CN107267198A - A kind of method that waste lubricating oil liquid-phase hydrogenatin prepares lube base oil - Google Patents
A kind of method that waste lubricating oil liquid-phase hydrogenatin prepares lube base oil Download PDFInfo
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- CN107267198A CN107267198A CN201710685062.4A CN201710685062A CN107267198A CN 107267198 A CN107267198 A CN 107267198A CN 201710685062 A CN201710685062 A CN 201710685062A CN 107267198 A CN107267198 A CN 107267198A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—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 nickel or cobalt metal, or compounds thereof
- C10G45/08—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 nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
- C10G2300/1007—Used oils
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
-
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1062—Lubricating oils
-
- 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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/10—Lubricating oil
Abstract
The invention discloses a kind of method that waste lubricating oil liquid-phase hydrogenatin prepares lube base oil, 10~60wt.% material is mixed with hydrogen in the step of the step of entering the step of liquid phase hydrogenation reactor carries out hydrogenation reaction, isolated through the thermal low-pressure separators liquid product of hydrogenation products after being mixed including waste lubricating oil raw material with hydrogen and described liquid product obtain lube base oil after entering stripper processing after drying, adsorption treatment, the isolated liquid product of thermal low-pressure separators is back to liquid phase hydrogenation reactor.After treatment, sulfur content and nitrogen content in base oil are significantly reduced waste lubricating oil raw material, and viscosity index (VI) is improved, and color number is significantly reduced, the yield ＞ 99% of lube base oil, the hydrogen consumption ＜ 0.55% of course of reaction.
Description
Technical field
Lubrication is prepared the present invention relates to the regeneration field of waste lubricating oil, more particularly to a kind of waste lubricating oil liquid-phase hydrogenatin
The method of oil base oil.
Background technology
Lubricating oil in use, a large amount of oxidations produced due to the consumption of the oxidation of itself under high temperature and additive
The impurity such as the metal fillings, the dust that are brought in thing, colloid, asphalitine etc., and mechanical wear and environment, can cause lubricating oil to reduce
Or even the effects such as reduction friction, reduction are worn and torn, cooled is lost, go bad after reaching to a certain degree, must just be replaced, change
The oil got off reforms into waste lubricating oil.Because chloride, sulphur, phosphorus, condensed-nuclei aromatics of aromatic hydrocarbons polymerization generation etc. organise in waste lubricating oil
Compound has extremely strong toxicity or carcinogenicity, deals with improperly, both causes the wasting of resources, and environment is endangered again.Waste lubricating oil becomes in fact
Matter composition only a few percent, its main body still based on oil, if being handled through proper technology, remove rotten composition and external contaminant,
The base oil of satisfactory quality can be regenerated.Compared with being processed into fuel oil, reclaimed oil has higher added value,
And waste oil regeneration is simpler than petroleum refining lubricating oil technological process, cost is low.
The technology of waste oil regenerating commonly used both at home and abroad at present can be divided into three classes：Physical filtering, solvent refining and hydrofinishing
Technique.
First, physical filtering technique
Waste hydraulic oil is carried out coarse filtration elimination by Chinese patent CN102827681A (a kind of Waste hydraulic oil regeneration technology) successively
Impurity therein, is then heated to 60~80 DEG C, then heated waste hydraulic oil is carried out into fine filtering by the waste hydraulic oil through coarse filtration；
Filter screen average pore size filter screen average pore size in 74~1055 μm, fine filtering process is 5~105 μm in coarse filtration process；Will be through processing
The waste hydraulic oil crossed carries out reheating to 80~150 DEG C, then carries out oil vacuum cleaning, then gained waste hydraulic oil is transported to filled out
There is progress decolouring removal of impurities in the chromatographic column of carclazyte or flyash；Gained waste hydraulic oil is added under 40~60 DEG C, stirring condition
Additive is reconciled, and produces regeneration of hydraulic oil.
Waste hydraulic oil disclosed in Chinese patent CN102229850A (renovation process and equipment of a kind of waste hydraulic oil) regenerates
Method includes following technique successively：Impurity sedimentation technique, impurity crude filtering technology, heating technique, membrane separation process and recoil technique.
The membrane separation process uses porous ceramic film, and its average pore size is 0.01~0.5 μm；The recoil technique uses high-tension pulse
Punching, backwash liquid is generally film penetrating fluid, and kickback pressure is 0.1~1.0MPa, and recoil time is 5~40s, and recoil interval time is
0.25~3h.This again generating apparatus can be very good purification, regeneration liquid waste force feed, but pollutant can be attached to film in use
Surface cause serious fouling membrane, Membrane Filtration Flux declines, and needs periodic cleaning membrane module.United States Patent (USP) US4411790
(Process for the treatment of a hydrocarbon charge by high temperature
Ultrafiltration a kind of technique of use ceramic super-filtering film reclaiming waste oil) is disclosed, fuel-displaced quality and flux are in patent
In be not discussed in detail, and equally exist the membrane pollution problem that inorganic film process waste oil is present.
Chinese patent CN102952622A (the pure physical cleaning method of waste oil circular regeneration) provides a kind of waste oil and circulated again
Raw pure physical cleaning method, comprises the following steps：80 DEG C will be heated in waste oil sucting reaction kettle and stir；Opening centrifugal pump makes
Waste oil is circulated in reactor, is removed all moisture inside oil and other light things that evaporate using low temperature distillation, vacuum separation method；
Waste oil is heated to 100~120 DEG C, absorption is put into and expects and stir；Waste oil is heated to 130~160 DEG C, drainage and protection is put into
Oily material is simultaneously stirred；Absorption material and drainage and protection oily material are filtered out；Make the oil after filtering out using the method for infiltration
The filter bag that liquid infiltrates into 3 μm exports fluid, finished product oil.
However, the present inventor is using having found during physical filtering PROCESS FOR TREATMENT waste lubricating oil, above-mentioned method according to
So there is problems with：1. the rate of filtration of waste oil is slow, efficiency is low, easily blocks filter, it is necessary to artificial cleaning, labor intensity
Greatly；2. the process high energy consumption being dehydrated is, it is necessary to which repeatedly dehydrating operations could remove the moisture in reclaimed oil；3. the volume of equipment is huge
Greatly, cost is high, complex operation.
2nd, solvent refining processes
Refined conventional solvent is the characteristic for utilizing its polarity closer to the polarity of undesirable components, in heating stirring process
In so that undesirable components are gradually dissolved in solvent, and ideal composition is insoluble, to reach separation undesirable components and preferable group
The purpose divided.It is as excellent solvent necessary requirement：Selectivity is good, extracting ability is strong；Heat and chemical stability are good, are resistant to
Acid, alkali, oxidant, the effect of reducing agent；Simple and safe operation, toxicity, corrosivity, excitant are small, melt boiling point relatively low；Price is low
It is honest and clean, wide material sources.Because the condition to solvent requirement is quite harsh, it is difficult to which finding out a kind of solvent can meet what is possessed as solvent
Full terms.
《Using chemical industry》" sulfolane double solvents is to useless lubrication by one of the 7th the 1272-1275 pages of phase of volume 45 in 2016
The document of the research of oil regeneration technique " refines waste lubricating oil, research extraction temperature, agent using sulfolane/ethylene glycol double solvents
The influence of oil volume ratio, ethylene glycol addition (mass ratio) to refining effect.As a result show, optimum process condition is：Agent oil body
Product compares 1.4,110 DEG C of extraction temperature, ethylene glycol addition 15%.At the process conditions, oil yield 84.6%, viscosity refers to
Number is up to 103.7, and colourity 1.5, -17.3 DEG C of condensation point, 211.5 DEG C of flash-point, carbon residue 0.58% substantially conforms to the lubricating oil of HVI 150
The standard of performance indications.
