CN102732301B - Method for producing bright stock - Google Patents
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- CN102732301B CN102732301B CN201110093207.4A CN201110093207A CN102732301B CN 102732301 B CN102732301 B CN 102732301B CN 201110093207 A CN201110093207 A CN 201110093207A CN 102732301 B CN102732301 B CN 102732301B
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Abstract
A production method of bright stock comprises the following steps of: (1) under the conditions of a residuum hydrotreatment reaction unit and a residuum hydrotreatment reaction, performing a contact reaction between hydrogen and the residuum raw material in the presence of a catalyst for residuum hydrotreatment, and separating to obtain hydrogenated residuum with its distillation range being more than 470 DEG C; (2) under the solvent deasphalting condition and in a solvent deasphalting unit, carrying out solvent refining on the hydrogenated residuum which is obtained from the step (1) with its distillation range being more than 470 DEG C, so as to obtain residuum which has undergone solvent refining; (3) in a hydrotreatment reaction unit and under the condition of hydrotreatment reaction, performing a contact reaction between the residuum which has undergone solvent refining and is obtained from the step (2) and a hydrotreatment catalyst, so as to obtain a hydrotreated solvent-refined oil; and 4) in a catalytic dewaxing reaction unit and under the condition of a catalytic dewaxing reaction, carrying out catalytic dewaxing reaction on the hydrotreated solvent-refined oil obtained from the step (3), and separating to obtain the product oil, namely bright stock.
Description
Technical field
The present invention relates to a kind of method of producing bright stock.
Background technology
Bright stock is a class of lubricant base, the blend component of Chang Zuowei I. C. engine oil, is used for improving the viscosity of I. C. engine oil under applied at elevated temperature environment, or is used as the main ingredient of automotive gear oils and industrial gear oil.The basic index of bright stock comprises kinematic viscosity, viscosity index and pour point.Wherein, kinematic viscosity is characteristic index, under 100 DEG C of conditions, the kinematic viscosity of bright stock is between 17-34 square millimeter/second, be divided into 90BS, 120BS and 150BS etc. several, wherein the kinematic viscosity range of 90BS bright stock is 17-22 square millimeter/second, the kinematic viscosity range of 120BS bright stock is 22-28 square millimeter/second, and the kinematic viscosity range of 150BS bright stock is 28-34 square millimeter/second, and the bright stock range of application that kinematic viscosity is higher is wider.The size of the kinematic viscosity of bright stock and the height of viscosity index relevant with crude oil kind, crude oil origin and production method, pour point then with dewaxing the degree of depth relevant.The raw material producing bright stock is generally the vacuum residuum of paraffinic crude, the lightweight deasphalted oil that the vacuum residuum of the heavy vacuum gas oil of intermediate base crude oil or vacuum residuum and part naphthenic base crude obtains after propane deasphalting, the size of the kinematic viscosity of bright stock and the height of product yield are by the restriction of crude oil kind and crude oil origin.
The method of traditional mode of production bright stock generally comprises following several step: vacuum residuum obtains the lightweight deasphalted oil after a kind of diasphaltene after propane deasphalting; Lightweight deasphalted oil obtains a kind of content of wax treated oil through solvent treatment; Content of wax treated oil obtains the pressed oil of depression of pour point through solvent dewaxing; Pressed oil is through bleaching earth adsorption refining acquisition bright stock product.Method due to traditional mode of production bright stock utilizes physical sepn means to produce, and do not change raw material composition in production process, therefore higher to feed quality requirements, and poor to the adaptability of the change of raw material.Under normal circumstances, when adopting produced in conventional processes bright stock, the carbon residue content of the lightweight deasphalted oil obtained after solvent deasphalting by vacuum residuum is not more than 1.0%, and color is not higher than 7.0.
