CN106190241A - A kind of waste lubricant oil by hydrogenation regeneration technology - Google Patents

A kind of waste lubricant oil by hydrogenation regeneration technology Download PDF

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Publication number
CN106190241A
CN106190241A CN201610662282.0A CN201610662282A CN106190241A CN 106190241 A CN106190241 A CN 106190241A CN 201610662282 A CN201610662282 A CN 201610662282A CN 106190241 A CN106190241 A CN 106190241A
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fixed bed
hydrogenation
bed reactors
mcm
oil
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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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
    • B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 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
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/0016—Working-up used lubricants to recover useful products ; Cleaning with the use of chemical agents
    • 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
    • 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
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not 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
    • C10G2300/20—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
    • 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)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Dispersion Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a kind of waste lubricating oil base oil hydrogenation regeneration technology, described technique includes pretreatment unit, hydrogenation regeneration unit and separative element, described hydrogenation regeneration unit uses fixed bed reactors, fixed bed reactors are filled with hydrogenation catalyst, described catalyst includes that carrier and active component, described carrier are incorporation hetero atom Cu in synthetic bone shelf structure2+MCM 41, described active component for nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc.The reaction condition of described fixed bed reactors is: reaction temperature is 280 370 DEG C, reaction pressure 3 8MPa, hydrogen to oil volume ratio 40 50, volume space velocity 0.5 2.5h‑1.Reclaimed oil total sulfur content can be controlled less than 5ppm by this technique, controls total nitrogen content therein within 10ppm simultaneously.

Description

A kind of waste lubricant oil by hydrogenation regeneration technology
Technical field
The present invention relates to a kind of process for regeneration of waste lubricating oil, be specifically related to a kind of useless lubrication using special catalyst to carry out Oil hydrogenation regeneration technology.
Background technology
In the epoch of this intense industrialization, the various vehicles and the extensive application of machinery, expedite the emergence of the extensive of lubricating oil Application.Lubricating oil can effectively reduce or remove the phase mutual friction between vehicles mechanical accessory, and it extensively should Minimizing sliding friction field for mechanical fitting, machine tool and other spare parts of engine, industrial equipment and factory.Lubricating oil After used a period of time, the high temperature produced due to work and mechanical shearing, aoxidize and use the foreign body etc. that environment produces, moisten Lubricating oil gradually loses lubricating function, it is necessary to replace with new lubricating oil.The used greasy property that this cyclic process produces The lubricating oil reduced, the most referred to as waste lubricating oil.
China is the second-biggest-in-the-world lubricating oil country of consumption being only second to the U.S., and China's lubricating oil aggregate demand in 2010 is 490- 5100000 tons, it is contemplated that to the year two thousand twenty, lubricating oil aggregate demand is 600-800 ten thousand tons.The annual waste lubricating oil produced is the most big, as Fruit is discarded in environment, can cause serious environmental pollution, it is therefore necessary to waste lubricating oil is carried out reclaiming.
Worldwide, the development of Technology of Used Lube Oil Regeneration substantially experienced by sour soil method → without acid system → hydrogenation The process of method.The technique of main flow is distillation-hydrogenation method at present.
Distillation-hydrogenation method is the most representative with the technique of Puralube (German) limited company.The flow process of this technique As follows:
1) pretreatment, in high temperature and high pressure environment, is sufficiently mixed hot hydrogen with raw oil, then sequentially enters flash distillation-steaming Evaporate knockout tower, make the mink cell focus rich in asphalitine and metal and lubricating oil and light Component seperation.The Colophonium that sub-argument goes out is after treatment Can be used as Colophonium blend component.It is to be exactly one to face hydrogen-deasphalting process that this unit operates it, it is therefore an objective to add the useless lubrication of heat damage Additive component in oil, and additive, asphalitine, metal and other solid impurities are separated from waste lubricating oil, with It is processed further remaining ingredient processing.
