis wax lubricating oil base oil according to claim 1, 2 or 5, wherein the crude product obtained in the step 3) is sequentially subjected to fractionation in an atmospheric tower and a vacuum tower to obtain gasoline, kerosene, diesel oil and base oil.
7. The method for processing the Fischer-Tropsch wax lubricant base oil according to claim 3, wherein the crude product obtained in the step 3) is sequentially fractionated in an atmospheric tower and a vacuum tower to obtain gasoline, kerosene, diesel oil and base oil.
8. The method for processing the Fischer-Tropsch wax lubricant base oil according to claim 4, wherein the crude product obtained in the step 3) is sequentially fractionated in an atmospheric tower and a vacuum tower to obtain gasoline, kerosene, diesel oil and base oil.
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