US4259170 discloses a kind of method that vacuum distilling cut by reduce pressure paraffinic crude or decompression commingled crude produces low pour point lubricant base, described cut comprises distillation fraction and diasphaltene vacuum residue, the method comprises by under dewaxing conditions described diasphaltene vacuum residue cut being contacted to carry out catalytic dewaxing to described diasphaltene vacuum residue with dewaxing catalyst, thus reduce its pour point, and solvent dewaxing is carried out to distillation fraction, described dewaxing catalyst contain silica alumina ratio be at least 12 and constraint factor be 1.0-12.0 crystal molecule sieve.
Zhang Weixing etc. report and a kind ofly adopt the deasphalted oil of Daqing crude oil to be the method for raw material production bright stock in " Producing Bright Stock With Hydrotreating Technique " (Fusun PetroleumCollege's journal, Vol.21, No.1,2001 (3): 27-30).The method is characterized in that the lightweight deasphalted oil that the Daqing crude oil that have selected viscosity index after solvent dewaxing higher (viscosity index is 92) is produced is raw material, through hydrotreatment, solvent dewaxing is carried out by after the component distillation of hydrotreatment, obtain pressed oil, pressed oil is refined through bleaching earth adsorption again thus obtains bright stock product.The pour point of the bright stock product obtained is-6 DEG C, and viscosity index is 105, and the product of viscosity index ratio produced in conventional processes improves 13 units.In the method, the condition of hydrotreatment reaction is hydrogen dividing potential drop 0.7-5.0 MPa, temperature of reaction 300-400 DEG C, air speed 0.3-1.5 hour-1, hydrogen to oil volume ratio 400-1500: 1.
CN101768470A discloses a kind of preparation method with high viscosity index (HVI) and low pour point bright stock, and wherein, the method comprises, and vacuum residuum is carried out solvent deasphalting by (1); (2) remove the part macromole polycyclic aromatic hydrocarbons in the deasphalted oil of gained lightweight, obtain content of wax treated oil; (3) the above-mentioned content of wax is refined oil-hydrogen mixture to contact with Hydrobon catalyst with hydrotreating catalyst respectively, obtain hydrogenation full distillate oil; (4) from above-mentioned hydrogenation full distillate oil, remove the light constituent that final boiling point is less than 500 DEG C, obtain content of wax hydrotreatment oil; (5) above-mentioned content of wax hydrotreatment oil is carried out solvent dewaxing, obtain pressed oil; (6) above-mentioned pressed oil is carried out catalytic dewaxing and hydrofining respectively, then products therefrom is carried out air lift.
But the output of the frivolous asphalt oil in existing solvent deasphalting unit is lower (being about the 18-25% of vacuum residuum), thus makes the production of bright stock be restricted.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of production bright stock newly.
The present invention relates to following content:
1, a kind of method of producing bright stock, comprise: (1) is under a residual hydrocracking reaction member and residual hydrocracking reaction conditions, by hydrogen, residual oil raw material and catalyst for hydrotreatment of residual oil contact reacts, being isolated to a kind of boiling range is residual oil after the hydrogenation of more than 470 DEG C; (2) under a Solvent deasphalting unit and solvent deasphalting conditions, the boiling range obtained step (1) is that the residual oil after more than 470 DEG C hydrogenation carries out solvent treatment, obtains the residual oil after a kind of solvent treatment; (3) under a hydrotreatment reaction member and hydrotreatment reaction conditions, the residual oil after the solvent treatment obtain hydrogen, step (2) and hydrotreating catalyst contact reacts, obtain the solvent-refined oil after a kind of hydrotreatment; (4) under a catalytic dewaxing reaction member and catalytic dewaxing reaction conditions, the solvent-refined oil after the hydrotreatment obtain step (3) carries out catalytic dewaxing reaction, is isolated to bright stock product oil.
2, the method according to 1, is characterized in that, through the separation described in step (1), obtaining a kind of boiling range is residual oil after the hydrogenation of more than 500 DEG C.
