CN106167719A - A kind of hydrorefining basic oil lubricating oil technique - Google Patents

A kind of hydrorefining basic oil lubricating oil technique Download PDF

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Publication number
CN106167719A
CN106167719A CN201610694455.7A CN201610694455A CN106167719A CN 106167719 A CN106167719 A CN 106167719A CN 201610694455 A CN201610694455 A CN 201610694455A CN 106167719 A CN106167719 A CN 106167719A
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catalyst
oil
fixed bed
kit
bed reactors
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朱忠良
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Xishan Lvchun Plastic Products Factory
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Xishan Lvchun Plastic Products Factory
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
    • 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
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1062—Lubricating oils
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • C10G2300/70—Catalyst aspects
    • 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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a kind of hydrorefining basic oil lubricating oil technique, described technique includes solvent refining unit, hydrogenation desulfurization and denitrogenation unit and hydrofinishing unit, described hydrogenation desulfurization and denitrogenation unit uses fixed bed reactors, being filled with hydrogenation catalyst in fixed bed reactors, described catalyst includes carrier and active component.Described carrier is incorporation hetero atom Co in synthetic bone shelf structure2+KIT 1.Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc.Described catalyst is possibly together with catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixture.The reaction condition of described fixed bed reactors is: reaction temperature is 350 370 DEG C, reaction pressure 9 11MPa, hydrogen to oil volume ratio 300 600, volume space velocity 1.0 2.5h‑1.Lube base oil total sulfur content can be controlled, less than 5ppm, to control the total nitrogen content in base oil within 10ppm by this technique simultaneously.

Description

A kind of hydrorefining basic oil lubricating oil technique
Technical field
The present invention relates to a kind of lube base oil processing technique, be specifically related to a kind of profit using special catalyst to carry out Lubricant base oil hydrofining technology.
Background technology
The raising of lube product quality, it is desirable to base oil has a higher Viscosity Index, less evaporation loss, more preferably Oxidation stability and low temperature flow.Such as in order to produce, the 5W meeting GF-2 and G-3 standard is oily or long-life automatic biography Hydrodynamic, it is necessary to use some or all of II class meeting API base oil criteria for classification or III class base oil, and with conventional It is to use hydrogenation work that solvent refining I class base oil then cannot modulate this up-to-standard series products, II class and III class base oil Skill produces, and its quality index is: saturated hydrocarbons mass fraction is all higher than 90%, and sulfur nutrient is respectively less than 0.03%；In viscosity Index aspect, II class is 80-120, and Group III is more than 120.
The companies such as Exxon develop a kind of group technology combined by lubricating oil solvent with hydrotreating, i.e. By the charging of hydrotreater, first pass through solvent refining to reduce the nitride in charging and condensed-nuclei aromatics content.Owing to changing Being apt to feedstock quality, hydrotreating can be carried out under the temperature and pressure relatively relaxed.The most not only can improve the viscous of base oil Degree index, and viscosity loss is little, and light stability is good.Further, since hydroprocessing condition compares mitigation, the knot of paraffin in raw material Structure seldom wrecks, therefore. and during obtained hydrogenated oil solvent dewaxing, its filtering property connects with solvent-refined oil very much Closely, the hydrogenated oil obtained by distillate direct hydrogenation processes, during solvent dewaxing, the rate of filtration is the slowest. need to add Add filter aid to improve the dewaxing rate of filtration.Due to the existing solvent refining unit in most of refineries, therefore this technique is used only to need to increase Add a set of medium pressure hydrogenation treatment facility, just can go out high viscosity index (HVI) base oil from low-quality crude oil production, have and require less investment while yielding quicker results Feature.
In order to preferably improve the product quality of solvent refining-hydrotreating group technology, Exxon company and stone section of China Institute all have employed the hydrogen addition technology of multiple reactors in series.In the RHC technique of Exxon exploitation, it is provided with three reactors, first Individual reactor selects harsher hydroconversion condition, it is therefore an objective to improving the viscosity index (VI) of product, second reactor is to overcome The thermodynamical equilibrium restriction to aromatic hydrogenation, selects the operation temperature lower than first reactor, is beneficial to aromatic hydrogenation, the One, two reactor fillings is all the KF-840 nickel-molybdenum catalyst not having acidity, and the 3rd reactor filling is then hydrogenation activity Strong catalyst, it is therefore an objective to reduce the carcinogen in oil product and improve the light stability of product. thus obtained it is hydrogenated to Oil, after distillation excision light oil, carries out solvent dewaxing to reduce its pour point.This technique in 1999 Exxon-Mobil's Baytown refinery puts into commercial production.
