CN104560193B - The preparation method of lube base oil and/or solvent naphtha - Google Patents

The preparation method of lube base oil and/or solvent naphtha Download PDF

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Publication number
CN104560193B
CN104560193B CN201310515598.3A CN201310515598A CN104560193B CN 104560193 B CN104560193 B CN 104560193B CN 201310515598 A CN201310515598 A CN 201310515598A CN 104560193 B CN104560193 B CN 104560193B
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alkene
polymer raw
lewis acid
hydrogen
acid catalysts
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CN104560193A (en
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张耀
段庆华
刘依农
李玲
辛世豪
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
    • C10G69/126—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step polymerisation, e.g. oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1081—Alkanes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1088—Olefins
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/10—Lubricating oil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/18—Solvents

Abstract

The present invention provides the preparation methods of a kind of lube base oil and/or solvent naphtha, including：（1）In the presence of Lewis acid catalysts polymerisation occurs for polymer raw；The polymer raw includes alkene, alcohol and non-essential alkane, and by percentage to the quality, olefin(e) centent is 0.2%~2% 10% or more, by the oxygen content that alcohol provides in the polymer raw；On the basis of the alkene and by percentage to the quality, content >=85% of alpha-olefin in the alkene；The mass ratio of the Lewis acid catalysts and alkene in polymer raw is 1:200~1:5, the mass ratio of oxygen element is 2 in the Lewis acid catalysts and polymer raw:1~70:1；（2）Step（1）Polymerizate further occur hydrofinishing and/or hydroisomerizing reaction；（3）Collection step（2）Reaction product in initial boiling point obtain the fraction of lube base oil and/or the end point of distillation less than 340 DEG C more than 340 DEG C of fraction and obtain solvent naphtha.Lube base oil and/or solvent naphtha product colour that the method for the present invention obtains are shallow, oxidation stability and thermal stability are good, low temperature performance well.

Description

The preparation method of lube base oil and/or solvent naphtha
Technical field
The present invention relates to the preparation methods of a kind of lube base oil and/or solvent naphtha, more particularly to a kind of to be closed by Fischer-Tropsch The method for preparing lube base oil and/or solvent naphtha at oil.
Background technology
Under 150~350 DEG C and 2~15MPa of reaction condition, CO catalytic hydrogenations can be generated by C using Fischer-tropsch process1 ~C100Gas, liquid, the solid hydrocarbon of range.It is broadly divided into F- T synthesis light oil and expense according to the difference of fraction Hold in the palm wax.Under nowadays petroleum resources situation in short supply, using the processing route of F- T synthesis liquid fuel was prepared or chemical products Gradually is supported and obtain fast development.Since Fischer-Tropsch synthesis oil and natural oil product have larger difference, to produce combustion Material oil is relatively low for leading processing scheme economic benefit, how to carry out secondary operation, voluminous high value added product is Fischer-tropsch process Practitioner needs the problem of concern.
Have the study found that solvent naphtha can be directly acquired by hydro-upgrading using Fischer-Tropsch light distillate, which has There is the features such as high selection dissolubility, high stability, colorless and odorless, low-viscosity, but product is almost made of n-alkane, has There are higher cloud point and condensation point.It is needed thus using hydrofinishing-hydroisomerizing joint processing scheme, such as US5, in 866,748 What is be previously mentioned uses C8~C20The method that Fischer-Tropsch synthesis oil prepares isomery solvent naphtha, the cryogenic property and viscosity of prepared solvent naphtha It is obviously improved.It will be apparent that the alkene being possessed of higher values in Fischer-Tropsch synthesis oil is thoroughly wasted.
Currently, F- T synthesis weighs the processing scheme of wax mostly for the purpose of catalytic cracking or being hydrocracked production fuel oil, such as Preceding described, economy is poor.In addition to this, higher boiling Fischer-Tropsch wax can be converted into the profit of high viscosity index under the conditions of hydroisomerizing Lubricant base oil, i.e. GTL base oils, but compared with II classes of API, III class base oil, cryogenic property uses deep without significant advantage Degree hydroisomerizing can cause cracking intensification and yield to decline to improve the method for cryogenic property, therefore up for researching and developing a kind of production The process of high value added product.
