CN115678610A - Method for preparing lubricating oil base oil from Fischer-Tropsch wax - Google Patents
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- 239000002199 base oil Substances 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000010687 lubricating oil Substances 0.000 title abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 156
- 238000006243 chemical reaction Methods 0.000 claims abstract description 155
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 131
- 238000006722 reduction reaction Methods 0.000 claims abstract description 50
- 239000003921 oil Substances 0.000 claims abstract description 47
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- 230000004913 activation Effects 0.000 claims abstract description 23
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- 238000011105 stabilization Methods 0.000 claims abstract description 22
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- 239000002638 heterogeneous catalyst Substances 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 13
- 239000012495 reaction gas Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
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- 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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Abstract
The invention provides a method for preparing lubricating oil base oil from Fischer-Tropsch wax. The method comprises the following steps: cutting the Fischer-Tropsch wax to obtain a first fraction, a second fraction and tower bottom wax; respectively carrying out isomerization reaction on the first fraction and the second fraction by using a first activated isomerization catalyst and a second activated isomerization catalyst to obtain first isomerized oil and second isomerized oil; respectively carrying out refining reaction on the first isomerous oil and the second isomerous oil by using a first activated refined catalyst and a second activated refined catalyst to obtain a first base oil product and a second base oil product; the preparation method of the first activated isomerization catalyst and the second activated isomerization catalyst comprises the following steps: carrying out reduction reaction on the first isomerization catalyst and the second isomerization catalyst to obtain a reduced first isomerization catalyst and a reduced second isomerization catalyst; and carrying out initial activation and stabilization reaction on the reduced first isomerization catalyst and the reduced second isomerization catalyst to obtain a first activated isomerization catalyst and a second activated isomerization catalyst.
Description
Technical Field
The invention relates to the technical field of Fischer-Tropsch wax processing, in particular to a method for preparing lubricating oil base oil from Fischer-Tropsch wax.
Background
The indirect coal liquefaction technology converts the synthesis gas into Fischer-Tropsch wax products through a Fischer-Tropsch synthesis process, has the characteristics of low contents of sulfur, nitrogen and aromatic hydrocarbon and high viscosity index, and the refined Fischer-Tropsch wax obtained through further processing has high content (> 99%) of saturated chain hydrocarbons, and is a high-quality raw material for producing API III + lubricating oil base oil.
The processing of the coal-based Fischer-Tropsch base oil is mainly completed through a reaction route of hydroisomerization pour point depression. The Fischer-Tropsch wax mainly comprises normal hydrocarbon, so that the problems of high solidification point (50-100 ℃) and high isomerization and pour point depression difficulty exist, in addition, the Fischer-Tropsch wax fraction range is wide, the processing steps are more in the actual processing, the flow path is long, and the deviation of each process easily causes the problem that the key index of the product is blocked and the product is difficult to reach the standard. This requires a Fischer-Tropsch wax processing scheme that matches the isomeric pour point depression.
In the prior art, fischer-Tropsch wax is subjected to isomerization processing by adopting continuous isomerization treatment of one or more catalysts, and API III + base oil products with high viscosity-temperature performance and good low-temperature fluidity, such as 4, 6# and the like for vehicles can be produced. Although the Fischer-Tropsch wax isomerization processing method is researched more at present, the existing processing scheme still has many defects aiming at the characteristics of the raw material of wide carbon number distribution range (20-100) and high solidification point (50-100 ℃). For example, wide-fraction Fischer-Tropsch wax is used as a raw material, the indexes of base oil with different viscosities in the product cannot be qualified at the same time, the obtained fractions of base oil with different grades have wide ranges, and the fractions are unacceptable in certain scenes and are easy to generate waste; the narrow-fraction Fischer-Tropsch wax is adopted as the raw material, so that the requirement that a base oil product needs to be as narrow as possible in a fraction range can be met, the difficulty of industrialization is increased due to too many cut fractions, the cost is greatly increased, and the fluctuation of the cutting precision of the raw material can cause the fluctuation of the product quality, and the problem that the indexes such as the fraction width, the viscosity, the evaporation loss and the like cannot be met is solved.
Disclosure of Invention
The invention mainly aims to provide a method for preparing lubricating base oil by Fischer-Tropsch wax, which aims to solve the problems that the cost for preparing the lubricating base oil by Fischer-Tropsch wax is higher and the indexes of the lubricating base oil cannot be considered at the same time in the prior art.
