CN103013644B - Method for producing base oil from waste lubricating oil - Google Patents
Method for producing base oil from waste lubricating oil Download PDFInfo
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- CN103013644B CN103013644B CN201110283920.5A CN201110283920A CN103013644B CN 103013644 B CN103013644 B CN 103013644B CN 201110283920 A CN201110283920 A CN 201110283920A CN 103013644 B CN103013644 B CN 103013644B
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Abstract
The invention relates to a method for producing base oil from waste lubricating oil. The method comprises the steps that: (1) the waste lubricating oil is separated at a separation unit, such that at least a distillate I at a distillation range of 320-450 DEG C and a distillate II at a distillation range of 420-520 DEG C are obtained; (2) in a hydrogenation processing unit, under the existence of hydrogen and a hydrogenation processing condition, the distillate I and the distillate II obtained in the step (1) are alternately subjected to a contact reaction with a hydrogenation processing catalyst, such that a hydrogenated distillate I and a hydrogenated distillate II are obtained; and (3) the hydrogenated distillate I and the hydrogenated distillate II obtained in the step (2) are respectively subjected to stripping, such that a lubricating base oil I and a lubricating base oil II are obtained.
Description
Invention field
The present invention relates to a kind of waste oil treatment, particularly relate to a kind of method that waste lubricating oil is processed.Adopt present method, when processing waste lubricating oil, can obtain the rerefined oil base oil of high yield.
Technical background
As everyone knows, along with the development of machinery industry, particularly automobile industry and improving constantly of automobile pollution, lubricant consumption is increasing, and the output of spent lubricant is also more and more.The traditional treatment method of waste lubricating oil is general adopts the methods such as discarded or burning, but the random discharge of these waste lubricating oil agent is discarded or burning not only to environment, and be also a kind of waste to resource.
US4512878 discloses a kind of method of regenerated lubricating oil, comprising: (a) heat pre-treatment (heat soaking the used oil); (b) oil after distillation heat pre-treatment; (c) overhead product distillation being obtained is by a protection bed that has active substance to form; (d) by hydrotreatment, process the overhead product of processing through protection bed; Optionally, the method comprises dehydration, de-light oil step in heat pre-treatment.
CN200710098992.6 discloses a kind of waste lubricating oil hydrogenation reproducing method, and the method is mainly that raw material waste lubricating oil is implemented to dehydration, filtration and adsorption treatment, removes moisture, mechanical impurity, colloid, bituminous matter and most of beavy metal impurity wherein; Waste lubricating oil after adsorption treatment carries out the further imurity-removal of pre-hydrofining in protectant reactor is housed; Through pre-hydrorefined waste lubricating oil, enter hydrogenation main reactor, under the effect of hydrogenation catalyst, realize hydrofining, make the undesirable components hydrogenation in stock oil saturated, product carries out fractionation cutting.
CN200710011419.7 discloses a kind of reclaiming method of waste lubricating oil, comprises that following process is: (1) filters waste lubricating oil, removes mechanical impurity; (2) carry out after filtering processed; (3) to waste lubricating oil, mix 0～10% catalytic cracking recycle oil, extraction oil or the liquefied coal coil of recycle stock by weight, then it is distilled, isolate light constituent, heavy constituent and residue; (4) heavy constituent is carried out hydrofining processing reaction; (5) hydrofining effluent reclaims and obtains lubricant base.
CN01106012.3 discloses a kind of combined technique that reclaims waste lubricating oil.Adopt suspension bed hydrogenation process process, utilize original scrap metal and compound in waste oil, as catalyzer, waste oil is directly carried out to hydrotreatment, then, light constituent product separation refining through simple filtration, distillation, fixed bed hydrogenation, gets final product to obtain product Reclaimed Base Oil and byproduct lightweight oil.
In prior art, can adopt the method that comprises hydrotreatment can realize regeneration recovery lubricant base from waste lubricating oil.But, because the hydrotreatment reaction member in the method is short effective running period, the practical application of the method is restricted.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of producing lubricant base from waste lubricating oil that new, yield and operational stability have obviously been improved.
The present invention relates to following content:
1. from a method for waste lubricating oil production basis oil, comprising: (1) at separating unit, by waste lubricating oil fractionation by distillation, at least obtain boiling range and be the overhead product II that the overhead product I of 320 ℃-450 ℃ and boiling range are 420 ℃-520 ℃; (2), at hydrotreating unit, under hydrogen existence and hydrotreatment reaction conditions, the overhead product I that step (1) is obtained and overhead product II replace and hydrotreating catalyst contact reacts, obtain respectively overhead product I and overhead product II through hydrotreatment; (3) the overhead product I through hydrotreatment respectively step (2) being obtained and overhead product II stripping, obtain lubricant base I and lubricant base II.
2. according to the method described in 1, it is characterized in that described fractionation by distillation at least obtains boiling range and be the overhead product II that the overhead product I of 350 ℃-430 ℃ and boiling range are 430 ℃-510 ℃.
3. according to the method described in 1, it is characterized in that, hydrotreatment reaction conditions comprises: pressure is 4.5-16MPa, temperature 250-390 ℃, and volume space velocity is 0.3-4.5h
-1, hydrogen to oil volume ratio is 300-1200.
4. according to the method described in 3, it is characterized in that, hydrotreatment reaction conditions comprises: pressure 6-14MPa, and temperature 270-370 ℃, volume space velocity is 0.5-3.5h
-1, hydrogen to oil volume ratio is 350-1000.
5. according to the method described in 4, it is characterized in that, hydrotreatment reaction conditions comprises: pressure 8-12MPa, and temperature 280-360 ℃, volume space velocity is 1-3h
-1, hydrogen to oil volume ratio is 450-800.
6. according to the method described in 1, it is characterized in that, described step (2) is I with hydrotreating catalyst
a, described I
acontain the carrier that is selected from aluminum oxide and/or silica-alumina, be selected from nickel and/or cobalt, the hydrogenation active metals component of molybdenum and/or tungsten, contain or do not contain and be selected from fluorine, in boron and phosphorus one or more adjuvant components and containing or containing organic additive, take catalyzer as benchmark, take the nickel of oxide compound and/or the content of cobalt as 1～5 % by weight, the content of molybdenum and/or tungsten is 12～35 % by weight, the fluorine that is selected from element, in boron and phosphorus, the content of one or more adjuvant components is 0～9 % by weight, described organism is 0-2 with take the mol ratio of hydrogenation active metals component sum of oxide compound.