3, the method according to 1, is characterized in that, the hydrotreatment reaction conditions of described step (1) comprising: temperature 330 ~ 450 DEG C, hydrogen dividing potential drop 6 ~ 20MPa, volume space velocity 0.2 ~ 1.5h
-1, hydrogen to oil volume ratio 500 ~ 1500: 1; The hydrotreatment reaction conditions of described step (3) comprising: temperature 330 ~ 420 DEG C, hydrogen dividing potential drop 6 ~ 20MPa, volume space velocity 0.3 ~ 2h
-1, hydrogen to oil volume ratio 500 ~ 1500: 1; The catalytic dewaxing reaction conditions of described step (4) comprising: hydrogen dividing potential drop 1-20MPa, and temperature is 250-400 DEG C, volume space velocity 0.3-3h during liquid
-1, hydrogen to oil volume ratio is 100-3000: 1.
4, the method according to 3, is characterized in that, the hydrotreatment reaction conditions of described step (1) comprising: temperature 350 ~ 430 DEG C, hydrogen dividing potential drop 8 ~ 18MPa, volume space velocity 0.3 ~ 1.2h
-1, hydrogen to oil volume ratio 600 ~ 1200: 1; The hydrotreatment reaction conditions of described step (3) comprising: temperature 350 ~ 400 DEG C, hydrogen dividing potential drop 8 ~ 18MPa, volume space velocity 0.4 ~ 1.2h
-1, hydrogen to oil volume ratio 600 ~ 1200: 1; The catalytic dewaxing reaction conditions of described step (4) comprising: hydrogen dividing potential drop 4-18MPa, and temperature is 280-390 DEG C, volume space velocity 0.4-2h during liquid
-1, hydrogen to oil volume ratio is 200-2000: 1.
5, the method according to 1, it is characterized in that, described solvent deasphalting conditions comprises: solvent and boiling range are the residual oil volume ratio after more than 470 DEG C hydrogenation is 2 ~ 10: 1, extraction tower head temperature 20 ~ 150 DEG C, pressure 2 ~ 6MPa, described solvent is selected from one or more in C3-C7 alkane or alkene, condensate oil, light naphthar, gasoline.
6, the method according to 5, it is characterized in that, described solvent deasphalting conditions comprises: solvent and boiling range are the residual oil volume ratio after more than 470 DEG C hydrogenation is 3 ~ 8: 1, extraction tower head temperature 30 ~ 120 DEG C, pressure 3 ~ 5MPa, described solvent is the mixed solvent of one or more in propane or propane and ethane, propylene, butane and pentane.
7, the method according to 1, is characterized in that, described step (3) is I with hydrotreating catalyst
a, described I
acontaining the carrier being 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, containing or not containing being selected from fluorine, in boron and phosphorus one or more adjuvant components and containing or not containing organic additive, take catalyzer as benchmark, be 1 ~ 5 % by weight with the content of the nickel of oxide basis and/or cobalt, the content of molybdenum and/or tungsten is 12 ~ 35 % by weight, fluorine is selected from element, in boron and phosphorus, the content of one or more adjuvant components is 0 ~ 9 % by weight, described organism with the mol ratio of the hydrogenation active metals component sum of oxide basis for 0-2.
8, the method according to 7, is characterized in that, described catalyzer is by γ-Al
2o
3support tungsten and nickel oxide and auxiliary agent fluorine formed, it forms (weight): nickel oxide 1 ~ 5%, Tungsten oxide 99.999 12 ~ 35%, and fluorine is 1 ~ 9%, and surplus is γ-Al
2o
3.
9, the method according to 7, it is characterized in that, fluorine-containing, the phosphorus hydrogenation catalyst of described catalyzer to be a kind of with silica-alumina be 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, fluorine 1-10 % by weight, phosphorus oxide 0.5-8 % by weight, surplus is silica-alumina; Or the hydrogenation catalyst of containing fluorin of to be a kind of with silica-alumina be 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, fluorine 1-10 % by weight, and surplus is carrier; Or hydrogenation catalyst of containing phosphor and the preparation thereof of to be a kind of with silica-alumina be 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.
