CN106381212A - Hydrogenation and regeneration process for waste lubricating oil - Google Patents
Hydrogenation and regeneration process for waste lubricating oil Download PDFInfo
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- CN106381212A CN106381212A CN201610659466.1A CN201610659466A CN106381212A CN 106381212 A CN106381212 A CN 106381212A CN 201610659466 A CN201610659466 A CN 201610659466A CN 106381212 A CN106381212 A CN 106381212A
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- hydrogenation
- fixed bed
- lubricating oil
- sba
- oil
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-
- 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
- C10M175/0025—Working-up used lubricants to recover useful products ; Cleaning by thermal processes
- C10M175/0041—Working-up used lubricants to recover useful products ; Cleaning by thermal processes by hydrogenation processes
-
- 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
- B01J29/03—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
-
- 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
-
- 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
- C10M175/0083—Lubricating greases
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
-
- 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 hydrogenation and regeneration process for waste lubricant base oil. The process uses a pretreatment unit, a hydrogenation and regeneration unit and a separation unit, wherein the hydrogenation and regeneration unit employs a fixed bed reactor which is filled with a hydrogenation catalyst; the hydrogenation catalyst 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 dimolybdenum nitride (Mo2N), tungsten nitride (W2N), molybdenum carbide (Mo2C) and tungsten carbide (WC). The reaction conditions of the fixed bed reactor are that reaction temperature is 280 to 370 DEG C; reaction pressure is 3 to 8 MPa; a hydrogen-oil volume ratio is 40 to 50; and volume space velocity is 0.5 to 2.5/h. The process enables the total sulfur content of regenerated lubricating oil to be lower than 5 ppm and the total nitrogen content of the regenerated lubricating oil to be within 10 ppm.
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 complex or the mixture of MSU-G, SBA-15 and HMS.Described activity
Group is divided into nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc.Described 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, 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..
An object of the present invention is that, provides the compound of a kind of 3 kinds different mesopore molecular sieves to work in coordination with effect to show
Should be with special catalytic performance, described cooperative effect shows desulfuration purification aspect, and special catalytic performance is then to show right
In the raising of the service life of catalyst and catalysis activity.
In catalyst field, according to the definition of IUPAC (IUPAC), aperture is less than the title of 2nm
For micropore；Aperture is more than the referred to as macropore of 50nm；Aperture referred to as mesoporous (or claiming mesopore) between 2 to 50nm.Mesoporous material
It is a kind of new material with huge specific surface area and three-dimensional open-framework between micropore and macropore for aperture, it has
The excellent specific property that other porous materials do not have：There is the pore passage structure of 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, described mesoporous material, when for catalytic field, is all single use, such as MCM system
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 is to be situated between
Based on hole-mesoporous-microporous composite molecular sieve and micropore-mesoporous-microporous composite molecular sieve.Adopt being combined to show of 3 kinds of different mesopore molecular sieves
Go out cooperative effect and the research of special catalytic performance, have not yet to see report.
The catalyst carrier of the present invention is complex or the mixture of MSU-G, SBA-15 and HMS.Described complex or mixed
In compound, the weight of MSU-G, SBA-15 and HMS is than for 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 adopts is all the existing molecular sieve of catalytic field, and it 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 it has height
The crosslinked and relatively thick skeleton wall of skeleton of degree and there is superpower heat stability and hydrothermal stability, its skeleton hole with vertical
It is cross-linked with each other in layer with 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, has two-dimentional six side's through-hole structures, has P3mm space group.In XRD
In diffracting spectrum, main peak near about 1 °, for (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 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 preferably, and the relatively unordered organizational structure of short distance and aperture modulation scope be more simultaneously
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, from each mesoporous material, carries out compound pairing, screens through extensive, filters out MSU-G, SBA-15
With the compound of HMS or mixing.Inventor finds, in numerous complex/mixture, only MSU-G, SBA-15 and HMS tri-
The compound or mixing of person, just enables the collaborative lifting of hydrofinishing effect, and enables to catalysis activity not reduce for a long time, make
Can be greatly increased with the life-span.In other words, only the specific of MSU-G, SBA-15 and HMS three of the present invention is combined or mixes,
Just solve collaborative and two technical problems of service life simultaneously.Other cooperations, or not possessing synergism, or use the longevity
Life is shorter.
Described complex, can adopt being simply mixed of 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 it
The preparation method of thing is the known method of catalyst field, and the present invention is no longer repeated with regard to it.
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), nitridation two molybdenum MO are only controlled2N, 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 only in mol ratio:(0.4-0.6):(0.28-0.45):(0.8-1.2), when, 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.
The total content of described active component is the 1%-15%, preferably 3-12%, further preferred 5-10% of vehicle weight.
For example, described content can for 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..
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.
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 described catalyst passes through to choose spy
MSU-G, SBA-15 and HMS complex/mixture of certainty ratio is as carrier, and nitridation two molybdenum choosing special ratios
MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc are as active component so that this catalyst produces cooperative effect, to again
The hydrodesulfurization of raw lubricating oil can control in total sulfur content less than 5ppm, the total nitrogen content in reclaimed oil is controlled simultaneously
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.Described 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.
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.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 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 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.Described 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.
Test final product, 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.
Test final product, 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.
Test final product, 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.
Test final product, 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.
Test final product, 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.
Test final product, 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.
Test final product, total sulfur content is reduced to 29ppm, and total alkaline nitrogen content is reduced to 32ppm.
Embodiment 1 and comparative example 1-6 show, the present invention adopts MSU-G, SBA-15 and HMS complex of special ratios/mixed
Compound, as carrier, when replacing with single carrier or complex carrier two-by-two, does not all reach the technique effect of the present invention, 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, described hydrogenation desulfurization and denitrogenation unit creates unforeseeable technique effect.
Comparative example 7
Omit the MO in embodiment 12N, remaining condition is constant.
Test final product, total sulfur content is reduced to 42ppm, and total alkaline nitrogen content is reduced to 47ppm.
Comparative example 8
Omit the WC in embodiment 1, remaining condition is constant.
Test final product, 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 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.
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 (6)
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 complex or the mixture of MSU-G, SBA-15 and HMS；Described active component
For nitrogenizing two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc, 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.
2. hydrogenation regeneration technology as claimed in claim 1 is it is characterised in that the weight ratio of MSU-G, SBA-15 and HMS is for 1:
(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 is it is characterised in that the total content of described active component is vehicle weight
3-12%, 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.
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