To achieve the above object, according to one aspect of the present invention, there is provided a method for preparing a lubricant base oil from fischer-tropsch wax, the method comprising: step S1, carrying out first cutting on Fischer-Tropsch wax to obtain a first fraction; performing second cutting on the Fischer-Tropsch wax to obtain a second fraction and tower bottom wax; the temperature of the first cutting is 450-500 ℃, and the temperature of the second cutting is 520-570 ℃; s2, carrying out a first isomerization reaction on the first fraction by using a first activated isomerization catalyst to obtain first isomerized oil; carrying out a second isomerization reaction on the second fraction by using a second activated isomerization catalyst to obtain second isomerized oil; s3, carrying out a first refining reaction on the first isomerous oil by using a first activated refining catalyst to obtain a first base oil product, and carrying out a second refining reaction on the second isomerous oil by using a second activated refining catalyst to obtain a second base oil product; the preparation method of the first activated isomerization catalyst and the second activated isomerization catalyst comprises the following steps: step A, carrying out reduction reaction on a first heterogeneous catalyst and a second heterogeneous catalyst to obtain a reduced first heterogeneous catalyst and a reduced second heterogeneous catalyst; and step B, carrying out initial activation stabilization reaction on the reduced first isomerization catalyst and the reduced second isomerization catalyst to obtain a first activated isomerization catalyst and a second activated isomerization catalyst.
Further, in the step A, the temperature of the reduction reaction is 200-300 ℃, preferably 240-260 ℃; preferably, the time of the reduction reaction is 1 to 24 hours, preferably 3 to 8 hours; preferably, the reduction reaction uses hydrogen as the reaction gas; preferably, the pressure of the reduction reaction is 1 to 10MPa, preferably 3 to 6MPa.
Further, in the step B, the initial-living stable reaction is sequentially carried out under the gradient temperature rise condition of a first reaction temperature, a second reaction temperature and a third reaction temperature, wherein the first reaction temperature is 250-280 ℃, the second reaction temperature is 280-300 ℃, the third reaction temperature is 300-320 ℃, and the reaction time under the first reaction temperature, the second reaction temperature and the third reaction temperature is respectively and independently 4-24 h.
Further, the first isomerization catalyst and the second isomerization catalyst are each independently a noble metal-supported molecular sieve catalyst; preferably the noble metal is selected from Pt and/or Pd; preferably, the molecular sieve is selected from any one of ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, SAPO-11, SAPO-41 and SSZ-32.
Further, the method for preparing the first activated purified catalyst and the second activated purified catalyst comprises: step A', carrying out a second reduction reaction on the first refined catalyst and the second refined catalyst to obtain a reduced first refined catalyst and a reduced second refined catalyst; and step B', performing a second initial activation stabilization reaction on the reduced first refined catalyst and the reduced second refined catalyst to obtain a first activated refined catalyst and a second activated refined catalyst.
Further, in the step A', the temperature of the second reduction reaction is 200-300 ℃, preferably 240-260 ℃; preferably, the time of the second reduction reaction is 1 to 24 hours, preferably 3 to 8 hours; preferably, the second reduction reaction uses hydrogen as a reaction gas; preferably, the pressure of the second reduction reaction is 1 to 10MPa, preferably 3 to 6MPa; preferably, in step B', the second initial living stable reaction is sequentially performed under the gradient temperature rising condition of a fourth reaction temperature, a fifth reaction temperature and a sixth reaction temperature, wherein the fourth reaction temperature is 200 to 220 ℃, the fifth reaction temperature is 220 to 230 ℃, the sixth reaction temperature is 230 to 290 ℃, and the reaction time at the fourth reaction temperature, the fifth reaction temperature and the sixth reaction temperature is independently 4 to 24 hours.
Further, the first and second purification catalysts are noble metal supported alumina catalysts, preferably the noble metals include Pt and/or Pd.
Further, in step S2, the hydrogen partial pressure of the first isomerization reaction and the second isomerization reaction is each independently 1 to 10MPa, preferably 3 to 6MPa, and preferably, the hydrogen-oil ratio of the first isomerization reaction and the second isomerization reaction is each independently 300 to 1200, preferably 500 to 800; preferably, the volume space velocity of the first isomerization reaction and the volume space velocity of the second isomerization reaction are respectively and independently 0.1-5.0 h -1 Preferably 0.5 to 2.0h -1 (ii) a Preferably, the reaction temperature of the first isomerization reaction and the second isomerization reaction are each independently 320 to 380 ℃.
Further, in step S3, the hydrogen partial pressures of the first purification reaction and the second purification reaction are each independently 1 to 10MPa, preferably 3 to 6MPa, and preferably, the hydrogen-oil ratios of the first purification reaction and the second purification reaction are each independently 300 to 1200, preferably 500 to 800; preferably, the volume space velocity of the first refining reaction and the volume space velocity of the second refining reaction are respectively and independently 0.1-5.0 h -1 Preferably 0.5 to 2.0h < -1 >; preferably, the reaction temperature of the first purification reaction and the reaction temperature of the second purification reaction are each independently 230 to 290 ℃.