10, the method according to 9, is characterized in that, described catalyzer, and described catalyzer contains and is selected from containing one or more in oxygen or nitrogenous organism, described organism with the mol ratio of the nickel of oxide basis, molybdenum and tungsten sum for 0.03-2.
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, described organism with the mol ratio of the nickel of oxide basis, molybdenum and tungsten sum for 0.08-1.5.
12, the method according to 7, it is characterized in that, fluorine-containing, the phosphorus hydrogenation catalyst of described catalyzer to be a kind of with aluminum oxide be 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 0.5-8 % by weight, fluorine 1-10 % by weight, surplus is aluminum oxide; Or the hydrogenation catalyst of containing fluorin of to be a kind of with aluminum oxide be carrier, 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; Or the hydrogenation catalyst of containing phosphor of to be a kind of with aluminum oxide be carrier, nickel oxide 1-10 % by weight is consisted of after this catalyzer roasting, 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, with oxide basis, the mol ratio of tungsten and molybdenum is greater than 2.6 to 30.
13, the method according to 12, is characterized in that, described catalyzer contains and is selected from containing one or more in oxygen or nitrogenous organism, described organism with the mol ratio of the nickel of oxide basis, molybdenum and tungsten sum for 0.03-2.
14, catalyzer according to claim 13, 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, described organism with the mol ratio of the nickel of oxide basis, molybdenum and tungsten sum for 0.08-1.5.
15, the method according to 1, is characterized in that, described step (3) comprises and catalyst I with hydrotreating catalyst
athe catalyst I of layered arrangement
b, described layering makes described stock oil in hydrotreatment reaction zone 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.
16, the method according to 15, is characterized in that, by volume and with described catalyst I
afor benchmark, catalyst I
bcontent be 5-30%
17, the method according to 16, is characterized in that, by volume and with described catalyst I
afor benchmark, catalyst I
bcontent be 6-15%.
18, the method according to 15, 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%.
19, the method according to 18, is characterized in that, by volume and with described catalyst I
afor benchmark, described catalyst I
ccontent be 5-40%.
20, the method according to 19, is characterized in that, by volume and with described catalyst I
afor benchmark, described catalyst I
ccontent be 10-30%.
21, the method according to 1, is characterized in that, comprises the step of a post-refining after described step (4).
The present inventor is surprised to find, and when the residual oil raw material after hydrotreatment carries out solvent treatment again under solvent deasphalting conditions, the frivolous asphalt oil yield as producing bright stock can be made to significantly improve.
According to method provided by the invention, described residual oil is one or more in vacuum residuum and/or long residuum.The device of described residual hydrocracking reaction is usual residual hydrocracking reaction unit.Such as, can be usual fixed-bed reactor, also can be moving-burden bed reactor or ebullated bed reactor.Described catalyst for hydrotreatment of residual oil is the usual catalyzer in this area or catalyst combination.
About Residual cracking technique and the catalyzer that adopts thereof at CN1626625A, CN1648215A, CN1690172A, CN1782031A, CN1966616A, CN101152632A, CN101332430A, CN101462080A, CN1400285A, CN1400288A, CN1262306A, there is description in CN1382776A, CN101210200A, quote as a reference in the lump here.
According to method provided by the invention, the method for described solvent deasphalting and condition can be customary way and condition.Generally comprise mixing, extracting and settlement separate three steps, such as, can carry out in the extracting be made up of extraction tower and sedimentation tower two towers, sedimenting system.First deliver to extraction tower by after vacuum residuum and solvent, in extraction tower, carry out abundant extracting, and then carry out settlement separate in sedimentation tower, complete solvent deasphalting process.Described deasphalting solvent is the mixed solvent of one or more in propane or propane and ethane, propylene, butane and pentane, when the mixed solvent of one or more during described solvent is propane and ethane, propylene, butane and pentane, the content of propane is generally more than 80 % by weight, be preferably more than 90 % by weight, more preferably more than 95 % by weight.