《Petroleum journal (PETROLEUM PROCESSING)》One of the 6th the 1031-1036 pages of phase of volume 28 in 2012 is " molten based on three carbon alcohol
The document of the refined regeneration waste lubricating oil of agent " uses three carbon alcohol (isopropanol, normal propyl alcohol) polar solvent to be wadding for extractant, ethylenediamine
The solidifying refined regeneration waste lubricating oil of agent combination.Optimum process condition is：Extractant isopropanol, Refining times 25min, extraction temperature
40 DEG C, agent/oil quality is than 9, flocculant mass fraction 1.2%.Under the conditions of the process for refining, the performance indications of reclaimed oil are obtained
Be obviously improved, glutinous temperature index reached more than 130, flash-point more than 210 DEG C, acid number be 0.05mg KOH/g, ash content be down to 0.01% with
Under, contents of heavy metal elements be remarkably decreased, regeneration oily yield is 76.8%, substantially conforming to the basic oil index of HVI 150.
《Petroleum refining and chemical industry》" the extraction-flocculence regenerated profit of the 2nd the 84-88 pages of phase of volume 46 in 2015
The document of the research of lubricating oil " is by extractant of hexamethylene-isopropyl alcohol mixed solvent, KOH solution is flocculant, using extraction-wadding
Solidifying method reclaims the base oil fractions in waste lubricating oil.Determine that optimum process condition is through experimental study：Hexamethylene and isopropyl
The mass ratio 1 of alcohol：The mass ratio 7 of 2, KOH mass fractions 15%, organic solvent and KOH solution：1, agent oil quality compares 2：1, refine
Temperature 45 C, Refining times 30min.Waste lubricating oil is refined on this condition, the yield of reclaimed oil is 83.4%, its face
Color is clear light yellow, compared with waste lubricating oil, and the performance indications of reclaimed oil have very big improvement, basically reach HVI 150
The requirement of lube base oil performance indications.
However, the present inventor is had found during using solvent refining processes processing waste lubricating oil, above-mentioned method according to
So there is problems with：1. the price of solvent is higher, loses larger, causes production cost higher；2. the yield of reclaimed oil is low, warp
Ji property is poor.
3rd, hydrofining technology
More on waste lubricant oil by hydrogenation regeneration technology report is to use fixed bed and/or boiling bed hydrogenation technique.
Waste lubricating oil base oil disclosed in Chinese patent CN106433776A (a kind of waste lubricant oil by hydrogenation regeneration technology) adds
Hydrogen regeneration technology includes pretreatment unit, hydrogenation regeneration unit and separative element, and the hydrogenation regeneration unit is anti-using fixed bed
Answer and hydrogenation catalyst is filled with device, fixed bed reactors, the catalyst includes carrier and active component, the carrier is
MSUG, SBA-15 and HMS compound or mixture, the active component are two molybdenum Mo of nitridation2N, tungsten nitride W2N, molybdenum carbide
Mo2C and tungsten carbide wc mixture.Described catalyst also contains catalyst aid, and the catalyst aid is Cr2O3、ZrO2、
CeO2、V2O5And NbOPO4Mixture.The reaction condition of the fixed bed reactors is：Reaction temperature is 280~370 DEG C, instead
Answer 3~8MPa of pressure, hydrogen to oil volume ratio 40~50,0.5~2.5h of volume space velocity-1.The technique can be by reclaimed oil total sulfur
Content control is less than 5ppm, while to total nitrogen content therein control within 10ppm.
Give up and moisten disclosed in Chinese patent CN106398765A (a kind of method that waste lubricating oil long distillate is hydrogenated with regeneration)
Lubricating oil long distillate hydrogenation regeneration process includes floating bed hydrocracking waste lubricating oil in the presence of containing oil soluble catalyst
With the preprocessing process of electro-desalting removal of impurities, hydro-upgrading, hydrofining and the cut of the full distillate oil by pretreatment are cut
Cut, and the oil-soluble catalyst and fixed bed hydrogenation catalyst of the floating bed hydrogenation there is provided above-mentioned regeneration technology.By pre-
Processing, then by follow-up hydro-upgrading, deep desulfuration, denitrogenation, the various undesirable components in waste lubricating oil can be removed, changed
Kind oil quality.Hydrofinishing and cut cutting using full cut, on the one hand improve the resource recovery of waste lubricating oil, separately
On the one hand flexible products scheme is obtained, the high income of oil product is regenerated, the diesel oil and base oil quality index of production all reach
To standard requirement.
Chinese patent CN101797509A (a kind of used lubricating oil complete hydrogenation type regenerated catalyst and preparation method thereof and should
With) disclosed in used lubricating oil complete hydrogenation type regenerated catalyst be made up of catalyst carrier and active component, active component is WO3、
NiO and auxiliary agent Si, wherein WO328~38%, the NiO for accounting for total catalyst weight accounts for 4~8%, Si of total catalyst weight and accounts for and urge
The 2~3% of agent gross weight, surplus is alumina support；The specific surface area of the catalyst is 230~265m2/ g, pore volume is
0.47~0.55ml/g.Catalyst is the characteristic for waste lubricating oil, and W, Ni two-component metal combination of selection special ratios are made
For active component, and adjuvant component Si is equipped with, the selection and rational proportion by each component obtain higher high active of hydrogenation catalysis
And selectivity.With superhigh specific surface area, large aperture, faintly acid, the full cut of waste lubricating oil can be hydrogenated with, with very strong
Removing S, N, O and undesirable components hydrogenation saturability, and with extremely strong demetalization and anti-metal ability.
Raw material waste lubricating oil is mainly implemented de- by Chinese patent CN101041789A (waste lubricating oil hydrogenation reproducing method)
Water, filtering and adsorption treatment, remove moisture therein, mechanical admixture, colloid, asphalitine and most of beavy metal impurity；By
Waste lubricating oil after adsorption treatment carries out the further imurity-removal of pre- hydrofinishing in equipped with protectant reactor；Through pre-add
The refined waste lubricating oil of hydrogen enters hydrogenation main reactor, and hydrofinishing is realized in the presence of hydrogenation catalyst, is made in feedstock oil
Undesirable components hydrogenation saturation, product carry out fractionation cutting.Can be lube base oil or mediation group by waste lubricant oil regeneration
Point, the waste lubricating oil rate of recovery can reach more than 90%.
Chinese patent CN101173202A (a kind of recoverying and utilizing method of waste lubricating oil) is using filtering, the de- gold of electric dehydration
The combination for the technique such as category, boiling bed hydrogenation demetalization, boiling bed hydrogenation be refined, and operating condition is optimized, it will can give up
Most impurity is effectively removed in lubricating oil, and improves some such as colourity, oxidation stability, neutralization number properties, together
When improve the yield of lube base oil, realize the recovery and effectively utilization of waste lubricating oil.
However, the present inventor is had found during using hydrofining technology processing waste lubricating oil, above-mentioned method according to
So there is problems with：1. more high-tension apparatus is contained in technological process, operating procedure is complicated；2. in fixed bed hydrogenation technique
The hydrogen to oil volume ratio of use is very big, it is necessary to set up circulating hydrogen compressor and desulphurization of recycle hydrogen unit, and plant investment is high；3. temperature is reacted
Degree and temperature rise are uneven, and the coke deposit rate on catalyst is very fast.