Further, the method further comprises: step S4, performing third cutting on the first base oil to obtain a first light oil product and No. 4 base oil; performing fourth cutting on the second base oil to obtain a second light oil product and No. 6 base oil; preferably, the temperature of the distillate of the first light oil product and the second light oil product is less than 380 ℃, the temperature of the distillate of the No. 4 base oil is more than 390 ℃, and the temperature of the distillate of the No. 6 base oil is more than 370 ℃.
By applying the technical scheme of the invention, the selected activated isomerization catalyst can have a certain selective cracking function on the composition of 95 percent of high fractions in Fischer-Tropsch wax raw material fractions through proper activation reaction. The isomerization catalyst is first subjected to a reduction reaction, so that the noble metal (such as Pt) in the isomerization catalyst can be reduced to a state of a nano metal cluster, and the hydrogenation function of the noble metal can be better exerted. And then, initial activation and stabilization reaction are carried out on the heterogeneous catalyst, so that the overall acidity distribution of the catalyst can be optimized, active sites in pores are reserved, reaction material molecules can enter deep layers in catalyst pore channels to carry out further heterogeneous cracking reaction, and heavy residues are reduced. When the range of the raw material fraction is moderate, qualified base oil products can be obtained only by selecting relatively mild operating conditions; when the range of the raw material fraction is wide and heavy, qualified base oil products can be obtained only by increasing the severity of the operation conditions. After the isomerous oil is subjected to additional refining and cutting, high-quality 4# or 6# base oil can be obtained.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiment(s) of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
figure 1 shows a flow diagram for the preparation of a lubricant base oil from fischer-tropsch wax according to the invention.
Detailed Description
It should be noted that, in the present application, the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As analyzed by the background art, the wide-fraction fischer-tropsch wax is adopted as a raw material in the prior art, the indexes of base oil with different viscosities in the product cannot be qualified at the same time, the obtained fractions of base oil with different grades have wide ranges, which are unacceptable in certain scenes and are easy to generate waste; the narrow-fraction Fischer-Tropsch wax is adopted as the raw material, so that the requirement that a base oil product needs to be as narrow as possible in a fraction range can be met, the difficulty of industrialization is increased due to too many cut fractions, the cost is greatly increased, and the fluctuation of the cutting precision of the raw material can cause the fluctuation of the product quality, and the problem that the indexes such as the fraction width, the viscosity, the evaporation loss and the like cannot be met is solved. In order to solve the above problems, the present application provides a process for preparing a lubricant base oil from a fischer-tropsch wax.
In an exemplary embodiment of the present application, there is provided a process for preparing a lubricant base oil from a fischer-tropsch wax, the process comprising: step S1, carrying out first cutting on Fischer-Tropsch wax to obtain a first fraction; performing second cutting on the Fischer-Tropsch wax to obtain a second fraction and tower bottom wax; the temperature of the first cutting is 450-500 ℃, and the temperature of the second cutting is 520-570 ℃; s2, carrying out a first isomerization reaction on the first fraction by using a first activated isomerization catalyst to obtain first isomerized oil; carrying out a second isomerization reaction on the second fraction by using a second activated isomerization catalyst to obtain second isomerized oil; s3, carrying out a first refining reaction on the first isomerous oil by using a first activated refining catalyst to obtain a first base oil product, and carrying out a second refining reaction on the second isomerous oil by using a second activated refining catalyst to obtain a second base oil product; the preparation method of the first activated isomerization catalyst and the second activated isomerization catalyst comprises the following steps: step A, carrying out reduction reaction on a first heterogeneous catalyst and a second heterogeneous catalyst to obtain a reduced first heterogeneous catalyst and a reduced second heterogeneous catalyst; and step B, carrying out initial activation and stabilization reaction on the reduced first isomerization catalyst and the reduced second isomerization catalyst to obtain a first activated isomerization catalyst and a second activated isomerization catalyst.
In the existing industrial production, due to the fluctuation of the properties of raw materials or the change of the operation condition of a device, the properties of the cut narrow-cut Fischer-Tropsch wax raw materials are often not ideal enough, so that a series of problems are caused in subsequent processing, particularly, when the proportion of heavy components in the raw materials is increased, the viscosity of base oil products is increased, and the product viscosity can be reduced by retaining light components, but the evaporation loss of the products is increased. The full-fraction Fischer-Tropsch wax is cut into two narrow-fraction Fischer-Tropsch waxes suitable for processing, the fraction is in a wide range from moderate to heavy, the tolerance to the range of the fraction is high, and the requirement on the cutting precision of raw materials is reduced. And carrying out isomerization reaction on the first fraction and the second fraction alternately by using an activated isomerization catalyst to obtain the isomerized oil.