In concrete aforesaid way, the condition optimization of described solvent deasphalting makes in the deasphalted oil of gained lightweight, and carbon residue content is not higher than 2 % by weight, and colourity is not more than No. 8, the content of N.heptane insolubles is not more than 100ppm, and doing of lightweight deasphalted oil is not more than 700 DEG C.The condition of described solvent deasphalting makes in the deasphalted oil of gained lightweight, and carbon residue content is not higher than 1.5 % by weight, and colourity is not more than No. 7.5, and the content of N.heptane insolubles is not more than 80ppm.In the present invention, unless stated otherwise, described colourity refers to the colourimetric number adopting GB/T6540 to record.
According to method provided by the invention, wherein, the hydrotreatment reaction of described step (3) is the colloid, sulphur, the nitrogen compound that remove in raw material and aromatic saturation, ring-opening reaction, transforms into useful bright stock component to make them.Therefore, be enough under the prerequisite realizing this object, described method and condition can be customary way and condition, and used catalyst can be selected from prior art one or more that can realize arbitrarily in the catalyzer of this function.They can be commercially available commodity or adopt any existing method preparation.
This type of catalyzer usually containing heat-resistant inorganic oxide carrier and load hydrogenation active metals component on this carrier, containing or do not conform to be selected from fluorine, boron and phosphorus one or more adjuvant components and containing or do not conform to organic additive.Wherein, described heat-resistant inorganic oxide carrier is selected from one or more in the various heat-resistant inorganic oxides being commonly used for support of the catalyst and/or matrix.Such as, one or more in optional self-alumina, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, alumina-silica magnesium, silica-magnesias, silica-zirconia, silica thoria, silica-berylias, silica-titania, silica-zirconia, titania-zirconia, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia, silica-alumina, zirconia, natural zeolite, clay, are preferably aluminum oxide and/or silica-alumina.Described organic additive is selected from the organic compound containing one or more 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.Such as, oxygen-containing organic compound can enumerate 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 enumerate quadrol, EDTA and ammonium salt thereof.
In a specific embodiment, described catalyzer is I
a, I
abe selected from one or more in following catalyzer, comprise:
Catalyzer disclosed in CN85104438, it is by γ-Al
2o
3support tungsten and nickel oxide and auxiliary agent fluorine formed, it forms (weight): nickel oxide 1 ~ 5%, Tungsten oxide 99.999 12 ~ 35%, and fluorine is 1 ~ 9%.
It take silica-alumina as fluorine-containing, phosphorus hydrogenation catalyst and the preparation thereof of carrier that CN1853780A discloses a kind of, 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.The method preparation of fluorine, phosphorus, molybdenum, nickel and tungsten introduced by this catalyzer to silicaalumina carrier by comprising, wherein, consisting of after the consumption of each component makes 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.
It take silica-alumina as hydrogenation catalyst of containing fluorin and the preparation thereof of carrier that CN1853779A discloses a kind of, 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 silicaalumina carrier introducing fluorine, molybdenum, nickel and tungsten, wherein, consisting of after the consumption of each component makes 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, surplus is carrier.
It take silica-alumina as hydrogenation catalyst of containing phosphor and the preparation thereof of carrier that CN1853781A discloses a kind of, 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 silicaalumina carrier introducing phosphorus, molybdenum, nickel and tungsten, wherein, consisting of after the consumption of each component makes 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.
It take aluminum oxide as fluorine-containing, phosphorus hydrogenation catalyst and the preparation thereof of carrier that CN1853781A discloses a kind of, 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.The method preparation of fluorine, phosphorus, molybdenum, nickel and tungsten introduced by this catalyzer to alumina supporter by comprising, wherein, consisting of after the consumption of each component makes 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.