CN1,207,116 discloses a kind of high-purity alkane solvent fluid composition and preparation method thereof.It is characterized in that, high Purity solvent oil is by n-alkane and the isoparaffin containing methyl branch is constituted, and has excellent cryogenic property and low-viscosity, Preparation method includes：（1）Fischer Tropsch waxes are hydrocracked on bifunctional catalyst and isomerization；（2）To boiling range Range C5+~565 DEG C of products are fractionated, and 160~343 DEG C of high-purity solvent oil is obtained.
CN101,230,290 disclose a kind of method by Fischer-Tropsch wax production solvent naphtha, lube base oil and wax, side Method includes：（1）Fischer-Tropsch wax is contacted with Hydrobon catalyst in hydrofinishing district, after obtaining a kind of plus hydrogen saturation, deoxidation Fischer-Tropsch wax is categorized into two kinds of fractions of weight in distillation zone；（2）The hydrogenated isomery of light fraction, through detaching after hydrofinishing To at least one solvent naphtha and a kind of lube base oil；（3）Wax and Hydrobon catalyst will be weighed in hydrofining reaction area Contact, obtains a kind of wax of decoloration.
US6,605,206 discloses a kind of increase C10The method of the above hydrocarbon products comprising：（1）By Fischer-Tropsch product point For Fischer-Tropsch wax and light liquid hydrocarbons；（2）The hydrogenated isomery of Fischer-Tropsch wax prepare higher boiling, low pour point hydrocarbon component；（3）Fischer-Tropsch lightweight Alcohol deoxidation prepares alkene in hydrocarbon；（4）Olefinic polymerization prepares high-molecular-weight hydrocarbons；（5）Cutting separation diesel oil, base oil component.According to Boiling point is different, can prepare the lube base oil of different viscosity ranks.
US2,004,267,071 discloses a kind of processing scheme of F- T synthesis light oil, which is characterized in that Fischer-Tropsch lightweight Distillate（C5~C19）After dehydroxylation converts alcohol to alkene and molecular sieve adsorbing and removing oxygenatedchemicals, through ionic liquid Diesel oil and lubricating oil component can be obtained using hydrofinishing in catalysis in olefine polymerization.
Invention content
The present invention provides the preparation methods of a kind of lube base oil and/or solvent naphtha, including：
（1）In the presence of Lewis acid catalysts polymerisation occurs for polymer raw；
The polymer raw includes alkene, alcohol and non-essential alkane, by percentage to the quality, alkene in the polymer raw Hydrocarbon content is 0.2%~2% 10% or more, by the oxygen content that alcohol provides；On the basis of the alkene and by percentage to the quality, Content >=85% of alpha-olefin in the alkene；The mass ratio of the Lewis acid catalysts and alkene in polymer raw is 1:200 ~1:5, the mass ratio of oxygen element is 2 in the Lewis acid catalysts and polymer raw:1~70:1；
（2）Step（1）Polymerizate further occur hydrofinishing and/or hydroisomerizing reaction；
（3）Collection step（2）Reaction product in initial boiling point more than 340 DEG C of fraction obtain lube base oil and/or Fraction of the end point of distillation less than 340 DEG C obtains solvent naphtha.
In the polymer raw, the alkene can select C5~C20Single alkene or mixed olefins, with quality hundred Divide than counting, contains 0.5%~35% C in preferred alkenes5~C7Alkene, 40%~90% C8~C12Alkene, 2%~30% C13~ C16Alkene, 0.5%~15% C17~C20Alkene, most preferably 1%~25% C5~C7Alkene, 55%~90% C8~C12Alkene Hydrocarbon, 2%~25% C13~C16Alkene, 0.5%~10% C17~C20Alkene.On the basis of the alkene and with mass percent It counts, content >=85% of alpha-olefin in the alkene, preferably >=95%.
Olefin(e) centent in the polymer raw is 10% or more, preferably 25% or more, most preferably 40% or more.
Alcohol in the polymer raw is selected from C1~C12Single alcohol or mixed alcohol, preferably C2~C10Single n-alkanol or Mix n-alkanol, most preferably C2~C10Single primary alconol or mixing primary alconol.
