CN106244311A - A kind of waste lubricant oil by hydrogenation regeneration technology - Google Patents
A kind of waste lubricant oil by hydrogenation regeneration technology Download PDFInfo
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- CN106244311A CN106244311A CN201610691969.7A CN201610691969A CN106244311A CN 106244311 A CN106244311 A CN 106244311A CN 201610691969 A CN201610691969 A CN 201610691969A CN 106244311 A CN106244311 A CN 106244311A
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- hydrogenation
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- bed reactors
- oil
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 28
- 230000008929 regeneration Effects 0.000 title claims abstract description 27
- 238000011069 regeneration method Methods 0.000 title claims abstract description 27
- 239000002699 waste material Substances 0.000 title claims abstract description 17
- 239000000314 lubricant Substances 0.000 title description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000010687 lubricating oil Substances 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000003921 oil Substances 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 tungsten nitride Chemical class 0.000 claims abstract description 14
- 229910020057 NbOPO4 Inorganic materials 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910039444 MoC Inorganic materials 0.000 claims abstract description 11
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 11
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 11
- 239000010937 tungsten Substances 0.000 claims abstract description 11
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 239000011733 molybdenum Substances 0.000 claims abstract description 9
- 229910003178 Mo2C Inorganic materials 0.000 claims abstract description 5
- 239000002199 base oil Substances 0.000 claims abstract description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052717 sulfur Inorganic materials 0.000 abstract description 18
- 239000011593 sulfur Substances 0.000 abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 12
- 230000000694 effects Effects 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 239000012467 final product Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000002808 molecular sieve Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 235000016768 molybdenum Nutrition 0.000 description 8
- 238000006477 desulfuration reaction Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000002079 cooperative effect Effects 0.000 description 6
- 230000023556 desulfurization Effects 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 5
- 238000004939 coking Methods 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- CNHRNMLCYGFITG-UHFFFAOYSA-A niobium(5+);pentaphosphate Chemical compound [Nb+5].[Nb+5].[Nb+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O CNHRNMLCYGFITG-UHFFFAOYSA-A 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000013335 mesoporous material Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 241000772415 Neovison vison Species 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000004508 fractional distillation Methods 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 125000004122 cyclic group Chemical class 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229940069576 puralube Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
- C10M175/0025—Working-up used lubricants to recover useful products ; Cleaning by thermal processes
- C10M175/0041—Working-up used lubricants to recover useful products ; Cleaning by thermal processes by hydrogenation processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
-
- B01J35/19—
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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 carrier and active component, described carrier is complex or the mixture of MSU G, SBA 15 and HMS, and described active component is 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 complex or the mixture of MSU-G, SBA-15 and HMS.Described activity
Component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc.Described catalyst is possibly together with urging
Changing auxiliary agent, described catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixture.The reaction condition of described fixed bed reactors
For: 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..
An object of the present invention is that, it is provided that the compound of a kind of 3 kinds of different mesopore molecular sieves works in coordination with effect to show
Should be with special catalytic performance, described cooperative effect shows that desulfuration purification aspect, special catalytic performance are then to show right
On the service life of catalyst and the raising of catalysis activity.
In catalyst field, according to the definition of IUPAC (IUPAC), the aperture title less than 2nm
For micropore；The aperture referred to as macropore more than 50nm；Aperture the most mesoporous (or claiming mesopore) between 2 to 50nm.Mesoporous material
Being a kind of aperture new material with huge specific surface area and three-dimensional open-framework between micropore and macropore, it has
The excellent specific property that other porous material does not has: there is the pore passage structure of high-sequential；The single distribution in aperture, and aperture size
Can change at relative broad range；Mesoporous various shapes, hole wall composition and character controllable；Height can be obtained by optimum synthesis condition
Heat stability and hydrothermal stability.
But in present applications ' the tail must be taken, described mesoporous material, when for catalytic field, is all single use, such as MCM system
Row, such as MCM-22, MCM-36, MCM-41, MCM-48, MCM-49, MCM56, such as MSU series, such as MSU-1, MSU-2, MSU-
4, MSU-X, MSU-G, MSU-S, MSU-J etc., and SBA series, such as SBA-1, SBA-2, SBA-3, SBA-6, SBA-7, SBA-
8, SBA-11, SBA-15, SBA-16 etc., and other mesoporous series etc..