7. according to the method described in 6, it is characterized in that, described catalyzer is by γ-Al
2o
3support tungsten and nickel oxide and auxiliary agent fluorine forms, it forms (weight): nickel oxide 1～5%, and Tungsten oxide 99.999 12～35%, fluorine is 1～9%, surplus is γ-Al
2o
3.
8. according to the method described in 6, it is characterized in that, described catalyzer is a kind of fluorine-containing, phosphorus hydrogenation catalyst that silica-alumina is carrier of take, consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, fluorine 1-10 % by weight, phosphorus oxide 0.5-8 % by weight, surplus is silica-alumina; Or take the hydrogenation catalyst of containing fluorin that silica-alumina is carrier, consisting of after this catalyzer roasting for a kind of: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, fluorine 1-10 % by weight, surplus is carrier; Or take for a kind of hydrogenation catalyst of containing phosphor and the preparation thereof that silica-alumina is carrier, consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, phosphorus oxide 1-9 % by weight, surplus is silica-alumina, and wherein the mol ratio of Tungsten oxide 99.999 and molybdenum oxide is greater than 2.6 to 30.
9. according to the method described in 6, it is characterized in that, described catalyzer is a kind of fluorine-containing, phosphorus hydrogenation catalyst that aluminum oxide is carrier of take, consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, phosphorus oxide 0.5-8 % by weight, fluorine 1-10 % by weight, surplus is aluminum oxide; Or take the hydrogenation catalyst of containing fluorin that aluminum oxide is carrier, consisting of after this catalyzer roasting for a kind of: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are 10 to 50 % by weight, fluorine 1-10 % by weight, all the other are aluminum oxide; Or take for a kind of the hydrogenation catalyst of containing phosphor that aluminum oxide is carrier, after this catalyzer roasting, consist of nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, phosphorus oxide 1-9 % by weight, surplus is aluminum oxide, wherein, in oxide compound, the mol ratio of tungsten and molybdenum is greater than 2.6 to 30.
10. according to the method described in 8 or 9, it is characterized in that, described catalyzer, described catalyzer contains and is selected from containing one or more in oxygen or nitrogenous organism, and described organism is 0.03-2 with take the mol ratio of nickel, molybdenum and tungsten sum of oxide compound.
11. catalyzer according to claim 10, it is characterized in that, described oxygen-containing organic compound is selected from one or more in Organic Alcohol, organic acid, and organic compounds containing nitrogen is organic amine, and described organism is 0.08-1.5 with take the mol ratio of nickel, molybdenum and tungsten sum of oxide compound.
12. according to the method described in 1, it is characterized in that, described step (2) comprises and catalyst I with hydrotreating catalyst
athe catalyst I of layered arrangement
b, described layering makes described stock oil in hydrotreatment reaction member order and catalyst I
band catalyst I
acontact, by volume and with described catalyst I
afor benchmark, catalyst I
bcontent for being greater than 0 to being less than or equal to 80%, wherein, described catalyst I
bthe content of hydrogenation active metals component be catalyst I
athe 10-30% of hydrogenation active metals component concentration.
13. according to the method described in 12, it is characterized in that, by volume and with described catalyst I
afor benchmark, catalyst I
bcontent be 5-30%
14. according to the method described in 13, it is characterized in that, by volume and with described catalyst I
afor benchmark, catalyst I
bcontent be 6-15%.
15. according to the method described in 12, it is characterized in that, in described catalyst I
awith catalyst I
bbetween comprise catalyst I
c, by volume and with described catalyst I
afor benchmark, described catalyst I
ccontent for being greater than 0 to being less than or equal to 80%, wherein, described catalyst I
cthe content of hydrogenation active metals component be catalyst I
athe content of hydrogenation active metals component be greater than 30% to being less than or equal to 70%.
16. according to the method described in 15, it is characterized in that, by volume and with described catalyst I
afor benchmark, described catalyst I
ccontent be 5-40%.
17. according to the method described in 16, it is characterized in that, by volume and with described catalyst I
afor benchmark, described catalyst I
ccontent be 10-30%.
18. according to the method described in 1, it is characterized in that, at hydrotreating unit step (2) Suo Shu, be included under hydrogen and hydrotreatment reaction conditions, overhead product I through hydrotreatment and overhead product II are replaced and hydrotreating catalyst contact reacts for bis-times, wherein, secondary hydrotreatment temperature of reaction is lower than a hydrotreatment temperature of reaction 10-50 ℃.
19. according to the method described in 18, it is characterized in that, described secondary hydrotreatment temperature of reaction is lower than a hydrotreatment temperature of reaction 20-30 ℃.
20. according to the method described in 18 or 19, it is characterized in that, described secondary hydrotreatment reaction conditions comprises: pressure 4.5-16MPa, and temperature 250-360 ℃, volume space velocity is 0.5-6h
-1, hydrogen to oil volume ratio is 300-1200.
21. according to the method described in 20, it is characterized in that, described hydrofining reaction condition comprises: pressure 6-14MPa, and temperature 260-350 ℃, volume space velocity is 1-4h
-1, hydrogen to oil volume ratio is 350-1000.
22. according to the method described in 21, it is characterized in that, described hydrofining reaction condition comprises: pressure 8-12MPa, and temperature 280-330 ℃, volume space velocity is 1.5-3.5h
-1, hydrogen to oil volume ratio is 450-800.
23. according to the method described in 1, it is characterized in that the separating unit in described step (1), before by described waste lubricating oil fractionation by distillation, comprises and filtering and/or washing step.
According to method provided by the invention, wherein, described boiling range refers to distillation yield and is more than or equal to 5% to distillation temperature corresponding to the overhead product that is less than or equal to 95%, being enough to provide under the prerequisite that can meet the described hydrotreated feedstock requirement of step (2), the concrete operations of described separating unit are not particularly limited.The method of described distillation is known in this field, for at least obtaining boiling range, be the overhead product II that the overhead product I of 320 ℃-450 ℃ and boiling range are 420 ℃-520 ℃, preferably boiling range is the overhead product II that the overhead product I of 350 ℃-430 ℃ and boiling range are 430 ℃-510 ℃, in actually operating, can comprise the operating unit of flash distillation, air distillation and underpressure distillation, to complete desirable separation.
In addition, optionally, at described separating unit, before by described waste lubricating oil fractionation by distillation, can also comprise and filtering and/or washing step, to remove solid impurity and the water that wherein may contain.Described filtration and dewatering are this area conventional process, do not repeat here.