Defect and the production cost that the technology of lube base oil is present are produced for above-mentioned utilization waste lubricant oil by hydrogenation
Higher the problem of, is, it is necessary to which a kind of new technical scheme solves the above problems.
The content of the invention
Goal of the invention：In order to overcome, operating procedure present in existing waste lubricant oil by hydrogenation regeneration technology is complicated, produce
Equipment cost investment is big, the defect that cost is higher, and lube base is prepared the invention provides a kind of waste lubricating oil liquid-phase hydrogenatin
The method of oil.
Technical scheme：In order to solve the above technical problems, technical scheme is as follows：
A kind of method that waste lubricating oil liquid-phase hydrogenatin prepares lube base oil, including waste lubricating oil raw material are mixed with hydrogen
Enter the step of liquid phase hydrogenation reactor carries out hydrogenation reaction, hydrogenation products afterwards through the isolated liquid product of thermal low-pressure separators
The step of and described liquid product enter the step for obtaining lube base oil after stripper is handled after drying, adsorption treatment
Suddenly, 10~60wt.% material and hydrogen mix and are back to liquid phase and add in the isolated liquid product of the thermal low-pressure separators
Hydrogen reactor.
A kind of method that waste lubricating oil liquid-phase hydrogenatin prepares lube base oil, comprises the following steps：
(1) the waste lubricating oil raw material after vacuum distillation and hydrogen are well mixed in the first mixing dissolver and obtain mixed hydrogen
The preheated liquid phase hydrogenation reactors that flow into of material I, the mixed hydrogen material I carry out hydrogenation reaction；
(2) hydrogenation products that step (1) is obtained flow into thermal low-pressure separators, from the outflow of thermal low-pressure separators top
Gas enters cleaning system, and the 10~60wt.% Matter Transfers flowed out from the thermal low-pressure separators bottom are molten to the second mixing
Solution device is well mixed with hydrogen obtains mixed hydrogen material II, and the mixed hydrogen material II flows into liquid phase hydrogenation reactor and be hydrogenated with instead
Should；The rest materials flowed out from the thermal low-pressure separators bottom enter stripper；
(3) gas flowed out from the stripper top enters cleaning system, the material flowed out from the stripper bottom
Lube base oil is produced after drying, absorption.
Preferably, the 30~50wt.% Matter Transfers flowed out in step (2) from the thermal low-pressure separators bottom are to second
Mixing dissolver is well mixed with hydrogen obtains mixed hydrogen material II, and the mixed hydrogen material II flows into liquid phase hydrogenation reactor and added
Hydrogen reacts.
Wherein, low point of gas of outflow heat includes unreacted in hydrogenation process at the top of thermal low-pressure separators in step (2)
H2And the most H produced in hydrogenation process2S、NH3And C1~C4 alkane；Stripping tower top in step (3)
The gas of portion's outflow includes micro H2、H2S、NH3And C1~C4 alkane.
The boiling range of waste lubricating oil raw material described in step (1) after vacuum distillation be 300~360 DEG C, 360~420 DEG C,
Any one or a few mixture in 420~520 DEG C.The operation temperature that above-mentioned waste lubricating oil vacuum distillation is generally used
For 250~320 DEG C, operating pressure is 0.001~0.1mbar, and this is known to professional and technical personnel in the field.
The volume ratio of hydrogen described in step (1) and waste lubricating oil raw material is 50~100.
Preferably, the volume ratio of hydrogen described in step (1) and waste lubricating oil raw material is 60~80.
The first catalyst bed is set from top to bottom by mixed hydrogen material I flow directions in liquid phase hydrogenation reactor described in step (1)
Layer, the second beds and the 3rd beds.
The catalyst of first beds is MoO3-Al2O3, pore volume is 1.0~1.5cm3/ g, average pore size is
20~50nm；The catalyst of second beds is NiO-MoO-Al2O3, pore volume is 0.8~1.2cm3/ g, average hole
Footpath is 20~30nm；The catalyst of 3rd beds is NiO-WO3-Al2O3, pore volume is 0.6~1.0cm3/ g, puts down
Equal aperture is 10~20nm.
The preparation of first beds, the second beds and catalyst used in the 3rd beds
Process is as follows：
First hydrogenation catalyst MoO3-Al2O3Preparation process：
Pseudo-thin diasphore with great pore volume powder, binding agent hydroxypropyl methyl cellulose are well mixed in kneader, added
Concentration is 0.1mol/L dilute nitric acid solution, mediates uniform rear extrusion molding；Obtained through 120 DEG C of dry 10h, 600 DEG C of roasting 4h
Big pore volume Al2O3Carrier.According to the composition of catalyst, using equi-volume impregnating, by big pore volume Al2O3Carrier impregnation contains molybdenum
The aqueous solution of sour ammonium, MoO is obtained through 120 DEG C of dry 10h, 450 DEG C of roasting 4h3-Al2O3Catalyst；The MoO3-Al2O3Catalysis
The pore volume of agent is 1.0~1.5cm3/ g, average pore size is 20~50nm；MoO in catalyst3Content be 3%, Al2O3Content
For 97%.
Second hydrogenation catalyst NiO-MoO-Al2O3Preparation process：
Pseudo-thin diasphore with great pore volume powder, binding agent hydroxypropyl methyl cellulose are well mixed in kneader, added
Concentration is 0.1mol/L dilute nitric acid solution, mediates uniform rear extrusion molding；Obtained through 120 DEG C of dry 10h, 600 DEG C of roasting 4h
Big pore volume Al2O3Carrier.According to the composition of catalyst, using equi-volume impregnating, by big pore volume Al2O3Carrier impregnation contains nitre
The aqueous solution of sour nickel and ammonium molybdate, NiO-MoO-Al is obtained through 120 DEG C of dry 10h, 450 DEG C of roasting 4h2O3Catalyst；It is described
NiO-MoO-Al2O3The pore volume of catalyst is 0.8~1.2cm3/ g, average pore size is 20~30nm；NiO content in catalyst
For 2%, MoO3Content be 13%, Al2O3Content be 85%.
3rd hydrogenation catalyst NiO-WO3-Al2O3Preparation process：
Pseudo-thin diasphore with great pore volume powder, binding agent hydroxypropyl methyl cellulose are well mixed in kneader, added
Concentration is 0.1mol/L dilute nitric acid solution, mediates uniform rear extrusion molding；Obtained through 120 DEG C of dry 10h, 600 DEG C of roasting 4h
Big pore volume Al2O3Carrier.According to the composition of catalyst, using equi-volume impregnating, by big pore volume Al2O3Carrier impregnation contains nitre
The aqueous solution of sour nickel and ammonium metatungstate, NiO-WO is obtained through 120 DEG C of dry 10h, 450 DEG C of roasting 4h3-Al2O3Catalyst；It is described
NiO-WO3-Al2O3The pore volume of catalyst is 0.6~1.0cm3/ g, average pore size is 10~20nm；NiO content in catalyst
For 4%, WO3Content be 24%, Al2O3Content be 72%.
First beds, the second beds and the 3rd beds account for the body of total beds
Product percentage is respectively 5~25%, 20~50% and 25~75%.
Preferably, first beds, the second beds and the 3rd beds account for total catalyst
The percent by volume of bed is respectively 10~20%, 30~40% and 40~60%.