Two kinds of carriers of a few studies literature research compound, such as Y/SBA-15, Y/SAPO-5 etc., majority is to be situated between
Hole-mesoporous-microporous composite molecular sieve and micropore-mesoporous-microporous composite molecular sieve are main.Use the compound with performance of 3 kinds of different mesopore molecular sieves
Go out cooperative effect and the research of special catalytic performance, have not yet to see report.
The catalyst carrier of the present invention is complex or the mixture of MSU-G, SBA-15 and HMS.Described complex or mixed
In compound, the weight ratio of MSU-G, SBA-15 and HMS is 1:(0.8-1.2): (0.4-0.7), preferably 1:(1-1.15):
(0.5-0.7)。
MSU-G, SBA-15 and HMS mesopore molecular sieve that the present invention uses is all the existing molecular sieve of catalytic field, and it is
Through obtaining widely studied and application at catalytic field.
MSU-G is a kind of to have vesicle structure shape particle shape and the mesopore molecular sieve of layered framework structure, and it has height
Degree skeleton crosslinking and relatively thick skeleton wall and there is superpower heat stability and hydrothermal stability, its skeleton hole is with vertical
Being cross-linked with each other in layer and the hole being parallel to layer, diffusion path is the shortest because its vesicle shell is thick.The vesicle shape particle of MSU-G molecular sieve
Form facilitates reagent to enter the catalytic center of layered framework, and its catalysis activity is the highest.
SBA-15 belongs to the one of mesopore molecular sieve, has two-dimentional six square tube pore structures, has P3mm space group.At XRD
In diffracting spectrum, main peak is near about 1 °, for (10) crystal face peak.Secondary strong peak is followed successively by (11) peak and (20) peak.Other peaks are relatively
Weak, it is difficult to observe.Additionally, the silicon dioxide on SBA-15 skeleton is generally amorphous state, observe not in Radix Rumicis XRD diffraction
To obvious diffraction maximum.SBA-15 has a bigger aperture (maximum up to 30nm), thicker hole wall (wall thickness is up to 6.4nm), because of
And there is preferable hydrothermal stability.
Hexagonal mesoporous silicon HMS has long-range order and the most unordered hexagonal mesoporous duct of short distance, and its hole wall compares HCM41S
Type mesoporous material is thicker, thus hydrothermal stability is more preferable, and short distance is the most unordered simultaneously organizational structure and aperture modulation scope are more
Greatly, make HMS material have higher molecular transport efficiency and absorption property, be suitable in the activity as bulky molecular catalysis reaction
The heart.
The present invention, from each mesoporous material, carries out compound pairing, screens through widely, filter out MSU-G, SBA-15
With the compound of HMS or mixing.Inventor finds, in numerous complex/mixture, and only MSU-G, SBA-15 and HMS tri-
Compound or the mixing of person, could realize the collaborative lifting of hydrofinishing effect, and enables to catalysis activity and do not reduce for a long time, makes
Can be greatly increased with the life-span.In other words, the only specific compound or mixing of MSU-G, SBA-15 and HMS three of the present invention,
Solve collaborative and two technical problems in service life the most simultaneously.Other coordinate, or do not possess synergism, or use the longevity
Order shorter.
Described complex, can use being simply mixed of MSU-G, SBA-15 and HMS three, it would however also be possible to employ be combined two-by-two
After mixing, such as MSU-G/SBA-15 complex, the mixing of MSU-G/HMS and SBA-15/HMS complex.Described being combined can
To use known electrostatic matching method, ion exchange, two step crystallization methods etc. to be prepared.These mesopore molecular sieves are combined with it
The preparation method of thing is the known method of catalyst field, and the present invention no longer repeats with regard to it.
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 total content of described active component is the 1%-15% of vehicle weight, preferably 3-12%, further preferred 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..