According to method provided by the invention, the hydrotreating unit of described step (2), colloid, metal, sulphur, the nitrogen compound removing in raw material of take is object.Therefore, be enough to realize under the prerequisite of this object, described method and condition can be customary way and condition, and used catalyst can be selected from one or more in the catalyzer that can realize arbitrarily this function in prior art.They can be commercially available commodity or adopt any existing method preparation.
This type of catalyzer conventionally contain heat-resistant inorganic oxide carrier and load on hydrogenation active metals component on this carrier, containing or containing be selected from fluorine, boron and phosphorus one or more adjuvant components and containing or containing organic additive.Wherein, described heat-resistant inorganic oxide carrier is selected from one or more in the various heat-resistant inorganic oxides that are commonly used for support of the catalyst and/or matrix.For example, one or more in optional self-alumina, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, aluminum oxide-magnesium oxide, silicon oxide-magnesium oxide, silicon oxide-zirconium white, silicon oxide-Thorotrast, silicon oxide-beryllium oxide, silicon oxide-titanium oxide, silicon oxide-zirconium white, oxidation titania-zirconia, silica-alumina-Thorotrast, silica-alumina-titanium oxide, silica-alumina-magnesium oxide, silica-alumina-zirconium white, natural zeolite, clay, are preferably aluminum oxide and/or silica-alumina.Described organic additive is selected from containing one or more the organic compound in oxygen or organic compounds containing nitrogen, and preferred oxygen-containing organic compound is selected from one or more in Organic Alcohol and organic acid; Preferred organic compounds containing nitrogen is selected from one or more in organic amine.For example, oxygen-containing organic compound can be enumerated ethylene glycol, glycerol, polyoxyethylene glycol (molecular weight is 200-1500), Diethylene Glycol, butyleneglycol, acetic acid, toxilic acid, oxalic acid, nitrilotriacetic acid, 1, one or more in 2-CDTA, citric acid, tartrate, oxysuccinic acid, organic compounds containing nitrogen can be enumerated quadrol, EDTA and ammonium salt thereof.
In embodiment, described catalyzer is I
a, I
abe selected from one or more in following catalyzer, comprise:
The disclosed catalyzer of CN85104438, it is by γ-Al
2o
3support tungsten and nickel oxide and auxiliary agent fluorine forms, it forms (weight): nickel oxide 1～5%, and Tungsten oxide 99.999 12～35%, fluorine is 1～9%.
CN1853780A discloses a kind of fluorine-containing, phosphorus hydrogenation catalyst of take that silica-alumina is carrier and preparation thereof, consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, fluorine 1-10 % by weight, phosphorus oxide 0.5-8 % by weight, surplus is silica-alumina.This catalyzer is by comprising prepared by method from tungsten to silica-alumina carrier that introduce fluorine, phosphorus, molybdenum, nickel and, wherein, the consumption of each component makes consisting of after catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, fluorine 1-10 % by weight, phosphorus oxide 0.5-8 % by weight, surplus is silica-alumina.
CN1853779A discloses a kind of hydrogenation catalyst of containing fluorin and preparation thereof that silica-alumina is carrier of take, consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, fluorine 1-10 % by weight, and surplus is carrier.The preparation method of this catalyzer comprises to silica-alumina carrier introducing fluorine, molybdenum, nickel and tungsten, wherein, the consumption of each component makes consisting of after catalyzer roasting: nickel oxide 1-10 % by weight, and molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, fluorine 1-10 % by weight, surplus is carrier.
CN1853781A discloses a kind of hydrogenation catalyst of containing phosphor and preparation thereof that silica-alumina is carrier of take, consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, phosphorus oxide 1-9 % by weight, surplus is silica-alumina, and wherein the mol ratio of Tungsten oxide 99.999 and molybdenum oxide is greater than 2.6 to 30.The preparation method of this catalyzer comprises to silica-alumina carrier introducing phosphorus, molybdenum, nickel and tungsten, wherein, the consumption of each component makes consisting of after catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, phosphorus oxide 1-9 % by weight, surplus is silica-alumina, and the mol ratio of described Tungsten oxide 99.999 and molybdenum oxide is greater than 2.6 to 30.
CN1853781A discloses a kind of fluorine-containing, phosphorus hydrogenation catalyst of take that aluminum oxide is carrier and preparation thereof, consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, phosphorus oxide 0.5-8 % by weight, fluorine 1-10 % by weight, surplus is aluminum oxide.This catalyzer is by comprising prepared by method from tungsten to alumina supporter that introduce fluorine, phosphorus, molybdenum, nickel and, wherein, the consumption of each component makes consisting of after catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, fluorine 1-10 % by weight, phosphorus oxide 0.5-8 % by weight, surplus is aluminum oxide.
CN1872959A discloses a kind of hydrogenation catalyst of containing fluorin and preparation thereof that aluminum oxide is carrier of take, consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are 10 to 50 % by weight, fluorine 1-10 % by weight, and all the other are aluminum oxide.The preparation method of this catalyzer comprises to alumina supporter introducing fluorine, molybdenum, nickel and tungsten, wherein, the consumption of each component makes consisting of after catalyzer roasting: nickel oxide 1-10 % by weight, and molybdenum oxide and Tungsten oxide 99.999 sum are 10 to 50 % by weight, fluorine 1-10 % by weight, surplus is aluminum oxide.
CN1872960A discloses a kind of hydrogenation catalyst of containing phosphor and preparation thereof that aluminum oxide is carrier of take, after this catalyzer roasting, consist of nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, phosphorus oxide 1-9 % by weight, surplus is aluminum oxide, wherein, in oxide compound, the mol ratio of tungsten and molybdenum is greater than 2.6 to 30.This catalyzer is introduced phosphorus, molybdenum, nickel and tungsten by comprising in alumina supporter, wherein, the consumption of each component makes consisting of after catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, phosphorus oxide 1-9 % by weight, surplus is aluminum oxide, wherein, in oxide compound, the mol ratio of tungsten and molybdenum is greater than 2.6 to 30.
In the disclosed catalyzer of CN1853780A, CN1853779A, CN1853781A, CN1872959A and CN1872960A, preferably also contain organic additive, wherein, described organism with take the mol ratio of hydrogenation active metals component sum of oxide compound and be preferably 0.08-1.5 as 0.03-2.
About the more detailed preparation method of above-mentioned catalyzer, all on the books in above-mentioned patent documentation, the part using them as content of the present invention is quoted in the lump here.