Solvent refining-hydrotreating group technology the RHT of Shi Ke institute of China exploitation.Being provided with two reactors, first anti- Answer that device loads is to have high desulfurization, denitrogenation and the tungsten-Raney nickel RL-1 of hydrogenation open-loop performance.Second reactor filling Be have the saturated performance of high aromatic hydrogenation, do not have acidity catalyst build RJW-2, according to a set of working ability of this technology building Lube oil hydrogenation processing means for 20Mt/a is constructed and put into operation in Jingmen general petrochemical works November calendar year 2001.
But in above-mentioned technique, in desulfurization removing nitric unit, using Ni-Mo or Ni-W catalyst, wherein Ni belongs to noble metal, Price is higher, and secondly the above-mentioned catalyst desulfurizing denitrogenation degree of depth is limited, it is impossible to total sulfur content is removed to below 10ppm.The most such as What provides a kind of hydrorefining basic oil lubricating oil technique, can be effectively by the sulfur in lube base oil in desulfurization removing nitric unit Content controls at below 10ppm, to meet standard, simultaneously can effectively remove nitride therein, is face one of this area A difficult problem.
Summary of the invention
It is an object of the invention to propose a kind of hydrorefining basic oil lubricating oil technique, this technique can will lubricate oil base Total sulfur content in plinth oil is reduced to below 10ppm, to meet lubricating oil standard.Meanwhile, going back of the catalyst that this technique uses The removing ratio making nitride in base oil is more significant.
For reaching this purpose, the present invention by the following technical solutions:
A kind of hydrorefining basic oil lubricating oil technique, described technique includes solvent refining unit, hydrogenation desulfurization and denitrogenation list Unit and hydrofinishing unit.
Described hydrogenation desulfurization and denitrogenation unit uses fixed bed reactors, is filled with hydrogenation catalyst in fixed bed reactors, Described catalyst includes carrier and active component.Described carrier is incorporation hetero atom Co in synthetic bone shelf structure2+KIT-1.Institute State active component for nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc.Described catalyst is also Containing catalyst aid, described catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixture.Described fixed bed reactors anti- The condition is answered to be: reaction temperature is 350-370 DEG C, reaction pressure 9-11MPa, hydrogen to oil volume ratio 300-600, volume space velocity 1.0- 2.5h-1。
In the present invention, not having particular/special requirement for solvent refining unit, it can use existing equipment and technique, this Specific restriction is not done in invention.
Typical but non-limiting solvent refining unit generally comprises extraction and solvent recovery two parts.With furfural treatment it is Example, raw material inversely contacts, in certain temperature (in extraction tower (in the past with packed column, use rotating disc column in the recent period) with furfural As be 60～130 DEG C) with solvent ratio (generally 1～4:1) under the conditions of, be divided into biphase.Undesirable components is present in the extraction of bottom Taking in liquid, in order to both ensure raffinate oil quality, the most do not reduce productivity, extraction tower should keep higher tower top temperature and relatively low tower End temperature (the general temperature difference is 20～50 DEG C).Raw material needs before entering extraction tower to remove air, in order to avoid furfural oxidation.Furfural enters extraction tower Before need drying, in order to avoid reducing its solvability.
Raffinate contains furfural less, use flush distillation and stripping to reclaim furfural；Extract contains furfural more, use Multiple-effect evaporation and stripping reclaim furfural to reduce energy consumption.The heat stability of furfural is poor, thus the heating-up temperature of solvent recovery is not Should be more than 230 DEG C.
The recovery process of aqueous furfural, formulates according to following feature, i.e. the azeotropic mixture steam of furfural and water condenses also After being cooled to uniform temperature, the water-soluble liquid phase containing a small amount of furfural and the furfuryl aldehyde solution phase containing a small amount of water can be divided into.
KIT-1 molecular sieve has one-dimensional channels and crosses each other to form three-dimensional disordered structure, and this structure is conducive to catalysis, absorption During material transmission.Pure silicon mesopore molecular sieve KIT-1 has heat stability more more preferable than MCM-241, HMS and hydrothermally stable Property.The present invention through in numerous mesoporous materials, such as KIT-1, KIT-6, MCM-22, MCM-36, MCM-48, MCM-49, MCM56 etc., carry out contrast test selection, find that only KIT-1 can reach the goal of the invention of the present invention, and other mesoporous materials are all Having such-and-such defect, there is the technical difficulty being difficult to overcome when being applied in the present invention, therefore the present invention selects to use KIT-1 is as carrier basis.
