CN106118739A - A kind of waste lubricant oil by hydrogenation regeneration technology - Google Patents
A kind of waste lubricant oil by hydrogenation regeneration technology Download PDFInfo
- Publication number
- CN106118739A CN106118739A CN201610674669.8A CN201610674669A CN106118739A CN 106118739 A CN106118739 A CN 106118739A CN 201610674669 A CN201610674669 A CN 201610674669A CN 106118739 A CN106118739 A CN 106118739A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hydrogenation
- fixed bed
- bed reactors
- carrier
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
-
- 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
- C10M175/0033—Working-up used lubricants to recover useful products ; Cleaning by thermal processes using distillation processes; devices therefor
-
- 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
-
- 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
- C10M175/02—Working-up used lubricants to recover useful products ; Cleaning mineral-oil based
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
Abstract
The invention discloses a kind of waste lubricating oil base oil hydrogenation regeneration technology, described technique includes pretreatment unit, hydrogenation regeneration unit and separative element, described hydrogenation regeneration unit uses fixed bed reactors, fixed bed reactors are filled with hydrogenation catalyst, described catalyst includes that carrier and active component, described carrier are incorporation hetero atom Cu in synthetic bone shelf structure2+MCM 41, described active component for nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc.Described catalyst is possibly together with catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixture.The reaction condition of described fixed bed reactors is: reaction temperature is 280 370 DEG C, reaction pressure 3 8MPa, hydrogen to oil volume ratio 40 50, volume space velocity 0.5 2.5h‑1.Reclaimed oil total sulfur content can be controlled less than 5ppm by this technique, controls total nitrogen content therein within 10ppm simultaneously.
Description
Technical field
The present invention relates to a kind of process for regeneration of waste lubricating oil, be specifically related to a kind of useless lubrication using special catalyst to carry out
Oil hydrogenation regeneration technology.
Background technology
In the epoch of this intense industrialization, the various vehicles and the extensive application of machinery, expedite the emergence of the extensive of lubricating oil
Application.Lubricating oil can effectively reduce or remove the phase mutual friction between vehicles mechanical accessory, and it extensively should
Minimizing sliding friction field for mechanical fitting, machine tool and other spare parts of engine, industrial equipment and factory.Lubricating oil
After used a period of time, the high temperature produced due to work and mechanical shearing, aoxidize and use the foreign body etc. that environment produces, moisten
Lubricating oil gradually loses lubricating function, it is necessary to replace with new lubricating oil.The used greasy property that this cyclic process produces
The lubricating oil reduced, the most referred to as waste lubricating oil.
China is the second-biggest-in-the-world lubricating oil country of consumption being only second to the U.S., and China's lubricating oil aggregate demand in 2010 is 490-
5100000 tons, it is contemplated that to the year two thousand twenty, lubricating oil aggregate demand is 600-800 ten thousand tons.The annual waste lubricating oil produced is the most big, as
Fruit is discarded in environment, can cause serious environmental pollution, it is therefore necessary to waste lubricating oil is carried out reclaiming.
Worldwide, the development of Technology of Used Lube Oil Regeneration substantially experienced by sour soil method → without acid system → hydrogenation
The process of method.The technique of main flow is distillation-hydrogenation method at present.
Distillation-hydrogenation method is the most representative with the technique of Puralube (German) limited company.The flow process of this technique
As follows:
1) pretreatment, in high temperature and high pressure environment, is sufficiently mixed hot hydrogen with raw oil, then sequentially enters flash distillation-steaming
Evaporate knockout tower, make the mink cell focus rich in asphalitine and metal and lubricating oil and light Component seperation.The Colophonium that sub-argument goes out is after treatment
Can be used as Colophonium blend component.It is to be exactly one to face hydrogen-deasphalting process that this unit operates it, it is therefore an objective to add the useless lubrication of heat damage
Additive component in oil, and additive, asphalitine, metal and other solid impurities are separated from waste lubricating oil, with
It is processed further remaining ingredient processing.
