CN106433776A - Hydrogenation regeneration process of waste lubricating oil - Google Patents
Hydrogenation regeneration process of waste lubricating oil Download PDFInfo
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- CN106433776A CN106433776A CN201610879648.XA CN201610879648A CN106433776A CN 106433776 A CN106433776 A CN 106433776A CN 201610879648 A CN201610879648 A CN 201610879648A CN 106433776 A CN106433776 A CN 106433776A
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- Prior art keywords
- hydrogenation
- catalyst
- lubricating oil
- fixed bed
- hydrogenation regeneration
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Classifications
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
-
- 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
- B01J29/80—Mixtures of different zeolites
-
- 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
Abstract
The invention discloses a hydrogenation regeneration process for base oil of waste lubricating oil. The process comprises a pretreatment unit, a hydrogenation regeneration unit and a separation unit, wherein the hydrogenation regeneration unit uses a fixed bed reactor, a hydrogenation catalyst is filled in the fixed bed reactor, and comprises a carrier and an active component, the carrier is a compound or mixture of MSU-G, SBA-15 and HMS, and the active component is a mixture of MO2N, W2N, Mo2C and WC. The catalyst further comprises a catalytic promoter, the catalytic promoter is a mixture of Cr2O3, ZrO2, CeO2, V2O5 and NbOPO4. The reaction conditions of the fixed bed reactor are that the reaction temperature is 280 to 370 DEG C, the reaction pressure is 3 to 8MPa, the volume ratio of hydrogen to oil is 40 to 50, and the volume space velocity is 0.5 to 2.5h <-1>. By adopting the hydrogenation regeneration process of the waste lubricating oil, the total sulfur content of regenerated lubricating oil is controlled to be less than 5ppm, furthermore, the total nitrogen content in the regenerated lubricating oil is controlled within 10ppm.
Description
Technical field
The present invention relates to a kind of process for regeneration of waste lubricating oil, and in particular to a kind of useless lubrication for 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 which 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 that the high temperature for producing due to working and mechanical shearing, oxidation and use environment are produced etc., profit
Lubricating oil gradually loses lubricating function, it is necessary to replaced with new lubricating oil.The used greasy property that this cyclic process is produced
The lubricating oil of reduction, technical referred to as waste lubricating oil.
China is the second-biggest-in-the-world lubricating oil country of consumption for 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 for 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 (Germany) limited company.The flow process of the 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
Knockout tower is evaporated, makes 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.The unit operates which to be exactly one to face hydrogen-deasphalting process, it is therefore an objective to which heating destroys useless lubrication
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 include two reaction under high pressure rooms, the first reative cell (also known as
" protection reative cell ") metal for failing to completely remove in pretreatment is removed, while also functioning to the effect of preliminary desulfurization.Second reaction
In room, the alkene key molecule of catalyst and lubricating oil and aromatic hydrocarbons key molecule are fully contacted, and so that hydrogenation reaction is quickly carried out, while rising
Act on to complete desulfurization removing nitric.
3) finished product is separated and product is processed and reuse.Product is admitted to height-low pressure separator, through high-temperature pressure-reduction and
Low-temperature reduced-pressure, in the by-product that the catalytic hydrogenation stage produces, such as chloride and sulfide, and unreacted hydrogen is admitted to together
Alkali-water wash system, is neutralized reaction, and chloride and sulfide are removed, and remaining hydrogen is purified and recycles.?
The lubricating oil for 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 is removed to 100ppm or so, it is impossible to which 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, while nitride therein effectively can be removed, and the regeneration of waste lubricating oil is realized, is 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, the 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 causing of the catalyst that the technique is adopted
In reclaimed oil, the removing of nitride is than more significant.
For reaching this purpose, the present invention is employed the following technical solutions：
A kind of non-lubricated oil hydrogenation regeneration technology, the technique includes pretreatment unit, hydrogenation regeneration unit and separates single
Unit.
The hydrogenation regeneration unit adopts fixed bed reactors, is filled with hydrogenation catalyst in fixed bed reactors, described
Catalyst includes carrier and active component.The carrier is complex or the mixture of MSU-G, SBA-15 and HMS.The activity
Group is divided into two molybdenum MO of nitridation2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc.Described catalyst also contains urges
Change auxiliary agent, the catalyst aid is Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Mixture.The fixed bed reactors anti-
The condition is answered to be：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, which 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
, so as to by the additive heat resolve in waste lubricating oil.
