CN103045303A - Preparation method of base oil of refrigerator oil - Google Patents
Preparation method of base oil of refrigerator oil Download PDFInfo
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- CN103045303A CN103045303A CN201110314562XA CN201110314562A CN103045303A CN 103045303 A CN103045303 A CN 103045303A CN 201110314562X A CN201110314562X A CN 201110314562XA CN 201110314562 A CN201110314562 A CN 201110314562A CN 103045303 A CN103045303 A CN 103045303A
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- base oil
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- 239000003921 oil Substances 0.000 title claims abstract description 127
- 239000002199 base oil Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000002994 raw material Substances 0.000 claims abstract description 41
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000000341 volatile oil Substances 0.000 claims abstract description 10
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000010779 crude oil Substances 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 24
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000010791 quenching Methods 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000005194 fractionation Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 241000282326 Felis catus Species 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 229910052680 mordenite Inorganic materials 0.000 claims description 2
- 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 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 20
- 239000010721 machine oil Substances 0.000 abstract description 18
- 238000000605 extraction Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000004227 thermal cracking Methods 0.000 abstract 1
- 229910052725 zinc Inorganic materials 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 20
- 238000005057 refrigeration Methods 0.000 description 18
- 238000004458 analytical method Methods 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 11
- 239000002480 mineral oil Substances 0.000 description 9
- 235000010446 mineral oil Nutrition 0.000 description 9
- 238000005520 cutting process Methods 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 239000010725 compressor oil Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 239000002826 coolant Substances 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 239000002421 finishing Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000003507 refrigerant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000009283 thermal hydrolysis Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 244000144992 flock Species 0.000 description 1
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002895 organic esters Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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- Lubricants (AREA)
Abstract
The invention relates to a preparation method of base oil of refrigerator oil; the density is 950Kg/m3～1000Kg/m3Kinematic viscosity at 100 ℃ of 200-1500 mm2Performing thermal cracking on crude oil/s or naphthenic base atmospheric residue at the temperature of more than 360 ℃ serving as a raw material, performing hydrofining reaction on fractions at the temperature of 360-420 ℃ and hydrogen, and performing inlet-shaped furfural extraction on hydrogenated oil to obtain bran essential oil; performing hydrogenation pour point depression reaction on the bran essential oil and hydrogen; mixing the hydrogenation pour point depression produced oil with argil, and filtering and removing the argil to obtain argil refined oil, wherein the argil refined oil is the base oil of the refrigerator oil; the active metal components of the hydrorefining catalyst are W, Ni and CoOne or a combination of Mo; the active metal component of the hydrodewaxing catalyst is one or the combination of Ni and Zn; the method widens the raw material sources of the base oil of the refrigerating machine oil, and produces the product which meets the GB/T16630-1996 standard.
Description
Technical field
The present invention relates to the preparation method of refrigerator oil base oil, particularly utilize the heavy hydrocarbon oil thermocracking process to produce a kind of preparation method of refrigerator oil base oil.
Background technology
Refrigerator oil is the refrigeration compressor special lube, is the vital integral part that determines and affect refrigerating function and effect in the refrigeration system.High-quality refrigerator oil not only must possess thermochemical stability and intermiscibility good when coexisting with refrigeration agent, also must have good low-temperature fluidity, oilness, anti-bubble concurrently, and must be easy to produce, and raw material sources are reliable, and environment is not polluted.Refrigerator oil generally comprises base oil and various additive be used to improving other performance of refrigerator oil.The salient features of refrigerator oil such as rheological, viscosity temperature characteristic, low-temperature fluidity, flash-point and all determined by basic oil properties with the mutual solubility of refrigeration agent etc.Therefore, the selection of refrigerator oil mainly concentrates in the selection of base oil.
The base oil of refrigerator oil can be divided into mineral oil origin and synthetic oil type two large classes.The production of mineral oil origin refrigerator oil generally obtains base oil through techniques such as solvent treatment, solvent dewaxing, hydrogenation or clay finishings, adds the multiple additives blending again and forms.The base oil of compressor oil generally will account for more than 95% of processed oil, so the quality good or not of base oil is directly connected to the quality level of compressor oil processed oil, and the quality of base oil has direct relation with its refining depth.The base oil that refining depth is dark, its heavy aromatics, gum level are just few.Carbon residue is low, and the susceptibility of oxidation inhibitor is all right, and the quality of base oil is just high, and its carbon deposit tendency in compressor assembly is little, and oil-water separativeness is good, and work-ing life is relatively just longer.The base oil of synthetic oil type is that the organic liquid base oil that obtains of the method with chemosynthesis is again through allotment or add the lubricating oil that multiple additives is made.Its base oil major part is polymkeric substance or macromolecular organic compound.The kind of synthetic oil is a lot, and the synthetic oil that is used as compressor oil mainly contains 5 kinds of synthetic hydrocarbon (poly-1-olefin), organic ester (dibasic acid esters), polyalkylene glycol, fluorosilicon oil and phosphoric acid ester etc.Synthetic oil has oxidation stability, and the carbon deposit tendency is little, and the temperature range that can surpass plain mineral oil is lubricated, and long service life can satisfy the service requirements that general mineral oil origin compressor oil can not bear.But the high more expensive of the cost ratio mineral oil origin compressor oil of synthetic oil type compressor oil.