2) catalytic hydrogenation.Specially designed antigravity system comprises two reaction under high pressure rooms, the first reative cell (also known as
" protection reative cell ") remove the metal failing in pretreatment to completely remove, also function to the effect of preliminary desulfurization simultaneously.Second reaction
In room, catalyst is fully contacted with alkene key molecule and the aromatic hydrocarbons key molecule of lubricating oil, makes hydrogenation reaction quickly carry out, rises simultaneously
To complete desulfurization removing nitric effect.
3) finished product separates and product processes and reuse.Product is admitted to height-low pressure separator, through high-temperature pressure-reduction and
Low-temperature reduced-pressure, at the by-product that the catalytic hydrogenation stage produces, such as chloride and sulfide, is admitted to together with unreacted hydrogen
Alkali-water wash system, is neutralized reaction, chloride and sulfide and is removed, and remaining hydrogen is purified and recycles.?
The lubricating oil produced in reaction enters stripping-distillation column and carries out fractional distillation, obtains Petroleum, diesel oil and lube cut, at the bottom of tower
Residue returns the distillation column freshening of pretreatment stage.
But in above-mentioned technique, in catalytic hydrogenation unit, the catalyst desulfurizing denitrogenation degree of depth of employing is limited, can only be by total sulfur
Content is removed to about 100ppm, it is impossible to total sulfur content is reduced to 10ppm even below 5ppm.The most how to provide a kind of useless
Lube base oil hydrogenation regeneration technology, can effectively control the sulfur content in lubricating oil at 10ppm in desulfurization removing nitric unit
Hereinafter, to meet standard, can effectively remove nitride therein simultaneously, and realize the regeneration of waste lubricating oil, be that this area faces
A difficult problem.
Summary of the invention
It is an object of the invention to propose a kind of waste lubricant oil by hydrogenation regeneration technology, this technique can be by waste lubricant oil by hydrogenation
Regeneration, and the total sulfur content of reclaimed oil is reduced to below 10ppm, meanwhile, also making of the catalyst that this technique uses
In reclaimed oil, the removing ratio of nitride is more significant.
For reaching this purpose, the present invention by the following technical solutions:
A kind of non-lubricated oil hydrogenation regeneration technology, described technique includes pretreatment unit, hydrogenation regeneration unit and separates single
Unit.
Described hydrogenation regeneration unit uses fixed bed reactors, is filled with hydrogenation catalyst in fixed bed reactors, described
Catalyst includes carrier and active component.Described carrier is incorporation hetero atom Cu in synthetic bone shelf structure2+MCM-41.Described work
Property component for nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc.Described catalyst possibly together with
Catalyst aid, described catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixture.The reaction bar of described fixed bed reactors
Part is: reaction temperature is 280-370 DEG C, reaction pressure 3-8MPa, hydrogen to oil volume ratio 40-50, volume space velocity 0.5-2.5h-1。
In the present invention, not having particular/special requirement for pretreatment unit, it can use existing equipment and technique, such as
Flash distillation-separated equipment, to realize the separation of mink cell focus, lubricating oil and lighter hydrocarbons.
Preferably, the pretreatment of the present invention is preferably carried out under hydroconversion condition, to realize Linqing heat treatment-deasphalting mesh
, thus by the additive heat resolve in waste lubricating oil.
Pretreated lubricating oil enters hydrofinishing unit.Described hydrofinishing unit uses fixed bed reactors, Gu
Being filled with hydrogenation catalyst in fixed bed reactor, described catalyst includes carrier and active component..
MCM-41 is ordered into mesoporous material, and its duct is that six side's ordered arrangement, size are uniform, aperture size can with synthesis time
The difference adding directed agents and synthetic parts changes between 1.5～10nm, lattice parameter about 4.5nm, specific pore volume about 1mL/g,
MCM-41 uniform pore diameter, has higher specific surface area (1000m2/ g) and big adsorption capacity (0.7mL/g), the most organic
The free diffusing of molecule.The present invention through in numerous mesoporous materials, such as MCM-22, MCM-36, MCM-48, MCM-49,
MCM56, carries out contrast test selection, finds that only MCM-41 can reach the goal of the invention of the present invention, and other mesoporous materials are all
Having such-and-such defect, there is the technical difficulty being difficult to overcome when being applied in the present invention, therefore the present invention selects to use
MCM-41 is as carrier basis.