In the polymer raw by alcohol provide oxygen content be 0.2%~2%, preferably 0.25%~1.5%, most preferably 0.3%~ 1%。
Alkane can not included in polymer raw of the present invention, can also include alkane.The alkane is C4~C20 Alkane, preferably C6~C20Alkane, most preferably C7~C20Alkane.When in the polymer raw including alkane, the alkane The mass ratio of hydrocarbon and the alkene is 10:1~1:10, preferably 5:1~1:5, most preferably 3:1~1:3.
The polymer raw preferably conforms to the Fischer-Tropsch synthesis oil of above-mentioned condition.
The mass ratio of the Lewis acid catalysts and alkene in polymer raw is 1:200~1:5, preferably 1:100~1: 10, most preferably 1:80~1:13.
The mass ratio of the Lewis acid catalysts and oxygen element in polymer raw is 2:1~70:1, preferably 4:1~40:1, Most preferably 5:1~30:1.
The Lewis acid catalysts are selected from aluminum halide, alkyl aluminium halide, alkyl aluminum, halogenation boron, tin halides, iron halide, halogen Change copper, halogenated titanium, antimony halides, zinc halide, one or more in gallium halide, for example, can select boron trifluoride, alchlor, Aluminium ethide, Chloroethyl aluminium, aluminium bromide, stannic chloride, ferric trichloride, copper chloride, stannous chloride, titanium tetrachloride, antimony chloride, chlorination It is one or more in zinc, gallium chloride, preferably aluminum halide, alkyl aluminium halide, alkyl aluminum, halogenation boron, such as trifluoro can be selected Change one or more in boron, alchlor, aluminium ethide, Chloroethyl aluminium and aluminium bromide, most preferably boron trifluoride, tri-chlorination It is one or more in aluminium, aluminium ethide and Chloroethyl aluminium.
The process conditions that polymerisation occurs in the presence of Lewis acid catalysts for the polymer raw are：
The temperature of polymerisation is -10~120 DEG C, preferably -5~100 DEG C, most preferably 0~80 DEG C；
The time of polymerisation is 15~360min, preferably 30~300min, most preferably 45~280min.
When using gaseous state Lewis acid catalysts when, occur polymerisation pressure be 0.1~1MPa, preferably 0.12~ 0.75MPa, most preferably 0.15~0.5MPa.
In step（1）Preparation method in, it is preferred to use stratification/be separated by filtration, wash, adsorb and the way of distillation in One or more methods post-process polymerizate.
In step（1）Preparation method in, other than above-mentioned Lewis acid catalysts, without additionally adding other catalysis Agent aid.
In step（2）In, to step（1）Polymerizate the method for hydrofining reaction further occur be：By step （1）Polymerizate contacted with hydrogen in the presence of Hydrobon catalyst.
The Hydrobon catalyst can select group vib or VIII B races metal, for example, can select molybdenum, nickel, ruthenium, Group vibs or VIII B races metallic catalyst one or more in rhodium, cobalt, platinum and palladium, be preferably supported on carrier, the load Body can be selected one or more in silica, aluminium oxide, clay, magnesia, titanium oxide and zirconium oxide；
Hydrogen partial pressure in the hydrofining reaction is 1~25MPa, preferably 2~20MPa, most preferably 3~15MPa；
The temperature of the hydrofining reaction is 150~350 DEG C, preferably 160~300 DEG C, most preferably 180~260 DEG C；
During hydrofining reaction occurs, the hydrogen and step（1）Polymerizate between volume ratio（Hydrogen oil Than）For 100~2000 (v/v), preferably 200~1500 (v/v), most preferably 250~1000 (v/v)；The body when liquid of the hydrogen Product air speed is 0.2~5h-1, preferably 0.5~3h-1, most preferably 0.6~2.5h-1。
In step（2）In, to step（1）Polymerizate further occur hydroisomerizing reaction method be：By step （1）Polymerizate contacted with hydrogen in the presence of hydroisomerization catalyst.
The hydroisomerization catalyst can select group vib or VIII B races metal, for example, can select molybdenum, nickel, ruthenium, Group vibs or VIII B races metallic catalyst one or more in rhodium, cobalt, platinum and palladium, be preferably supported on carrier, the load Body can select amorphous oxide and/or molecular sieve containing acid function, the amorphous oxide that can select Al2O3、 SiO2-Al2O3、ZrO2, the molecular sieve can select aluminosilicate-type and/or silicoaluminophosphate molecular sieve analog, the aluminosilicate-type point Son sieve can select one kind in Y, Beta, ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35 and ZSM-38 or A variety of, the silicoaluminophosphate molecular sieve analog can be selected one or more in SAPO-11, SAPO-31 and SAPO-41.