By inquiring about domestic patent, the patent relevant with refrigerator oil has following several pieces:
(1) application number: 200780008494.6, " refrigerated machine oil composition ".The present invention relates to refrigerated machine oil composition, it is characterized in that the kinematic viscosity that contains at 40 ℃ is 0.11～8mm
2The mixing base oil of/s, this mixing base oil contains: be 5mm 40 ℃ kinematic viscosity (A)
2The low viscosity base oil that/s is following and (B) be 20～400mm 40 ℃ kinematic viscosity
2The high viscosity base oil of/s (A) contains at least a base oil that is selected from mineral oil, synthetic hydrocarbon compounds, oxygenatedchemicals and the sulfocompound with (B) being.
(2) application number: 01814730.5, " refrigerated machine oil composition ".Refrigerated machine oil composition of the present invention is to contain to have ester ring type ring and following general formula-COOR
1(in the formula, R
1The alkyl of expression carbonatoms 1-30) 2 ester groups of expression and the refrigerated machine oil composition that this 2 ester groups are bonded to the ester ring type di-carboxylic acid ester cpds on the carbon atom that adjoins each other on the ester ring type ring, good to improve its oilness, refrigeration property consistency, thermal hydrolysis stability and electrical insulating property, the while can also be improved the efficient of refrigeration system.
(3) application number: 01814731.3, " refrigerated machine oil composition ".Refrigerated machine oil composition of the present invention, wherein contain the ester ring type polycarboxylic acid ester cpds that uses following compound (a)-(c) to obtain, when using with HFC refrigeration agent and the natural series coolant such as carbonic acid gas or hydrocarbon, can balance good satisfy the over-all propertiess such as oilness, refrigeration agent consistency, thermal hydrolysis stability and electrical insulating property.
(4) application number: 97122040.9, " a kind of refrigerated machine oil composition " discloses a kind of refrigerated machine oil composition, contains viscosity 10-150mm
2The C of the soft wax cracking of/s
5-C
18The mixedαolefin stand oil, this stand oil is synthetic according to conventional alpha-olefin polymerization technique, adds additive and can produce the refrigerator oil fabulous with refrigeration agent HCFCS consistency
(5) application number: 200480043857.6, " refrigerator oil composition for carbon dioxide coolant ".The invention discloses a kind of refrigerator oil composition for carbon dioxide coolant, it can be used for adopting the refrigeration system under the supercritical state of carbon dioxide coolant, rate of heat exchange in the time of particularly can improving supercritical co by heat exchanger, simultaneously, have good weather resistance and oilness.
(6) application number: 200580007040.8, " refrigerator oil ".Refrigerator oil of the present invention is characterised in that and contains: nitrogen divides less than or equal to 50 quality ppm and aromatic series and divides (%CA) to be the mineral oil of 5-25.Use refrigerator oil of the present invention, can high level and balancedly have stability, oilness concurrently and with the consistency of refrigeration agent, refrigerating and air conditioning device steadily in the long term can turn round.
(7) application number: 200710175413.3, " a kind of refrigerated machine oil composition and preparation method thereof ".This patent discloses a kind of refrigerated machine oil composition, and said composition contains mixedαolefin stand oil and the additive as base oil.
(8) application number: 200810223449.9, " production method of base oil of air-conditioner refrigeration oil ".The present invention relates to a kind of production method of base oil of air-conditioner refrigeration oil, with in patent ZL 02104842.8 hydrogenated oil greater than 360 ℃ the cut raw material as hydrodewaxing, the generation oil of hydrodewaxing carries out clay finishing again after the normal pressure flash distillation; The mutual solubility of this base oil and refrigeration agent freonll-11 is good, pour point, flock point are low, and the sulphur nitrogen content is low, satisfies totally-enclosed air conditioner refrigerating compressor take freonll-11 as refrigeration agent to the requirement of refrigerator oil base oil.
