CN102485846A - Preparation method of transformer oil base oil - Google Patents
Preparation method of transformer oil base oil Download PDFInfo
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- CN102485846A CN102485846A CN2010105789684A CN201010578968A CN102485846A CN 102485846 A CN102485846 A CN 102485846A CN 2010105789684 A CN2010105789684 A CN 2010105789684A CN 201010578968 A CN201010578968 A CN 201010578968A CN 102485846 A CN102485846 A CN 102485846A
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- 239000003921 oil Substances 0.000 title claims abstract description 139
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002199 base oil Substances 0.000 title abstract description 46
- 239000002994 raw material Substances 0.000 claims abstract description 54
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000000295 fuel oil Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000004927 clay Substances 0.000 claims abstract 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 36
- 239000003054 catalyst Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 7
- 238000005194 fractionation Methods 0.000 claims description 6
- 239000010779 crude oil Substances 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000005336 cracking Methods 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 67
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 238000007670 refining Methods 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 125000003118 aryl group Chemical group 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract description 3
- 239000012188 paraffin wax Substances 0.000 abstract description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 125000005842 heteroatom Chemical group 0.000 abstract description 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 239000003208 petroleum Substances 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 239000000084 colloidal system Substances 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- 125000003367 polycyclic group Chemical group 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 28
- 239000002585 base Substances 0.000 description 21
- 238000004458 analytical method Methods 0.000 description 15
- 238000005520 cutting process Methods 0.000 description 12
- 239000000341 volatile oil Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 238000009874 alkali refining Methods 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000000881 depressing effect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Lubricants (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a preparation method of petroleum transformer oil; heating inferior heavy oil, naphthenic base atmospheric and vacuum residue oil or/and paraffin base atmospheric and vacuum residue oil serving as raw materials, then feeding the heated raw materials into a reactor, and cooling and fractionating a reacted product to obtain 260-360 fractions; the fraction is subjected to hydrofining to remove S, N, O heteroatoms, and olefin saturation and aromatic hydrogenation are carried out; hydrofined oil is subjected to solvent refining to remove polycyclic short side chain aromatic hydrocarbons, sulfur-containing, oxygen-containing, nitrogen-containing compounds and colloid asphaltenes in the oil, so as to obtain refined oil; removing high pour point components from the refined oil by hydrogenation pour point depression; the hydrogenation pour point depression reaction oil is subjected to clay refining to obtain clay refined oil which is the transformer base oil; the method widens the raw material source of the transformer oil base oil, and the obtained transformer oil base oil has good viscosity-temperature performance and meets the standards of IEC60296(2003), ASTM D3487, GB 2536-90 and SH 0040-91.
Description
Technical field
The present invention relates to a kind of preparation method of transformer oil base oil, particularly utilize the heavy hydrocarbon oil thermocracking process to produce the preparation method of transformer oil base oil.
Background technology
Transformer oil is the necessary medium of X-former work, mainly plays insulation and heat radiation, the safe operation of its quality quality direct relation X-former.At first obtain after paraffin mineral type transformer oil is used for the patent of X-former from professor ElihuThomson in 1887; Along with the upgrading of X-former is more and more harsher to mineral type transformer oil performance requriements, the trend of paraffinic based oil appears substituting with the naphthenic base transformer oil.The naphthenic base transformer oil has low pour point, solvability excellence, Heat stability is good, the good characteristics of degassing property, and its performance depends on the performance of transformer oil base oil to a great extent.Usually; Paraffinic base transformer oil base oil paraffinicity is high; Performances such as anti-gassing at transformer oil come with some shortcomings, and the naphthenic base transformer oil base oil can satisfy requirements such as the insulation, cooling of transformer oil, again can long-term stable operation; Therefore, become generally acknowledged transformer oil optimal selection component.
Because the transformer oil performance is relevant with the composition of institute's hydrocarbonaceous, therefore, the production technique of transformer oil changes with the difference of feedstock property.Poor, the easy liberation of hydrogen of straight-chain paraffin low-temperature fluidity in the oil product; Be the undesirable components in the transformer oil: the anti-gassing performance of aromatic hydrocarbons is good; But the polycyclic aromatic hydrocarbons oxidation stability is poor; Easy oxidation discoloration precipitates with generating, and also must in the course of processing, remove or reduce its content usually, so need select production technique to different transformer oil basic material character.