Although pure silicon KIT-1 mesopore molecular sieve hydro-thermal performance is outstanding, but inventor's research is later discovered that, it adds Hetero atom or surface are after chemical modification, and its hydrothermal stability obtains bigger raising.Therefore, it is modified by the present invention, with Increase its catalysis activity.The approach that KIT-1 mesopore molecular sieve is modified is by the present invention: in KIT-1 building-up process, adds Co2+ Saline solution, before KIT-1 framework of molecular sieve structure is formed, by isomorphous substitution by Co2+Replace part backbone element thus embedding Enter in the skeleton of molecular sieve, improve catalysis activity, absorption and the thermodynamic stability of KIT-1 mesopore molecular sieve on the whole Can etc..
Although the method being modified KIT-1 mesopore molecular sieve or approach are a lot, inventor finds, the catalysis of the present invention Agent can only use doping Co2+KIT-1 could realize sulfur content as carrier and control and the balance of loss of octane number, inventor tastes Try to adulterate in KIT-1: Al3+、Fe3+、Zn2+、Ga3+In the ion at generation anionic surface center, find all to realize institute State effect.Exchanged Cu by ion with another modified approach of inventor2+It is supported on KIT-1 inner surfaces of pores to compare, the present invention Isomorphous substitution approach more stable.Although described mechanism is current and unclear, but this has no effect on the enforcement of the present invention, invention People is according to well-known theory and it is experimentally confirmed that there is cooperative effect between itself and the active component of the present invention.
Described Co2+Doping in KIT-1 must control within specific content range, and its doping is with weight Meter, for the 0.56%-0.75% of KIT-1 weight, such as 0.57%, 0.58%, 0.59%, 0.6%, 0.61%, 0.62%, 0.63%, 0.64%, 0.65%, 0.66%, 0.67%, 0.68%, 0.69%, 0.7%, 0.71%, 0.72%, 0.73%, 0.74 etc..
Inventor finds, outside this range, can cause drastically reducing of lubricant base-oil denitrification and desulfurized effect.More Pleasurable, work as Co2+When doping in KIT-1 controls in the range of 0.63%-0.72%, its desulphurizing ability is By force, when drawing with Co2+Doping is transverse axis, during curve chart with target desulfurized effect as the longitudinal axis, and sulfur content in this content range Can control within the scope of extremely low, its desulfurized effect produced, far beyond expection, belongs to unforeseeable technique effect.
The total content of described active component is the 1%-15% of carrier KIT-1 weight, preferably 3-12%, further preferred 5- 10%.Such as, described content can be 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5% etc..
In the present invention, it is particularly limited to active component for nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc Mixed proportion, inventor find, the effect that different mixed proportions reaches is entirely different.Inventor finds, nitrogenizes two molybdenums MO2N, tungsten nitride W2N, molybdenum carbide Mo2The mixed proportion (mol ratio) of C and tungsten carbide wc is 1:(0.4-0.6): (0.28- 0.45): (0.8-1.2), nitridation two molybdenum MO are only controlled2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc exists In the range of Gai, sulfur content in lube base oil can be realized and control at below 10ppm and denitrification ability notable.Namely Saying, four kinds of active components of the present invention are only 1:(0.4-0.6 in mol ratio): (0.28-0.45): time (0.8-1.2), just tool Standby cooperative effect.Outside this molar ratio range, or omit or replace any one component, all can not realize collaborative effect Should.
Preferably, two molybdenum MO are nitrogenized2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc is 1:(0.45- 0.5): (0.35-0.45): (0.8-1.0), more preferably 1:(0.45-0.48): (0.4-0.45): (0.9-1.0), Preferably 1:0.48:0.42:0.95.
An object of the present invention also resides in the promoter providing described catalyst.Catalyst of the present invention also contains Having catalyst aid, described catalyst aid is TiO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate).
Although in hydrofinishing particularly hydrodesulfurization field, had maturation catalyst aid, such as P, F and B etc., its For regulating the character of carrier, weaken interaction strong between metal and carrier, improve the surface texture of catalyst, improve metal Reducibility, promote active component to be reduced to lower valency, to improve the catalytic performance of catalyst.But above-mentioned P, F and B catalysis helps Agent application with the carrier of the present invention with active component time, for high-sulfur component, it promotes the effect of catalytic desulfurization/refined ?.