The hydrogenation reaction temperature that first beds are carried out is 240~330 DEG C, and pressure is 5~15MPa, air speed
For 4~20h-1；The hydrogenation reaction temperature that second beds are carried out is 260~360 DEG C, and pressure is 5~15MPa, empty
Speed is 2~5h-1；The hydrogenation reaction temperature that 3rd beds are carried out is 250~350 DEG C, and pressure is 5~15MPa, empty
Speed is 1.5~6h-1。
Preferably, the hydrogenation reaction temperature that first beds are carried out is 280~320 DEG C, pressure is 8~
12MPa, air speed is 5~10h-1；The hydrogenation reaction temperature that second beds are carried out is 300~340 DEG C, and pressure is 8
~12MPa, air speed is 2.5~3.5h-1；The hydrogenation reaction temperature that 3rd beds are carried out is 280~320 DEG C, pressure
Power is 8~12MPa, and air speed is 2.5~4h-1。
The operation temperature of thermal low-pressure separators described in step (2) is 230~330 DEG C, and operating pressure is 1~10MPa.
Preferably, the operation temperature of thermal low-pressure separators described in step (2) be 260~300 DEG C, operating pressure be 2~
5MPa。
Mixed described in step (2) after hydrogen material II is mixed with the hydrogenation products flowed out from the second beds and flow into the 3rd
Beds carry out hydrogenation reaction.
The volume ratio that hydrogen and recycle stock in hydrogen material II are mixed described in step (2) is 80~190.
The operation temperature of stripper described in step (3) is 230~330 DEG C, and operating pressure is 0.5~1MPa.
Cleaning system described in step (2) and step (3) is water elution NH3System, alkali cleaning take off H2S system and micro H2
With the combustion system of C1~C4 alkane.
The equipment dried described in step (3), adsorbed is the drying chamber of filling activated carbon.
Beneficial effect：Compared with prior art, advantage of the invention is as follows：
(1) present invention carries out hydrotreating using dissolved hydrogen to waste lubricating oil, greatly reduces the hydrogen consumption of course of reaction；And
By the way that the partial material of thermal low-pressure separators bottom further to be mixed to hydrogen and the beds of reactor the 3rd are recycled to, it is ensured that
There is enough hydrogen to be dissolved in the waste lubricating oil raw material for surrounding catalyst all the time in course of reaction, reaction efficiency is high；Nothing is followed
Ring hydrogen, equipment is few, and plant investment cost is low, and operating cost is also reduced；
(2) by the way that the partial material of thermal low-pressure separators bottom further to be mixed to hydrogen and the catalyst of reactor the 3rd is recycled to
Bed, in addition to being conducive to improving the concentration of the dissolved hydrogen needed for reacting, also helps the reaction of the 3rd beds of regulation
Temperature；
(3) catalyst that the present invention is used is big pore volume, the catalyst of large aperture, reduces mass transfer in liquid phase diffusional resistance；
(4) liquid phase specific heat capacity of the invention is big, and the heat of reaction release is taken away in time, so that system temperature fluctuation is small, disappears
Except " focus " on catalyst, catalyst carbon deposit speed is substantially reduced；
(5) operating flexibility is big, can process the waste lubricating oil raw material of different fractions section.Waste lubricating oil raw material is by the present invention
After method processing, sulfur content and nitrogen content in base oil are significantly reduced；Viscosity index (VI) is improved；Color number is significantly reduced；
The yield ＞ 99% of lube base oil, the hydrogen consumption ＜ 0.55% of course of reaction.
Brief description of the drawings
Fig. 1 is the reaction schematic diagram of the specific embodiment of the invention.
Wherein：1- feed pumps, 2- the first dissolvers of mixing, 3- heating furnaces, 4- reactors, the beds of 41- first,
The beds of 42- second, the beds of 43- the 3rd, 5- thermal low-pressure separators, 6- circulating pumps, the mixing dissolvers of 7- second,
8- strippers, 9- drying chambers.
Embodiment
According to following embodiments, the present invention may be better understood.However, as it will be easily appreciated by one skilled in the art that real
Apply the content described by example and be merely to illustrate the present invention, without should be also without limitation on sheet described in detail in claims
Invention.
Material, reagent used in following embodiments etc., unless otherwise specified, are commercially obtained.Implement
The experimental method of unreceipted actual conditions in example, generally according to normal condition, or the condition advised according to manufacturing firm.
The preparation process of first beds, the second beds and catalyst used in the 3rd beds
It is as follows：
First hydrogenation catalyst MoO3-Al2O3Preparation process：
Pseudo-thin diasphore with great pore volume powder, binding agent hydroxypropyl methyl cellulose are well mixed in kneader, added
Concentration is 0.1mol/L dilute nitric acid solution, mediates uniform rear extrusion molding；Obtained through 120 DEG C of dry 10h, 600 DEG C of roasting 4h
Big pore volume Al2O3Carrier.According to the composition of catalyst, using equi-volume impregnating, by big pore volume Al2O3Carrier impregnation contains molybdenum
The aqueous solution of sour ammonium, MoO is obtained through 120 DEG C of dry 10h, 450 DEG C of roasting 4h3-Al2O3Catalyst；The MoO3-Al2O3Catalysis
The pore volume of agent is 1.0~1.5cm3/ g, average pore size is 20~50nm；MoO in catalyst3Content be 3%, Al2O3Content
For 97%.
Second hydrogenation catalyst NiO-MoO-Al2O3Preparation process：
Pseudo-thin diasphore with great pore volume powder, binding agent hydroxypropyl methyl cellulose are well mixed in kneader, added
Concentration is 0.1mol/L dilute nitric acid solution, mediates uniform rear extrusion molding；Obtained through 120 DEG C of dry 10h, 600 DEG C of roasting 4h
Big pore volume Al2O3Carrier.According to the composition of catalyst, using equi-volume impregnating, by big pore volume Al2O3Carrier impregnation contains nitre
The aqueous solution of sour nickel and ammonium molybdate, NiO-MoO-Al is obtained through 120 DEG C of dry 10h, 450 DEG C of roasting 4h2O3Catalyst；It is described
NiO-MoO-Al2O3The pore volume of catalyst is 0.8~1.2cm3/ g, average pore size is 20~30nm；NiO content in catalyst
For 2%, MoO3Content be 13%, Al2O3Content be 85%.
3rd hydrogenation catalyst NiO-WO3-Al2O3Preparation process：
Pseudo-thin diasphore with great pore volume powder, binding agent hydroxypropyl methyl cellulose are well mixed in kneader, added
Concentration is 0.1mol/L dilute nitric acid solution, mediates uniform rear extrusion molding；Obtained through 120 DEG C of dry 10h, 600 DEG C of roasting 4h
Big pore volume Al2O3Carrier.According to the composition of catalyst, using equi-volume impregnating, by big pore volume Al2O3Carrier impregnation contains nitre
The aqueous solution of sour nickel and ammonium metatungstate, NiO-WO is obtained through 120 DEG C of dry 10h, 450 DEG C of roasting 4h3-Al2O3Catalyst；It is described
NiO-WO3-Al2O3The pore volume of catalyst is 0.6~1.0cm3/ g, average pore size is 10~20nm；NiO content in catalyst
For 4%, WO3Content be 24%, Al2O3Content be 72%.
Embodiment 1
The property of waste lubricating oil raw material is shown in Table 1.
Catalyst and admission space：
Liquid phase hydrogenation reactor 4 sets 3 beds, is the first catalyst bed successively according to order from the top down
The 41, second beds 42 of layer and the 3rd beds 43.What is loaded in first beds 41 is that the first hydrogenation is urged
Agent MoO3-Al2O3, its pore volume is 1.0cm3/ g, average pore size is 20nm；What is loaded in second beds 42 is second
Hydrogenation catalyst NiO-MoO-Al2O3, its pore volume is 0.8cm3/ g, average pore size is 20nm；Loaded in 3rd beds 43
Be the 3rd hydrogenation catalyst NiO-WO3-Al2O3, its pore volume is 0.6cm3/ g, average pore size is 10nm.Reacted with liquid-phase hydrogenatin
On the basis of the admission space of device, shared by the first beds 41, the second beds 42 and the 3rd beds 43
Percent by volume is respectively 5%, 20% and 75%.