CN1110709 discloses a kind of method with production of transformer oil with hydrocracking tail oil, and this method is through in hydrocracking tail oil, adding aromatic hydrocarbon and naphthene base crude oil to improve its light stability; CN1174225 discloses a kind of transformer oil and method for making thereof, and this method is that raw material is produced transformer oil with the catalytic pyrolysis light oil that is rich in aromatic hydrocarbons.
USP U.S.Pat.No.5; 167; 847 to relate to a kind of be the method for raw material production transformer oil with the paraffinic based oil, and this method is produced the transformer oil component through hydrogen cracking, solvent dewaxing process, in this component, call in oxidation inhibitor and pour point depressant after its performance be equal to the naphthenic base transformer oil; USP U.S.Pat.No.4,018,666 relates to a kind of is raw material with paraffinic based oil 310-400 ℃ cut, removes aromatic hydrocarbons and polar material through solvent treatment, produces transformer oil.
CN 1254523C discloses the working method and the method for use thereof of transformer oil anti-gassing method additive; CN1438299 discloses a kind of working method and method of use thereof of anti-evolving-gas additive of transformer oil, is that 250 to 500 ℃ of petroleum fractionss are raw material with boiling point, adopts hydroprocessing technique to produce anti-evolving-gas additive of transformer oil.
CN 101386794A, CN 101386792A, CN 101386791A disclose a kind of transformer oil base oil and preparation method thereof and application, Suizhong-36 crude oil → fractionation → X-former distillate → furfural treatment → denitrogenation → clay-filtered → transformer oil product.
CN200510132293.X discloses a kind of working method of ultrahigh voltage transformer oil, and this method is produced ultrahigh voltage transformer oil with the naphthenic base distillate through two-stage hydrogenation pre-treatment prodn. art.The transformer oil of China is transformer oil and ultrahigh voltage transformer oil two big classes according to the different voltage grade separations of power transmission and transformation.Ultrahigh voltage transformer oil is applicable to the X-former of 500KV and similar the requirement in the electrical equipment is arranged.Transformer oil is applicable to the X-former of (containing 330KV) below the 330KV and similar the requirement in the electrical equipment is arranged.
CN200710010169.5 discloses a kind of environment-friendly type transformer oil and preparation method thereof; This method is a raw material with vegetables oil and tankage thereof, through alkali refining, dehydration, esterification alcoholysis, stop that neutralization, washing are refining, underpressure distillation, decolorization filtering and 0.1～5.0wt% oxidation inhibitor is gone in blending, 0.1～5.0wt% pour point depressant makes.
Can know that from above-mentioned disclosed technical literature scheme existing transformer oil fabricating technology is divided into several types, one type of naphthenic base crude with better character adopts conventional transformer oil production technique to produce transformer oil; One type is raw material with the paraffinic base distillate, adopts specific production technique to produce transformer oil or blending component; Produce transformer oil or anti-evolving-gas additive of transformer oil with high aromatic component raw material for one type; Last type is the raw material production ultrahigh voltage transformer oil with the naphthenic base distillate, improves the service rating of transformer oil.
Summary of the invention
The purpose of this invention is to provide a kind of is the preparation method of feedstock production transformer foundation oil with inferior heavy oil or time processing heavy oil.This method has not only enlarged transformer foundation oil raw material sources, transformer foundation oil of preparing and naphthenic base transformer foundation oil phase ratio, and it is moderate to have a degassing property, and viscosity temperature characteristic is good, naphthenic hydrocarbon and aromatic hydrocarbon content characteristics such as suit.
The present invention is a raw material with inferior heavy oil, the normal vacuum residuum of naphthenic base, the normal vacuum residuum of paraffinic base; After being heated to suitable temperature of reaction, getting into has in the adiabatic reactor that disperses inner member or sky, and reacted product obtains 260 ℃～360 ℃ cuts through cooling, fractionation; This cut removes heteroatomss such as S, N, O through unifining, and carries out the saturated and aromatic hydrogenation of alkene; Hydrofined oil removes many rings short-side chain aromatic hydrocarbon, sulfur-bearing in the oil, contains oxygen, nitrogenous chemical combination and gum asphalt through solvent treatment, obtains solvent-refined oil; Solvent-refined oil removes high pour point component through the hydrogenation pour point depression; Hydrogenation pour point depression reaction oil is through clay-filtered, and the clay-filtered oil that obtains is exactly a transformer foundation oil.