The present invention passes through in numerous conventional cocatalyst component, and carries out in amount of activated component selecting, compounding, Find eventually to use TiO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate) is obvious to the catalyst facilitation of the present invention, energy Significantly improve its hydrothermal stability, and improve its anti-coking deactivation, thus improve its service life.
Described TiO2、CeO2、V2O5And NbOPO4Between there is no fixing ratio, say, that TiO2、CeO2、V2O5With NbOPO4Each respective content reaches effective dose.Preferably, the TiO that the present invention uses2、CeO2、V2O5And NbOPO4 Respective content is the 1-7% of (respectively) carrier quality, preferably 2-4%.
Although there is no specific proportion requirement between catalyst aid of the present invention, but each auxiliary agent allowing for reaching To the requirement of effective dose, the 1-7% of the content of catalyst aid effect, such as carrier quality i.e. can be played.The present invention is selecting During find, omit or replace one or more in described auxiliary agent, all do not reach the present invention technique effect (improve water Heat stability, reduces coking and improves service life), say, that exist between the catalyst aid of the present invention and specifically coordinate pass System.
It is true that the present invention once attempted the niobium phosphate NbOPO in catalyst aid4Replace with five oxidation two girl Nb2O5, Have found that while in auxiliary agent and have also been introduced Nb, but its technique effect is significantly lower than niobium phosphate NbOPO4, not only hydrothermal stability is slightly for it Difference, its beds coking is relatively rapid, thus causes catalyst duct to block, and beds pressure drop rise is relatively Hurry up.The present invention the most once attempted introducing other phosphate, although but this trial introduces phosphate anion, but equally exist hydro-thermal Stability is the most slightly worse, and its beds coking is relatively rapid, thus causes catalyst duct to block, beds pressure drop Rise relatively fast.
Although present invention introduces catalyst aid have so many advantage, but the present invention should be noted that, introduce catalysis Auxiliary agent is only one of preferred version, even if not introducing this catalyst aid, nor affects on the enforcement of main inventive purpose of the present invention. Not introducing the catalyst aid particularly niobium phosphate of the present invention, it is compared to the scheme of introducing catalyst aid, and its defect is only phase To.This defect i.e. is that it is relative to other prior aries outside the present invention relative to the defect introduced after catalyst aid, Mentioned by the present invention had superiority or new features yet suffer from.This catalyst aid is not to solve technical problem underlying of the present invention Indispensable technological means, its simply further optimization to technical solution of the present invention, solve new technical problem.
The preparation method of described catalyst can take infusion process and other alternative methods, the people in the art of routine The prior art unrestricted choice that member can grasp according to it, the present invention repeats no more.The typical but non-limiting example of the present invention As follows:
Sodium silicate, cetyl trimethylammonium bromide (CTAB), sodium ethylene diamine tetracetate (EDTA) and distilled water are massaged You mix the ratio than 1:0.25:1:60, load with in teflon-lined autoclave pressure, after stirring under 373K Constant temperature 24h, the pH of re-adjustments mixture are 10.5, after constant temperature 4 times, take out product, with distilled water cyclic washing to filtrate PH=7, then under 373K, constant temperature overnight, obtains the KIT-1 with surfactant.KIT-1 with surfactant is existed Roasting 1.5h under 523K, then roasting 6h in air atmosphere under 813K, obtains KIT-1 powder body.By this powder body 0.1mol/L Salpeter solution carry out pickling (control solid-to-liquid ratio is 1:10), under room temperature stir 0.5h, filter, be washed with distilled water to filtrate Dry under pH=7,373K and obtain matrix KIT-1 molecular sieve.
Preferably, the reaction condition of described fixed bed reactors is: reaction temperature is 360-370 DEG C, reaction pressure 10- 10.5MPa, hydrogen to oil volume ratio 400-600, volume space velocity 1.5-2.0h-1。
Preferably, described desulfurization removing nitric technological process includes, mixes from solvent-refined lube base oil with hydrogen After, through optional heat exchanger heat exchange, then after the heating of heated stove, entrance fixed bed reactors carry out hydrogenation desulfurization and denitrogenation, and reaction is produced Thing separates through gas-liquid separation tower.Optionally, gas phase returns and mixes with base oil and hydrogen, and liquid phase enters follow-up hydrofinishing list Unit.
Preferably, described hydrogenation desulfurization and denitrogenation fixed bed reactors include 1-5 beds, further preferred 2-3 Individual beds.
