CN106345517A - Waste-lubricating-oil hydrogenation regeneration process - Google Patents
Waste-lubricating-oil hydrogenation regeneration process Download PDFInfo
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- CN106345517A CN106345517A CN201610694582.7A CN201610694582A CN106345517A CN 106345517 A CN106345517 A CN 106345517A CN 201610694582 A CN201610694582 A CN 201610694582A CN 106345517 A CN106345517 A CN 106345517A
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- hydrogenation
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- 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
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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
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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
-
- 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
-
- 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
Abstract
The invention discloses a waste-lubricating-oil hydrogenation regeneration process. The waste-lubricating-oil hydrogenation regeneration process is characterized in that a pretreatment unit, a hydrogenation regeneration unit and a separating unit are involved, the hydrogenation regeneration unit adopts a fixed-bed reactor filled with a hydrogenation catalyst, the catalyst includes a carrier and an activated component, the carrier is of a synthesized skeleton structure doped with KIT-1 of heteroatom of Co<2+>, the activated component is a mixture of MO2N, W2N, Mo2C and WC (wolfram carbide), and the catalyst further includes a catalytic additive which is a mixture of TiO2, CeO2, V2O5 and NbOPO4. The reaction conditions of the fixed-bed reactor are as follows: the reaction temperature is 280-370DEG C, the reaction pressure is 3-8MPa, the hydrogen-to-oil volume ratio is 40-50 and the volume space velocity is 0.5-2.5 hours/<1>. With the process, the total sulfur content of lubricating oil is controlled to be lower than 5ppm, and meanwhile, the total nitrogen content in the lubricating oil is controlled within 10ppm.
Description
Technical field
The present invention relates to a kind of process for regeneration of waste lubricating oil is and in particular to a kind of useless lubrication being carried out using special catalyst
Oil hydrogenation regeneration technology.
Background technology
In the epoch of this intense industrialization, the extensive application of the various vehicles and machinery, expedites 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 the mechanical fitting of engine, industrial equipment and factory, machine tool and other spare parts.Lubricating oil
After used a period of time, foreign body being produced due to high temperature and mechanical shearing, oxidation and the use environment of work generation etc., profit
Lubricating oil gradually loses lubricating function it is necessary to be replaced with new lubricating oil.The used greasy property that this cyclic process produces
The lubricating oil reducing, technically 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 ten thousand tons of 600-800.The annual waste lubricating oil producing is so big, such as
Fruit is discarded in environment, can cause serious environmental pollution it is therefore necessary to carry out reclaiming to waste lubricating oil.
Worldwide, the development of Technology of Used Lube Oil Regeneration substantially experienced the acid system → hydrogenation of sour soil method → no
The process of method.The technique of main flow is distillation-hydrogenation method at present.
Distillation-hydrogenation method is 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, hot hydrogen and raw oil is sufficiently mixed, then sequentially enters flash distillation-steaming
Evaporate knockout tower, make to separate with lubricating oil and light component with the mink cell focus of metal rich in asphalitine.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 it is therefore an objective to heating destroys useless lubrication that this unit operates it
Additive component in oil, and additive, asphalitine, metal and other solid impurities are separated from waste lubricating oil, with
Remaining ingredient is processed further 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 the alkene key molecule of lubricating oil and aromatic hydrocarbons key molecule, so that hydrogenation reaction is quickly carried out, rises simultaneously
To the effect of complete desulfurization removing nitric.
3) finished product separates and product is processed and reuse.Product is admitted to height-low pressure separator, through high-temperature pressure-reduction and
Low-temperature reduced-pressure, the by-product producing in the catalytic hydrogenation stage, such as chloride and sulfide, it is admitted to together with unreacted hydrogen
Alkali-water wash system, is neutralized reaction, and chloride and sulfide are removed, and remaining hydrogen is purified and recycles.?
The lubricating oil producing in reaction enters stripping-distillation column and carries out fractional distillation, obtains Petroleum, diesel oil and lube cut, bottom of towe
Residue returns the distillation column freshening of pretreatment stage.
But in above-mentioned technique, in catalytic hydrogenation unit, the catalyst desulfurizing denitrogenation depth of employing is limited, can only be by total sulfur
Content be removed to 100ppm about it is impossible to total sulfur content is reduced to 10ppm or even below 5ppm.Therefore how to provide a kind of useless
Lube base oil is hydrogenated with regeneration technology, effectively can control the sulfur content in lubricating oil in 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.
Content of the invention
It is an object of the invention to proposing 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 the making of catalyst that this technique adopts
In reclaimed oil, the removing of nitride is than more significant.