Specifically, technical scheme provided by the invention is: with density at 950Kg/m
3～1000Kg/m
3Crude oil,＞350 ℃ naphthenic base long residuum,＞500 ℃ of vacuum residuum are raw material; Be heated to after 360～480 ℃ to get into to have through process furnace and disperse in inner member or the empty adiabatic reactor; Disperseing inner member is bubble deck, valve tray, traverse baffle or filler; Control raw material 10～180 minutes residence time in reactor drum, pressure 0.1～2.0MPa; The reactant flow that reactor drum comes out is cooled off through quenching oil, and quenching oil is the cut between thermally splitting is given birth to olefiant 360 ℃～450 ℃, or the cut between 150 ℃～280 ℃, is cooled to 300～380 ℃; Thermally splitting generates oil and obtains 260-360 ℃ of cut through the fractionation cutting; 260-360 ℃ of cut and hydrogen mixing post-heating to 250 ℃～400 ℃ are got into the hydrofining reaction beds, and control reaction bed temperature is 250 ℃～400 ℃, and the hydrogen dividing potential drop is 2.0～20MPa, and volume space velocity is 0.2～2.0h
-1, hydrogen to oil volume ratio 300: 1～1500: 1; The hydrogenated oil that obtains from reactor drum gets in the tower from the solvent tower bottom; With advance tower furfural counter current contact from top and carry out heat and mass; Operational condition is: solvent ratio 1: 1.3～3.5 (mass ratio), 70～100 ℃ of tower top temperatures, 40～70 ℃ of column bottom temperatures; Obtain the chaff essential oil from effusive the raffinating oil of extracting cat head through removing furfural; Chaff essential oil and hydrogen mixing post-heating to 200 ℃～350 ℃ get into hydrogenation pour point depression reaction beds, and control reaction bed temperature is 200 ℃～380 ℃, and the hydrogen dividing potential drop is 3.0～20MPa, and volume space velocity is 0.2～2.0h
-1, hydrogen to oil volume ratio 300: 1～1000: 1; The hydrogenation pour point depression generation oil that comes out from reactor drum mixes with carclazyte; The carclazyte consumption generates 2～10% of oil quality for the hydrogenation pour point depression; Carclazyte and the living olefiant mixtinite of pour point depression are heated to 60～150 ℃; Mix after residence time 10-80 minute, carclazyte is removed by filter obtain clay-filtered oil, this clay-filtered oil is transformer oil base oil.
Or rather, technical scheme of the present invention is: with density at 950Kg/m
3～1000Kg/m
3Crude oil,＞360 ℃ naphthenic base atmospheric resid component,＞500 ℃ of vacuum residuum are raw material; Be heated to after 390～430 ℃ to get into to have through process furnace and disperse in inner member or the empty adiabatic reactor; Inner member is bubble deck, valve tray, traverse baffle or filler; Control raw material 20～90 minutes residence time in reactor drum, pressure 0.1～1.6MPa; The reactant flow that reactor drum comes out is cooled off through quenching oil, and quenching oil is to divide or the cut between 150～280 ℃ between thermally splitting is given birth to olefiant 360～450 ℃, is cooled to 300～360 ℃; Thermally splitting generates oil and obtains 260-360 ℃ of cut through the fractionation cutting; 260～360 ℃ of cuts and hydrogen mixing post-heating to 280 ℃～350 ℃ are got into the hydrofining reaction beds, and control reaction bed temperature is 290 ℃～360 ℃, and the hydrogen dividing potential drop is 5.0～16MPa, and volume space velocity is 0.5～1.0h
-1, hydrogen to oil volume ratio 300: 1～800: 1; The hydrogenated oil that comes out from reactor drum is through furfural solvent treatment technology, and operational condition is: solvent ratio 1: 1.9～2.6 (mass ratio), and 80～90 ℃ of tower top temperatures, 50～60 ℃ of column bottom temperatures, raffinating oil obtains the chaff essential oil through removing furfural; Chaff essential oil and hydrogen mixing post-heating to 260 ℃～320 ℃ get into hydrogenation pour point depression reaction beds, and control reaction bed temperature is 270 ℃～330 ℃, and the hydrogen dividing potential drop is 3.0～10MPa, and volume space velocity is 0.8～1.5h
-1, hydrogen to oil volume ratio 300: 1～500: 1; The hydrogenation pour point depression generates oil to be mixed with carclazyte; The carclazyte consumption generates 3～6% of oil quality for the hydrogenation pour point depression; Carclazyte and pour point depression are given birth to olefiant mixture heating up to 90～120 ℃; Mix after residence time 30-50 minute, remove by filter carclazyte and obtain clay-filtered oil, this clay-filtered oil is transformer oil base oil.