The acidity of silica MCM-41 own is the most weak, is directly used as catalyst activity relatively low.Therefore, it is changed by the present invention
Property, to increase its catalysis activity.The approach that MCM-41 mesopore molecular sieve is modified is by the present invention: be situated between to the Siliceous MCM-41 of finished product
Porous molecular sieve inner surfaces of pores introduces Cu2+, this approach can be exchanged Cu by ion2+It is supported on the inner surface of MCM-41,
Thus improve catalysis activity, absorption and the Thermodynamically stable performance etc. of MCM-41 mesopore molecular sieve on the whole.
Although the method being modified MCM-41 mesopore molecular sieve or approach are a lot, inventor finds, the present invention urges
Agent can only use doping Cu2+MCM-41 could realize sulfur content control and denitrification effect as carrier, inventor attempts
MCM-41 adulterates: Al3+、Fe3+、Zn2+、Ga3+In the ion at generation anionic surface center, discovery all can not realize described
Effect.Although described mechanism is current and unclear, but this has no effect on the enforcement of the present invention, and inventor is according to well-known theory and reality
Checking is real, there is cooperative effect between itself and the active component of the present invention.
Described Cu2+Doping in MCM-41 must control within specific content range, and its doping is with weight
Meter, for the 0.56%-0.75% of MCM-41 weight, such as 0.57%, 0.58%, 0.59%, 0.6%, 0.61%, 0.62%,
0.63%, 0.64%, 0.65%, 0.66%, 0.67%, 0.68%, 0.69%, 0.7%, 0.71%, 0.72%, 0.73%,
0.74 etc..
Inventor finds, outside this range, can cause drastically reducing of waste lubricating oil denitrogenation and desulfurized effect.More make us
Joyful, work as Cu2+When doping in MCM-41 controls in the range of 0.63%-0.72%, its desulphurizing ability is the strongest, when
Draw with Cu2+Doping is transverse axis, and during curve chart with target desulfurized effect as the longitudinal axis, in this content range, sulfur content can control
Within the scope of extremely low, its desulfurized effect produced, far beyond expection, belongs to unforeseeable technique effect.
The total content of described active component is the 1%-15% of carrier MCM-41 weight, preferably 3-12%, further preferably
5-10%.Such as, described content can be 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%,
7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%,
13.5%, 14%, 14.5% etc..
In the present invention, it is particularly limited to active component for nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Mixed proportion, inventor find, the effect that different mixed proportions reaches is entirely different.Inventor finds, nitrogenizes two molybdenums
MO2N, tungsten nitride W2N, molybdenum carbide Mo2The mixed proportion (mol ratio) of C and tungsten carbide wc is 1:(0.4-0.6): (0.28-
0.45): (0.8-1.2), nitridation two molybdenum MO are only controlled2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc exists
In the range of Gai, sulfur content in lube base oil can be realized and control at below 10ppm and denitrification ability notable.Namely
Saying, four kinds of active components of the present invention are only 1:(0.4-0.6 in mol ratio): (0.28-0.45): time (0.8-1.2), just tool
Standby cooperative effect.Outside this molar ratio range, or omit or replace any one component, all can not realize collaborative effect
Should.
Preferably, two molybdenum MO are nitrogenized2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc is 1:(0.45-
0.5): (0.35-0.45): (0.8-1.0), more preferably 1:(0.45-0.48): (0.4-0.45): (0.9-1.0),
Preferably 1:0.48:0.42:0.95.
The three of the purpose of the present invention are to provide the promoter of described catalyst.Catalyst of the present invention possibly together with
Catalyst aid, described catalyst aid is TiO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate).