In some embodiments, the fischer-tropsch wax used herein is a wax phase feedstock obtained by fischer-tropsch synthesis and oil wax separation, the fischer-tropsch wax having a boiling range of from 350 to 700 ℃ and having the properties of the boiling range as shown in table 1:
TABLE 1
| Percentage of fraction% | Distillation temperature/. Degree.C |
| 0.5 | 388 |
| 5 | 427 |
| 10 | 451 |
| 30 | 496 |
| 50 | 535 |
| 70 | 579 |
| 90 | 642 |
| 95 | 665 |
| 99.5 | 696 |
| 0.5 | 388 |
Since the light and heavy fractions of the feedstock inevitably overlap at a temperature near the cut point, which results in the light fraction inevitably leaving some heavy components, and thus affecting the overall properties, the present application provides a process for the preparation of a fischer-tropsch oil base oil by first cutting a fischer-tropsch wax to obtain two narrow fractions, namely a first fraction, a second fraction and a bottom wax. The 95% cut point of the first fraction is between 450 and 500 ℃, the 95% cut point of the second fraction is between 520 and 570 ℃, the 5% cut point is between 400 and 450 ℃, and the distillation range is shown in table 2:
TABLE 2
The activating isomerization catalyst selected by the application can have a certain selective cracking function on the composition of 95% of high fractions in Fischer-Tropsch wax raw material fractions through a proper activating reaction. The isomerization catalyst is first subjected to a reduction reaction, so that the noble metal (such as Pt) in the isomerization catalyst can be reduced to a state of a nano metal cluster, and the hydrogenation function of the noble metal can be better exerted. And then, initial activation and stabilization reaction are carried out on the heterogeneous catalyst, so that the overall acidity distribution of the catalyst can be optimized, active sites in pores are reserved, reaction material molecules can enter deep layers in catalyst pore channels to carry out further heterogeneous cracking reaction, and heavy residues are reduced. When the range of the raw material fraction is moderate, qualified base oil products can be obtained only by selecting relatively mild operating conditions; when the range of the raw material fraction is wide and heavy, qualified base oil products can be obtained only by increasing the severity of the operation conditions. After the isomerous oil is subjected to additional refining and cutting, high-quality 4# or 6# base oil can be obtained.
In some embodiments, the temperature of the reduction reaction in step a is 200 to 300 ℃, preferably 240 to 260 ℃; preferably, the time of the reduction reaction is 1 to 24 hours, preferably 3 to 8 hours; preferably, the reduction reaction uses hydrogen as the reaction gas; preferably, the pressure of the reduction reaction is 1 to 10MPa, preferably 3 to 6MPa. The isomerization catalyst is firstly subjected to reduction reaction, so that noble metals such as Pt in the isomerization catalyst can be reduced to a state of nano metal clusters, and the hydrogenation function of the noble metals such as Pt is better exerted.
In some embodiments, in the step B, the initial-living stable reaction is sequentially performed under a gradient temperature rise condition of a first reaction temperature, a second reaction temperature and a third reaction temperature, wherein the first reaction temperature is 250 to 280 ℃; the second reaction temperature is 280-300 ℃; the third reaction temperature is 300-320 ℃; the reaction time at the first reaction temperature, the second reaction temperature and the third reaction temperature is respectively and independently 4-24 h. The initial activation stabilization reaction is a pre-carbon deposition process of the catalyst, the activity of the fresh catalyst is very high, and the performance of the catalyst can quickly reach a stable state by performing the initial activation stabilization reaction. Different initial activation stabilization methods can affect the equilibrium performance of the catalyst. The purpose of gradient temperature rise of the initial activation stabilization reaction is to adjust the strength and distribution state of acid active sites on a carrier through pre-carbon deposition reactions in different stages and different strengths, and to set low, medium and high temperature sections, mainly to inhibit strong acid sites of a catalyst, and to avoid the phenomenon that a large amount of carbon deposition is generated in disorder to block pore channels and cover the acid sites in the pores of the catalyst.
The type of isomerization catalyst is not particularly limited herein, and in some embodiments, to enhance catalyst reactivity and facilitate recovery, it is preferred that the first isomerization catalyst and the second isomerization catalyst are each independently a noble metal-supported molecular sieve catalyst; preferably the noble metal is selected from Pt and/or Pd; preferably, the molecular sieve is selected from any one of ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, SAPO-11, SAPO-41 and SSZ-32.
In some embodiments, the method of preparing the first activated polishing catalyst and the second activated polishing catalyst comprises: step A', carrying out a second reduction reaction on the first refined catalyst and the second refined catalyst to obtain a reduced first refined catalyst and a reduced second refined catalyst; and step B', performing a second initial activation stabilization reaction on the reduced first refined catalyst and the reduced second refined catalyst to obtain a first activated refined catalyst and a second activated refined catalyst. In the noble metal catalyst which is prepared just before, since noble metals such as Pt and Pd in the catalyst are in an oxidized state and hydrogen is required to reduce the noble metals to a metal state to have a hydrogenation function, it is necessary to activate a purified catalyst before use.