The present invention uses catalyst for refining at the hydrofining reaction bed, and the activity of such catalysts metal component is W, Ni, and Co, a kind of or combination more than two kinds among the Mo accounts for 10～40% of catalyst weight in oxide compound active metal component content, and carrier is Al
2O
3Or Al
2O
3-SiO
2Carry out sulfidizing before the use; Use the pour point depression catalyzer at hydrogenation pour point depression reaction bed, the activity of such catalysts metal component is Ni, and a kind of or its combination among the Zn accounts for 1～10% of catalyst weight in the oxide compound active metallic content, and carrier is mordenite or ZSM-5 molecular sieve and Al
2O
3Mixtinite, weight ratio are 1: 1, and can carry out sulfidizing before using also can be without sulfidizing.
Compared with prior art; The present invention is that often to subtract residual oil with inferior heavy oil, the normal vacuum residuum of paraffinic base and naphthenic base be raw material; The transformer oil base oil that utilizes thermally splitting, unifining, solvent treatment, hydrogenation pour point depression, clay-filtered combination process to produce, this product meets IEC60296 (2003), ASTMD3487, GB 2536-90 and SH0040-91 standard; This method is not only widened the transformer oil base oil raw material sources, solve the problems such as single and resource scarcity of originating, and the viscosity temperature characteristic of the transformer oil base oil that obtains is good.
Embodiment
Further set forth technical scheme of the present invention and effect below in conjunction with embodiment.
Embodiment 1
With the normal residual oil of naphthenic base is raw material, and feedstock property is seen table 1, carries out thermocracking process, and the thermocracking process operational condition is seen table 2.Obtain the transformer oil base oil raw material through the cut cutting, this raw material obtains transformer foundation oil through hydrogenation, furfural, pour point depression and carclazyte production technique.Each production technique operating parameters is seen table 3, table 4, table 5, table 6.Base oil viscosity temperature characteristic table 6, hydrogenation catalyst character is seen table 7.This base oil meets IEC60296 (2003), ASTM D3487, GB 2536-90 and SH0040-91 standard.
Embodiment 2
Subtracting residual oil with naphthenic base is raw material, and feedstock property is seen table 1, carries out thermocracking process, and the thermocracking process operational condition is seen table 2.Obtain the transformer oil base oil raw material through the cut cutting, this raw material obtains transformer foundation oil through hydrogenation, furfural, pour point depression and carclazyte production technique.Each production technique operating parameters is seen table 3, table 4, table 5, table 6.The sticking warm nature of base oil is seen table 6, and the hydrogenation catalyst property analysis is seen table 7.This base oil meets IEC60296 (2003), ASTM D3487, GB 2536-90 and SH0040-91 standard.
Embodiment 3
With inferior heavy oil A is raw material, and feedstock property is seen table 1, carries out thermocracking process, and the thermocracking process operational condition is seen table 2.Obtain the transformer oil base oil raw material through the cut cutting, this raw material obtains transformer foundation oil through hydrogenation, furfural, pour point depression and carclazyte production technique.Each production technique operating parameters is seen table 3, table 4, table 5, table 6.The base oil viscosity temperature characteristic is seen table 6, and the hydrogenation catalyst property analysis is seen table 7.This base oil meets IEC60296 (2003), ASTM D3487, GB 2536-90 and SH0040-91 standard.