When the hydrotreating catalyst of described step (2) comprises and catalyst I
athe catalyst I of layered arrangement
btime, described catalyst I
bhave compared with catalyst I
alow hydrogenation active metals component concentration, described catalyst I
bthe content of hydrogenation active metals component be catalyst I
athe 10-30% of the content of hydrogenation active metals component, is preferably 12-25%.Putting before this, the present invention is to described catalyst I
bbe not particularly limited, they can be that commercially available commodity also can adopt prior art preparation arbitrarily.
In embodiment, this type of catalyzer conventionally contain heat-resistant inorganic oxide carrier and load on hydrogenation active metals component on this carrier, containing or not containing being selected from one or more adjuvant components in fluorine, boron, phosphorus and alkaline-earth metal.With catalyst I
bfor benchmark, described catalyst I
btake the nickel of oxide compound and/or the content of cobalt as 0.5-4 % by weight, be preferably 1.0-3 % by weight, the content of molybdenum and/or tungsten is 2.5-9 % by weight, be preferably 3.5-6.5 % by weight, the content that is selected from one or more adjuvant components in fluorine, boron, phosphorus and alkaline-earth metal of element of take is 0-5 % by weight, and the total amount that meets nickel and/or cobalt and molybdenum and/or W content is catalyst I
athe 10-30% of the content of hydrogenation active metals component, is preferably 12-25%.
For example, in CN1344781, CN1966616 and CN101134173A, the preparation method of disclosed catalyzer just can be used to preparation and meets the catalyzer that the present invention requires.Here the part using them as content of the present invention is quoted in the lump.
Hydrotreating catalyst I when described step (2)
awith catalyst I
bbetween also comprise catalyst I
ctime, described catalyst I
cthe content of hydrogenation active metals component be catalyst I
ahydrogenation active metals component concentration be greater than 30 to being less than or equal to 70 % by weight, be preferably 40-60%.Putting before this, the present invention is to described catalyst I
bbe not particularly limited, they can be that commercially available commodity also can adopt prior art preparation arbitrarily.
In embodiment, this type of catalyzer conventionally contain heat-resistant inorganic oxide carrier and load on hydrogenation active metals component on this carrier, containing or not containing being selected from one or more adjuvant components in fluorine, boron, phosphorus and alkaline-earth metal.With catalyst I
cfor benchmark, described catalyst I
ctake the nickel of oxide compound and/or the content of cobalt as 0.3-8 % by weight, be preferably 0.5-7.5 % by weight, the content of molybdenum and/or tungsten is 0.5-15 % by weight, is preferably 0.8-12 % by weight, and the total amount that meets nickel and/or cobalt and molybdenum and/or W content is catalyst I
athe 30-70% of the content of hydrogenation active metals component, is preferably 40-60%.
For example, in CN1626625A, CN1690172A, CN1782031A and CN1782033A, the preparation method of disclosed catalyzer just can be used to preparation and meets the catalyzer that the present invention requires.Here the part using them as content of the present invention is quoted in the lump.
The reactor of described hydrotreating unit can be the reactor that can be used for hydrotreatment reaction that prior art provides arbitrarily, for example fixed-bed reactor.Described reactor can be one, and now, the overhead product I that will be obtained by step (1) and overhead product II are by switching, alternately with hydrotreating catalyst contact reacts; Described reactor can be also two or more, for example, for the situation that comprises that two or more catalyzer couplings are used, different catalysts can be packed into the reactor of two or more series connection successively, and the overhead product I that will be obtained by step (1) and overhead product II be by switching, alternately with hydrotreating catalyst contact reacts in the reactor of connecting; Or by two covers arranged side by side or overlap the reactor system of aforesaid one or more series connection more, and the overhead product I being obtained by step (1) and overhead product II be by switching, realize continuously, alternately with reactor system arranged side by side in hydrotreating catalyst contact reacts.
Described stripping take that to remove the small molecule hydrocarbon compounds that comprises the heteroatomic compounds such as hydrogen sulfide and may generate producing through hydrotreatment be object, is being enough to realize under the prerequisite of this object, and the present invention is not particularly limited described steam stripped method and condition.For example, take the stripping that water vapour is stripping medium (generally including atmospheric stripping and decompression stripping).About these gas stripping process and operational condition, be this area customary way and condition, do not repeat here.
According to method provided by the invention, when comprising the reactions steps of secondary hydrotreatment, secondary hydrotreatment reaction used catalyst can be identical with a described anti-applications catalyst of hydrotreatment, and for example, being selected from hydrotreating catalyst is I
ain one or more catalyzer.In a preferred embodiment.The anti-applications catalyst of described secondary hydrotreatment is selected from the Hydrobon catalyst of not fluorine-containing and/or molecular sieve.They can be commercially available commodity or adopt any existing method preparation.
This type of catalyzer conventionally contains heat-resistant inorganic oxide carrier, hydrogenation active metals component, contains or does not contain auxiliary agent phosphorus and contains or do not contain organic additive.Wherein, described heat-resistant inorganic oxide carrier is selected from one or more in the various heat-resistant inorganic oxides that are commonly used for support of the catalyst and/or matrix.For example, one or more in optional self-alumina, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, aluminum oxide-magnesium oxide, silicon oxide-magnesium oxide, silicon oxide-zirconium white, silicon oxide-Thorotrast, silicon oxide-beryllium oxide, silicon oxide-titanium oxide, silicon oxide-zirconium white, oxidation titania-zirconia, silica-alumina-Thorotrast, silica-alumina-titanium oxide, silica-alumina-magnesium oxide, silica-alumina-zirconium white, natural zeolite, clay, are preferably aluminum oxide.Described organic additive is selected from containing one or more the organic compound in oxygen or organic compounds containing nitrogen, and preferred oxygen-containing organic compound is selected from one or more in Organic Alcohol and organic acid; Preferred organic compounds containing nitrogen is selected from one or more in organic amine.For example, oxygen-containing organic compound can be enumerated ethylene glycol, glycerol, polyoxyethylene glycol (molecular weight is 200-1500), Diethylene Glycol, butyleneglycol, acetic acid, toxilic acid, oxalic acid, nitrilotriacetic acid, 1, one or more in 2-CDTA, citric acid, tartrate, oxysuccinic acid, organic compounds containing nitrogen can be enumerated quadrol, EDTA and ammonium salt thereof.