For reaching this purpose, the present invention employs 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 adopts fixed bed reactors, is filled with hydrogenation catalyst in fixed bed reactors, described
Catalyst includes carrier and active component.Described carrier is to mix hetero atom co in synthesis framing structure2+Kit-1.Described work
Property group be divided into nitridation two molybdenum mo2N, tungsten nitride w2N, molybdenum carbide mo2C and the mixture of tungsten carbide wc.Described catalyst also contains
Catalyst aid, described catalyst aid is tio2、ceo2、v2o5And nbopo4Mixture.The reaction bar of described fixed bed reactors
Part 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, there is no particular/special requirement for pretreatment unit, it can adopt existing equipment and technique, for example
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 adopts fixed bed reactors, Gu
It is filled with hydrogenation catalyst, described catalyst includes carrier and active component in fixed bed reactor..
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 more preferable heat stability and hydrothermally stable than mcm-241, hms
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., carries out contrast test selection, finds the goal of the invention only having kit-1 can reach the present invention, other mesoporous materials are all
There is such-and-such defect, there is the technical difficulty being difficult to overcome when being applied in the present invention, the therefore present invention selects to use
Kit-1 is as carrier basis.
Although pure silicon kit-1 mesopore molecular sieve hydro-thermal performance is very outstanding, inventor's research is later discovered that, its addition
, after chemical modification, its hydrothermal stability obtains bigger raising for hetero atom or surface.Therefore, the present invention is modified to it, with
Increase its catalysis activity.The present invention approach modified to kit-1 mesopore molecular sieve is: 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 to improve on the whole catalysis activity, absorption and the thermodynamic stability of kit-1 mesopore molecular sieve in the skeleton of molecular sieve
Can etc..
Although the method that kit-1 mesopore molecular sieve is modified or approach are a lot, inventor finds, the catalysis of the present invention
Agent can only be using doping co2+Kit-1 just enable sulfur content as carrier and control and the balance of loss of octane number, inventor tastes
Try doping: al in kit-13+、fe3+、zn2+、ga3+In the ion producing anionic surface center, find not enabling institute
State effect.Modification approach another with inventor passes through ion exchange by cu2+It is supported on kit-1 inner surfaces of pores to compare, the present invention
Isomorphous substitution approach more stable.Although described mechanism is not known at present, this has no effect on the enforcement of the present invention, invention
According to well-known theory and it is experimentally confirmed that there is cooperative effect in it and the active component of the present invention between to people.
Described co2+Must control within specific content range in the doping in kit-1, its doping is with weight
Meter, be 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%th, 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 lead to drastically reducing of waste lubricating oil denitrogenation and desulfurized effect.More make us
Joyful, work as co2+When the doping in kit-1 controls in the range of 0.63%-0.72%, its desulphurizing ability is the strongest, when
Draw with co2+When doping is transverse axis, curve chart with target desulfurized effect as the longitudinal axis, in this content range, sulfur content can control
Within the scope of extremely low, the desulfurized effect that it produces, far beyond expection, belongs to unforeseeable technique effect.
The total content of described active component is the 1%-15%, preferably 3-12%, further preferred 5- of carrier kit-1 weight
10%.For example, described content can for 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%,
7%th, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%,
13.5%th, 14%, 14.5% etc..
In the present invention, being particularly limited to active component is nitridation two molybdenum mo2N, tungsten nitride w2N, molybdenum carbide mo2C and tungsten carbide wc
Mixed proportion, inventor finds, 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), only control nitridation two molybdenum mo2N, tungsten nitride w2N, molybdenum carbide mo2The mol ratio of c and tungsten carbide wc exists
Should in the range of, can realize that in lube base oil, sulfur content controls in below 10ppm and denitrification ability is notable.Namely
Say, four kinds of active components of the present invention are 1:(0.4-0.6 only in mol ratio): (0.28-0.45): when (0.8-1.2), just have
Standby cooperative effect.Outside this molar ratio range, or omit or replace any one component, do not enable 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
There is catalyst aid, described catalyst aid is tio2、ceo2、v2o5And nbopo4The mixture of (niobium phosphate).
Although in hydrofinishing particularly hydrodesulfurization field, there is a catalyst aid of maturation, such as p, f and b etc., its
For adjusting the property of carrier, weaken strong interaction 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 in application with the carrier of the present invention with active component when, for high sulphur 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, compounds,
Find eventually to adopt 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 improving its service life.
Described tio2、ceo2、v2o5And nbopo4Between there is no the ratio of fixation that is to say, that tio2、ceo2、v2o5With
nbopo4Each respective content reaches effective dose.Preferably, the tio that the present invention adopts2、ceo2、v2o5And nbopo4
Respective content is the 1-7% of (respectively) carrier quality, preferably 2-4%.