Embodiment 4
With inferior heavy oil B is raw material, and feedstock property is seen table 1, carries out thermocracking process, and the thermocracking process operational condition is seen table 2.Obtain the transformer oil base oil raw material through the cut cutting, this raw material obtains transformer foundation oil through hydrogenation, furfural, pour point depression and carclazyte production technique.Each production technique operating parameters is seen table 3, table 4, table 5, table 6.The base oil viscosity temperature characteristic is seen table 6, and the hydrogenation catalyst property analysis is seen table 7.This base oil meets IEC60296 (2003), ASTM D3487, GB 2536-90 and SH0040-91 standard.
Embodiment 5
With inferior heavy oil C is raw material, and feedstock property is seen table 1, carries out thermocracking process, and the thermocracking process operational condition is seen table 2.Obtain the transformer oil base oil raw material through the cut cutting, this raw material obtains transformer foundation oil through hydrogenation, furfural, pour point depression and carclazyte production technique.Each production technique operating parameters is seen table 3, table 4, table 5, table 6.The base oil viscosity temperature characteristic is seen table 6, and the hydrogenation catalyst property analysis is seen table 7.This base oil meets IEC60296 (2003), ASTM D3487, GB 2536-90 and SH0040-91 standard.
Embodiment 6
With inferior heavy oil D is raw material, and feedstock property is seen table 1, carries out thermocracking process, and the thermocracking process operational condition is seen table 2.Obtain the transformer oil base oil raw material through the cut cutting, this raw material obtains transformer foundation oil through hydrogenation, furfural, pour point depression and carclazyte production technique.Each production technique operating parameters is seen table 3, table 4, table 5, table 6.The base oil viscosity temperature characteristic is seen table 6, and the hydrogenation catalyst property analysis is seen table 7.This base oil meets IEC60296 (2003), ASTM D3487, GB 2536-90 and SH0040-91 standard.
Embodiment 7
With inferior heavy oil E is raw material, and feedstock property is seen table 1, carries out thermocracking process, and the thermocracking process operational condition is seen table 2.Obtain the transformer oil base oil raw material through the cut cutting, this raw material obtains transformer foundation oil through hydrogenation, furfural, pour point depression and carclazyte production technique.Each production technique operating parameters is seen table 3, table 4, table 5, table 6.The base oil viscosity temperature characteristic is seen table 6, and the hydrogenation catalyst property analysis is seen table 7.This base oil meets IEC60296 (2003), ASTM D3487, GB 2536-90 and SH0040-91 standard.
Embodiment 8
With inferior heavy oil F is raw material, and feedstock property is seen table 1, carries out thermocracking process, and the thermocracking process operational condition is seen table 2.Obtain the transformer oil base oil raw material through the cut cutting, this raw material obtains transformer foundation oil through hydrogenation, furfural, pour point depression and carclazyte production technique.Each production technique operating parameters is seen table 3, table 4, table 5, table 6.The base oil viscosity temperature characteristic is seen table 6, and the hydrogenation catalyst property analysis is seen table 7.This base oil meets IEC60296 (2003), ASTM D3487, GB 2536---and 90 and the SH0040-91 standard.
Embodiment 9
With the paraffinic base long residuum is raw material, and feedstock property is seen table 1, carries out thermocracking process, and the thermocracking process operational condition is seen table 2.Obtain the transformer oil base oil raw material through the cut cutting, this raw material obtains transformer foundation oil through hydrogenation, furfural, pour point depression and carclazyte production technique.Each production technique operating parameters is seen table 3, table 4, table 5, table 6.The base oil viscosity temperature characteristic is seen table 6, and the hydrogenation catalyst property analysis is seen table 7.This base oil meets IEC60296 (2003), ASTM D3487, GB 2536---and 90 and the SH0040-91 standard.
Embodiment 10
With paraffinic base vacuum residuum is raw material, and feedstock property is seen table 1, carries out thermocracking process, and the thermocracking process operational condition is seen table 2.Obtain the transformer oil base oil raw material through the cut cutting, this raw material obtains transformer foundation oil through hydrogenation, furfural, pour point depression and carclazyte production technique.Each production technique operating parameters is seen table 3, table 4, table 5, table 6.The base oil viscosity temperature characteristic is seen table 6, and the hydrogenation catalyst property analysis is seen table 7.This base oil meets IEC60296 (2003), ASTM D3487, GB 2536---and 90 and the SH0040-91 standard.