Although in hydrofinishing particularly hydrodesulfurization field, had maturation catalyst aid, such as P, F and B etc., its
For regulating the character of carrier, weaken interaction strong between metal and carrier, improve the surface texture of catalyst, improve metal
Reducibility, promote active component to be reduced to lower valency, to improve the catalytic performance of catalyst.But above-mentioned P, F and B catalysis helps
Agent application with the carrier of the present invention with active component time, for high-sulfur component, it promotes the effect of catalytic desulfurization/refined
?.
The present invention passes through in numerous conventional cocatalyst component, and carries out in amount of activated component selecting, compounding,
Find eventually to use TiO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate) is obvious to the catalyst facilitation of the present invention, energy
Significantly improve its hydrothermal stability, and improve its anti-coking deactivation, thus improve its service life.
Described TiO2、CeO2、V2O5And NbOPO4Between there is no fixing ratio, say, that TiO2、CeO2、V2O5With
NbOPO4Each respective content reaches effective dose.Preferably, the TiO that the present invention uses2、CeO2、V2O5And NbOPO4
Respective content is the 1-7% of (respectively) carrier quality, preferably 2-4%.
Although there is no specific proportion requirement between catalyst aid of the present invention, but each auxiliary agent allowing for reaching
To the requirement of effective dose, the 1-7% of the content of catalyst aid effect, such as carrier quality i.e. can be played.The present invention is selecting
During find, omit or replace one or more in described auxiliary agent, all do not reach the present invention technique effect (improve water
Heat stability, reduces coking and improves service life), say, that exist between the catalyst aid of the present invention and specifically coordinate pass
System.
It is true that the present invention once attempted the niobium phosphate NbOPO in catalyst aid4Replace with five oxidation two girl Nb2O5,
Have found that while in auxiliary agent and have also been introduced Nb, but its technique effect is significantly lower than niobium phosphate NbOPO4, not only hydrothermal stability is slightly for it
Difference, its beds coking is relatively rapid, thus causes catalyst duct to block, and beds pressure drop rise is relatively
Hurry up.The present invention the most once attempted introducing other phosphate, although but this trial introduces phosphate anion, but equally exist hydro-thermal
Stability is the most slightly worse, and its beds coking is relatively rapid, thus causes catalyst duct to block, beds pressure drop
Rise relatively fast.
Although present invention introduces catalyst aid have so many advantage, but the present invention should be noted that, introduce catalysis
Auxiliary agent is only one of preferred version, even if not introducing this catalyst aid, nor affects on the enforcement of main inventive purpose of the present invention.
Not introducing the catalyst aid particularly niobium phosphate of the present invention, it is compared to the scheme of introducing catalyst aid, and its defect is only phase
To.This defect i.e. is that it is relative to other prior aries outside the present invention relative to the defect introduced after catalyst aid,
Mentioned by the present invention had superiority or new features yet suffer from.This catalyst aid is not to solve technical problem underlying of the present invention
Indispensable technological means, its simply further optimization to technical solution of the present invention, solve new technical problem.
The preparation method of described catalyst can take infusion process and other alternative methods, the people in the art of routine
The prior art unrestricted choice that member can grasp according to it, the present invention repeats no more.
Preferably, the reaction condition of described fixed bed reactors is: reaction temperature is 320-340 DEG C, reaction pressure 4-
6MPa, hydrogen to oil volume ratio 40-50, volume space velocity 1.5-2.0h-1。
Preferably, described hydrofining technology flow process includes, after mixing from the lubricating oil of pretreatment with hydrogen, through optional
Heat exchanger heat exchange, then enter fixed bed reactors after the heating of heated stove and be fixed a reactor, product enters point
From unit.
Preferably, described hydrogenation desulfurization and denitrogenation fixed bed reactors include 1-5 beds, further preferred 2-3
Individual beds.
The separative element of the present invention does not the most do specific restriction, its objective is to realize hydrogen and reclaims, obtain reclaimed oil and
Other by-products.Typical but non-limiting example includes, is introduced into depressurized system from hydrorefined product and reduces pressure,
Realize gas-liquid separation.Gas-phase product returns hydrofinishing unit through alkali cleaning, and liquid phase enters stripping-distillation column and carries out fractional distillation, tower top
Obtaining Petroleum, side line respectively obtains diesel oil and lubricating oil, heavy oil and residue and discharges from the bottom of tower.This separative element is all known skill
Art, the application does not do specific detailed restriction.