Pretreated lubricating oil enters hydrofinishing unit.The hydrofinishing unit adopts fixed bed reactors, Gu
Hydrogenation catalyst is filled with fixed bed reactor, the catalyst includes carrier and active component..
An object of the present invention is that, provides the compound to show collaboration effect of a kind of 3 kinds different mesopore molecular sieves
Should be with special catalytic performance, in terms of the cooperative effect shows desulfuration purification, and special catalytic performance is then to show right
In the raising of the service life and catalysis activity of catalyst.
In catalyst field, according to the definition of IUPAC (IUPAC), title of the aperture less than 2nm
For micropore；Referred to as macropore of the aperture more than 50nm；Aperture is 2 to referred to as mesoporous (or the claiming mesopore) between 50nm.Mesoporous material
It is a kind of new material with huge specific surface area and three-dimensional open-framework of aperture between micropore and macropore, it has
The excellent specific property that other porous materials do not have：Pore passage structure with high-sequential；The single distribution in aperture, and aperture size
Can change in relative broad range；Mesoporous various shapes, hole wall composition and property controllable；Height can be obtained by optimum synthesis condition
Heat stability and hydrothermal stability.
But in present applications ' the tail must be taken, the mesoporous material is all single use, such as MCM system when for catalytic field
Row, such as MCM-22, MCM-36, MCM-41, MCM-48, MCM-49, MCM56, such as MSU series, such as MSU-1, MSU-2, MSU-
4th, MSU-X, MSU-G, MSU-S, MSU-J etc., and SBA series, such as SBA-1, SBA-2, SBA-3, SBA-6, SBA-7, SBA-
8th, SBA-11, SBA-15, SBA-16 etc., and other mesoporous series etc..
Compound, such as Y/SBA-15, Y/SAPO-5 etc. of two kinds of carriers of a few studies literature research, majority be to be situated between
Based on hole-mesoporous-microporous composite molecular sieve and micropore-mesoporous-microporous composite molecular sieve.Adopt the compound with performance of 3 kinds of different mesopore molecular sieves
Go out the research of cooperative effect and special catalytic performance, have not yet to see report.
The catalyst carrier of the present invention is the complex of MSU-G, SBA-15 and HMS or mixture.The complex or mixed
In compound, the weight ratio of MSU-G, SBA-15 and HMS is 1:(0.8-1.2):(0.4-0.7), preferably 1:(1-1.15):
(0.5-0.7).
MSU-G, SBA-15 and HMS mesopore molecular sieve that the present invention is adopted is all the existing molecular sieve of catalytic field, and which is
Through obtaining widely studied and application in catalytic field.
MSU-G is a kind of mesopore molecular sieve with vesicle structure shape particle shape and layered framework structure, and which has height
Degree skeleton crosslinking and relatively thick skeleton wall and with superpower heat stability and hydrothermal stability, its skeleton hole with vertical
It is cross-linked with each other in layer and parallel to the hole of layer, diffusion path is very short because its vesicle shell is thick.The vesicle shape particle of MSU-G molecular sieve
Form facilitates reagent to enter the catalytic center of layered framework, and its catalysis activity is very high.
SBA-15 belongs to one kind of mesopore molecular sieve, with two-dimentional six sides through-hole structure, with P3mm space group.In XRD
In diffracting spectrum, main peak near about 1 °, is (10) crystal face peak.Secondary strong peak is followed successively by (11) peak and (20) peak.Other peaks are relatively
Weak, it is difficult to observe.Additionally, the silicon dioxide on SBA-15 skeleton is generally amorphous state, observe not in Radix Rumiciss XRD diffraction
To obvious diffraction maximum.SBA-15 has a larger aperture (maximum is up to 30nm), thicker hole wall (wall thickness is up to 6.4nm), because
And there is preferable hydrothermal stability.
Hexagonal mesoporous silicon HMS has long-range order and the relatively unordered hexagonal mesoporous duct of short distance, and its hole wall compares HCM41S
Type mesoporous material is thicker, thus hydrothermal stability is more preferable, while the relatively unordered organizational structure of short distance and aperture modulation scope are more
Greatly, make HMS material have higher molecular transport efficiency and absorption property, be suitable in the activity as bulky molecular catalysis reaction
The heart.