A kind of method that waste lubricating oil liquid-phase hydrogenatin prepares lube base oil, is shown in Fig. 1, comprises the following steps：
(1) by the boiling range after vacuum distillation be 300~360 DEG C of waste lubricating oil raw materials by feed pump 1 and hydrogen first
Uniformly be mixed to get mixed hydrogen material I in mixing dissolver 2, the mixed hydrogen material I after the preheating of heating furnace 3, according to from
Upper downward mode enters the first beds 41 and the second beds 42 set in liquid phase hydrogenation reactor 4,
The MoO loaded in first beds 413-Al2O3The NiO-MoO-Al loaded in catalyst and the second beds 422O3
Hydrogenation reaction is carried out in the presence of catalyst；The operating condition of progress hydrogenation reaction is on the first beds 41：Temperature
For 240 DEG C, pressure is 5MPa, and air speed is 20h-1, the volume ratio of hydrogen and waste lubricating oil raw material is 50；In the second beds
The operating condition of progress hydrogenation reaction is on 42：Temperature is 260 DEG C, and pressure is 5MPa, and air speed is 5h-1, hydrogen and waste lubricating oil
The volume ratio of raw material is 30；
(2) Matter Transfer for the 10wt.% for flowing out the bottom of thermal low-pressure separators 5, by circulating pump 6 and hydrogen second
Mixed hydrogen material II is uniformly mixed to get in mixing dissolver 7, the volume ratio of hydrogen and recycle stock is in mixed hydrogen material II
140, the mixed hydrogen material II enters liquid phase after being mixed with the hydrogenation products I flowed out in step (1) from the second beds 42
The 3rd beds 43 set in hydrogenation reactor 4, the NiO-WO loaded in the 3rd beds 433-Al2O3Urge
Hydrogenation reaction is carried out in the presence of agent, the operating condition that hydrogenation reaction is carried out on the 3rd beds 43 is：Temperature is
250 DEG C, pressure is 5MPa, and air speed is 1.5h-1, the volume ratio of hydrogen and waste lubricating oil raw material is 40；
(3) hydrogenation products II flowed out from the 3rd beds 43 enter thermal low-pressure separators 5, thermal low-pressure separators 5
Operation temperature be 230 DEG C, operating pressure is 1MPa；Step (1) and step are included from the outflow of the top of thermal low-pressure separators 5
(2) unreacted H in the hydrogenation process described in2And produced in step (1) and hydrogenation process described in step (2)
Raw most H2S、NH3And the hot low point of gas of C1~C4 alkane enters cleaning system；From the bottom of thermal low-pressure separators 5 stream
The 10wt.% gone out Matter Transfer is well mixed the mixed hydrogen thing obtained described in step (2) into the second mixing dissolver 7 with hydrogen
Material II；The 90wt.% flowed out from the bottom of thermal low-pressure separators 5 material then enters stripper 8, the operation temperature of the stripper 8
Spend for 230 DEG C, operating pressure is 0.5MPa；
(4) micro H is included from the top of stripper 8 outflow described in step (3)2、H2S、NH3And C1~C4 alkane
Stripping tower overhead gas enters cleaning system；Enter the dry of filling activated carbon from the material of the stripper bottom outflow described in step (3)
Dry tank 9；The material flowed out from the bottom of drying chamber 9 is lube base oil.
(5) analysis result：The hydrogen consumption of the property of lube base oil, the yield of lube base oil and course of reaction
It is shown in Table 2.
Embodiment 2
The property of waste lubricating oil raw material is shown in Table 1.
Catalyst and admission space：
Liquid phase hydrogenation reactor 4 sets 3 beds, is the first catalyst bed successively according to order from the top down
The 41, second beds 42 of layer and the 3rd beds 43.What is loaded in first beds 41 is that the first hydrogenation is urged
Agent MoO3-Al2O3, its pore volume is 1.5cm3/ g, average pore size is 50nm；What is loaded in second beds 42 is second
Hydrogenation catalyst NiO-MoO-Al2O3, its pore volume is 1.2cm3/ g, average pore size is 30nm；Loaded in 3rd beds 43
Be the 3rd hydrogenation catalyst NiO-WO3-Al2O3, its pore volume is 1.0cm3/ g, average pore size is 20nm.Reacted with liquid-phase hydrogenatin
On the basis of the admission space of device, shared by the first beds 41, the second beds 42 and the 3rd beds 43
Percent by volume is respectively 25%, 50% and 25%.
A kind of method that waste lubricating oil liquid-phase hydrogenatin prepares lube base oil, is shown in Fig. 1, comprises the following steps：
(1) by the boiling range after vacuum distillation be 360~420 DEG C of waste lubricating oil raw materials by feed pump 1 and hydrogen first
Uniformly be mixed to get mixed hydrogen material I in mixing dissolver 2, the mixed hydrogen material I after the preheating of heating furnace 3, according to from
Upper downward mode enters the first beds 41 and the second beds 42 set in liquid phase hydrogenation reactor 4,
The MoO loaded in first beds 413-Al2O3The NiO-MoO-Al loaded in catalyst and the second beds 422O3
Hydrogenation reaction is carried out in the presence of catalyst；The operating condition of progress hydrogenation reaction is on the first beds 41：Temperature
For 330 DEG C, pressure is 15MPa, and air speed is 4h-1, the volume ratio of hydrogen and waste lubricating oil raw material is 100；In the second catalyst bed
The operating condition of progress hydrogenation reaction is on layer 42：Temperature is 360 DEG C, and pressure is 15MPa, and air speed is 2h-1, hydrogen and useless lubrication
The volume ratio of oily raw material is 80；
(2) Matter Transfer for the 60wt.% for flowing out the bottom of thermal low-pressure separators 5, by circulating pump 6 and hydrogen second
Mixed hydrogen material II is uniformly mixed to get in mixing dissolver 7, the volume ratio of hydrogen and recycle stock is in mixed hydrogen material II
190, the mixed hydrogen material II enters liquid phase after being mixed with the hydrogenation products I flowed out in step (1) from the second beds 42
The 3rd beds 43 set in hydrogenation reactor 4, the NiO-WO loaded in the 3rd beds 433-Al2O3Urge
Hydrogenation reaction is carried out in the presence of agent, the operating condition that hydrogenation reaction is carried out on the 3rd beds 43 is：Temperature is
350 DEG C, pressure is 15MPa, and air speed is 6h-1, the volume ratio of hydrogen and waste lubricating oil raw material is 120；
(3) hydrogenation products II flowed out from the 3rd beds 43 enter thermal low-pressure separators 5, thermal low-pressure separators 5
Operation temperature be 330 DEG C, operating pressure is 10MPa；Step (1) and step are included from the outflow of the top of thermal low-pressure separators 5
(2) unreacted H in the hydrogenation process described in2And produced in step (1) and hydrogenation process described in step (2)
Raw most H2S、NH3And the hot low point of gas of C1~C4 alkane enters cleaning system；From the bottom of thermal low-pressure separators 5 stream
The 60wt.% gone out Matter Transfer is well mixed the mixed hydrogen thing obtained described in step (2) into the second mixing dissolver 7 with hydrogen
Material II；The 40wt.% flowed out from the bottom of thermal low-pressure separators 5 material then enters stripper 8, the operation temperature of the stripper 8
Spend for 330 DEG C, operating pressure is 1MPa；
(4) micro H is included from the top of stripper 8 outflow described in step (3)2、H2S、NH3And C1~C4 alkane
Stripping tower overhead gas enters cleaning system；Enter the dry of filling activated carbon from the material of the bottom of stripper 8 outflow described in step (3)
Dry tank 9；The material flowed out from the bottom of drying chamber 9 is lube base oil.