For example, the disclosed a kind of Hydrobon catalyst of CN1085934, this catalyzer contains by magnesium oxide, nickel oxide, Tungsten oxide 99.999 and aluminum oxide, and it consists of: magnesium oxide 0.1～1.9%, nickel oxide 2.5～6%, Tungsten oxide 99.999 24～34% and surplus aluminum oxide.
The disclosed a kind of hydrogenation catalyst of containing phosphor that aluminum oxide is carrier of take of CN1872960A, after this catalyzer roasting, consist of nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, phosphorus oxide 1-9 % by weight, surplus is aluminum oxide, wherein, in oxide compound, the mol ratio of tungsten and molybdenum is greater than 2.6 to 30.
Mono-kind of CN1840618A be take hydrogenation catalyst and the preparation thereof that silica-alumina is carrier, consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, and molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, and surplus is carrier.
In CN1872960A and the disclosed catalyzer of CN1840618A, preferably also contain organic additive, wherein, described organism with take the mol ratio of hydrogenation active metals component sum of oxide compound and be preferably 0.08-1.5 as 0.03-2.
These catalyzer all can be used as described secondary hydrotreating catalyst for the present invention.About the more detailed preparation method of above-mentioned catalyzer, all on the books in above-mentioned patent documentation, the part using them as content of the present invention is quoted in the lump here.
When comprising the reactions steps of secondary hydrotreatment, can adopt streams that any existing heat transfer technology heat exchange makes to be derived from the hydrogenator temperature when entering secondary hydrogenator to meet described requirement.Described secondary hydrogenator can be the reactor that can be used for hydrotreatment reaction that prior art provides arbitrarily, for example fixed-bed reactor.Described secondary hydrogenator can be one, through the overhead product I of a hydrogenator of heat exchange and overhead product II by switching, alternately with secondary hydrogenator in hydrotreating catalyst contact reacts; Described secondary hydrogenator can be two or more reactor systems arranged side by side, through the overhead product I of a hydrogenator of heat exchange and overhead product II by switching, realize continuously, alternately with secondary hydrogenator system arranged side by side in hydrotreating catalyst contact reacts.
According to method provided by the invention, by treating that regenerated lube stock is cut into the hydrotreatment that hockets of at least two cuts, when realization is carried out hydrogenation regeneration to waste lubricating oil material, can obviously improve the service efficiency of catalyzer, for example, within identical runtime, generate oil and there is better character.When adopting the preferred hydrotreatment of the present invention district used catalyst coupling, this effect can further improve.The method of the invention provides is suitable for processing waste lubricating oil material under various operating modes, to obtain the lubricant base that can repeat again use.
Embodiment
The present invention is described further for the following examples.
Embodiment 1
A waste lubricating oil, its source is 4S shop waste lubricating oil, its character is in Table 1.
(1) separating unit and operation thereof:
Being separated in vacuum distillation apparatus of waste lubricating oil material carried out.
Obtain boiling range and be the overhead product II that the overhead product I of 350 ℃-430 ℃ and boiling range are 430 ℃-510 ℃.The character of overhead product I and overhead product II is in Table 2.
(2) hydrotreating unit and operation thereof:
Hydrogenation place catalyst I
aaccording to the open method preparation of CN85104438, it consists of: nickel oxide 3 % by weight, and Tungsten oxide 99.999 25 % by weight, fluorine is weight 4%, surplus is γ-Al
2o
3.
Reactor is fixed-bed reactor, overhead product I and overhead product II are by switching, alternately introducing reactor (comprising: first half introducing reactor of overhead product I is reacted with catalyzer contact reacts, switch to afterwards overhead product II, after half introducing reactor of overhead product II is reacted, repeat aforesaid process).Reaction conditions is in Table 3.
(3) stripping and operation thereof:
Stripping carries out in decompression stripper plant, and stripping medium is water vapour.
Through stripping, obtain the product of regeneration: base oil I and base oil II, product property is in Table 4.
Comparative example 1
Waste lubricating oil raw material is identical with embodiment 1.
(1) separating unit and operation thereof:
Waste lubricating oil material is separated in vacuum distillation apparatus and carries out.
Through described distillation, obtain boiling range and be the overhead product of 350 ℃-510 ℃.The character of overhead product is in Table 5.
(2) hydrotreating unit and operation thereof:
Owing to entering the raw material of hydrotreating unit, be the single overhead product of 350 ℃-510 ℃, hydrotreatment reaction does not have as the blocked operation of embodiment 1.Catalyzer is identical with embodiment 1, and reaction conditions is identical with the reaction conditions of overhead product II in embodiment 1.
(3) hydrotreatment products is separated:
Hydrotreatment reaction product obtains the base oil product of the two kind regeneration identical with embodiment 1 boiling range through underpressure distillation separation: base oil I and base oil II, product property is in Table 6.