It take aluminum oxide as hydrogenation catalyst of containing fluorin and the preparation thereof of carrier that CN1872959A discloses a kind of, 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, consisting of after the consumption of each component makes 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, surplus is aluminum oxide.
It take aluminum oxide as hydrogenation catalyst of containing phosphor and the preparation thereof of carrier that CN1872960A discloses a kind of, nickel oxide 1-10 % by weight is consisted of after this catalyzer roasting, 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, with oxide basis, the mol ratio of tungsten and molybdenum is greater than 2.6 to 30.This catalyzer introduces phosphorus, molybdenum, nickel and tungsten by comprising in alumina supporter, wherein, consisting of after the consumption of each component makes 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, with oxide basis, the mol ratio of tungsten and molybdenum is greater than 2.6 to 30.
In catalyzer disclosed in CN1853780A, CN1853779A, CN1853781A, CN1872959A and CN1872960A, preferably also containing organic additive, wherein, described organism with the mol ratio of the hydrogenation active metals component sum of oxide basis for 0.03-2 is preferably 0.08-1.5.
About the more detailed preparation method of above-mentioned catalyzer, all on the books in above-mentioned patent documentation, in the lump their parts as content of the present invention are quoted here.
When the hydrotreating catalyst of described step (3) comprises and catalyst I
athe catalyst I of layered arrangement
btime, described catalyst I
bthere is comparatively 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 arbitrary prior art to prepare.
In a specific embodiment, this type of catalyzer usually containing heat-resistant inorganic oxide carrier and load hydrogenation active metals component on this carrier, containing or do not conform to and be selected from one or more adjuvant components in fluorine, boron, phosphorus and alkaline-earth metal.With catalyst I
bfor benchmark, described catalyst I
bwith the content of the nickel of oxide basis and/or cobalt for 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, in the content being selected from one or more adjuvant components in fluorine, boron, phosphorus and alkaline-earth metal of element for 0-5 % by weight, and the total amount meeting 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%.
Such as, the preparation method of catalyzer disclosed in CN1344781, CN1966616 and CN101134173A just can be used to prepare the catalyzer meeting application claims.Here in the lump their parts as content of the present invention are quoted.
As the hydrotreating catalyst I of described step (3)
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 arbitrary prior art to prepare.
In a specific embodiment, this type of catalyzer usually containing heat-resistant inorganic oxide carrier and load hydrogenation active metals component on this carrier, containing or do not conform to and be selected from one or more adjuvant components in fluorine, boron, phosphorus and alkaline-earth metal.With catalyst I
cfor benchmark, described catalyst I
cwith the content of the nickel of oxide basis and/or cobalt for 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, be preferably 0.8-12 % by weight, and the total amount meeting 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%.
Such as, the preparation method of catalyzer disclosed in CN1626625A, CN1690172A, CN1782031A and CN1782033A just can be used to prepare the catalyzer meeting application claims.Here in the lump their parts as content of the present invention are quoted.
According to method provided by the invention, described catalytic dewaxing reaction member is for the purpose of hydrocracking macromole straight chain hydrocarbon.Wherein used catalyst is selected from one or more in catalytic dewaxing well known in the art, isomerization dewaxing catalyzer.
This type of catalyzer is selected from the nickel of group VIII, platinum and/or metallic palladium component and mesoporous molecular sieve containing at least one usually.Described mesoporous molecular sieve is similarly well known in the art, such as, can be selected from one or more in ZSM-5, ZSM-11, ZSM-12, ZSN-22, ZSM-23, ZSM-35, ZSM-38, SAPO-11 and SAPO-41.Be benchmark in metal and with catalyzer, the content of described group VIII metal is preferably 0.1-10 % by weight, more preferably 0.1-5 % by weight, is more preferably 0.1-3 % by weight.They can be commercially available commodity, also can be to adopt the preparation of any one prior art.