2) catalytic hydrogenation.Specially designed antigravity system comprises two reaction under high pressure rooms, the first reative cell (also known as " protection reative cell ") remove the metal failing in pretreatment to completely remove, also function to the effect of preliminary desulfurization simultaneously.Second reaction In room, catalyst is fully contacted with alkene key molecule and the aromatic hydrocarbons key molecule of lubricating oil, makes hydrogenation reaction quickly carry out, rises simultaneously To complete desulfurization removing nitric effect.
3) finished product separates and product processes and reuse.Product is admitted to height-low pressure separator, through high-temperature pressure-reduction and Low-temperature reduced-pressure, at the by-product that the catalytic hydrogenation stage produces, such as chloride and sulfide, is admitted to together with unreacted hydrogen Alkali-water wash system, is neutralized reaction, chloride and sulfide and is removed, and remaining hydrogen is purified and recycles.? The lubricating oil produced in reaction enters stripping-distillation column and carries out fractional distillation, obtains Petroleum, diesel oil and lube cut, at the bottom of tower Residue returns the distillation column freshening of pretreatment stage.
But in above-mentioned technique, in catalytic hydrogenation unit, the catalyst desulfurizing denitrogenation degree of depth of employing is limited, can only be by total sulfur Content is removed to about 100ppm, it is impossible to total sulfur content is reduced to 10ppm even below 5ppm.The most how to provide a kind of useless Lube base oil hydrogenation regeneration technology, can effectively control the sulfur content in lubricating oil at 10ppm in desulfurization removing nitric unit Hereinafter, to meet standard, can effectively remove nitride therein simultaneously, and realize the regeneration of waste lubricating oil, be that this area faces A difficult problem.
Summary of the invention
It is an object of the invention to propose a kind of waste lubricant oil by hydrogenation regeneration technology, this technique can be by waste lubricant oil by hydrogenation Regeneration, and the total sulfur content of reclaimed oil is reduced to below 10ppm, meanwhile, also making of the catalyst that this technique uses In reclaimed oil, the removing ratio of nitride is more significant.
For reaching this purpose, the present invention by the following technical solutions:
A kind of non-lubricated oil hydrogenation regeneration technology, described technique includes pretreatment unit, hydrogenation regeneration unit and separates single Unit.
Described hydrogenation regeneration 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 Cu in synthetic bone shelf structure2+MCM-41.Described work Property component for nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc.Described fixed bed reactors Reaction condition is: reaction temperature is 280-370 DEG C, reaction pressure 3-8MPa, hydrogen to oil volume ratio 40-50, volume space velocity 0.5- 2.5h-1。
In the present invention, not having particular/special requirement for pretreatment unit, it can use existing equipment and technique, such as Flash distillation-separated equipment, to realize the separation of mink cell focus, lubricating oil and lighter hydrocarbons.
Preferably, the pretreatment of the present invention is preferably carried out under hydroconversion condition, to realize Linqing heat treatment-deasphalting mesh , thus by the additive heat resolve in waste lubricating oil.
Pretreated lubricating oil enters hydrofinishing unit.Described hydrofinishing unit uses fixed bed reactors, Gu Being filled with hydrogenation catalyst in fixed bed reactor, described catalyst includes carrier and active component..
MCM-41 is ordered into mesoporous material, and its duct is that six side's ordered arrangement, size are uniform, aperture size can with synthesis time The difference adding directed agents and synthetic parts changes between 1.5～10nm, lattice parameter about 4.5nm, specific pore volume about 1mL/g, MCM-41 uniform pore diameter, has higher specific surface area (1000m2/ g) and big adsorption capacity (0.7mL/g), the most organic The free diffusing of molecule.The present invention through in numerous mesoporous materials, such as MCM-22, MCM-36, MCM-48, MCM-49, MCM56, carries out contrast test selection, finds that only MCM-41 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 MCM-41 is as carrier basis.
The acidity of silica MCM-41 own is the most weak, is directly used as catalyst activity relatively low.Therefore, it is changed by the present invention Property, to increase its catalysis activity.The approach that MCM-41 mesopore molecular sieve is modified is by the present invention: be situated between to the Siliceous MCM-41 of finished product Porous molecular sieve inner surfaces of pores introduces Cu2+, this approach can be exchanged Cu by ion2+It is supported on the inner surface of MCM-41, Thus improve catalysis activity, absorption and the Thermodynamically stable performance etc. of MCM-41 mesopore molecular sieve on the whole.