Hydrogen partial pressure in the hydroisomerizing reaction is 1~20MPa, preferably 2~18MPa, most preferably 4~16MPa；
The temperature of the hydroisomerizing reaction is 250~400 DEG C, preferably 260~380 DEG C, most preferably 280~360 DEG C；
In hydroisomerizing reaction process occurs, the hydrogen and step（1）Polymerizate between volume ratio（Hydrogen oil Than）For 100~2000 (v/v), preferably 200~1800 (v/v), most preferably 300~1500 (v/v)；The body when liquid of the hydrogen Product air speed is 0.2~3h-1, preferably 0.3~2.5h-1, most preferably 0.6~2h-1。
In step（3）In, the lube base oil of different model can be prepared according to different demands, it only need to be to step（2） Reaction product in initial boiling point more than 340 DEG C fraction carry out atmospheric and vacuum distillation cutting.
In step（3）In, the solvent naphtha of different model can be prepared according to different demands, it only need to be to step（2）Reaction Fraction of the end point of distillation less than 340 DEG C carries out atmospheric and vacuum distillation cutting in product.
The polymerization technique of the method for the present invention is simple, high income.The lube base oil production being prepared by the method for the present invention Product are of light color, oxidation stability and thermal stability are good, have higher Viscosity Index and excellent cryogenic property；By present invention side Solvent naphtha product colour that method is prepared is shallow, oxidation stability and thermal stability are good, has lower condensation point.
Specific implementation mode
Unless stated otherwise, percentage mentioned below is mass percent.
The analysis method that present embodiment is applied is as follows：
Carbon number distribution is measured according to RIPP-GC47 Fischer-Tropsch oil phase n-alkanols and carbon number distribution；
Sulfur content is measured according to ASTM D7039 light oil sulfur content methods；
Nitrogen content is according to trace n2 method in SH/T0657 Naphtha solvents（Oxidizing fire and chemoluminescence method）It measures；
Oxygen content is according to ASTM D5622-95 determination of oxygen content（Elemental analyzer method）It measures；
Iodine number is measured according to SH/T0243-92 solvent naphtha iodine number deter minations；
Lube base oil dynamic viscosity is surveyed by GB265 oil product kinematic viscosity measuring methods and dynamic viscosity calculating method Amount；
Viscosity Index is calculated according to GB2541 oil product viscosity index (VI) calculation tables；
Pour point is measured according to GB3535 petroleum products pour point measuring methods；
Condensation point is measured according to GB510 petroleum products questionable points measuring methods.
Embodiment 1,2 and comparative example 1
Polymer raw used by embodiment 1,2 and comparative example 1 is the mixed olefins of allotment, and composition is shown in Table 1.
The composition of polymer raw in 1 embodiment 1,2 of table and comparative example 1
Embodiment 1,2 and comparative example 1 prepare lubrication according to the polymeric reaction condition of table 2 and hydrofining reaction condition respectively Oil base oil and solvent naphtha.
Table 2
The production obtained after polymerisation, hydrofining reaction is carried out to the polymer raw of embodiment 1,2 and comparative example 1 respectively Object carries out distillation cutting, less than 340 DEG C fractions cut into 80~120 DEG C, 120~175 DEG C, 175~200 DEG C, 200~260 DEG C, 2mm is respectively cut into according to viscosity demand in 260~340 DEG C of fractions, 340 DEG C or more fractions2/s、4mm2/s、8mm2/ s and 10+mm2/ S products the results are shown in Table 3~table 9.
3 material balance data of table
The physicochemical property of lube base oil is as shown in table 4 in embodiment 1.
The physical and chemical index of lube base oil in 4 embodiment 1 of table
The physicochemical property of solvent naphtha is as shown in table 5 in embodiment 1.
The physical and chemical index of solvent naphtha in 5 embodiment 1 of table
The physicochemical property of lube base oil is as shown in table 6 in embodiment 2.