Through the lubricating oil that the waste lubricant oil by hydrogenation regeneration technology of the present invention obtains, according to the requirement of technique, can arrange
Different side lines obtains the lube base oil of various criterion, and this arranges and can realize by adjusting the side stream temperature of distillation column,
The present invention repeats no more.
The waste lubricant oil by hydrogenation regeneration technology of the present invention is by choosing specific catalyst, and described catalyst is miscellaneous by mixing
Atom Cu2+MCM-41 as carrier, and choose the nitridation two molybdenum MO of special ratios2N, tungsten nitride W2N, molybdenum carbide Mo2C and
Tungsten carbide wc is as active component, and described catalyst is possibly together with catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5With
NbOPO4Mixture so that this catalyst produce cooperative effect, the hydrodesulfurization to reclaimed oil can control to contain at total sulfur
Total nitrogen content in reclaimed oil, less than 5ppm, is controlled within 10ppm by amount simultaneously.
Detailed description of the invention
The waste lubricant oil by hydrogenation regeneration technology of the present invention is illustrated by the present invention by following embodiment.
Embodiment 1
Preparing catalyst by infusion process, carrier is doping Cu2+MCM-41, Cu2+Doping in MCM-41
Control at the 0.65% of carrier quality.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Total content is carrier quality 10%, its mol ratio is 1:0.4:0.3:0.8.
Described Catalyst packing enters fixed bed reactors, and the reaction tube of described reactor is by the stainless steel of internal diameter 50mm
Becoming, beds is set to 3 layers, and reaction bed temperature UGU808 type temp controlled meter is measured, and raw material waste lubricating oil is by north
The double plunger micro pump of capital satellite manufactory manufacture carries continuously, and hydrogen is supplied and use Beijing Sevenstar-HC D07-by gas cylinder
11A/ZM mass-flow gas meter coutroi velocity, loaded catalyst is 2kg.Reacted product is laggard through the cooling of water-bath room temperature
Row gas-liquid separation.
Raw materials used is the useless 5W30 lubricating oil from Great Wall.
Raw material is the most preprocessed, and flash distillation-separated equipment is passed through in this pretreatment, it is achieved mink cell focus, lubricating oil and lighter hydrocarbons
Separation.Described pretreatment is carried out under hydroconversion condition, to realize Linqing heat treatment-deasphalting purpose, thus by useless lubrication
Additive heat resolve in oil.
Pretreated lubricating oil enters hydrofinishing unit.Described hydrofinishing unit uses fixed bed reactors, Gu
Fixed bed reactor is filled with described Hydrobon catalyst.The reaction condition controlling fixed bed reactors is: reaction temperature is
320 DEG C, reaction pressure 4MPa, hydrogen to oil volume ratio 50, volume space velocity 1.5h-1。
The product of hydrogenated reaction enters depressurized system and reduces pressure, it is achieved gas-liquid separation.Gas-phase product returns through alkali cleaning
Hydrofinishing unit, liquid phase enters stripping-distillation column and carries out fractional distillation, and tower top obtains Petroleum, and side line respectively obtains diesel oil and profit
Lubricating oil, heavy oil and residue are discharged from the bottom of tower.
The lube product that test finally gives, total sulfur content is reduced to 4ppm, and total alkaline nitrogen content is reduced to 8ppm.
Embodiment 2
Preparing catalyst by infusion process, carrier is doping Cu2+MCM-41, Cu2+Doping in MCM-41
Control at the 0.7% of carrier quality.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Total content is carrier quality 10%, its mol ratio is 1:0.6:0.45): 1.2.
Remaining condition is same as in Example 1.
Testing final product, total sulfur content is reduced to 3ppm, and total alkaline nitrogen content is reduced to 10ppm.
Comparative example 1
The carrier of embodiment 1 is replaced with γ-Al2O3, remaining condition is constant.
Testing final product, total sulfur content is reduced to 21pm, and total alkaline nitrogen content is reduced to 32ppm.