For foreign patent, mainly inquired about United States Patent (USP), the United States Patent (USP) that relates to mainly contains:
(1) patent No.: 4248726, a kind of high viscosity refrigerated machine oil composition.This full-bodied refrigerated machine oil composition comprise polyethylene or alkyl ether compound (A) and (B) and weight account for epoxy compounds, epoxy aliphatic ester and or the epoxidised vegetables oil of the Racemic glycidol ethers of A, B gross weight 0.1-10wt%.
(2) patent No.: 4497721,4800030,5342533,6074573, refrigerated machine oil composition.The invention discloses a kind of refrigerated machine oil composition, at least contain a kind of mineral oil and a kind of synthetic oil or mixing oil, at least contain a kind of glycidyl compound or phosphide or ester class etc., this refrigerated machine oil composition shows very high stability when contacting with refrigerant containing halogen, establishment with the generation of refrigerant containing halogen reaction hydrogenchloride and and refrigeration agent preferably consistency is arranged.Therefore this refrigerated machine oil composition has good lubricant effect.
(3) patent No.: US3953319A has proposed hydrofining-vitriolization-urea dewaxing-clay finishing refrigerator oil production method.
From above-mentioned disclosed technical literature scheme as can be known, the base oil component of refrigerator oil has two kinds: mineral oil and synthetic oil.And basic oil properties plays conclusive effect to the performance of refrigerator oil, by domestic and international contrastive analyze on patent, and the synthetic refrigerator oil of research in the majority, but synthetic refrigerator oil cost is high, applies being subject to certain restrictions.The consistency that the application requiring of refrigerator oil and refrigeration agent are good, and under the operating mode of harshness, have good lubricity and oxidation stability, and not with refrigeration agent generation chemical reaction.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who prepares refrigerator oil base oil take cycloalkyl heavy oil inferior or time processing cycloalkyl heavy oil as raw material.The method has enlarged the refrigerator oil base oil raw material sources to the strong adaptability of raw material, and the refrigerator oil base oil product of preparing meets the standard of GB/T16630-1996.
Technical scheme provided by the invention is:
Take naphthenic base crude inferior or time processing cycloalkyl heavy oil as raw material, after the process furnace heating, enter from the bottom to top in an in-built dispersion inner member or the adiabatic reactor without inner member, reactor reactant flow out enters normal, vacuum fractionation tower fractionation and obtains the refrigerator oil base oil feedstock fraction after quenching oil cooling; This cut removes the heteroatomss such as S, N, O through hydrofining, and carries out olefin saturated and aromatic hydrogenation; 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 hydrodewaxing; The hydrodewaxing reaction oil is through clay-filtered, and the clay-filtered oil that obtains is exactly refrigerator oil base oil.
Specifically, technical scheme provided by the invention is: take density as 950Kg/m
3～1000Kg/m
3Crude oil and long residuum,＞360 ℃ cycloalkyl long residuum is raw material, be heated to through process furnace and enter after 360～480 ℃ in in-built dispersion inner member or the adiabatic reactor without inner member, inner member is bubble deck, valve tray, traverse baffle or non-activity packing layer, control raw material 10～180 minutes residence time in reactor, pressure 0.1～2.0MPa; Reactor reactant flow is out cooled off through quenching oil, and quenching oil is that thermally splitting generates oil after the cooling, is cooled to 300～380 ℃; Thermally splitting generates oil and cuts out 360～420 ℃ of cuts through fractionation; 360～420 ℃ of cuts and hydrogen mixing post-heating to 250 ℃～400 ℃ are entered the hydrofining reaction bed, 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 enters 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 1.5～3.5: 1 (volume ratio), 85～115 ℃ of tower top temperatures, 55～85 ℃ of column bottom temperatures; Obtain the chaff essential oil from raffinating oil of extracting cat head outflow through removing furfural; Chaff essential oil and hydrogen mixing post-heating to 200 ℃～350 ℃ enter the hydrodewaxing reaction bed, and control reaction bed temperature is 250 ℃～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; Generating oil from reactor hydrodewaxing out mixes with carclazyte, be heated to 80～170 ℃, the carclazyte consumption be hydrodewaxing generate oil quality 2～10%, mix when stopping after 10-80 minute, carclazyte removed by filter obtain clay-filtered oil, this clay-filtered oil is refrigerator oil base oil.