Although not having specific proportion requirement between catalyst aid of the present invention, each auxiliary agent allows for reaching
To the requirement of effective dose, the content of catalyst aid effect, the 1-7% of such as carrier quality can be played.The present invention is selecting
During find, omitting or replacing one or more of described auxiliary agent, the technique effect all not reaching the present invention (improves water
Heat stability, reduces coking and improves service life) close that is to say, that there is specific cooperation between the catalyst aid of the present invention
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 leading to catalyst duct to block, beds pressure drop rise is relatively
Hurry up.The present invention also once attempted introducing other phosphate, although this attempt introducing phosphate anion, but equally existed hydro-thermal
Stability is relatively slightly worse, and its beds coking is relatively rapid, thus leading to catalyst duct to block, beds pressure drop
Rise relatively fast.
Although present invention introduces catalyst aid has so many advantage, the present invention should be noted that, introduces 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.
Do not introduce the catalyst aid particularly niobium phosphate of the present invention,, compared to the scheme introducing catalyst aid, its defect is only phase for it
To.I.e. this defect be with respect to introduce catalyst aid after defect, its with respect to other prior arts outside the present invention,
Institute mentioned by the present invention is advantageous or new features yet suffer from.This catalyst aid is not to solve technical problem underlying of the present invention
Indispensable technological means, it is optimization further to technical solution of the present invention, solves new technical problem.
The preparation method of described catalyst can take infusion process and other alternative methods of routine, people in the art
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:
By sodium silicate, cetyl trimethylammonium bromide (ctab), sodium ethylene diamine tetracetate (edta) and distillation hydromassage
You mix the ratio than 1:0.25:1:60, load with 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 be 1:10), stir 0.5h under room temperature, 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 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 with hydrogen from the lubricating oil of pretreatment, through optional
Heat exchanger heat exchange, then enter fixed bed reactors after heated stove heat 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 do specific restriction yet, its objective is to realize hydrogen and reclaims, obtain reclaimed oil and
Other by-products.Typical but non-limiting example includes, and is introduced into depressurized system from hydrorefined product and is reduced 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
Obtain Petroleum, side line respectively obtains diesel oil and lubricating oil, heavy oil and residue are discharged from bottom of towe.This separative element is all known skill
Art, the application does not do specific detailed restriction.
The lubricating oil obtaining through the waste lubricant oil by hydrogenation regeneration technology of the present invention, according to the requirement of technique, can be arranged
Different side lines obtains the lube base oil of various criterion, and this setting can be realized 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 passed through to choose specific catalyst, and it is miscellaneous that described catalyst passes through incorporation
Atom co2+Kit-1 as carrier, and the nitridation two molybdenum mo choosing special ratios2N, tungsten nitride w2N, molybdenum carbide mo2C and carbon
Change tungsten wc as active component, described catalyst also contains catalyst aid, described catalyst aid is tio2、ceo2、v2o5With
nbopo4Mixture so that this catalyst produces cooperative effect, the hydrodesulfurization of reclaimed oil can be controlled and contains in total sulfur
Amount is less than 5ppm, the total nitrogen content in reclaimed oil is controlled within 10ppm simultaneously.
Specific embodiment
The present invention is illustrated to the waste lubricant oil by hydrogenation regeneration technology of the present invention by following embodiments.
Embodiment 1
Catalyst is prepared by infusion process, carrier is doping co2+Kit-1, co2+Doping control in kit-1
Make the 0.65% of carrier quality.Described active component nitrogenizes two molybdenum mo2N, tungsten nitride w2N, molybdenum carbide mo2C's 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 is entered fixed bed reactors, the reaction tube of described reactor is by the stainless steel of internal diameter 50mm
Become, beds are set to 3 layers, reaction bed temperature is measured with ugu808 type temp controlled meter, and raw material waste lubricating oil is by north
The double plunger micro pump continuous conveying that capital satellite manufactory manufactures, hydrogen is supplied by gas cylinder and uses Beijing Sevenstar-HC d07-
11a/zm gas mass flow gauge coutroi velocity, loaded catalyst is 2kg.Reacted product cools down laggard through water-bath room temperature
Row gas-liquid separation.
Raw materials used is useless 5w30 lubricating oil from Great Wall.
Raw material is first preprocessed, and flash distillation-separated equipment is passed through in this pretreatment, realizes 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 adopts fixed bed reactors, Gu
It is filled with described Hydrobon catalyst in fixed bed reactor.The reaction condition of control 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 is reduced pressure, and realizes 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 bottom of towe.
Test the lube product finally giving, total sulfur content is reduced to 3ppm, and total alkaline nitrogen content is reduced to 7ppm.
Embodiment 2
Catalyst is prepared by infusion process, carrier is doping co2+Kit-1, co2+Doping control in kit-1
Make the 0.7% of carrier quality.Described active component nitrogenizes two molybdenum mo2N, tungsten nitride w2N, molybdenum carbide mo2C's 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 Example 1.