The present invention carries out being combined pairing from each mesoporous material, screens through extensive, filters out MSU-G, SBA-15
Compound or mixing with HMS.Inventor has found, in numerous complex/mixture, only MSU-G, SBA-15 and HMS tri-
Person compound or mix, could realize the collaboration lifting of hydrofinishing effect, and enable to catalysis activity and do not reduce for a long time, make
Can be greatly increased with the life-span.In other words, the specific compound or mixing of only MSU-G, SBA-15 and HMS three of the present invention,
Just while solving collaboration and two technical problems of service life.Other coordinate, or not possessing synergism, or using the longevity
Life is shorter.
The complex, can adopt being simply mixed for MSU-G, SBA-15 and HMS three, it would however also be possible to employ be combined two-by-two
Mixing afterwards, such as MSU-G/SBA-15 complex, the mixing of MSU-G/HMS and SBA-15/HMS complex.Described being combined can
To be prepared using known electrostatic matching method, ion exchange, two step crystallization methods etc..These mesopore molecular sieves are combined with which
The preparation method of thing is the known method of catalyst field, and the present invention is no longer repeated with regard to which.
In the present invention, active component is particularly limited to for two molybdenum MO of nitridation2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Mixed proportion, inventor has found, the effect that different mixed proportions reaches is entirely different.Inventor has found, 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 two molybdenum MO of control nitridation2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc exists
Should in the range of, sulfur content control can be realized in lube base oil in below 10ppm and denitrification ability is notable.Namely
Say, four kinds of active components of the present invention are 1 only in mol ratio:(0.4-0.6):(0.28-0.45):(0.8-1.2), when, just have
Standby cooperative effect.Outside the molar ratio range, or omit or any one component is replaced, can not all realize collaboration 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), most
It is preferred that 1:0.48:0.42:0.95.
The total content of the active component is the 1%-15%, preferably 3-12%, further preferred 5-10% of vehicle weight.
For example, the content can be 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%,
7.5%th, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%,
14%th, 14.5% etc..
An object of the present invention also resides in the promoter for providing the catalyst.Catalyst of the present invention also contains
There is catalyst aid, the catalyst aid is Cr2O3、ZrO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate).
Although hydrofinishing be particularly hydrodesulfurization field, had maturation catalyst aid, such as P, F and B etc., its
For the property of carrier is adjusted, 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 is helped
Agent in application with the carrier of the present invention with active component when, for high sulphur component, which promotes the effect of catalytic desulfurization/refined
?.
The present invention is passed through in numerous conventional cocatalyst component, and is carried out in amount of activated component selecting, compounded, most
Find eventually to adopt Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Catalyst facilitation of the mixture of (niobium phosphate) to the present invention
Substantially, its hydrothermal stability can be significantly improved, and its anti-coking deactivation is improved, so as to improve its service life.
The Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Between do not have fixation ratio, that is to say, that Cr2O3、ZrO2、
CeO2、V2O5And NbOPO4Each respective content reaches effective dose.Preferably, the Cr that the present invention is adopted2O3、ZrO2、
CeO2、V2O5And NbOPO4Respective content is the 1-7% of (respectively) carrier quality, preferably 2-4%.
Although without specific proportion requirement between catalyst aid of the present invention, but each auxiliary agent allows for reaching
To the requirement of effective dose, i.e., can play the content of catalyst aid effect, the 1-7% of such as carrier quality.The present invention is being selected
During find, omit or replace one or more in the auxiliary agent, all do not reach the present invention technique effect (improve water
Heat stability, reduces coking and improves service life), that is to say, that there is specific cooperation between the catalyst aid of the present invention and close
System.
It is true that the present invention was once attempted the niobium phosphate NbOPO in catalyst aid4Replace with five oxidations, two girl Nb2O5,
Have found that while in auxiliary agent and Nb is have also been introduced, but its technique effect is significantly lower than niobium phosphate NbOPO4, not only hydrothermal stability is slightly for which
Difference, its beds coking is relatively rapid, and so as to cause catalyst duct to block, beds pressure drop rise is relatively
Hurry up.The present invention also once attempts introducing other phosphate, but this trial although introduces phosphate anion, but equally exists hydro-thermal
Stability is relatively slightly worse, and its beds coking is relatively rapid, so as to cause catalyst duct to block, beds pressure drop
Rise relatively fast.
Although present invention introduces catalyst aid has 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 the catalyst aid, nor affects on the enforcement of main inventive purpose of the present invention.