In some embodiments, the temperature of the second reduction reaction in step a' is from 200 to 300 ℃, preferably from 240 to 260 ℃; preferably, the second reduction reaction time is 1 to 24 hours, preferably 3 to 8 hours; preferably, the second reduction reaction uses hydrogen as a reaction gas; preferably, the second reduction pressure is 1 to 10MPa, preferably 3 to 6MPa; preferably, in the step B', the second initial living stable reaction is sequentially performed under the gradient temperature rise condition of a fourth reaction temperature, a fifth reaction temperature and a sixth reaction temperature, wherein the fourth reaction temperature is 200 to 220 ℃; the fifth reaction temperature is 220-230 ℃; the sixth reaction temperature is 230-290 ℃; and the reaction time at the fourth reaction temperature, the fifth reaction temperature and the sixth reaction temperature is independently 4 to 24 hours.
The type of the purified catalyst is not particularly limited, and any purified catalyst commonly used in the art may be applied to the present invention. In some embodiments, the first and second purification catalysts are noble metal supported alumina catalysts, preferably the noble metals include Pt and/or Pd.
The conditions for the isomerization reaction are not particularly limited herein. In some embodiments of the present invention, the,in step S2, the hydrogen partial pressures of the first isomerization reaction and the second isomerization reaction are each independently 1 to 10MPa, preferably 3 to 6MPa, and preferably, the hydrogen-oil ratios of the first isomerization reaction and the second isomerization reaction are each independently 300 to 1200, preferably 500 to 800; preferably, the volume space velocity of the first isomerization reaction and the volume space velocity of the second isomerization reaction are respectively and independently 0.1-5.0 h -1 Preferably 0.5 to 2.0h -1 (ii) a Preferably, the reaction temperature of the first isomerization reaction and the second isomerization reaction are each independently 320 to 380 ℃. In the isomerization reaction stage, different reaction temperatures can obtain base oil products with different properties. In order to obtain base oil products # 4 and # 6, it is necessary to control the temperature within the above range.
In some embodiments, in step S3, the hydrogen partial pressures of the first and second refining reactions are each independently from 1 to 10MPa, preferably from 3 to 6MPa, preferably the hydrogen-to-oil ratios of the first and second refining reactions are each independently from 300 to 1200, preferably from 500 to 800; preferably, the volume space velocity of the first refining reaction and the volume space velocity of the second refining reaction are respectively and independently 0.1-5.0 h -1 Preferably 0.5 to 2.0h -1 (ii) a Preferably, the reaction temperature of the first purification reaction and the reaction temperature of the second purification reaction are each independently 230 to 290 ℃.
In some embodiments, the method further comprises: s4, performing third cutting on the first base oil to obtain a first light oil product and a No. 4 base oil product; performing fourth cutting on the second base oil to obtain a second light oil product and No. 6 base oil; preferably, the temperature of the distillate of the first light oil product and the second light oil product is less than 380 ℃, the temperature of the distillate of the No. 4 base oil is more than 390 ℃, and the temperature of the distillate of the No. 6 base oil is more than 370 ℃.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
The process for preparing the lubricating base oil from the Fischer-Tropsch wax is shown in figure 1, and specifically comprises the following steps:
(1) Fischer-Tropsch wax was cut to yield a first fraction (fraction range: 5% cut point 379 ℃ C., 95% cut point 494 ℃ C.) and a second fraction (fraction range: 5% cut point 448 ℃ C., 95% cut point 558 ℃ C.).
(2) The first isomerization catalyst and the second isomerization catalyst are both Pt-ZSM-48 catalysts.
Activating the Pt-ZSM-48 catalyst:
(a) Reduction reaction: the reaction gas is hydrogen, the temperature is 250 ℃, the time is 6h, the pressure is 3.5MPa,
(b) And (3) performing initial activation and stabilization reaction, heating to the first reaction temperature of 270 ℃ after reduction is finished, reacting for 12h, the second reaction temperature of 290 ℃, reacting for 12h, the third reaction temperature of 310 ℃, and reacting for 12h to obtain a first activated isomerization catalyst and a second activated isomerization catalyst.
And carrying out a first isomerization reaction on the first fraction by using a first activated isomerization catalyst to obtain first isomerized oil. And carrying out a second isomerization reaction on the second fraction by using a second activated isomerization catalyst to obtain second isomerized oil.
The hydrogen partial pressure of the first isomerization reaction and the second isomerization reaction is 3.5MPa, and the hydrogen-oil volume ratio is 600:1, volume space velocity of 0.8h -1 (ii) a The temperature of the first isomerization reaction is shown in Table 3, and the temperature of the second isomerization reaction is shown in Table 4.