Comparative example 2
The carrier of embodiment 1 is replaced with unadulterated MCM-41, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 19ppm, and total alkaline nitrogen content is reduced to 36ppm.
Comparative example 3
Cu by embodiment 12+Replace with Zn2+, remaining condition is constant.
Testing final product, total sulfur content is reduced to 23ppm, and total alkaline nitrogen content is reduced to 41ppm.
Comparative example 4
By the Cu in embodiment 12+Doping in MCM-41 controls at the 0.5% of carrier quality, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 37ppm, and total alkaline nitrogen content is reduced to 43ppm.
Comparative example 5
By the Cu in embodiment 12+Doping in MCM-41 controls at the 0.8% of carrier quality, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 47ppm, and total alkaline nitrogen content is reduced to 40ppm.
Embodiment 1 shows with comparative example 1-5, certain content scope that the application uses and certain loads metal ion
MCM-41 carrier, when replacing with other known carriers of this area, or carrier is identical but Cu2+During doping difference, all reach
Less than the technique effect of the present invention, the therefore Cu of the certain content scope of the present invention2+Doping MCM-41 carrier and catalyst other
Possessing cooperative effect between component, described hydrogenation desulfurization and denitrogenation unit creates unforeseeable technique effect.
Comparative example 6
Omit the MO in embodiment 12N, remaining condition is constant.
Testing final product, total sulfur content is reduced to 56ppm, and total alkaline nitrogen content is reduced to 67ppm.
Comparative example 7
Omitting the WC in embodiment 1, remaining condition is constant.
Testing final product, total sulfur content is reduced to 65ppm, and total alkaline nitrogen content is reduced to 76ppm.
Above-described embodiment and comparative example 6-7 explanation, several active component of catalyst of the hydrodesulfurization of the present invention it
Between there is specific contact, be omitted or substituted one of which or several, all can not reach the certain effects of the application, it was demonstrated that it produces
Give birth to cooperative effect.
Embodiment 3
Containing catalyst aid TiO in catalyst2、CeO2、V2O5And NbOPO4, its content is respectively 1%, 1.5%, 1% and
3%, remaining is same as in Example 1.
Testing final product, after it uses 3 months, beds pressure drop is not any change, and uses compared to same
The beds pressure drop of time embodiment 1 reduces 14%.
Comparative example 8
Compared to embodiment 3, by NbOPO therein4Omitting, remaining condition is identical.
Testing final product, after it uses 3 months, beds pressure drop raises, and uses the time real compared to same
The beds pressure drop executing example 1 only reduces 3%.
Comparative example 9
Compared to embodiment 3, by CeO therein2Omitting, remaining condition is identical.
Testing final product, after it uses 3 months, beds pressure drop raises, and uses the time real compared to same
The beds pressure drop executing example 1 only reduces 4%.
Embodiment 3 shows with comparative example 8-9, there is conspiracy relation between the catalyst aid of the present invention, when being omitted or substituted
When one of them or several component, all can not reach the minimizing coking when present invention adds catalyst aid thus stop catalyst bed
The technique effect that lamination falling-rising is high.That is, its catalyst aid demonstrating the present invention can improve the service life of described catalyst,
And other catalyst aid effects are not as this specific catalyst aid.
Applicant states, the present invention illustrates the technique of the present invention by above-described embodiment, but the invention is not limited in
Above-mentioned technique, does not i.e. mean that the present invention has to rely on above-mentioned detailed catalysts and could implement.Those of skill in the art
Member is it will be clearly understood that any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and the interpolation of auxiliary element, tool
Body way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (7)
1. a waste lubricating oil base oil hydrogenation regeneration technology, described technique includes pretreatment unit, hydrogenation regeneration unit and divides
From unit, it is characterised in that
Described hydrogenation regeneration unit uses fixed bed reactors, is filled with hydrogenation catalyst, described catalysis in fixed bed reactors
Agent includes that carrier and active component, described carrier are incorporation hetero atom Cu in synthetic bone shelf structure2+MCM-41, described activity group
It is divided into nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc, described catalyst is possibly together with 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。
It is hydrogenated with regeneration technology the most as claimed in claim 1, it is characterised in that hetero atom Cu2+Doping be MCM-41 weight
0.63%-0.72%.