The physical and chemical index of lube base oil in 6 embodiment 2 of table
The physicochemical property of solvent naphtha is as shown in table 7 in embodiment 2.
The physical and chemical index of solvent naphtha in 7 embodiment 2 of table
The physicochemical property of lube base oil is as shown in table 8 in comparative example 1.
The physical and chemical index of lube base oil in 8 comparative example 1 of table
The physicochemical property of solvent naphtha is as shown in table 9 in comparative example 1.
The physical and chemical index of solvent naphtha in 9 comparative example 1 of table
Compared with comparative example 1, the viscosity-temperature characteristics of the lube base oil prepared by Examples 1 to 2 can be good, and cryogenic property is excellent Different, prepared solvent naphtha has low-down condensation point.
Embodiment 3
Polymer raw used by embodiment 3 is certain F- T synthesis light oil A, and physicochemical property is shown in Table 10.
The physicochemical property of 10 F- T synthesis light oil A of table
Project Respective value
20 DEG C of density/(Kgm-3) 0.738
Oxygen content/% 0.218
Sulfur content (ugg-1) 2
Alcohol content/% 1.546
Nitrogen content (ugg-1) 4
Arene content/% 0
Olefin(e) centent/% 65.152
The carbon number distribution of this F- T synthesis light oil is as shown in table 11.
The carbon number distribution of 11 F- T synthesis light oil A of table
H-NMR characterizations are carried out to this F- T synthesis light oil, peak of the chemical shift near 4.8~5.2 is alpha-olefin CH2The chemical shift of hydrogen atom in=structure, peak of the chemical shift near 5.7~6.0 are hydrogen in the position=CH- structures of alpha-olefin end The chemical shift of atom, peak of the chemical shift near 5.3~5.5 are the chemical potential of hydrogen atom in internal olefin-CH=CH- structures It moves.It is computed the integral area at each peak, alpha-olefin in this F- T synthesis light oil can be calculated and account for total olefin quality 95.7%, interior alkene accounts for the 4.3% of total olefin quality.
Polymerisation is carried out to this F- T synthesis light oil, it is anti-that obtained polymerizate carries out further hydroisomerizing It answers, prepared by lube base oil and solvent naphtha to the distillation cutting of hydroisomerizing product.
Polymerisation and the condition of hydroisomerizing reaction are shown in Table 12.
Table 12
To 2mm is respectively cut into according to viscosity demand higher than 340 DEG C or more fractions in hydroisomerizing product2/s、4mm2/s、 8mm2/ s and 10+mm2/ s products, less than 340 DEG C fractions be respectively cut into 80~120 DEG C, 120~175 DEG C, 175~200 DEG C, 200~260 DEG C, 260~340 DEG C of fractions, the results are shown in Table 13~table 15.
Material balance data is as shown in table 13.
13 material balance data of table
Lube base oil nature is as shown in table 14.
The physical and chemical index of 14 lube base oil of table
Solvent oil nature is as shown in Table 15.
The physical and chemical index of 15 solvent naphtha of table
Comparative example 2
The F- T synthesis light oil A of embodiment 3 is subjected to after deoxidation treatment 2 polymer raw as a comparison case.
Using the oxygen in low-carbon alcohols-aqueous solution extraction method removing F- T synthesis light oil, F- T synthesis light oil after deoxidation Physicochemical property be shown in Table 16.
The physicochemical property of F- T synthesis light oil after 16 deoxidation of table
Project Respective value
20 DEG C of density/(Kgm-3) 0.741
Oxygen content/% 0.02
Sulfur content (ugg-1) 1
Alcohol content/% 0.13
Nitrogen content (ugg-1) 2
Arene content/% 0
Olefin(e) centent/% 63.307
Using reaction condition same as Example 3, lube base oil and molten is prepared using the polymer raw of comparative example 2 Agent oil.The material balance data of comparative example 2 is shown in Table 17, and the physical and chemical index of lube base oil and solvent naphtha is shown in Table 18, table 19.
The material balance data of 17 comparative example 2 of table
The physical and chemical index of 18 comparative example of table, 2 lube base oil
The physical and chemical index of 19 comparative example of table, 2 solvent naphtha
It is not difficult to find out, compared with comparative example 2, the lube base oil prepared by embodiment 3 has very high yield, institute The Viscosity Index for obtaining the lube base oil of same viscosity is obviously higher than lube base oil in comparative example 2, obtained Solvent naphtha low temperature performance excellent.