(3) The first and second purification catalysts are Pt-loaded alumina catalysts, and the first and second purification catalysts are activated by:
(a) Reduction reaction: the reaction gas is hydrogen, the temperature is 250 ℃, the time is 6h, the pressure is 3.5MPa,
(b) Initial activation and stabilization reaction: and after the reduction is finished, the temperature is reduced to a fourth reaction temperature of 220 ℃, the reaction time is 12 hours, a fifth reaction temperature is 240 ℃, the reaction time is 12 hours, and the temperature rise rate is 5 ℃/h, so that a first activated refined catalyst and a second activated refined catalyst are obtained.
Carrying out a first refining reaction on the first isomerous oil by using a first activated refining catalyst to obtain a first base oil product, carrying out a second refining reaction on the second isomerous oil by using a second activated refining catalyst to obtain a second base oil product, wherein the temperatures of the first refining reaction and the second refining reaction are equalThe reaction temperature is 260 ℃, the hydrogen partial pressure is 3.5MPa, the hydrogen-oil ratio is 600 -1 。
(4) And intermittently feeding the first base oil product and the second base oil product into the reactor, and respectively cutting the products to obtain 4# base oil, 6# base oil and corresponding light oil products.
Example 2
Different from example 1, in the step (1), the range of fractions of the first fraction (5% cut point: 372 ℃ C., 95% cut point: 475 ℃ C.), the range of fractions of the second fraction (5% cut point: 430 ℃ C., 95% cut point: 535 ℃ C.) were obtained;
the temperature of the first isomerization reaction is shown in table 3, and the temperature of the second isomerization reaction is shown in table 4.
Example 3
In contrast to example 1, in step (2), the first isomerization catalyst is activated:
(a) Reduction reaction: the temperature is 200 ℃, the time is 3h, the pressure is 3MPa,
(b) And (3) performing initial activation and stabilization reaction, heating to the first reaction temperature of 280 ℃ after reduction is finished, reacting for 24h, the second reaction temperature of 300 ℃, reacting for 24h, the third reaction temperature of 320 ℃, and reacting for 24h to obtain a first activated isomerization catalyst and a second activated isomerization catalyst.
The temperature of the first isomerization reaction is shown in table 3, and the temperature of the second isomerization reaction is shown in table 4.
Example 4
In contrast to example 1, in step (2), the first isomerization catalyst is activated:
(a) Reduction reaction: the temperature is 300 ℃, the time is 8h, the pressure is 10MPa,
(b) And (3) performing initial activation and stabilization reaction, heating to the first reaction temperature of 260 ℃ after reduction is finished, and reacting for 4h, the second reaction temperature of 280 ℃, the reaction time of 4h, the third reaction temperature of 300 ℃, and the reaction time of 4h to obtain a first activated isomerization catalyst and a second activated isomerization catalyst.
The temperatures of the first isomerization reaction and the second isomerization reaction are shown in tables 3 and 4.
Example 5
Unlike example 1, in step (3), the first purified catalyst and the second purified catalyst were activated:
(a) Reduction reaction: the temperature is 200 ℃, the time is 8h, the pressure is 3MPa,
(b) Initial activity stabilization reaction: and after the reduction is finished, the temperature is reduced to the fourth reaction temperature of 200 ℃, the reaction time is 24 hours, the fifth reaction temperature is 220 ℃, and the reaction time is 24 hours, so that the first activated refined catalyst and the second activated refined catalyst are obtained.
Example 6
Unlike example 1, in step (3), the first purified catalyst and the second purified catalyst were activated:
(a) Reduction reaction: the temperature is 300 ℃, the time is 3h, the pressure is 10MPa,
(b) Initial activity stabilization reaction: and after the reduction is finished, the temperature is reduced to 210 ℃ at the fourth reaction temperature for 4 hours, 230 ℃ at the fifth reaction temperature for 24 hours, so that the first activated refined catalyst and the second activated refined catalyst are obtained.
Example 7
In contrast to example 1, the first isomerization catalyst and the second isomerization catalyst were activated:
(b) And (3) carrying out initial activation and stable reaction, and after reduction is finished, heating to the first reaction temperature of 270 ℃ for 12h. Then, the temperature was increased to the temperature of the first isomerization reaction and the second isomerization reaction as shown in tables 3 and 4.
Comparative example 1
In contrast to example 1, the first isomerization catalyst and the second isomerization catalyst were activated:
(a) Reduction reaction: the temperature is 350 ℃, the time is 4h, the pressure is 3.5MPa,
(b) And (3) performing initial activation and stabilization reaction, cooling to the first reaction temperature of 250 ℃ after reduction is finished, starting feeding, and heating to the reaction temperatures of the first isomerization reaction and the second isomerization reaction in tables 3 and 4 at the heating rate of 10 ℃/h.