The analysis of table 1 feedstock property
Table 2 thermally splitting operating parameters and property analysis
Table 3 unifining operational condition and property analysis
Table 4 furfural operational condition and chaff essential oil property analysis
Table 5 hydrogenating and pour point depressing operational condition and pour point depression oiliness matter are analyzed
Table 6 carclazyte operational condition and white essential oil property analysis
The analysis of table 7 catalyst property
Claims (4)
1. the preparation method of a transformer oil raw material, it is characterized in that: or/and the normal vacuum residuum of paraffinic base is raw material, through heat cracking reaction, fractionation obtains 260～360 ℃ of cuts with inferior heavy oil, the normal vacuum residuum of naphthenic base; This cut obtains transformer foundation oil through unifining, solvent treatment, hydrogenation pour point depression, clay-filtered oil;
The processing condition of heat cracking reaction are: temperature in is 360 ℃～480 ℃, 10～180 minutes residence time, pressure 0.1～2.0MPa;
Getting into the first hydrogenation reaction bed carries out hydrofining reaction under the Hydrobon catalyst effect processing condition is: temperature is 250 ℃～400 ℃, and the hydrogen dividing potential drop is 2.0～20MPa, and volume space velocity is 0.2～2.0h
-1, hydrogen to oil volume ratio 300: 1～1500: 1;
Carrying out the solvent-refined processing condition of furfural is: the solvent quality ratio is 1: 1.3～3.5,70～100 ℃ of tower top temperatures, 40～70 ℃ of column bottom temperatures;
Getting into the processing condition of under the Hydrodewaxing catalyst effect, carrying out the reaction of hydrogenation pour point depression in the second hydrogenation reaction bed is: temperature is 200 ℃～380 ℃, and the hydrogen dividing potential drop is 2.0～20MPa, and volume space velocity is 0.2～2.0h
-1, hydrogen to oil volume ratio 300: 1～1000: 1;
Carrying out clay-treated processing condition is: the carclazyte consumption is 2～10% of a raw oil quality, 60～150 ℃ of mixing temperatures, residence time 10-80 minute.
2. according to the preparation method of the described transformer oil raw material of claim 1, it is characterized in that: described inferior heavy oil is: density 950Kg/m
3～1000.0Kg/m
3, 100 ℃ of kinematic viscosity 200～1500mm
2The crude oil of/s; The normal vacuum residuum of described naphthenic base is: naphthenic base crude through behind normal, the vacuum fractionation＞360 ℃ of naphthenic base crude long residuums and＞500 ℃ of vacuum residuum.
3. according to the preparation method of the described transformer oil raw material of claim 1; It is characterized in that: the first hydrogenation reaction bed uses Hydrobon catalyst, and the activity of such catalysts metal component is W, Ni; Co; A kind of or its combination among the Mo accounts for 10～40% of catalyst weight in the oxide compound active metallic content, and carrier is Al
2O
3, carry out sulfidizing before the use;
Second reaction bed uses Hydrodewaxing catalyst, and the activity of such catalysts metal component is W, Ni, and Co, a kind of or its combination among the Mo accounts for 10～40% of catalyst weight in the oxide compound active metallic content, and carrier is Al
2O
3Or Al
2O
3-SiO
2, and add auxiliary agent F or P, carry out sulfidizing before the use.
4. according to the preparation method of the described X-former raw material of claim 1, it is characterized in that:
The processing condition that get into heat cracking reaction are: temperature in is 390 ℃～430 ℃, 10～90 minutes residence time, pressure 0.1～0.6MPa;
Getting into the processing condition that the first hydrogenation reaction bed carries out hydrofining reaction is: temperature is 290 ℃～360 ℃, and the hydrogen dividing potential drop is 5～16MPa, and volume space velocity is 0.5～1.0h
-1, hydrogen to oil volume ratio 300: 1～800: 1;
Carrying out the solvent-refined processing condition of furfural is: solvent quality is than 1: 1.9～2.6,80～90 ℃ of tower top temperatures, 50～60 ℃ of column bottom temperatures;
Getting into the processing condition of carrying out the reaction of hydrogenation pour point depression in the second hydrogenation reaction bed is: temperature is 270 ℃～330 ℃, and the hydrogen dividing potential drop is 3.0～10MPa, and volume space velocity is 0.8～1.5h
-1, hydrogen to oil volume ratio 300: 1～500: 1;
Carrying out clay-treated processing condition is: the carclazyte consumption is 3～6% of a raw oil quality, 90～120 ℃ of mixing temperatures, residence time 30-50 minute.