(5) analysis result：The hydrogen consumption of the property of lube base oil, the yield of lube base oil and course of reaction
It is shown in Table 2.
Embodiment 3
The property of waste lubricating oil raw material is shown in Table 1.
Catalyst and admission space：
Liquid phase hydrogenation reactor 4 sets 3 beds, is the first catalyst bed successively according to order from the top down
The 41, second beds 42 of layer and the 3rd beds 43.What is loaded in first beds 41 is that the first hydrogenation is urged
Agent MoO3-Al2O3, its pore volume is 1.0cm3/ g, average pore size is 20nm；What is loaded in second beds 42 is second
Hydrogenation catalyst NiO-MoO-Al2O3, its pore volume is 0.8cm3/ g, average pore size is 20nm；Loaded in 3rd beds 43
Be the 3rd hydrogenation catalyst NiO-WO3-Al2O3, its pore volume is 0.6cm3/ g, average pore size is 10nm.Reacted with liquid-phase hydrogenatin
On the basis of the admission space of device 4, shared by the first beds 41, the second beds 42 and the 3rd beds 43
Percent by volume is respectively 10%, 30% and 60%.
A kind of method that waste lubricating oil liquid-phase hydrogenatin prepares lube base oil, is shown in Fig. 1, comprises the following steps：
(1) by the boiling range after vacuum distillation be 300~360 DEG C of waste lubricating oil raw materials by feed pump 1 and hydrogen first
Uniformly be mixed to get mixed hydrogen material I in mixing dissolver 2, the mixed hydrogen material I after the preheating of heating furnace 3, according to from
Upper downward mode enters the first beds 41 and the second beds 42 set in liquid phase hydrogenation reactor 4,
The MoO loaded in first beds 413-Al2O3The NiO-MoO-Al loaded in catalyst and the second beds 422O3
Hydrogenation reaction is carried out in the presence of catalyst；The operating condition of progress hydrogenation reaction is on the first beds 41：Temperature
For 280 DEG C, pressure is 8MPa, and air speed is 10h-1, the volume ratio of hydrogen and waste lubricating oil raw material is 60；In the second beds
The operating condition of progress hydrogenation reaction is on 42：Temperature is 300 DEG C, and pressure is 8MPa, and air speed is 3.5h-1, hydrogen and useless lubrication
The volume ratio of oily raw material is 40；
(2) Matter Transfer for the 30wt.% for flowing out the bottom of thermal low-pressure separators 5, by circulating pump 6 and hydrogen second
Mixed hydrogen material II is uniformly mixed to get in mixing dissolver 7, the volume ratio of hydrogen and recycle stock is in mixed hydrogen material II
80, the mixed hydrogen material II adds after being mixed with the hydrogenation products I flowed out in step (1) from the second beds 42 into liquid phase
The 3rd beds 43 set in hydrogen reactor 4, the NiO-WO loaded in the 3rd beds 433-Al2O3Catalysis
Hydrogenation reaction is carried out in the presence of agent, the operating condition that hydrogenation reaction is carried out on the 3rd beds 43 is：Temperature is 280
DEG C, pressure is 8MPa, and air speed is 2.5h-1, the volume ratio of hydrogen and waste lubricating oil raw material is 50；
(3) hydrogenation products II flowed out from the 3rd beds 43 enter thermal low-pressure separators 5, thermal low-pressure separators 5
Operation temperature be 260 DEG C, operating pressure is 2MPa；Step (1) and step are included from the outflow of the top of thermal low-pressure separators 5
(2) unreacted H in the hydrogenation process described in2And produced in step (1) and hydrogenation process described in step (2)
Raw most H2S、NH3And the hot low point of gas of C1~C4 alkane enters cleaning system；From the bottom of thermal low-pressure separators 5 stream
The 30wt.% gone out Matter Transfer is well mixed the mixed hydrogen thing obtained described in step (2) into the second mixing dissolver with hydrogen
Material II；The 70wt.% flowed out from the bottom of thermal low-pressure separators 5 material then enters stripper 8, the operation temperature of the stripper 8
Spend for 260 DEG C, operating pressure is 0.7MPa；
(4) micro H is included from the top of stripper 8 outflow described in step (3)2、H2S、NH3And C1~C4 alkane
Stripping tower overhead gas enters cleaning system；Enter the dry of filling activated carbon from the material of the bottom of stripper 8 outflow described in step (3)
Dry tank 9；The material flowed out from the bottom of drying chamber 9 is lube base oil.
(5) analysis result：The hydrogen consumption of the property of lube base oil, the yield of lube base oil and course of reaction
It is shown in Table 2.
Embodiment 4
The property of waste lubricating oil raw material is shown in Table 1.
Catalyst and admission space：
Liquid phase hydrogenation reactor 4 sets 3 beds, is the first catalyst bed successively according to order from the top down
The 41, second beds 42 of layer and the 3rd beds 43.What is loaded in first beds 41 is that the first hydrogenation is urged
Agent MoO3-Al2O3, its pore volume is 1.5cm3/ g, average pore size is 50nm；What is loaded in second beds 42 is second
Hydrogenation catalyst NiO-MoO-Al2O3, its pore volume is 1.2cm3/ g, average pore size is 30nm；Loaded in 3rd beds 43
Be the 3rd hydrogenation catalyst NiO-WO3-Al2O3, its pore volume is 1.0cm3/ g, average pore size is 20nm.Reacted with liquid-phase hydrogenatin
On the basis of the admission space of device, shared by the first beds 41, the second beds 42 and the 3rd beds 43
Percent by volume is respectively 20%, 40% and 40%.