Comparative example 3
Polymer raw used by comparative example 3 is certain F- T synthesis light oil B, and physicochemical property is shown in Table 20.
The physicochemical property of 20 F- T synthesis light oil B of table
Project Respective value
20 DEG C of density/(Kgm-3) 0.753
Oxygen content/% 0.32
Sulfur content (ugg-1) 2
Alcohol content/% 3.077
Nitrogen content (ugg-1) 5
Arene content/% 0
Olefin(e) centent/% 64.732
The carbon number distribution of this F- T synthesis light oil is as shown in table 21.
The carbon number distribution of 21 F- T synthesis light oil B of table
Continued 21
Carbon number Alkene N-alkane Isoparaffin Alcohol
14 3.817 1.973 0.057 0.138
15 3.27 1.898 0.067 0.127
16 2.515 1.743 0.074 0.099
17 1.608 1.502 0.069 0.093
18 1.222 1.219 0.073 0.066
19 0.993 0.939 0.087 0.054
20 0.952 0.698 0.069 0.066
21 0.758 0.516 0.053 0.051
22 0.624 0.388 0.052 0.03
23 0.612 0.3 0.048 0
24 0.508 0.232 0.039 0
25 0.411 0.183 0.033 0
26 0.301 0.149 0.029 0
27 0.195 0.137 0.019 0
28 0.04 0.106 0.026 0
29 0.013 0.109 0.024 0
30 0 0.097 0.027 0
31 0 0.076 0 0
32 0 0.052 0 0
It is total 64.732 30.566 1.625 3.077
H-NMR characterizations have been carried out to this F- T synthesis light oil raw material.It is computed the integral area at each peak, can be calculated Alpha-olefin accounts for the 76.3% of total olefin quality in this F- T synthesis light oil, and interior alkene accounts for the 23.7% of total olefin quality.
Polymerisation is carried out to this F- T synthesis light oil, it is anti-that obtained polymerizate carries out further hydroisomerizing It answers, prepared by lube base oil and solvent naphtha to the distillation cutting of hydroisomerizing product, wherein polymerisation catalysts AlCl3's adds Enter 3.2% that amount is polymer raw quality, polymeric reaction temperature is 60~75 DEG C, reaction time 320min, hydroisomerizing reaction Condition is the same as embodiment 3.
To 2mm is respectively cut into according to viscosity demand higher than 340 DEG C or more fractions in hydroisomerizing product2/s、4mm2/s、 8mm2/ s and 10+mm2/ s products, less than 340 DEG C fractions be respectively cut into 80~120 DEG C, 120~175 DEG C, 175~200 DEG C, 200~260 DEG C, 260~340 DEG C of fractions, the results are shown in Table 22~table 24.
The material balance data of 22 comparative example 3 of table
The property of lube base oil is as shown in table 23.
The physical and chemical index of 23 lube base oil of table
The property of solvent naphtha is as shown in table 24.
It is not difficult to find out, compared with Example 3, using containing C20The F- T synthesis light oil of the above alkene is prepared by raw material The cryogenic property of obtained lube base oil and solvent naphtha is poor, and the lube base oil tool for using the method for the present invention to prepare There is a very high yield, the cryogenic property of acquired lube base oil and solvent naphtha is obviously higher than same viscosity in comparative example 3 Lube base oil and solvent naphtha.