The hydrofinishing unit of the present invention does not the most do specific restriction, its objective is to realize hydrogenation saturated, it is achieved base oil is pacified Improve qualitatively.These techniques are all known, and the application does not do specific restriction.
The hydrogenation desulfurization and denitrogenation technique of the present invention is by choosing specific catalyst, and described catalyst is by mixing hetero atom Co2+KIT-1 as carrier, and choose the nitridation two molybdenum MO of special ratios2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide WC is as active component, and described catalyst is possibly together with catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5And NbOPO4 Mixture so that this catalyst produce cooperative effect, the hydrodesulfurization to lube base oil can control at total sulfur content low In 5ppm, the total nitrogen content in lube base oil is controlled within 10ppm simultaneously.
Detailed description of the invention
The hydrogenation desulfurization and denitrogenation technique of the present invention is illustrated by the present invention by following embodiment.
Embodiment 1
Preparing catalyst by infusion process, carrier is doping Co2+KIT-1, Co2+Doping control in KIT-1 System is at the 0.65% of carrier quality.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc Total content is the 10% of carrier quality, and its mol ratio is 1:0.4:0.3:0.8.
Described Catalyst packing enters fixed bed reactors, and the reaction tube of described reactor is by the stainless steel of internal diameter 50mm Becoming, beds is set to 3 layers, and reaction bed temperature UGU808 type temp controlled meter is measured, and raw material base oil is by Beijing The double plunger micro pump of satellite manufactory manufacture carries continuously, and hydrogen is supplied and use Beijing Sevenstar-HC D07-by gas cylinder 11A/ZM mass-flow gas meter coutroi velocity, loaded catalyst is 2kg.Reacted product is laggard through the cooling of water-bath room temperature Row gas-liquid separation.
Raw materials used for the lube base oil from decompression distillation three lines (be commonly called as subtracting three line).
Raw material first passes through furfural treatment unit, and then the hydrogenation desulfurization and denitrogenation unit of the entrance present invention, controls hydrodesulfurization Denitrification reaction condition is: temperature 360 DEG C, reaction pressure 10MPa, hydrogen to oil volume ratio 500, volume space velocity 2h-1.Subsequently enter hydrogenation Refined unit, hydrofinishing unit uses the catalyst RJW-2 of Beijing Shi Keyuan, and controlling hydrogenation temperature is 280 DEG C.
Testing final product, total sulfur content is reduced to 2ppm, and total alkaline nitrogen content is reduced to 7ppm.
Embodiment 2
Preparing catalyst by infusion process, carrier is doping Co2+KIT-1, Co2+Doping control in KIT-1 System is at the 0.7% of carrier quality.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc Total content is the 10% of carrier quality, and its mol ratio is 1:0.6:0.45): 1.2.
Remaining condition is same as in Example 1.
Testing final product, total sulfur content is reduced to 3ppm, and total alkaline nitrogen content is reduced to 5ppm.
Comparative example 1
The carrier of embodiment 1 is replaced with γ-Al2O3, remaining condition is constant.
Testing final product, total sulfur content is reduced to 33ppm, and total alkaline nitrogen content is reduced to 42ppm.
Comparative example 2
The carrier of embodiment 1 is replaced with unadulterated KIT-1, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 36ppm, and total alkaline nitrogen content is reduced to 45ppm.
Comparative example 3
Co by embodiment 12+Replace with Zn2+, remaining condition is constant.
Testing final product, total sulfur content is reduced to 31ppm, and total alkaline nitrogen content is reduced to 47ppm.
Comparative example 4
By the Co in embodiment 12+Doping in KIT-1 controls at the 0.5% of carrier quality, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 35ppm, and total alkaline nitrogen content is reduced to 51ppm.
Comparative example 5
By the Co in embodiment 12+Doping in KIT-1 controls at the 0.8% of carrier quality, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 32ppm, and total alkaline nitrogen content is reduced to 54ppm.
Embodiment 1 shows with comparative example 1-5, certain content scope that the application uses and certain loads metal ion KIT-1 carrier, when replacing with other known carriers of this area, or carrier is identical but Co2+During doping difference, all reach not To the technique effect of the present invention, the therefore Co of the certain content scope of the present invention2+Doping KIT-1 carrier and other components of catalyst Between possess cooperative effect, described hydrogenation desulfurization and denitrogenation unit creates unforeseeable technique effect.