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| CN103789019A (en) * | 2012-11-05 | 2014-05-14 | 中国石油化工股份有限公司 | Method for hydrogenation of medium-low temperature coal tar to produce transformer oil base oil |
| CN104342206A (en) * | 2013-07-29 | 2015-02-11 | 山东鹏奥石油科技有限公司 | Lubricating oil hydrodewaxing production technology |
| CN106753555A (en) * | 2016-12-08 | 2017-05-31 | 安徽凯奥新能源股份有限公司 | A kind of method that high-pressure hydrogenation prepares low condensation point transformer oil |
| CN106833740A (en) * | 2015-12-04 | 2017-06-13 | 中国石油天然气股份有限公司 | Preparation method of transformer oil base oil |
| CN108165339A (en) * | 2016-12-08 | 2018-06-15 | 中国石油天然气股份有限公司 | Cycloalkyl transformer oil composition |
| CN109456795A (en) * | 2018-11-30 | 2019-03-12 | 山东齐胜工贸股份有限公司 | A kind of technique of the production of Hydrodewaxing tail oil organic heat carrier oil and transformer oil |
| CN111289804A (en) * | 2020-03-03 | 2020-06-16 | 西南交通大学 | Method for evaluating correlation between transformer oil paper insulation dielectric response and paraffin content |
| CN114806634A (en) * | 2021-01-29 | 2022-07-29 | 中石油克拉玛依石化有限责任公司 | Transformer oil base oil and preparation method thereof |
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| CN103789019A (en) * | 2012-11-05 | 2014-05-14 | 中国石油化工股份有限公司 | Method for hydrogenation of medium-low temperature coal tar to produce transformer oil base oil |
| CN104342206A (en) * | 2013-07-29 | 2015-02-11 | 山东鹏奥石油科技有限公司 | Lubricating oil hydrodewaxing production technology |
| CN106833740B (en) * | 2015-12-04 | 2018-09-04 | 中国石油天然气股份有限公司 | Preparation method of transformer oil base oil |
| CN106833740A (en) * | 2015-12-04 | 2017-06-13 | 中国石油天然气股份有限公司 | Preparation method of transformer oil base oil |
| CN106753555A (en) * | 2016-12-08 | 2017-05-31 | 安徽凯奥新能源股份有限公司 | A kind of method that high-pressure hydrogenation prepares low condensation point transformer oil |
| CN108165339A (en) * | 2016-12-08 | 2018-06-15 | 中国石油天然气股份有限公司 | Cycloalkyl transformer oil composition |
| CN106753555B (en) * | 2016-12-08 | 2018-12-07 | 安徽凯奥新能源股份有限公司 | A kind of method that high-pressure hydrogenation prepares low condensation point transformer oil |
| CN109456795A (en) * | 2018-11-30 | 2019-03-12 | 山东齐胜工贸股份有限公司 | A kind of technique of the production of Hydrodewaxing tail oil organic heat carrier oil and transformer oil |
| CN111289804A (en) * | 2020-03-03 | 2020-06-16 | 西南交通大学 | Method for evaluating correlation between transformer oil paper insulation dielectric response and paraffin content |
| CN111289804B (en) * | 2020-03-03 | 2021-02-19 | 西南交通大学 | Method for evaluating correlation between transformer oil paper insulation dielectric response and paraffin content |
| CN114806634A (en) * | 2021-01-29 | 2022-07-29 | 中石油克拉玛依石化有限责任公司 | Transformer oil base oil and preparation method thereof |
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Effective date of registration: 20180718 Address after: 100007 Dongzhimen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee after: CNPC KARAMAY PETROCHEMICAL CO.,LTD. Patentee after: PetroChina Company Limited Address before: 100007 Oil Mansion, Oil Mansion, 9 Dongzhimen North Street, Dongcheng District, Beijing. Patentee before: PetroChina Company Limited |