The physical and chemical index of 24 solvent naphtha of table

Claims (15)

1. the preparation method of a kind of lube base oil and solvent naphtha, including：
(1) in the presence of Lewis acid catalysts polymerisation occurs for polymer raw；
The polymer raw includes alkene, alcohol and non-essential alkane, and by percentage to the quality, alkene contains in the polymer raw It measures 10% or more, be 0.2%~2% by the oxygen content that alcohol provides；On the basis of the alkene and by percentage to the quality, institute State content >=85% of alpha-olefin in alkene；The mass ratio of the Lewis acid catalysts and alkene in polymer raw is 1:200~ 1:5, the mass ratio of oxygen element is 2 in the Lewis acid catalysts and polymer raw:1~70:1；The Lewis acid catalysts Selected from boron trifluoride；
Alcohol in the polymer raw is selected from C2~C10Single primary alconol or mixing primary alconol；
By percentage to the quality, contain 0.5%~35% C in the alkene in the polymer raw5~C7Alkene, 40%~ 90% C8~C12Alkene, 2%~30% C13~C16Alkene, 0.5%~15% C17~C20Alkene；
(2) hydrofinishing and/or hydroisomerizing reaction further occur for the polymerizate of step (1)；
(3) fraction of the initial boiling point more than 340 DEG C obtains lube base oil in the reaction product of collection step (2) and the end point of distillation is small Solvent naphtha is obtained in 340 DEG C of fractions.
2. according to the method for claim 1, which is characterized in that by percentage to the quality, described on the basis of the alkene Content >=95% of alpha-olefin in alkene.
3. according to the method for claim 1, which is characterized in that by percentage to the quality, the alkene in the polymer raw Content is 25% or more.
4. according to the method for claim 1, which is characterized in that be by the oxygen content of alcohol offer in the polymer raw 0.25%~1.5%.
5. according to the method for claim 1, which is characterized in that include alkane in the polymer raw, the alkane is C4 ~C20Alkane, the mass ratio of the alkane and the alkene is 5:1~1:5.
6. according to the method for claim 1, which is characterized in that the polymer raw is Fischer-Tropsch synthesis oil.
7. according to the method described in one of claim 1-6, which is characterized in that the Lewis acid catalysts with polymerize original The mass ratio of alkene is 1 in material:100~1:10.
8. according to the method for claim 7, which is characterized in that the Lewis acid catalysts and oxygen element in polymer raw Mass ratio be 4:1~40:1.
9. according to the method for claim 7, which is characterized in that the polymer raw exists in Lewis acid catalysts to be issued The process conditions of raw polymerisation are：The temperature of polymerisation is -10~120 DEG C, and the time of polymerisation is 15~360min.
10. according to the method for claim 9, which is characterized in that the Lewis acid catalysts are gaseous state Lewis acid catalysis Agent, the pressure that polymerisation occurs are 0.1~1MPa.
11. according to the method described in one of claim 1-6, which is characterized in that in step (2), gather to step (1) Closing product the method for hydrofining reaction further occurs is：The polymerizate of step (1) is existed in Hydrobon catalyst It is lower to be contacted with hydrogen.
12. according to the method for claim 11, which is characterized in that the Hydrobon catalyst is selected from group vib or VIII B races metal, the hydrogen partial pressure in the hydrofining reaction are 1~25MPa, and the temperature of the hydrofining reaction is 150~350 DEG C, the volume ratio (hydrogen-oil ratio) between the hydrogen and the polymerizate of step (1) is 100~2000 (v/v), the hydrogen Volume space velocity is 0.2~5h when liquid-1。
13. according to the method described in one of claim 1-6, which is characterized in that in step (2), gather to step (1) The method that hydroisomerizing reacts further occurs for conjunction product：The polymerizate of step (1) is existed in hydroisomerization catalyst It is lower to be contacted with hydrogen.
14. according to the method for claim 13, which is characterized in that the hydroisomerization catalyst is selected from group vib or VIII B races metal, the hydrogen partial pressure in the hydroisomerizing reaction is 1~20MPa, and the temperature of the hydroisomerizing reaction is 250~400 DEG C, the volume ratio (hydrogen-oil ratio) between the hydrogen and the polymerizate of step (1) is 100~2000 (v/v), the hydrogen Volume space velocity is 0.2~3h when liquid-1。
15. according to the method described in one of claim 1-6, which is characterized in that in step (3), to the anti-of step (2) Fraction of the initial boiling point more than 340 DEG C and the fraction less than 340 DEG C in product is answered to carry out atmospheric and vacuum distillation cutting.
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CN102776022A (en) * 2011-05-11 2012-11-14 中国石油化工股份有限公司 High-viscosity poly alpha-olefin synthetic oil and preparation method thereof

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CN102776022A (en) * 2011-05-11 2012-11-14 中国石油化工股份有限公司 High-viscosity poly alpha-olefin synthetic oil and preparation method thereof

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