It is hydrogenated with regeneration technology the most as claimed in claim 1, it is characterised in that the total content of described active component is carrier MCM-
The 3-12% of 41 weight, preferably 5-10%.
It is hydrogenated with regeneration technology the most as claimed in claim 1, it is characterised in that nitrogenize two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide
Mo2The mol ratio of C and tungsten carbide wc is 1:(0.45-0.5): (0.35-0.45): (0.8-1.0), more preferably 1:
(0.45-0.48): (0.4-0.45): (0.9-1.0), most preferably 1:0.48:0.42:0.95.
It is hydrogenated with regeneration technology the most as claimed in claim 1, it is characterised in that the reaction condition of described fixed bed reactors is:
Reaction temperature is 320-340 DEG C, reaction pressure 4-6MPa, hydrogen to oil volume ratio 40-50, volume space velocity 1.5-2.0h-1。
It is hydrogenated with regeneration technology the most as claimed in claim 1, it is characterised in that described fixed bed reactors include 1-5 catalysis
Agent bed, preferably includes 2-3 beds.
It is hydrogenated with regeneration technology the most as claimed in claim 1, it is characterised in that TiO2、CeO2、V2O5And NbOPO4Respective content
It is respectively the 1-7%, preferably 2-4% of carrier quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610674669.8A CN106118739A (en) | 2016-08-16 | 2016-08-16 | A kind of waste lubricant oil by hydrogenation regeneration technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610674669.8A CN106118739A (en) | 2016-08-16 | 2016-08-16 | A kind of waste lubricant oil by hydrogenation regeneration technology |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106118739A true CN106118739A (en) | 2016-11-16 |
Family
ID=57259129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610674669.8A Pending CN106118739A (en) | 2016-08-16 | 2016-08-16 | A kind of waste lubricant oil by hydrogenation regeneration technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106118739A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110423642A (en) * | 2019-08-29 | 2019-11-08 | 陕西欧菲德环保科技有限公司 | A kind of waste used oil separating-purifying equipment |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1262969A (en) * | 2000-03-02 | 2000-08-16 | 南开大学 | Catalyst using TiO2 as carrier to load metal nitride Mo2N |
| CN1470327A (en) * | 2002-07-24 | 2004-01-28 | 北京石油化工学院 | Metal nitride catalyst preparing method and catalyst |
| CN1895777A (en) * | 2005-07-14 | 2007-01-17 | 北京化工大学 | Porous molecular-sieve catalyst for assembling carbide and its preparation |
| WO2013149014A1 (en) * | 2012-03-29 | 2013-10-03 | Wayne State University | Bimetal catalysts |
| CN105251527A (en) * | 2015-11-11 | 2016-01-20 | 中国石油大学(北京) | Composite molecular sieve and hydrodesulfurization catalyst prepared with composite molecular sieve as carrier |
-
2016
- 2016-08-16 CN CN201610674669.8A patent/CN106118739A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1262969A (en) * | 2000-03-02 | 2000-08-16 | 南开大学 | Catalyst using TiO2 as carrier to load metal nitride Mo2N |
| CN1470327A (en) * | 2002-07-24 | 2004-01-28 | 北京石油化工学院 | Metal nitride catalyst preparing method and catalyst |
| CN1895777A (en) * | 2005-07-14 | 2007-01-17 | 北京化工大学 | Porous molecular-sieve catalyst for assembling carbide and its preparation |
| WO2013149014A1 (en) * | 2012-03-29 | 2013-10-03 | Wayne State University | Bimetal catalysts |