Fig. 1 is refer to, a kind of method that waste lubricating oil liquid-phase hydrogenatin prepares lube base oil comprises the following steps：
(1) by the boiling range after vacuum distillation be 420~520 DEG C of waste lubricating oil raw materials by feed pump 1 and hydrogen first
Uniformly be mixed to get mixed hydrogen material I in mixing dissolver 2, the mixed hydrogen material I after the preheating of heating furnace 3, according to from
Upper downward mode enters the first beds 41 and the second beds 42 set in liquid phase hydrogenation reactor 4,
The MoO loaded in first beds 413-Al2O3The NiO-MoO-Al loaded in catalyst and the second beds 422O3
Hydrogenation reaction is carried out in the presence of catalyst；The operating condition of progress hydrogenation reaction is on the first beds 41：Temperature
For 320 DEG C, pressure is 12MPa, and air speed is 5h-1, the volume ratio of hydrogen and waste lubricating oil raw material is 80；In the second beds
The operating condition of progress hydrogenation reaction is on 42：Temperature is 340 DEG C, and pressure is 12MPa, and air speed is 2.5h-1, hydrogen and useless lubrication
The volume ratio of oily raw material is 60；
(2) Matter Transfer for the 50wt.% for flowing out the bottom of thermal low-pressure separators 5, by circulating pump 6 and hydrogen second
Mixed hydrogen material II is uniformly mixed to get in mixing dissolver 7, the volume ratio of hydrogen and recycle stock is in mixed hydrogen material II
120, the mixed hydrogen material II enters liquid phase after being mixed with the hydrogenation products I flowed out in step (1) from the second beds 42
The 3rd beds 43 set in hydrogenation reactor 4, the NiO-WO loaded in the 3rd beds 433-Al2O3Urge
Hydrogenation reaction is carried out in the presence of agent, the operating condition that hydrogenation reaction is carried out on the 3rd beds 43 is：Temperature is
320 DEG C, pressure is 12MPa, and air speed is 4h-1, the volume ratio of hydrogen and waste lubricating oil raw material is 80；
(3) hydrogenation products II flowed out from the 3rd beds 43 enter thermal low-pressure separators 5, thermal low-pressure separators 5
Operation temperature be 300 DEG C, operating pressure is 5MPa；Step (1) and step are included from the outflow of the top of thermal low-pressure separators 5
(2) unreacted H in the hydrogenation process described in2And produced in step (1) and hydrogenation process described in step (2)
Raw most H2S、NH3And the hot low point of gas of C1~C4 alkane enters cleaning system；From the bottom of thermal low-pressure separators 5 stream
The 50wt.% gone out Matter Transfer is well mixed the mixed hydrogen thing obtained described in step (2) into the second mixing dissolver 7 with hydrogen
Material II；The 50wt.% flowed out from the bottom of thermal low-pressure separators 5 material then enters stripper 8, the operation temperature of the stripper 8
Spend for 300 DEG C, operating pressure is 1MPa；
(4) micro H is included from the top of stripper 8 outflow described in step (3)2、H2S、NH3And C1~C4 alkane
Stripping tower overhead gas enters cleaning system；Enter the dry of filling activated carbon from the material of the bottom of stripper 8 outflow described in step (3)
Dry tank 9；The material flowed out from the bottom of drying chamber 9 is lube base oil.
(5) analysis result：The hydrogen consumption of the property of lube base oil, the yield of lube base oil and course of reaction
It is shown in Table 2.
Embodiment 5
The property of waste lubricating oil raw material is shown in Table 1.
Catalyst and admission space：
Liquid phase hydrogenation reactor 4 sets 3 beds, is the first catalyst bed successively according to order from the top down
The 41, second beds 42 of layer and the 3rd beds 43.What is loaded in first beds 41 is that the first hydrogenation is urged
Agent MoO3-Al2O3, its pore volume is 1.2cm3/ g, average pore size is 35nm；What is loaded in second beds 42 is second
Hydrogenation catalyst NiO-MoO-Al2O3, its pore volume is 1.0cm3/ g, average pore size is 25nm；Loaded in 3rd beds 43
Be the 3rd hydrogenation catalyst NiO-WO3-Al2O3, its pore volume is 0.8cm3/ g, average pore size is 15nm.Reacted with liquid-phase hydrogenatin
On the basis of the admission space of device 4, shared by the first beds 41, the second beds 42 and the 3rd beds 43
Percent by volume is respectively 15%, 35% and 50%.
Fig. 1 is refer to, a kind of method that waste lubricating oil liquid-phase hydrogenatin prepares lube base oil comprises the following steps：
(1) by the boiling range after vacuum distillation be 300~420 DEG C of waste lubricating oil raw materials by feed pump 1 and hydrogen first
Uniformly be mixed to get mixed hydrogen material I in mixing dissolver 2, the mixed hydrogen material I after the preheating of heating furnace 3, according to from
Upper downward mode enters the first beds 41 and the second beds 42 set in liquid phase hydrogenation reactor 4,
The MoO loaded in first beds 413/Al2O3The NiO-MoO-Al loaded in catalyst and the second beds 422O3
Hydrogenation reaction is carried out in the presence of catalyst；The operating condition of progress hydrogenation reaction is on the first beds 41：Temperature
For 300 DEG C, pressure is 10MPa, and air speed is 7.5h-1, the volume ratio of hydrogen and waste lubricating oil raw material is 70；In the second catalyst bed
The operating condition of progress hydrogenation reaction is on layer 42：Temperature is 320 DEG C, and pressure is 10MPa, and air speed is 3h-1, hydrogen and useless lubrication
The volume ratio of oily raw material is 50；
(2) Matter Transfer for the 40wt.% for flowing out the bottom of thermal low-pressure separators 5, by circulating pump 6 and hydrogen second
Mixed hydrogen material II is uniformly mixed to get in mixing dissolver 7, the volume ratio of hydrogen and recycle stock is in mixed hydrogen material II
100, the mixed hydrogen material II enters liquid phase after being mixed with the hydrogenation products I flowed out in step (1) from the second beds 42
The 3rd beds 43 set in hydrogenation reactor 4, the NiO-WO loaded in the 3rd beds 433-Al2O3Urge
Hydrogenation reaction is carried out in the presence of agent, the operating condition that hydrogenation reaction is carried out on the 3rd beds 43 is：Temperature is
300 DEG C, pressure is 10MPa, and air speed is 3.3h-1, the volume ratio of hydrogen and waste lubricating oil raw material is 65；
(3) hydrogenation products II flowed out from the 3rd beds 43 enter thermal low-pressure separators 5, thermal low-pressure separators 5
Operation temperature be 280 DEG C, operating pressure is 3MPa；Step (1) and step are included from the outflow of the top of thermal low-pressure separators 5
(2) unreacted H in the hydrogenation process described in2And produced in step (1) and hydrogenation process described in step (2)
Raw most H2S、NH3And the hot low point of gas of C1~C4 alkane enters cleaning system；From thermal low-pressure separators bottom stream
The 40wt.% gone out Matter Transfer is well mixed the mixed hydrogen thing obtained described in step (2) into the second mixing dissolver with hydrogen
Material II；The 60wt.% flowed out from the bottom of thermal low-pressure separators 5 material then enters stripper 8, the operation temperature of the stripper 8
Spend for 280 DEG C, operating pressure is 0.8MPa；
(4) micro H is included from the top of stripper 8 outflow described in step (3)2、H2S、NH3And C1~C4 alkane
Stripping tower overhead gas enters cleaning system；Enter the dry of filling activated carbon from the material of the bottom of stripper 8 outflow described in step (3)
Dry tank 9；The material flowed out from the bottom of drying chamber 9 is lube base oil.
(5) analysis result：The hydrogen consumption of the property of lube base oil, the yield of lube base oil and course of reaction
It is shown in Table 2.
Comparative example 1
This comparative example is compared with embodiment 5.
The property of waste lubricating oil raw material, catalyst and admission space are same as Example 5, but not by thermal low-pressure separators bottom
The Matter Transfer of portion's outflow.