The catalyst aid for not introducing the present invention is particularly niobium phosphate, and which is compared to the scheme for introducing catalyst aid, and its defect is only phase
To.I.e. the defect be with respect to introduce catalyst aid after defect, its with respect to other prior arts outside the present invention,
Advantageous or new features mentioned by the present invention are yet suffered from.The catalyst aid is not to solve technical problem underlying of the present invention
Indispensable technological means, which is optimization further to technical solution of the present invention, solves new technical problem.
The preparation method of the catalyst can take conventional infusion process and other alternative methods, people in the art
The prior art unrestricted choice that member can be grasped according to which, the present invention is repeated no more.
Preferably, the reaction condition of the 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, the 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 is entered point
From unit.
Preferably, the 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 recovery, obtain reclaimed oil and
Other by-products.Typical but non-limiting example includes, 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
Petroleum is obtained, side line respectively obtains diesel oil and lubricating oil, heavy oil and residue are discharged from bottom of towe.The 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 is obtained, according to the requirement of technique, can arrange
Different side lines obtains the lube base oil of various criterion, and the setting can be realized by adjusting the side stream temperature of distillation column,
The present invention is repeated no more.
The waste lubricant oil by hydrogenation regeneration technology of the present invention is by choosing specific catalyst, and the catalyst is special by choosing
MSU-G, SBA-15 and HMS complex/mixture of certainty ratio is used as carrier, and two molybdenum of nitridation for choosing special ratios
MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc are used as active component, and described catalyst also contains catalyst aid, institute
Catalyst aid is stated for Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Mixture so that the catalyst produces cooperative effect, to again
The hydrodesulfurization of raw lubricating oil can control in total sulfur content less than 5ppm, while existing to the total nitrogen content control in reclaimed oil
Within 10ppm.
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 the mixture of MSU-G, SBA-15 and HMS, and mixed proportion is 1:
1.1:0.5.The active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2The total content of C and tungsten carbide wc is carrier
The 10% of quality, its mol ratio is 1:0.4:0.3:0.8.
The Catalyst packing is entered fixed bed reactors, the reaction tube of the 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 of capital satellite manufactory manufacture, 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 the pretreatment passes through flash distillation-separated equipment, realizes mink cell focus, lubricating oil and lighter hydrocarbons
Separation.The pretreatment is carried out under hydroconversion condition, to realize Linqing heat treatment-deasphalting purpose, so as to by useless lubrication
Additive heat resolve in oil.
Pretreated lubricating oil enters hydrofinishing unit.The hydrofinishing unit adopts fixed bed reactors, Gu
The Hydrobon catalyst is filled with fixed bed reactor.Control fixed bed reactors reaction condition be：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 is returned 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.
The lube product that test finally gives, total sulfur content is reduced to 2ppm, and total alkaline nitrogen content is reduced to 6ppm.
Embodiment 2
Catalyst is prepared by infusion process, carrier is MSU-G/SBA-15 complex, MSU-G/HMS and SBA-15/
The ratio of the mixing of HMS complex, wherein MSU-G, SBA-15 and HMS is same as Example 1.The active component nitrogenizes two molybdenums
MO2N, tungsten nitride W2N, molybdenum carbide Mo2The total content of C and tungsten carbide wc 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.
The final product of test, total sulfur content is reduced to 3ppm, and total alkaline nitrogen content is reduced to 7ppm.
Comparative example 1
The carrier of embodiment 1 is replaced with MSU-G, remaining condition is constant.
The final product of test, total sulfur content is reduced to 32pm, and total alkaline nitrogen content is reduced to 41ppm.
Comparative example 2
The carrier of embodiment 1 is replaced with SBA-15, remaining condition is constant.
The final product of test, total sulfur content is reduced to 31ppm, and total alkaline nitrogen content is reduced to 27ppm.
Comparative example 3
The carrier of embodiment 1 is replaced with HMS, remaining condition is constant.
The final product of test, total sulfur content is reduced to 28ppm, and total alkaline nitrogen content is reduced to 32ppm.
Comparative example 4
Carrier in embodiment 1 is replaced with MSU-G/SBA-15 complex, remaining condition is constant.
The final product of test, total sulfur content is reduced to 27ppm, and total alkaline nitrogen content is reduced to 40ppm.
Comparative example 5
Carrier in embodiment 1 is replaced with SBA-15/HMS complex, remaining condition is constant.