Test final product, total sulfur content is reduced to 3ppm, and total alkaline nitrogen content is reduced to 9ppm.
Comparative example 1
The carrier of embodiment 1 is replaced with γ-al2o3, remaining condition is constant.
Test final product, total sulfur content is reduced to 41pm, and total alkaline nitrogen content is reduced to 57ppm.
Comparative example 2
The carrier of embodiment 1 is replaced with unadulterated kit-1, remaining condition is constant.
Test final product, total sulfur content is reduced to 37ppm, and total alkaline nitrogen content is reduced to 56ppm.
Comparative example 3
Co by embodiment 12+Replace with zn2+, remaining condition is constant.
Test final product, total sulfur content is reduced to 37ppm, and total alkaline nitrogen content is reduced to 54ppm.
Comparative example 4
By the co in embodiment 12+Doping in kit-1 controls the 0.5% of carrier quality, and remaining condition is constant.
Test final product, total sulfur content is reduced to 42ppm, and total alkaline nitrogen content is reduced to 57ppm.
Comparative example 5
By the co in embodiment 12+Doping in kit-1 controls the 0.8% of carrier quality, and remaining condition is constant.
Test final product, total sulfur content is reduced to 39ppm, and total alkaline nitrogen content is reduced to 55ppm.
Embodiment 1 and comparative example 1-5 show, certain content scope and certain loads metal ions that the application adopts
Kit-1 carrier, when replacing with other known carriers of this area, or carrier is identical but co2+When doping is different, 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 catalyst other components
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.
Test final product, total sulfur content is reduced to 47ppm, and total alkaline nitrogen content is reduced to 60ppm.
Comparative example 7
Omit the wc in embodiment 1, remaining condition is constant.
Test final product, total sulfur content is reduced to 49ppm, and total alkaline nitrogen content is reduced to 58ppm.
Above-described embodiment and the explanation of comparative example 6-7, several activearm of catalyst of the hydrodesulfurization of the present invention divides it
Between exist 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 its product
Give birth to cooperative effect.
Embodiment 3
Catalyst aid tio is contained in catalyst2、ceo2、v2o5And nbopo4, its content respectively 1%, 1.5%, 1% and
3%, remaining is same as Example 1.
Test final product, after it uses 3 months, beds pressure drop is not any change, use compared to same
The beds pressure drop of time embodiment 1 reduces 12%.
Comparative example 8
Compared to embodiment 3, by nbopo therein4Omit, remaining condition is identical.
Test final product, after it uses 3 months, beds pressure drop raises, real compared to same use time
The beds pressure drop applying example 1 only reduces 3.3%.
Comparative example 9
Compared to embodiment 3, by ceo therein2Omit, remaining condition is identical.
Test final product, after it uses 3 months, beds pressure drop raises, real compared to same use time
The beds pressure drop applying example 1 only reduces 3.7%.
Embodiment 3 and comparative example 8-9 show, there is conspiracy relation between the catalyst aid of the present invention, when being omitted or substituted
One of or several groups of timesharing, all can not reach the present invention and add minimizing coking during catalyst aid thus stoping catalyst bed
The high technique effect of lamination falling-rising.That is, it demonstrates the service life that the catalyst aid of the present invention can improve described catalyst,
And other catalyst aid effects are not so good 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, that is, do not 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, the equivalence replacement to each raw material of product of the present invention 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 kind of waste lubricating oil base oil is hydrogenated with regeneration technology, and described technique includes pretreatment unit, hydrogenation regeneration unit and divides
From unit it is characterised in that
Described hydrogenation regeneration unit adopts fixed bed reactors, is filled with hydrogenation catalyst, described catalysis in fixed bed reactors
Agent includes carrier and active component, and described carrier is to mix hetero atom co in synthesis framing structure2+Kit-1, described activearm
It is divided into nitridation two molybdenum mo2N, tungsten nitride w2N, molybdenum carbide mo2C and the mixture of tungsten carbide wc, described catalyst also contains catalysis
Auxiliary agent, described catalyst aid is tio2、ceo2、v2o5And nbopo4Mixture, 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.
2. hydrogenation regeneration technology as claimed in claim 1 is it is characterised in that hetero atom co2+Doping be kit-1 weight
0.63%-0.72%.
3. hydrogenation regeneration technology as claimed in claim 1 is 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. hydrogenation regeneration technology as claimed in claim 1 is 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. hydrogenation regeneration technology as claimed in claim 1 is 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.
6. hydrogenation regeneration technology as claimed in claim 1 is it is characterised in that described fixed bed reactors include 1-5 catalysis
Agent bed, preferably includes 2-3 beds.
7. hydrogenation regeneration technology as claimed in claim 1 is it is characterised in that tio2、ceo2、v2o5And nbopo4Respective content
It is respectively the 1-7%, preferably 2-4% of carrier quality.
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