| CN105251527A (en) * | 2015-11-11 | 2016-01-20 | 中国石油大学(北京) | Composite molecular sieve and hydrodesulfurization catalyst prepared with composite molecular sieve as carrier |
Non-Patent Citations (14)
| Title |
|---|
| F•维拉尼: "《稀土技术及其应用》", 31 July 1986, 烃加工出版社 * |
| 中国石油化工集团公司人事部，等: "《加氢裂化装置操作工》", 30 September 2008, 中国石化出版社 * |
| 何鸣元，等: "《石油炼制和基本有机化学品合成的绿色化学》", 31 January 2006, 中国石化出版社 * |
| 姜琳琳: "全馏分FCC汽油加氢改质中改性MCM-41催化性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 崔克清，等: "《化工工艺及安全》", 31 May 2004, 化学工业出版社 * |
| 张文成: "改性MCM-41 分子筛的制备及加氢催化性能研究", 《第十一届全国青年催化学术会议论文集（下）》 * |
| 李静海，等: "《展望21世纪的化学工程》", 31 October 2004, 化学工业出版社 * |
| 林世雄: "《石油炼制工程（第三版）》", 31 July 2000, 化学工业出版社 * |
| 王基铭: "《石油炼制辞典》", 30 September 2013, 中国石化出版社 * |
| 王海彦，等: "《石油加工工艺学》", 31 January 2014, 中国石化出版社 * |
| 王福安，等: "《绿色过程工程引论》", 31 October 2002, 化学工业出版社 * |
| 王雷，等: "《炼油工艺学》", 31 August 2011, 中国石化出版社 * |
| 邝生鲁: "《现代精细化工高新技术与产品合成工艺》", 31 December 1997, 科学技术文献出版社 * |
| 阎子峰: "《纳米催化技术》", 31 May 2003, 化学工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110423642A (en) * | 2019-08-29 | 2019-11-08 | 陕西欧菲德环保科技有限公司 | A kind of waste used oil separating-purifying equipment |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106118739A (en) | A kind of waste lubricant oil by hydrogenation regeneration technology | |
| CN106221749A (en) | A kind of waste lubricant oil by hydrogenation regeneration technology | |
| CN106221796A (en) | A kind of waste lubricant oil by hydrogenation regeneration technology | |
| CN106190238A (en) | A kind of waste lubricant oil by hydrogenation regeneration technology | |
| CN106221793A (en) | A kind of waste lubricant oil by hydrogenation regeneration technology | |
| CN106190241A (en) | A kind of waste lubricant oil by hydrogenation regeneration technology | |
| CN106190249A (en) | A kind of waste lubricant oil by hydrogenation regeneration technology | |
| CN106433776A (en) | Hydrogenation regeneration process of waste lubricating oil | |
| CN106221770A (en) | A kind of waste lubricant oil by hydrogenation regeneration technology | |
| CN106381211A (en) | Hydrogenation and regeneration process for waste lubricating oil | |
| CN106221783A (en) | A kind of waste lubricant oil by hydrogenation regeneration technology | |
| CN106190293A (en) | A kind of waste lubricant oil by hydrogenation regeneration technology | |
| CN106221752A (en) | A kind of waste lubricant oil by hydrogenation regeneration technology | |
| CN106221776A (en) | A kind of waste lubricant oil by hydrogenation regeneration technology | |
| CN106381214A (en) | A hydrogenation regenerating process for waste lubricating oil | |
| CN106190244A (en) | A kind of waste lubricant oil by hydrogenation regeneration technology | |
| CN106345517A (en) | Waste-lubricating-oil hydrogenation regeneration process | |
| CN106381213A (en) | Hydrogenation and regeneration process for waste lubricating oil | |
| CN106244311A (en) | A kind of waste lubricant oil by hydrogenation regeneration technology | |
| CN106381215A (en) | A hydrogenation regenerating process for waste lubricating oil | |
| CN106190297A (en) | A kind of residuum hydrodesulfurization RFCC group technology of sour crude | |
| CN106085501A (en) | A kind of hydrorefining basic oil lubricating oil technique | |
| CN106381212A (en) | Hydrogenation and regeneration process for waste lubricating oil | |
| CN106221771A (en) | A kind of coking crude benzene hydrodesulfurization | |
| CN106085503A (en) | A kind of hydrorefining paraffin wax technique |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20161116 |