Comparative example 2
In contrast to example 1, the first isomerization catalyst and the second isomerization catalyst were not subjected to an activation reaction.
TABLE 3
Note: viscosity index of No. 4 base oil is 3.5-4.5mm 2 S, evaporation loss index<12％。
TABLE 4
Note: the viscosity index of No. 6 base oil is 5.5-6.5mm 2 S, evaporation loss index<6％。
As can be seen from tables 3 and 4, the isomerization reactions of the examples can achieve a controlled viscosity at different temperatures, for example, the reaction temperature of example 1 is increased from 330 ℃ to 338 ℃ and the viscosity is increased from 4.45mm 2 The/s value became 4.21mm 2 The second isomerization reaction is similar to the first isomerization reaction in that viscosity control can be achieved as well. While the first isomerization temperature of comparative example 1 changed from 330 c to 338 c, there was almost no change in viscosity.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: the activating isomerization catalyst selected by the application can have a certain selective cracking function on the composition of 95% of high fractions in Fischer-Tropsch wax raw material fractions through a proper activating reaction. The isomerization catalyst is first subjected to a reduction reaction, so that the noble metal (such as Pt) in the isomerization catalyst can be reduced to a state of a nano metal cluster, and the hydrogenation function of the noble metal can be better exerted. And then, initial activation and stabilization reaction are carried out on the heterogeneous catalyst, so that the overall acidity distribution of the catalyst can be optimized, active sites in pores are reserved, reaction material molecules can enter deep layers in catalyst pore channels to carry out further heterogeneous cracking reaction, and heavy residues are reduced. When the range of the raw material fraction is moderate, qualified base oil products can be obtained only by selecting relatively mild operating conditions; when the range of the raw material fraction is wide and heavy, qualified base oil products can be obtained only by increasing the severity of the operation conditions. After the isomerous oil is subjected to additional refining and cutting, high-quality base oil No. 4 or 6 can be obtained.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A process for preparing a lubricant base oil from a fischer-tropsch wax, characterised in that the process comprises:
step S1, carrying out first cutting on Fischer-Tropsch wax to obtain a first fraction; performing second cutting on the Fischer-Tropsch wax to obtain a second fraction and bottom wax; the temperature of the first cutting is 450-500 ℃, and the temperature of the second cutting is 520-570 ℃;
s2, carrying out a first isomerization reaction on the first fraction by using a first activated isomerization catalyst to obtain first isomerized oil; carrying out a second isomerization reaction on the second fraction by using a second activated isomerization catalyst to obtain second isomerized oil;
s3, carrying out a first refining reaction on the first heterogeneous oil by using a first activated refining catalyst to obtain a first base oil product, and carrying out a second refining reaction on the second heterogeneous oil by using a second activated refining catalyst to obtain a second base oil product;
the preparation method of the first activated isomerization catalyst and the second activated isomerization catalyst comprises the following steps:
step A, carrying out reduction reaction on a first heterogeneous catalyst and a second heterogeneous catalyst to obtain a reduced first heterogeneous catalyst and a reduced second heterogeneous catalyst;
and B, performing initial activation stabilization reaction on the reduced first isomerization catalyst and the reduced second isomerization catalyst to obtain the first activated isomerization catalyst and the second activated isomerization catalyst.
2. The method according to claim 1, wherein in the step A, the temperature of the reduction reaction is 200-300 ℃, preferably 240-260 ℃;
preferably, the time of the reduction reaction is 1 to 24 hours, preferably 3 to 8 hours;
preferably, the reduction reaction uses hydrogen as a reaction gas;
preferably, the pressure of the reduction reaction is 1 to 10MPa, preferably 3 to 6MPa.
3. The method according to claim 1 or 2, wherein in the step B, the initial activation stabilization reaction is sequentially performed under a gradient temperature rise condition of a first reaction temperature, a second reaction temperature, and a third reaction temperature, wherein the first reaction temperature is 250 to 280 ℃, the second reaction temperature is 280 to 300 ℃, the third reaction temperature is 300 to 320 ℃, and the reaction time at the first reaction temperature, the second reaction temperature, and the third reaction temperature is independently 4 to 24 hours.
4. The process of any of claims 1 to 3, wherein the first isomerization catalyst and the second isomerization catalyst are each independently a noble metal-supported molecular sieve catalyst; preferably the noble metal is selected from Pt and/or Pd; preferably, the molecular sieve is selected from any one of ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, SAPO-11, SAPO-41 and SSZ-32.
5. The method of claim 1, wherein the first activated polishing catalyst and the second activated polishing catalyst are prepared by a method comprising:
step A', carrying out a second reduction reaction on the first refined catalyst and the second refined catalyst to obtain a reduced first refined catalyst and a reduced second refined catalyst;
and step B', performing a second initial activation stabilization reaction on the reduced first refined catalyst and the reduced second refined catalyst to obtain the first activated refined catalyst and the second activated refined catalyst.