An object of the present invention also resides in the promoter providing described catalyst.Catalyst of the present invention also contains
Having 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 by choosing spy
MSU-G, SBA-15 and HMS complex/mixture of certainty ratio is as carrier, and chooses nitridation two molybdenum of special ratios
MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc are as active component, and described catalyst is possibly together with catalyst aid, institute
Stating catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixture so that this catalyst produce cooperative effect, to reclaimed lubricating
The hydrodesulfurization of oil can control at total sulfur content less than 5ppm, controls the total nitrogen content in reclaimed oil at 10ppm simultaneously
Within.
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 the mixture of MSU-G, SBA-15 and HMS, and mixed proportion is 1:
1.1:0.5.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2The total content of C and tungsten carbide wc is carrier
The 10% of quality, its mol ratio is 1:0.4:0.3:0.8.
Described Catalyst packing 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 2ppm, and total alkaline nitrogen content is reduced to 6ppm.
Embodiment 2
Preparing catalyst by infusion process, carrier is MSU-G/SBA-15 complex, MSU-G/HMS and SBA-15/
The mixing of HMS complex, wherein the ratio of MSU-G, SBA-15 and HMS is same as in Example 1.Described active component nitrogenizes two molybdenums
MO2N, tungsten nitride W2N, molybdenum carbide Mo2The total content of C and tungsten carbide wc is the 10% of carrier quality, and its mol ratio is 1:0.6:
0.45):1.2。
Remaining condition is same as in Example 1.
Testing final product, total sulfur content is reduced to 3ppm, and total alkaline nitrogen content is reduced to 7ppm.
Comparative example 1
The carrier of embodiment 1 is replaced with MSU-G, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 32pm, and total alkaline nitrogen content is reduced to 41ppm.
Comparative example 2
The carrier of embodiment 1 is replaced with SBA-15, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 31ppm, and total alkaline nitrogen content is reduced to 27ppm.
Comparative example 3
The carrier of embodiment 1 is replaced with HMS, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 28ppm, and total alkaline nitrogen content is reduced to 32ppm.
Comparative example 4
Carrier in embodiment 1 is replaced with MSU-G/SBA-15 complex, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 27ppm, and total alkaline nitrogen content is reduced to 40ppm.
Comparative example 5
Carrier in embodiment 1 is replaced with SBA-15/HMS complex, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 32ppm, and total alkaline nitrogen content is reduced to 37ppm.
Comparative example 6
Carrier in embodiment 1 is replaced with MSU-G/HMS complex, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 29ppm, and total alkaline nitrogen content is reduced to 32ppm.
Embodiment 1 shows with comparative example 1-6, and the present invention uses MSU-G, SBA-15 and HMS complex of special ratios/mixed
Compound is as carrier, when replacing with single carrier or complex carrier two-by-two, does not all reach the technique effect of the present invention, therefore originally
MSU-G, SBA-15 and HMS complex/mixture of the special ratios of invention has as between carrier and other components of catalyst
Standby cooperative effect, described hydrogenation desulfurization and denitrogenation unit creates unforeseeable technique effect.
Comparative example 7
Omit the MO in embodiment 12N, remaining condition is constant.
Testing final product, total sulfur content is reduced to 42ppm, and total alkaline nitrogen content is reduced to 47ppm.
Comparative example 8
Omitting the WC in embodiment 1, remaining condition is constant.
Testing final product, total sulfur content is reduced to 48ppm, and total alkaline nitrogen content is reduced to 32ppm.
Above-described embodiment and comparative example 7-8 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 13%.
Comparative example 9
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 2.9%.
Comparative example 10
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 2.6%.
Embodiment 3 shows with comparative example 9-10, 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 complex or the mixture that carrier and active component, described carrier are MSU-G, SBA-15 and HMS；Described active component
For nitrogenizing two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc, described catalyst helps possibly together with catalysis
Agent, described catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixture, the reaction condition of described fixed bed reactors is: anti-
Temperature is answered to be 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 the weight ratio of MSU-G, SBA-15 and HMS is 1:
(0.8-1.2): (0.4-0.7), preferably 1:(1-1.15): (0.5-0.7).
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 vehicle weight
3-12%, 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.
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