The final product of test, total sulfur content is reduced to 32ppm, and total alkaline nitrogen content is reduced to 37ppm.
Comparative example 6
Carrier in embodiment 1 is replaced with MSU-G/HMS complex, remaining condition is constant.
The final product of test, total sulfur content is reduced to 29ppm, and total alkaline nitrogen content is reduced to 32ppm.
Embodiment 1 is shown with comparative example 1-6, and the present invention is using MSU-G, SBA-15 and HMS complex/mixed of special ratios
Compound when single carrier or complex carrier two-by-two is replaced with, does not all reach the technique effect of the present invention as carrier, therefore originally
MSU-G, SBA-15 and HMS complex/mixture of the special ratios of invention has as between carrier and catalyst other components
Standby cooperative effect, the hydrogenation desulfurization and denitrogenation unit generates unforeseeable technique effect.
Comparative example 7
Omit the MO in embodiment 12N, remaining condition is constant.
The final product of test, total sulfur content is reduced to 42ppm, and total alkaline nitrogen content is reduced to 47ppm.
Comparative example 8
The WC in embodiment 1 is omitted, remaining condition is constant.
The final product of test, total sulfur content is reduced to 48ppm, and total alkaline nitrogen content is reduced to 32ppm.
Above-described embodiment and the explanation of comparative example 7-8, several activearms of the catalyst of the hydrodesulfurization of the present invention divide it
Between exist specific contact, be omitted or substituted one of which or several, can not all reach the certain effects of the application, it was demonstrated that its product
Cooperative effect is given birth to.
Embodiment 3
Contain catalyst aid Cr in catalyst2O3、ZrO2、CeO2、V2O5And NbOPO4, its content be respectively 1%, 1.5%,
2%th, 1% and 3%, remaining is same as Example 1.
The final product of test, after which uses 3 months, beds pressure drop is not any change, and uses compared to same
The beds pressure drop of time embodiment 1 reduces 16.3%.
Comparative example 9
Compared to embodiment 3, by NbOPO therein4Omit, remaining condition is identical.
The final product of test, after which uses 3 months, beds pressure drop is raised, compared to same use time reality
The beds pressure drop for applying example 1 only reduces 6.2%.
Comparative example 10
Compared to embodiment 3, by CeO therein2Omit, remaining condition is identical.
The final product of test, after which uses 3 months, beds pressure drop is raised, compared to same use time reality
The beds pressure drop for applying example 1 only reduces 7.8%.
Embodiment 3 is shown with comparative example 9-10, there is conspiracy relation between the catalyst aid of the present invention, when being omitted or substituted
One of them or several groups of timesharing, can not all reach the present invention and add minimizing coking during catalyst aid so as to prevent catalyst bed
The elevated technique effect of lamination drop.That is, its catalyst aid for demonstrating the present invention can improve the service life of the catalyst,
And other catalyst aid effects are not so good as the 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 interpolation, the tool of auxiliary element
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 the technique includes pretreatment unit, hydrogenation regeneration unit and divides
From unit, it is characterised in that
The hydrogenation regeneration unit adopts fixed bed reactors, is filled with hydrogenation catalyst, the catalysis in fixed bed reactors
Agent includes carrier and active component, and the carrier is complex or the mixture of MSU-G, SBA-15 and HMS；The active component
For nitrogenizing two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc, described catalyst is also helped containing catalysis
Agent, the catalyst aid is Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Mixture, the reaction bar of the 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.
2. hydrogenation regeneration technology as claimed in claim 1, it is characterised in that the weight ratio of MSU-G, SBA-15 and HMS be:
(0.8-1.2):(0.4-0.7), preferably 1:(1-1.15):(0.5-0.7).
3. hydrogenation regeneration technology as claimed in claim 1, it is characterised in that the total content of the active component be
3-12%, preferably 5-10%.
4. hydrogenation regeneration technology as claimed in claim 1, it is characterised in that two molybdenum MO of nitridation2N, 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, it is characterised in that the reaction condition of the 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, it is characterised in that the fixed bed reactors include 1-5 catalysis
Agent bed, preferably includes 2-3 beds.
7. hydrogenation regeneration technology as claimed in claim 1, it is characterised in that Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Each
Content be respectively carrier quality 1-7%, preferably 2-4%.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110616082A (en) * | 2018-06-19 | 2019-12-27 | 云南师范大学 | Solar cell powered system for producing hydrogen by electrolyzing seawater and adding waste marine engine oil |
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