The character of table 1 waste lubricating oil
| Density/(kg/m3) | 0.8926 |
| Kinematic viscosity (100 ℃)/(mm2/s) | 6.954 |
| Kinematic viscosity (40 ℃)/(mm2/s) | 45.63 |
| Viscosity index | 109 |
| Zero pour/℃ | -18 |
| Color/number | 6.5 |
| Sulphur content/(mg/kg) | 2200 |
| Phosphorus content/(mg/kg) | 660 |
| Metal content/(mg/kg) | |
| Ca | 160 |
| Zn | 75 |
| Initial boiling point/℃ | 302 |
| 5％(V)/℃ | 312 |
| 95％//℃ | 532 |
Table 2 distillation overhead product character
| Overhead product | Overhead product I | Overhead product II |
| Density/(kg/m3) | 0.8732 | 0.9021 |
| Kinematic viscosity (100 ℃)/(mm2/s) | 4.432 | 10.56 |
| Kinematic viscosity (40 ℃)/(mm2/s) | 24.26 | 83.62 |
| Viscosity index | 101 | 110 |
| Pour point/℃ | -20 | -16 |
| Color/number | 5.4 | 7.5 |
| Sulphur content/(mg/kg) | 1400 | 1600 |
| Phosphorus content/(mg/kg) | 430 | 570 |
| Metal content/(mg/kg) | ||
| Ca | 62 | 78 |
| Zn | 0.1 | 0.1 |
| Boiling range | ||
| Initial boiling point/℃ | 335 | 422 |
| 5％(V)/℃ | 351 | 431 |
| 95％(V)/℃ | 428 | 509 |
Table 3 reaction conditions
| Charging | Overhead product I | Overhead product II |
| Reaction pressure/MPa | 8.0 | 8.0 |
| Temperature of reaction/℃ | 330 | 345 |
| Volume space velocity/h -1 | 1.2 | 1.2 |
| Hydrogen to oil volume ratio | 350∶1 | 350∶1 |
Table 4 treated oil character
| Treated oil | Base oil I | Base oil II |
| Gross weight yield/% | 34 | 57 |
| Density/(kg/m3) | 0.8732 | 0.9021 |
| Kinematic viscosity (100 ℃)/(mm2/s) | 4.432 | 10.45 |
| Kinematic viscosity (40 ℃)/(mm2/s) | 24.26 | 82.21 |
| Viscosity index | 101 | 110 |
| Pour point/℃ | -20 | -16 |
| Color/number | 2.0 | 3.0 |
| Sulphur content/(mg/kg) | 213 | 242 |
| Phosphorus content/(mg/kg) | 0.5 | 0.6 |
| Metal content/(mg/kg) | ||
| Ca | ＜0.1 | ＜0.1 |
| Zn | ＜0.1 | ＜0.1 |
| Boiling range | ||
| Initial boiling point/℃ | 335 | 422 |
| 5％(V)/℃ | 351 | 431 |
| 95％(V)/℃ | 428 | 509 |
Table 5 overhead product character
| Density/(kg/m3) | 0.8926 |
| Kinematic viscosity (100 ℃)/(mm2/s) | 6.954 |
| Kinematic viscosity (40 ℃)/(mm2/s) | 45.63 |
| Viscosity index | 109 |
| Pour point/℃ | -18 |
| Color/number | 6.5 |
| Sulphur content/(mg/kg) | 1560 |
| Phosphorus content/(mg/kg) | 550 |
| Metal content/(mg/kg) |
| Ca | 72 |
| Zn | 0.12 |
| Boiling range | |
| Initial boiling point/℃ | 316 |
| 5％(V)/℃ | 352 |
| 95％(V)/℃ | 508 |
Table 6 base oil character
| Treated oil | Base oil I | Base oil II |
| Gross weight yield/% | 31 | 53 |
| Density/(kg/m3) | 0.8732 | 0.9021 |
| Kinematic viscosity (100 ℃)/(mm2/s) | 4.51 | 10.32 |
| Kinematic viscosity (40 ℃)/(mm2/s) | ||
| Viscosity index | 100 | 109 |
| Pour point/℃ | -20 | -16 |
| Color/number | 1.0 | 1.5 |
| Sulphur content/(mg/kg) | 216 | 312 |
| Phosphorus content/(mg/kg) | 0.1 | 0.1 |
| Metal content/(mg/kg) | ||
| Ca | ＜0.1 | ＜0.1 |
| Zn | ＜0.1 | ＜0.1 |
| Boiling range | ||
| Initial boiling point/℃ | 342 | 426 |
| 5％(V)/℃ | 352 | 435 |
| 95％(V)/℃ | 429 | 508 |
Embodiment 2
A waste lubricating oil mixture, the mixture that its source is the waste internal-combustion engine oil in family saloon 4s shop and fishing marine diesel waste lubricating oil, its character is in Table 7.
(1) separating unit and operation thereof:
Above-mentioned waste lubricating oil mixture is heated to 125 ℃ at basin, then from tank bottom, passes into superheated vapour stripping washing 6 hours, the temperature that maintains system in stripping washing process is 120-125 ℃.After stripping washing finishes, carry out standing sedimentation, settling process Controlling System temperature is 80-85 ℃, and the settling time is 24 hours, and sedimentation finishes rear tank bottom to be cut to water.Through cutting the waste lubricating oil of water, introduce in vacuum distillation apparatus and distill, obtain boiling range and be the overhead product II that the overhead product I of 350 ℃-420 ℃ and boiling range are 420 ℃-510 ℃, the character of overhead product I and overhead product II is in Table 8.
(2) hydrotreating unit and operation thereof:
Hydrotreating catalyst is the I of layering
a, I
band I
ccombination, wherein, by volume and with I
afor benchmark, I
bcontent be 6%, I
ccontent be 18%.Reactor is two fixed-bed reactor arranged side by side, overhead product I and overhead product II are by switching, (described switching meets reacting in each reactor: first by 1/4th of overhead product I, introduce reactor and react with catalyzer contact reacts alternately to introduce reactor arranged side by side, switch to afterwards overhead product II, by 1/4th of overhead product II, introduce after reactor reacts and repeat aforesaid process).Reaction conditions is in Table 9.
Catalyst I
aaccording to the open method preparation of CN85104438, it consists of: nickel oxide 3 % by weight, and Tungsten oxide 99.999 25 % by weight, fluorine is weight 4%, surplus is γ-Al
2o
3.
Catalyst I
baccording to embodiment 5 preparation in CN1966616A, wherein hydrogenation active metals component is molybdenum and nickel, and in oxide compound and take catalyzer as benchmark, the content of molybdenum is 4.5 % by weight, and the content of nickel is 1.5 % by weight.
Catalyst I
caccording to the embodiment of CN1782033A 15 preparation, wherein hydrogenation active metals component is molybdenum and nickel, and in oxide compound and take catalyzer as benchmark, the content of molybdenum is 13.7 % by weight, and the content of nickel is 3 % by weight.
(3) stripping and operation thereof:
Stripping carries out in decompression stripper plant, and stripping medium is water vapour.
The base oil I and the base oil II that through stripping, obtain regeneration, the character of base oil I and base oil II is in Table 10.