6. The method according to claim 5, wherein in step A', the temperature of the second reduction reaction is 200 to 300 ℃, preferably 240 to 260 ℃;
preferably, the time of the second reduction reaction is 1 to 24 hours, preferably 3 to 8 hours;
preferably, the second reduction reaction uses hydrogen as a reaction gas;
preferably, the pressure of the second reduction reaction is 1 to 10MPa, preferably 3 to 6MPa;
preferably, in the step B', the second initial living stable reaction is sequentially performed under a gradient temperature rise condition of a fourth reaction temperature, a fifth reaction temperature, and a sixth reaction temperature, wherein the fourth reaction temperature is 200 to 220 ℃, the fifth reaction temperature is 220 to 230 ℃, the sixth reaction temperature is 230 to 290 ℃, and the reaction time at the fourth reaction temperature, the fifth reaction temperature, and the sixth reaction temperature is independently 4 to 24 hours.
7. The method according to claim 5 or 6, characterized in that the first and second refining catalysts are noble metal supported alumina catalysts, preferably the noble metals comprise Pt and/or Pd.
8. The process according to claim 1, wherein in step S2, the hydrogen partial pressure of the first isomerization reaction and the second isomerization reaction is independently 1 to 10MPa, preferably 3 to 6MPa,
preferably, the hydrogen-to-oil ratio of the first isomerization reaction and the second isomerization reaction is each independently from 300 to 1200, preferably from 500 to 800;
preferably, the volume space velocity of the first isomerization reaction and the volume space velocity of the second isomerization reaction are respectively and independently 0.1-5.0 h -1 Preferably 0.5 to 2.0h -1 ；
Preferably, the reaction temperature of the first isomerization reaction and the second isomerization reaction is each independently 320 to 380 ℃.
9. The method according to claim 1, wherein in step S3, the hydrogen partial pressures of the first and second purification reactions are each independently 1 to 10MPa, preferably 3 to 6MPa,
preferably, the hydrogen-oil ratio of the first purification reaction and the second purification reaction is each independently 300 to 1200, preferably 500 to 800;
preferably, the volume space velocity of the first refining reaction and the volume space velocity of the second refining reaction are respectively and independently 0.1-5.0 h -1 Preferably 0.5 to 2.0 hours -1 ；
Preferably, the reaction temperature of the first purification reaction and the reaction temperature of the second purification reaction are each independently 230 to 290 ℃.
10. The method according to any one of claims 1 to 9, further comprising:
s4, performing third cutting on the first base oil to obtain a first light oil product and No. 4 base oil; performing fourth cutting on the second base oil to obtain a second light oil product and No. 6 base oil;
preferably, the temperature of the distillate of the first light oil product and the second light oil product is less than 380 ℃, the temperature of the distillate of the No. 4 base oil is more than 390 ℃, and the temperature of the distillate of the No. 6 base oil is more than 370 ℃.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100300933A1 (en) * | 2007-09-28 | 2010-12-02 | Yuichi Tanaka | Method of manufacturing diesel fuel |
| CN103305267A (en) * | 2013-06-25 | 2013-09-18 | 中石化南京工程有限公司 | Method for producing high-grade lubricant base oil through hydrogenating of hydrocracking tail oil |
| CN110240938A (en) * | 2019-05-31 | 2019-09-17 | 国家能源投资集团有限责任公司 | For producing the system and method for lube base oil and high-melting-point Fischer-Tropsch wax |
| CN115254120A (en) * | 2021-04-30 | 2022-11-01 | 中国石油化工股份有限公司 | Pre-reduction type hydrogenation catalyst with high nickel content, preparation method and application thereof |
-
2022
- 2022-11-15 CN CN202211427282.4A patent/CN115678610A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100300933A1 (en) * | 2007-09-28 | 2010-12-02 | Yuichi Tanaka | Method of manufacturing diesel fuel |
| CN103305267A (en) * | 2013-06-25 | 2013-09-18 | 中石化南京工程有限公司 | Method for producing high-grade lubricant base oil through hydrogenating of hydrocracking tail oil |
| CN110240938A (en) * | 2019-05-31 | 2019-09-17 | 国家能源投资集团有限责任公司 | For producing the system and method for lube base oil and high-melting-point Fischer-Tropsch wax |
| CN115254120A (en) * | 2021-04-30 | 2022-11-01 | 中国石油化工股份有限公司 | Pre-reduction type hydrogenation catalyst with high nickel content, preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 陈彬等: "国内某基础油加氢装置催化剂的工业应用", 广东化工, vol. 44, no. 9, pages 242 - 243 * |
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