Although the method being modified MCM-41 mesopore molecular sieve or approach are a lot, inventor finds, the present invention urges Agent can only use doping Cu2+MCM-41 could realize sulfur content control and denitrification effect as carrier, inventor attempts MCM-41 adulterates: Al3+、Fe3+、Zn2+、Ga3+In the ion at generation anionic surface center, discovery all can not realize described Effect.Although described mechanism is current and unclear, but this has no effect on the enforcement of the present invention, and inventor is according to well-known theory and reality Checking is real, there is cooperative effect between itself and the active component of the present invention.
Described Cu2+Doping in MCM-41 must control within specific content range, and its doping is with weight Meter, for the 0.56%-0.75% of MCM-41 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 waste lubricating oil denitrogenation and desulfurized effect.More make us Joyful, work as Cu2+When doping in MCM-41 controls in the range of 0.63%-0.72%, its desulphurizing ability is the strongest, when Draw with Cu2+Doping is transverse axis, and during curve chart with target desulfurized effect as the longitudinal axis, in this content range, sulfur content 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 MCM-41 weight, preferably 3-12%, further preferably 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.
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.
Preferably, the reaction condition of described fixed bed reactors is: reaction temperature is 320-340 DEG C, reaction pressure 4- 6MPa, hydrogen to oil volume ratio 40-50, volume space velocity 1.5-2.0h-1。
Preferably, described hydrofining technology flow process includes, after mixing from the lubricating oil of pretreatment with hydrogen, through optional Heat exchanger heat exchange, then enter fixed bed reactors after the heating of heated stove and be fixed a reactor, product enters point From unit.
Preferably, described hydrogenation desulfurization and denitrogenation fixed bed reactors include 1-5 beds, further preferred 2-3 Individual beds.
The separative element of the present invention does not the most do specific restriction, its objective is to realize hydrogen and reclaims, obtain reclaimed oil and Other by-products.Typical but non-limiting example includes, is introduced into depressurized system from hydrorefined product and reduces pressure, Realize gas-liquid separation.Gas-phase product returns hydrofinishing unit through alkali cleaning, and liquid phase enters stripping-distillation column and carries out fractional distillation, tower top Obtaining Petroleum, side line respectively obtains diesel oil and lubricating oil, heavy oil and residue and discharges from the bottom of tower.This separative element is all known skill Art, the application does not do specific detailed restriction.
Through the lubricating oil that the waste lubricant oil by hydrogenation regeneration technology of the present invention obtains, according to the requirement of technique, can arrange Different side lines obtains the lube base oil of various criterion, and this arranges and can realize by adjusting the side stream temperature of distillation column, The present invention repeats no more.
The waste lubricant oil by hydrogenation regeneration technology of the present invention is by choosing specific catalyst, and described catalyst is miscellaneous by mixing Atom Cu2+MCM-41 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 so that this catalyst produces cooperative effect, and the hydrodesulfurization to reclaimed oil can control Total sulfur content is less than 5ppm, controls the total nitrogen content in reclaimed oil within 10ppm simultaneously.
Detailed description of the invention
The waste lubricant oil by hydrogenation regeneration technology of the present invention is illustrated by the present invention by following embodiment.
Embodiment 1
Preparing catalyst by infusion process, carrier is doping Cu2+MCM-41, Cu2+Doping in MCM-41 Control 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 carrier quality 10%, 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 waste lubricating oil is by north The double plunger micro pump of capital 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 is the useless 5W30 lubricating oil from Great Wall.
Raw material is the most preprocessed, and flash distillation-separated equipment is passed through in this pretreatment, it is achieved mink cell focus, lubricating oil and lighter hydrocarbons Separation.Described pretreatment is carried out under hydroconversion condition, to realize Linqing heat treatment-deasphalting purpose, thus by useless lubrication Additive heat resolve in oil.