Table 7 waste lubricating oil feedstock property
| Project | Character |
| Density/(kg/m3) | 880.4 |
| Kinematic viscosity (100 ℃)/(mm2/s) | 11.24 |
| Kinematic viscosity (40 ℃)/(mm2/s) | 98.79 |
| Viscosity index | 99 |
| Pour point/℃ | -10 |
| Color/number | ＞8 |
| Sulphur content/(mg/kg) | 4363 |
| Phosphorus content/(mg/kg) | 181 |
| Metal content/(mg/kg) | |
| Ca | 195 |
| Fe | 226 |
| Na | 539 |
| Zn | 1036 |
| Boiling range | |
| Initial boiling point/℃ | 289 |
| 5％(V)/℃ | 312 |
| 95％(V)/℃ | 546 |
Table 8 waste lubricating oil middle runnings character
| Project | Overhead product I | Overhead product II |
| Density/(kg/m3) | 879.6 | 882.8 |
| Kinematic viscosity (100 ℃)/(mm2/s) | 4.32 | 8.326 |
| Kinematic viscosity (40 ℃)/(mm2/s) | 22.33 | 62.87 |
| Viscosity index | 94 | 101 |
| Pour point/℃ | -15 | -12 |
| Color/number | 4 | 6 |
| Sulphur content/(mg/kg) | 1700 | 1500 |
| Phosphorus content/(mg/kg) | 800 | 760 |
| Metal content/(mg/kg) | ||
| Ca | 0.1 | 0.11 |
| Fe | 0.5 | 0.8 |
| Na | 3.3 | 5.4 |
| Zn | ＜0.1 | ＜0.1 |
| Boiling range |
| Initial boiling point/℃ | 338 | 426 |
| 5％(V)/℃ | 350 | 431 |
| 95％(V)/℃ | 428 | 509 |
Table 9 reaction conditions
| Project | Cut I | Cut II |
| Reaction pressure/MPa | 6.4 | 6.4 |
| Temperature of reaction/℃ | 340 | 350 |
| Volume space velocity/h -1 | 2.0 | 2.0 |
| Hydrogen to oil volume ratio | 500∶1 | 500∶1 |
Table 10 base oil character
| Base oil I | Base oil II | |
| Gross weight yield % | 44 | 38 |
| Density/(kg/m3) | 879.3 | 882.5 |
| Kinematic viscosity (100 ℃)/(mm2/s) | 4.29 | 8.318 |
| Kinematic viscosity (400 ℃)/(mm2/s) | 21.84 | 61.86 |
| Viscosity index | 96 | 103 |
| Pour point/℃ | -13 | -10 |
| Color/number | ＜0.5 | ＜1.0 |
| Sulphur content/(mg/kg) | 269 | 186 |
| Phosphorus content/(mg/kg) | 12 | 8 |
| Metal content/(mg/kg) | ||
| Ca | ＜0.1 | ＜0.1 |
| Fe | ＜0.1 | ＜0.1 |
| Na | ＜0.1 | ＜0.1 |
| Zn | ＜0.1 | ＜0.1 |
| Boiling range | ||
| Initial boiling point/℃ | 334 | 425 |
| 5％(V)/℃ | 351 | 432 |
| 95％(V)/℃ | 429 | 509 |
Embodiment 3
Except hydrotreating unit, other are identical with embodiment 2.
Hydrotreating unit has increased secondary hydrotreating step.Wherein, a hydrotreating catalyst is identical with embodiment 2.A hydrotreatment reaction conditions is in Table 11.
Secondary hydroprocessing catalysts is according to the open method preparation of CN1085934, and it consists of: magnesium oxide 1 % by weight, nickel oxide 4 % by weight, Tungsten oxide 99.999 29 % by weight and surplus aluminum oxide.The loaded catalyst of secondary hydrotreatment is 60 volume % of a hydrotreating catalyst.Secondary hydrotreatment reaction conditions is in Table 11.
The base oil I and the base oil II that through decompression stripping, obtain regeneration, the character of base oil I and base oil II is in Table 12.
Table 11 reaction conditions
Table 12 base oil character
| Base oil I | Base oil I I | |
| Gross weight yield/% | 47 | 43 |
| Density/(kg/m3) | 879.4 | 882.3 |
| Kinematic viscosity (100 ℃)/(mm2/s) | 4.310 | 8.312 |
| Kinematic viscosity (400 ℃)/(mm2/s) | 21.84 | 61.89 |
| Viscosity index | 97 | 103 |
| Pour point/℃ | -13 | -10 |
| Color/number | 0.5 | 1.0 |
| Sulphur content/(mg/kg) | 123 | 102 |
| Phosphorus content/(mg/kg) | 6 | 5 |
| Metal content/(mg/kg) | ||
| Ca | ＜0.1 | ＜0.1 |
| Fe | ＜0.1 | ＜0.1 |
| Na | ＜0.1 | ＜0.1 |
| Zn | ＜0.1 | ＜0.1 |
Claims (22)
1. from a method for waste lubricating oil production basis oil, comprising: (1) at separating unit, by waste lubricating oil fractionation by distillation, at least obtain boiling range and be the overhead product II that the overhead product I of 320 ℃-450 ℃ and boiling range are 420 ℃-520 ℃, (2), at hydrotreating unit, under hydrogen existence and hydrotreatment reaction conditions, the overhead product I that step (1) is obtained and overhead product II replace and hydrotreating catalyst contact reacts, obtain respectively overhead product I and overhead product II through hydrotreatment, (3) the overhead product I through hydrotreatment respectively step (2) being obtained and overhead product II stripping, obtain lubricant base I and lubricant base II, wherein, described step (2) is I with hydrotreating catalyst
a, described I
acontain the carrier that is selected from aluminum oxide and/or silica-alumina, be selected from nickel and/or cobalt, the hydrogenation active metals component of molybdenum and/or tungsten, contain or do not contain and be selected from fluorine, in boron and phosphorus one or more adjuvant components and containing or containing organic additive, take catalyzer as benchmark, take the nickel of oxide compound and/or the content of cobalt as 1～5 % by weight, the content of molybdenum and/or tungsten is 12～35 % by weight, the fluorine that is selected from element, in boron and phosphorus, the content of one or more adjuvant components is 0～9 % by weight, described organic additive is 0-2 with take the mol ratio of hydrogenation active metals component sum of oxide compound.
2. according to the method described in 1, it is characterized in that the fractionation by distillation through described step (1) at least obtains boiling range and be the overhead product II that the overhead product I of 350 ℃-430 ℃ and boiling range are 430 ℃-510 ℃.
3. according to the method described in 1, it is characterized in that, hydrotreatment reaction conditions comprises: pressure is 4.5-16MPa, and temperature is 250-390 ℃, and volume space velocity is 0.3-4.5h
-1, hydrogen to oil volume ratio is 300-1200.
4. according to the method described in 3, it is characterized in that, hydrotreatment reaction conditions comprises: pressure is 6-14MPa, and temperature is 270-370 ℃, and volume space velocity is 0.5-3.5h
-1, hydrogen to oil volume ratio is 350-1000.
5. according to the method described in 4, it is characterized in that, hydrotreatment reaction conditions comprises: pressure is 8-12MPa, and temperature is 280-360 ℃, and volume space velocity is 1-3h
-1, hydrogen to oil volume ratio is 450-800.