Fig. 1 is refer to, a kind of method that waste lubricating oil liquid-phase hydrogenatin prepares lube base oil comprises the following steps：
(1) by the boiling range after vacuum distillation be 300~420 DEG C of waste lubricating oil raw materials with hydrogen in the first mixing dissolver
Mixed hydrogen material I is uniformly mixed to get, the mixed hydrogen material I enters after heating furnace is preheated in the way of from the top down
Enter the first beds and the second beds set in liquid phase hydrogenation reactor, loaded in the first beds
MoO3-Al2O3The NiO-MoO-Al loaded in catalyst and the second beds2O3Carry out being hydrogenated with instead in the presence of catalyst
Should；The operating condition of progress hydrogenation reaction is on the first beds：Temperature is 300 DEG C, and pressure is 10MPa, and air speed is
7.5h-1, the volume ratio of hydrogen and waste lubricating oil raw material is 70；The operating condition of hydrogenation reaction is carried out on the second beds
For：Temperature is 320 DEG C, and pressure is 10MPa, and air speed is 3h-1, the volume ratio of hydrogen and waste lubricating oil raw material is 50；
(2) the hydrogenation products I flowed out from the second beds is directly entered the 3rd set in liquid phase hydrogenation reactor
Beds, the NiO-WO loaded in the 3rd beds3-Al2O3Hydrogenation reaction is carried out in the presence of catalyst,
The operating condition of progress hydrogenation reaction is on 3rd beds：Temperature is 340 DEG C, and pressure is 10MPa, and air speed is 2h-1, hydrogen
The volume ratio of gas and waste lubricating oil raw material is 35；
(3) hydrogenation products II flowed out from the 3rd beds enter thermal low-pressure separators, the behaviour of thermal low-pressure separators
Make temperature for 280 DEG C, operating pressure is 3MPa；Outflow is described comprising step (1) and step (2) at the top of from thermal low-pressure separators
Hydrogenation process in unreacted H2And the big portion produced in step (1) and hydrogenation process described in step (2)
The H divided2S、NH3And the hot low point of gas of C1~C4 alkane enters cleaning system；The whole flowed out from thermal low-pressure separators bottom
Material then enters stripper, and the operation temperature of the stripper is 280 DEG C, and operating pressure is 0.8MPa；
(4) micro H is included from the stripper top outflow described in step (3)2、H2S、NH3And C1~C4 alkane
Stripping tower overhead gas enters cleaning system；Enter the dry of filling activated carbon from the material of the stripper bottom outflow described in step (3)
Dry tank；Material from the dry pot bottom outflow is lube base oil.
(5) analysis result：The hydrogen consumption of the property of lube base oil, the yield of lube base oil and course of reaction
It is shown in Table 2.
Comparative example 2
This comparative example is compared with embodiment 5.
The property of waste lubricating oil raw material is same as Example 5.
The preparation method of catalyst is shown in Chinese patent CN101797509A embodiments 3.
According to Chinese patent CN101797509A (a kind of used lubricating oil complete hydrogenation type regenerated catalyst and preparation method thereof and
Using) in fixed bed hydrogenation technique described by embodiment 3, feedstock oil is continuously delivered into heat exchanger and reaction product with measuring pump
Heat exchange, is then mixed into heating furnace with hydrogen, is heated to after 330 DEG C of temperature enter reactor, reaction process condition reference should
The table 4 of embodiment, it is 15MPa to control reaction pressure, and reaction temperature is 360 DEG C, and air speed is 0.8h-1, hydrogen and waste lubricating oil are former
The volume ratio of material is 1500.Raw material enters high-pressure separator after reactor and catalyst react and carries out gas-liquid phase separation,
Gas phase is discharged into ammonia cleaning of evaporator from separator top and absorbs ammonia therein, hydrogen sulfide etc., the ammonia discharged from ammonia cleaning of evaporator top
Reaction unit is delivered to through circulating hydrogen compressor to recycle；Liquid phase after high pressure is separated, into low pressure separator, oil gas enters
After the separation of one step, component separation is carried out in fractionating column, lubricant base oil fraction is obtained.
Analysis result：The hydrogen consumption of the property of lube base oil, the yield of lube base oil and course of reaction is shown in Table
2。
The property of the waste lubricating oil raw material of table 1
Property, yield and the hydrogen consumption for the base oil that the embodiment of table 2 is obtained with comparative example are contrasted
From the point of view of the correction data of table 2, waste lubricating oil raw material is after the inventive method is handled, the sulfur content in base oil
Significantly reduced with nitrogen content；Viscosity index (VI) is improved；Color number is significantly reduced.The yield ＞ 99% of lube base oil, instead
The hydrogen of process is answered to consume ＜ 0.55%；And the sulfur content and nitrogen content of the base oil of comparative example are still higher, color number it is higher (2~
3), the hydrogen consumption up to 1.4% of the course of reaction of comparative example 2, far above the hydrogen consumption in embodiment.
Claims (10)
1. a kind of method that waste lubricating oil liquid-phase hydrogenatin prepares lube base oil, including after waste lubricating oil raw material is mixed with hydrogen
The step of carrying out hydrogenation reaction into liquid phase hydrogenation reactor, hydrogenation products are through the isolated liquid product of thermal low-pressure separators
Step and described liquid product enter the step of obtaining lube base oil after drying, adsorption treatment after stripper processing,
Characterized in that, 10~60wt.% material is back to liquid with hydrogen mixing in the isolated liquid product of thermal low-pressure separators
Phase hydrogenation reactor.
2. according to the method described in claim 1, it is characterised in that comprise the following steps：
(1) the waste lubricating oil raw material after vacuum distillation and hydrogen are well mixed in the first mixing dissolver and obtain mixed hydrogen material
The preheated liquid phase hydrogenation reactor that flows into of I, the mixed hydrogen material I carries out hydrogenation reaction；
(2) hydrogenation products that step (1) is obtained flow into thermal low-pressure separators, from the gas of thermal low-pressure separators top outflow
Into cleaning system, from 10~60wt.% Matter Transfers of thermal low-pressure separators bottom outflow to the second mixing dissolver
It is well mixed with hydrogen and obtains mixed hydrogen material II, the mixed hydrogen material II flows into liquid phase hydrogenation reactor and carries out hydrogenation reaction；From
The rest materials of the thermal low-pressure separators bottom outflow enter stripper；
(3) gas flowed out from the stripper top enters cleaning system, and the material warp flowed out from the stripper bottom is dry
Lube base oil is produced after dry, absorption.
3. method according to claim 2, it is characterised in that the waste lubricating oil described in step (1) after vacuum distillation is former
The boiling range of material includes any one or a few the mixture in 300~360 DEG C, 360~420 DEG C, 420~520 DEG C.
4. method according to claim 2, it is characterised in that the body of hydrogen described in step (1) and waste lubricating oil raw material
Product is than being 50~100.
5. method according to claim 2, it is characterised in that by mixed hydrogen in liquid phase hydrogenation reactor described in step (1)
Material I flow directions set the first beds, the second beds and the 3rd beds from top to bottom.
6. method according to claim 5, it is characterised in that the catalyst of first beds is MoO3-
Al2O3, pore volume is 1.0~1.5cm3/ g, average pore size is 20~50nm；The catalyst of second beds is NiO-
MoO-Al2O3, pore volume is 0.8~1.2cm3/ g, average pore size is 20~30nm；The catalyst of 3rd beds is
NiO-WO3-Al2O3, pore volume is 0.6~1.0cm3/ g, average pore size is 10~20nm.
7. method according to claim 5, it is characterised in that first beds, the second beds and
The percent by volume that 3rd beds account for total beds is respectively 5~25%, 20~50% and 25~75%.
8. method according to claim 5, it is characterised in that the hydrogenation reaction temperature that first beds are carried out
For 240~330 DEG C, pressure is 5~15MPa, and air speed is 4~20h-1；The hydrogenation reaction temperature that second beds are carried out
Spend for 260~360 DEG C, pressure is 5~15MPa, air speed is 2~5h-1；The hydrogenation reaction temperature that 3rd beds are carried out
Spend for 250~350 DEG C, pressure is 5~15MPa, air speed is 1.5~6h-1。
9. method according to claim 5, it is characterised in that hydrogen material II is mixed described in step (2) with being catalyzed from second
The 3rd beds, which are flowed into, after the hydrogenation products mixing of agent bed outflow carries out hydrogenation reaction.
10. method according to claim 2, it is characterised in that hydrogen and circulation in hydrogen material II are mixed described in step (2)
The volume ratio of material is 80~190.
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