Or rather, technical scheme of the present invention is: with density at 950Kg/m
3～1000Kg/m
3Crude oil and long residuum,＞360 ℃ of cycloalkyl long residuums are raw material, after process furnace is heated to 390 ℃～430 ℃, enter in in-built dispersion inner member or the adiabatic reactor without inner member, inner member can be bubble deck, valve tray, and non-activity packing layer, control raw material 20～90 minutes residence time in reactor, pressure 0.1～0.6MPa; Reactor reactant flow is out cooled off through quenching oil, and quenching oil is that thermally splitting generates oil after the cooling, is cooled to 300～330 ℃; Thermally splitting generates oil and cuts out 360～420 ℃ of cuts through fractionation; 360～420 ℃ of cuts and hydrogen mixing post-heating to 280 ℃～350 ℃ are entered the hydrofining reaction bed, 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; Through the furfural solvent process for refining, operational condition is from reactor hydrogenated oil out: solvent ratio 2.0～3.0: 1 (volume ratio), and 95～105 ℃ of tower top temperatures, 65～75 ℃ of column bottom temperatures, raffinating oil obtains the chaff essential oil through removing furfural; Chaff essential oil and hydrogen mixing post-heating to 270 ℃～350 ℃ enter the hydrodewaxing reaction bed, and control reaction bed temperature is 280 ℃～360 ℃, 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; Hydrodewaxing generates oil to be mixed with carclazyte, be heated to 110～150 ℃, the carclazyte consumption is 3～6% of hydrodewaxing generation oil quality, mixes after residence time 30-50 minute, remove by filter carclazyte and obtain clay-filtered oil, this clay-filtered oil is refrigerator oil base oil.
The present invention uses catalyst for refining at the hydrofining reaction bed, and the active metal component of catalyzer is W, Ni, and Co, one or two or more kinds combination 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 the hydrodewaxing reaction bed, the active metal component of catalyzer 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
3Mixture, weight ratio are 1: 1, and can carry out sulfidizing before using also can be without sulfidizing.
The invention solves the single and resource of refrigerator oil base oil raw material sources and wait less Current Situation, the refrigerator oil base oil raw material sources have been widened, take naphthenic base crude inferior or time processing cycloalkyl heavy oil as raw material, utilize thermally splitting-hydrofining-solvent treatment-hydrodewaxing-clay-filtered combination process, produce the refrigerator oil base oil product that meets the GB/T16630-1996 standard.
Embodiment
Further set forth technical solution of the present invention and effect below in conjunction with embodiment.
Embodiment 1
Take cycloalkyl long residuum A as raw material, feedstock property sees Table 1, carries out thermocracking process, and the thermocracking process operational condition sees Table 2.Obtain the refrigerator oil base oil raw material through the cut cutting, this raw material obtains refrigerator oil base oil through hydrogenation, furfural, pour point depression and carclazyte production technique.Each production technique operating parameters sees Table 3, table 4, table 5, table 6, and hydrogenation catalyst character sees Table 7.This base oil meets the GB/T16630-1996 standard.
Embodiment 2
Take naphthenic base crude B inferior as raw material, feedstock property sees Table 1, carries out thermocracking process, and the thermocracking process operational condition sees Table 2.Obtain the refrigerator oil base oil raw material through the cut cutting, this raw material obtains refrigerator oil base oil through hydrogenation, furfural, pour point depression and carclazyte production technique.Each production technique operating parameters sees Table 3, table 4, table 5, table 6, and the hydrogenation catalyst property analysis sees Table 7.This base oil meets the GB/T16630-1996 standard.
Embodiment 3
Take naphthenic base crude C inferior as raw material, feedstock property sees Table 1, carries out thermocracking process, and the thermocracking process operational condition sees Table 2.Obtain the refrigerator oil base oil raw material through the cut cutting, this raw material obtains refrigerator oil base oil through hydrogenation, furfural, pour point depression and carclazyte production technique.Each production technique operating parameters sees Table 3, table 4, table 5, table 6, and the hydrogenation catalyst property analysis sees Table 7.This base oil meets the GB/T16630-1996 standard.
Embodiment 4
Take naphthenic base crude D inferior as raw material, feedstock property sees Table 1, carries out thermocracking process, and the thermocracking process operational condition sees Table 2.Obtain the refrigerator oil base oil raw material through the cut cutting, this raw material obtains refrigerator oil base oil through hydrogenation, furfural, pour point depression and carclazyte production technique.Each production technique operating parameters sees Table 3, table 4, table 5, table 6, and the hydrogenation catalyst property analysis sees Table 7.This base oil meets the GB/T16630-1996 standard.