Comparative example 6
Omit the MO in embodiment 12N, remaining condition is constant.
Testing final product, total sulfur content is reduced to 56ppm, and total alkaline nitrogen content is reduced to 62ppm.
Comparative example 7
Omitting the WC in embodiment 1, remaining condition is constant.
Testing final product, total sulfur content is reduced to 49ppm, and total alkaline nitrogen content is reduced to 58ppm.
Above-described embodiment and comparative example 6-7 explanation, several active component of catalyst of the hydrodesulfurization of the present invention it Between there is specific contact, be omitted or substituted one of which or several, all can not reach the certain effects of the application, it was demonstrated that it produces Give birth to cooperative effect.
Embodiment 3
Containing catalyst aid TiO in catalyst2、CeO2、V2O5And NbOPO4, its content is respectively 1%, 1.5%, 1% and 3%, remaining is same as in Example 1.
Testing final product, after it uses 3 months, beds pressure drop is not any change, and uses compared to same The beds pressure drop of time embodiment 1 reduces 17%.
Comparative example 8
Compared to embodiment 3, by NbOPO therein4Omitting, remaining condition is identical.
Testing final product, after it uses 3 months, beds pressure drop raises, and uses the time real compared to same The beds pressure drop executing example 1 only reduces 6.2%.
Comparative example 9
Compared to embodiment 3, by CeO therein2Omitting, remaining condition is identical.
Testing final product, after it uses 3 months, beds pressure drop raises, and uses the time real compared to same The beds pressure drop executing example 1 only reduces 5.7%.
Embodiment 3 shows with comparative example 8-9, there is conspiracy relation between the catalyst aid of the present invention, when being omitted or substituted When one of them or several component, all can not reach the minimizing coking when present invention adds catalyst aid thus stop catalyst bed The technique effect that lamination falling-rising is high.That is, its catalyst aid demonstrating the present invention can improve the service life of described catalyst, And other catalyst aid effects are not as this specific catalyst aid.
Applicant states, the present invention illustrates the technique of the present invention by above-described embodiment, but the invention is not limited in Above-mentioned technique, does not i.e. mean that the present invention has to rely on above-mentioned detailed catalysts and could implement.Those of skill in the art Member is it will be clearly understood that any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and the interpolation of auxiliary element, tool Body way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.

Claims (7)

1. a hydrorefining basic oil lubricating oil technique, described technique includes solvent refining unit, hydrogenation desulfurization and denitrogenation unit With hydrofinishing unit, it is characterised in that
Described hydrogenation desulfurization and denitrogenation unit uses fixed bed reactors, is filled with hydrogenation catalyst in fixed bed reactors, described Catalyst includes that carrier and active component, described carrier are incorporation hetero atom Co in synthetic bone shelf structure2+KIT-1, described work Property component for nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc, described catalyst possibly together with Catalyst aid, described catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixture, the reaction bar of described fixed bed reactors Part is: reaction temperature is 350-370 DEG C, reaction pressure 9-11MPa, hydrogen to oil volume ratio 300-600, volume space velocity 1.0-2.5h-1。
2. hydrofining technology as claimed in claim 1, it is characterised in that hetero atom Co2+Doping be KIT-1 weight 0.63%-0.72%.
3. hydrofining technology as claimed in claim 1, it is characterised in that the total content of described active component is carrier KIT- The 3-12% of 1 weight, preferably 5-10%.
4. hydrofining technology as claimed in claim 1, it is characterised in that nitrogenize two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc is 1:(0.45-0.5): (0.35-0.45): (0.8-1.0), more preferably 1: (0.45-0.48): (0.4-0.45): (0.9-1.0), most preferably 1:0.48:0.42:0.95.
5. hydrofining technology as claimed in claim 1, it is characterised in that the reaction condition of described fixed bed reactors is: Reaction temperature is 360-370 DEG C, reaction pressure 10-10.5MPa, hydrogen to oil volume ratio 400-600, volume space velocity 1.5-2.0h-1。
6. hydrofining technology as claimed in claim 1, it is characterised in that described fixed bed reactors include 1-5 catalysis Agent bed, preferably includes 2-3 beds.
7. hydrofining technology as claimed in claim 1, it is characterised in that TiO2、CeO2、V2O5And NbOPO4Respective content It is respectively the 1-7%, preferably 2-4% of carrier quality.
CN201610694455.7A 2016-08-18 2016-08-18 A kind of hydrorefining basic oil lubricating oil technique Pending CN106167719A (en)

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