6. according to the method described in 1, it is characterized in that, described catalyzer is by γ-Al
2o
3support tungsten and nickel oxide and auxiliary agent fluorine forms, it forms (weight): nickel oxide 1～5%, and Tungsten oxide 99.999 12～35%, fluorine is 1～9%, surplus is γ-Al
2o
3.
7. according to the method described in 1, it is characterized in that, described catalyzer is a kind of fluorine-containing, phosphorus hydrogenation catalyst that silica-alumina is carrier of take, consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, fluorine 1-10 % by weight, phosphorus oxide 0.5-8 % by weight, surplus is silica-alumina; Or take the hydrogenation catalyst of containing fluorin that silica-alumina is carrier, consisting of after this catalyzer roasting for a kind of: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, fluorine 1-10 % by weight, surplus is carrier; Or take for a kind of hydrogenation catalyst of containing phosphor and the preparation thereof that silica-alumina is carrier, consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, phosphorus oxide 1-9 % by weight, surplus is silica-alumina, and wherein the mol ratio of Tungsten oxide 99.999 and molybdenum oxide is greater than 2.6 to 30.
8. according to the method described in 1, it is characterized in that, described catalyzer is a kind of fluorine-containing, phosphorus hydrogenation catalyst that aluminum oxide is carrier of take, consisting of after this catalyzer roasting: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, phosphorus oxide 0.5-8 % by weight, fluorine 1-10 % by weight, surplus is aluminum oxide; Or take the hydrogenation catalyst of containing fluorin that aluminum oxide is carrier, consisting of after this catalyzer roasting for a kind of: nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are 10 to 50 % by weight, fluorine 1-10 % by weight, all the other are aluminum oxide; Or take for a kind of the hydrogenation catalyst of containing phosphor that aluminum oxide is carrier, after this catalyzer roasting, consist of nickel oxide 1-10 % by weight, molybdenum oxide and Tungsten oxide 99.999 sum are greater than 10 to 50 % by weight, phosphorus oxide 1-9 % by weight, surplus is aluminum oxide, wherein, in oxide compound, the mol ratio of tungsten and molybdenum is greater than 2.6 to 30.
9. according to the method described in 7 or 8, it is characterized in that, described catalyzer, described catalyzer contains and is selected from containing one or more in oxygen or nitrogenous organism, and described organism is 0.03-2 with take the mol ratio of nickel, molybdenum and tungsten sum of oxide compound.
10. catalyzer according to claim 9, it is characterized in that, described oxygen containing organism is selected from one or more in Organic Alcohol, organic acid, and nitrogenous organism is organic amine, and described organism is 0.08-1.5 with take the mol ratio of nickel, molybdenum and tungsten sum of oxide compound.
11. according to the method described in 1, it is characterized in that, described step (2) comprises and catalyst I with hydrotreating catalyst
athe catalyst I of layered arrangement
b, described layering replaces in hydrotreatment reaction member order and catalyst I overhead product I and overhead product II that described step (1) obtains
band catalyst I
acontact, by volume and with described catalyst I
afor benchmark, catalyst I
bcontent for being greater than 0 to being less than or equal to 80%, wherein, described catalyst I
bthe content of hydrogenation active metals component be catalyst I
athe 10-30% of hydrogenation active metals component concentration.
12. according to the method described in 11, it is characterized in that, by volume and with described catalyst I
afor benchmark, catalyst I
bcontent be 5-30%
13. according to the method described in 12, it is characterized in that, by volume and with described catalyst I
afor benchmark, catalyst I
bcontent be 6-15%.
14. according to the method described in 11, it is characterized in that, in described catalyst I
awith catalyst I
bbetween comprise catalyst I
c, by volume and with described catalyst I
afor benchmark, described catalyst I
ccontent for being greater than 0 to being less than or equal to 80%, wherein, described catalyst I
cthe content of hydrogenation active metals component be catalyst I
athe content of hydrogenation active metals component be greater than 30% to being less than or equal to 70%.
15. according to the method described in 14, it is characterized in that, by volume and with described catalyst I
afor benchmark, described catalyst I
ccontent be 5-40%.
16. according to the method described in 15, it is characterized in that, by volume and with described catalyst I
afor benchmark, described catalyst I
ccontent be 10-30%.
17. according to the method described in 1, it is characterized in that, at hydrotreating unit step (2) Suo Shu, be included under hydrogen and hydrotreatment reaction conditions, overhead product I through hydrotreatment and overhead product II are replaced and hydrotreating catalyst contact reacts for bis-times, wherein, secondary hydrotreatment temperature of reaction is lower than a hydrotreatment temperature of reaction 10-50 ℃.
18. according to the method described in 17, it is characterized in that, described secondary hydrotreatment temperature of reaction is lower than a hydrotreatment temperature of reaction 20-30 ℃.
19. according to the method described in 17 or 18, it is characterized in that, described secondary hydrotreatment reaction conditions comprises: pressure is 4.5-16MPa, and temperature is 250-360 ℃, and volume space velocity is 0.5-6h
-1, hydrogen to oil volume ratio is 300-1200.
20. according to the method described in 19, it is characterized in that, described hydrofining reaction condition comprises: pressure is 6-14MPa, and temperature is 260-350 ℃, and volume space velocity is 1-4h
-1, hydrogen to oil volume ratio is 350-1000.
21. according to the method described in 20, it is characterized in that, described hydrofining reaction condition comprises: pressure is 8-12MPa, and temperature is 280-330 ℃, and volume space velocity is 1.5-3.5h
-1, hydrogen to oil volume ratio is 450-800.
22. according to the method described in 1, it is characterized in that the separating unit in described step (1), before by described waste lubricating oil fractionation by distillation, comprises and filtering and/or washing step.
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| CN103831082B (en) * | 2014-03-06 | 2016-11-16 | 青岛惠城环保科技股份有限公司 | A kind of preparation method of the adsorbent of Regeneration Treatment lubricating oil |
| CN105733793B (en) * | 2014-12-06 | 2018-07-06 | 中国石油化工股份有限公司 | A kind of waste lubricating oil hydrogenation reproducing method |
| CN109233988A (en) * | 2018-08-06 | 2019-01-18 | 天津大学 | The clean high-valued recycling and reusing method and apparatus of waste lubricating oil |
| CN113004969A (en) * | 2021-02-27 | 2021-06-22 | 新疆佳宇恒能源科技有限公司 | Hydrogenation method for regeneration of waste lubricating oil |
| CN113004941B (en) * | 2021-04-01 | 2022-10-11 | 厦门市汉臻能源科技有限公司 | Industrial purification method of waste engine oil |
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