Embodiment 5
Take naphthenic base crude E inferior as raw material, feedstock property sees Table 1, carries out thermocracking process, and the thermocracking process operational condition sees Table 2.Obtain the refrigerator oil base oil raw material through the cut cutting, this raw material obtains refrigerator oil base oil through hydrogenation, furfural, pour point depression and carclazyte production technique.Each production technique operating parameters sees Table 3, table 4, table 5, table 6, and the hydrogenation catalyst property analysis sees Table 7.This base oil meets the GB/T16630-1996 standard.
Embodiment 6
Take cycloalkyl long residuum F inferior as raw material, feedstock property sees Table 1, carries out thermocracking process, and the thermocracking process operational condition sees Table 2.Obtain the refrigerator oil base oil raw material through the cut cutting, this raw material obtains refrigerator oil base oil through hydrogenation, furfural, pour point depression and carclazyte production technique.Each production technique operating parameters sees Table 3, table 4, table 5, table 6, and the hydrogenation catalyst property analysis sees Table 7.This base oil meets the GB/T16630-1996 standard.
Embodiment 7
Take cycloalkyl long residuum G inferior as raw material, feedstock property sees Table 1, carries out thermocracking process, and the thermocracking process operational condition sees Table 2.Obtain the refrigerator oil base oil raw material through the cut cutting, this raw material obtains refrigerator oil base oil through hydrogenation, furfural, pour point depression and carclazyte production technique.Each production technique operating parameters sees Table 3, table 4, table 5, table 6, and the hydrogenation catalyst property analysis sees Table 7.This base oil meets the GB/T16630-1996 standard.
Embodiment 8
Take cycloalkyl long residuum G as raw material, feedstock property sees Table 1, carries out thermocracking process, and the thermocracking process operational condition sees Table 2.Obtain the refrigerator oil base oil raw material through the cut cutting, this raw material obtains refrigerator oil base oil through hydrogenation, furfural, pour point depression and carclazyte production technique.Each production technique operating parameters sees Table 3, table 4, table 5, table 6, and the hydrogenation catalyst property analysis sees Table 7.This base oil meets the GB/T16630-1996 standard.
The analysis of table 1 feedstock property
Table 2 thermally splitting operating parameters and property analysis
Table 3 hydrofining operational condition and property analysis
Table 4 furfural operational condition and chaff essential oil property analysis
Table 5 hydrodewaxing operational condition and pour point depression oil nature are analyzed
Table 6 carclazyte operational condition and white essential oil property analysis
The analysis of table 7 catalyst property
Claims (1)
1. the preparation method of a refrigerator oil base oil is characterized in that:
(1) take density as 950Kg/m
3～1000Kg/m
3, 100 ℃ of kinematic viscosity 200～1500mm
2The crude oil of/s, or＞360 ℃ cycloalkyl long residuum is raw material, be heated to through process furnace and enter in in-built dispersion inner member or the adiabatic reactor without inner member control raw material 10～180 minutes residence time in reactor, pressure 0.1～2.0MPa after 360～480 ℃; Reactor reactant flow is out cooled off through quenching oil, and quenching oil is that thermally splitting generates oil after the cooling, is cooled to 300～380 ℃; Thermally splitting generates oil and cuts out 360～420 ℃ of cuts through fractionation;
(2) 360～420 ℃ of cuts and hydrogen mixing post-heating to 250 ℃～400 ℃ are entered the hydrofining reaction bed, 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;
(3) hydrogenated oil that obtains from reactor enters 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 volume is than 1.5～3.5: 1, and 85～115 ℃ of tower top temperatures, 55～85 ℃ of column bottom temperatures; Obtain the chaff essential oil from raffinating oil of extracting cat head outflow through removing furfural;
(4) chaff essential oil and hydrogen mixing post-heating to 200 ℃～350 ℃ enter the hydrodewaxing reaction bed, and control reaction bed temperature is 250 ℃～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;
(5) generating oil from reactor hydrodewaxing out mixes with carclazyte, be heated to 80～170 ℃, the carclazyte consumption is 2～10% of hydrodewaxing generation oil quality, when mix stopping after 10-80 minute, carclazyte removed by filter obtain clay-filtered oil, this clay-filtered oil is refrigerator oil base oil;
The hydrofining reaction bed uses Hydrobon catalyst, and the active metal component of catalyzer 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 or Al
2O
3-SiO
2, carry out sulfidizing before the use;
The hydrodewaxing reaction bed uses Hydrodewaxing catalyst, and the active metal component of catalyzer 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
3Mixture.
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| CN109852459A (en) * | 2019-03-22 | 2019-06-07 | 合肥学院 | A kind of synthetic method containing molybdenum disulfide/spent bleaching clay compound lubricant dispersion system lubricating oil in esters |
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Effective date of registration: 20180719 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 |