Pretreated lubricating oil enters hydrofinishing unit.Described hydrofinishing unit uses fixed bed reactors, Gu Fixed bed reactor is filled with described Hydrobon catalyst.The reaction condition controlling fixed bed reactors is: reaction temperature is 320 DEG C, reaction pressure 4MPa, hydrogen to oil volume ratio 50, volume space velocity 1.5h-1。
The product of hydrogenated reaction enters depressurized system and reduces pressure, it is achieved gas-liquid separation.Gas-phase product returns through alkali cleaning Hydrofinishing unit, liquid phase enters stripping-distillation column and carries out fractional distillation, and tower top obtains Petroleum, and side line respectively obtains diesel oil and profit Lubricating oil, heavy oil and residue are discharged from the bottom of tower.
The lube product that test finally gives, total sulfur content is reduced to 4ppm, and total alkaline nitrogen content is reduced to 8ppm.
Embodiment 2
Preparing catalyst by infusion process, carrier is doping Cu2+MCM-41, Cu2+Doping in MCM-41 Control 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 carrier quality 10%, 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 10ppm.
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 21pm, and total alkaline nitrogen content is reduced to 32ppm.
Comparative example 2
The carrier of embodiment 1 is replaced with unadulterated MCM-41, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 19ppm, and total alkaline nitrogen content is reduced to 36ppm.
Comparative example 3
Cu by embodiment 12+Replace with Zn2+, remaining condition is constant.
Testing final product, total sulfur content is reduced to 23ppm, and total alkaline nitrogen content is reduced to 41ppm.
Comparative example 4
By the Cu in embodiment 12+Doping in MCM-41 controls at the 0.5% of carrier quality, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 37ppm, and total alkaline nitrogen content is reduced to 43ppm.
Comparative example 5
By the Cu in embodiment 12+Doping in MCM-41 controls at the 0.8% of carrier quality, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 47ppm, and total alkaline nitrogen content is reduced to 40ppm.
Embodiment 1 shows with comparative example 1-5, certain content scope that the application uses and certain loads metal ion MCM-41 carrier, when replacing with other known carriers of this area, or carrier is identical but Cu2+During doping difference, all reach Less than the technique effect of the present invention, the therefore Cu of the certain content scope of the present invention2+Doping MCM-41 carrier and catalyst other Possessing cooperative effect between component, 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 67ppm.
Comparative example 7
Omitting the WC in embodiment 1, remaining condition is constant.
Testing final product, total sulfur content is reduced to 65ppm, and total alkaline nitrogen content is reduced to 76ppm.
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.
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 (6)

1. a waste lubricating oil base oil hydrogenation regeneration technology, described technique includes pretreatment unit, hydrogenation regeneration unit and divides From unit, it is characterised in that
Described hydrogenation regeneration unit uses fixed bed reactors, is filled with hydrogenation catalyst, described catalysis in fixed bed reactors Agent includes that carrier and active component, described carrier are incorporation hetero atom Cu in synthetic bone shelf structure2+MCM-41, described activity group It is divided into nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc, the reaction of described fixed bed reactors Condition is: reaction temperature is 280-370 DEG C, reaction pressure 3-8MPa, hydrogen to oil volume ratio 40-50, volume space velocity 0.5-2.5h-1。
It is hydrogenated with regeneration technology the most as claimed in claim 1, it is characterised in that hetero atom Cu2+Doping be MCM-41 weight 0.63%-0.72%.
It is hydrogenated with regeneration technology the most as claimed in claim 1, it is characterised in that the total content of described active component is carrier MCM- The 3-12% of 41 weight, preferably 5-10%.
It is hydrogenated with regeneration technology the most 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.
It is hydrogenated with regeneration technology the most as claimed in claim 1, it is characterised in that the reaction condition of described fixed bed reactors is: Reaction temperature is 320-340 DEG C, reaction pressure 4-6MPa, hydrogen to oil volume ratio 40-50, volume space velocity 1.5-2.0h-1。
It is hydrogenated with regeneration technology the most 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.
CN201610662282.0A 2016-08-12 2016-08-12 A kind of waste lubricant oil by hydrogenation regeneration technology Pending CN106190241A (en)

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