Such as, a kind of catalytic dewaxing catalyst containing zeolite disclosed in CN1448484A, this catalyzer contains a kind of carrier containing zeolite and hydrogenation metal component, described zeolite is a kind of high-Si zeolite containing rare-earth five-membered ring structure, in this zeolite, the mol ratio of silicon oxide and aluminum oxide is 20-100, and with zeolite total amount for benchmark, the content of rare earth oxide is the heavy % of 0.1-2.5, sodium oxide content is the heavy % of 0.1-1.5, and this zeolite has special X-ray diffract spectral line.
A kind of dewaxing catalyst containing composite molecular screen disclosed in CN1803998A, this catalyzer contains and a kind ofly has the molecular sieve of one dimension central hole structure, a kind of molecular sieve with macroporous structure, wherein, the described molecular sieve with one dimension central hole structure is 80-99: 1-20 with the weight ratio of the molecular sieve with macroporous structure, the described molecular sieve with macroporous structure contains non-framework silicon, with oxide basis and with this molecular sieve for benchmark, the content of described silicon is 1-20 % by weight.
Disclosed in CN1382526A, a kind of catalyzer of containing Si-P-Al molecular sieve contains at least one aluminium silicophosphate molecular sieve, the degree of crystallinity of described aluminium silicophosphate molecular sieve is at least 70%, the preparation method of this aluminium silicophosphate molecular sieve comprises dry for the mixture of the aluminium silicophosphate molecular sieve and a kind of aqueous acid that contain organic formwork agent also roasting, and the weight ratio of described acid and molecular sieve is 0.001-1.
CN101722037A a catalyst for hydrogenation de-waxing of lubricating oil distillate, preparation and application thereof, this catalyzer contains molecular sieve and hydrogenation metal component, it is benchmark in metal and with catalyzer, the content of hydrogenation metal component is 0.1 % by weight-5 % by weight, it is characterized in that, described molecular sieve is the mixture of TON type molecular sieve and ZSM-5, and with molecular sieve total amount for benchmark, in the mixture of described molecular sieve, the content of ZSM-5 molecular sieve is 0.1 % by weight-4 % by weight.Deng disclosed catalyst for hydrogenation de-waxing, all there is good wax hygrogenating isomerization reaction performance, all can be used as hydroisomerisation catalysts for the present invention.
The more detailed method of preparation about above-mentioned catalyzer, all on the books in above-mentioned patent documentation, in the lump their parts as content of the present invention are quoted here.
According to method provided by the invention, wherein step (1) is customary way and condition with the method be separated described in step (4) and condition.Such as adopt the method for distillation to be separated, the method for described distillation is known in this field, usually can comprise the operating unit of one or more flash distillation, air distillation and underpressure distillation, to complete desired separation.
When comprising a post-refining step after described step (4), existing method known arbitrarily during lubricating oil can be adopted to process.Such as, the method for hydrofinishing or clay-treated method.
Stock oil of the present invention be naphthenic base crude, in the mixture of one or more in the vacuum residuum of m-naphthenic base crude or intermediate base crude oil or paraffinic base or long residuum.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet that the invention provides method.
This flow process comprises residual hydrocracking reaction member, Solvent deasphalting unit, hydrotreatment reaction member, catalytic dewaxing reaction member.
Embodiment
The present invention is described further for the following examples.
Example 1
Bright stock is produced according to the flow process shown in Fig. 1.Residual oil raw material is a kind of VACUUM TOWER BOTTOM oil, and its character lists in table 1.
Residual hydrocracking reaction member operates:
Residual hydrogenation process is carried out according to method disclosed in CN101210200; adopt two reactors; one anti-middle filling hydrogenation protecting agent and hydrodemetallation (HDM) agent; Hydrobon catalyst is filled in second reactor; proportions's (volume ratio) is 5: 45: 50; the commercial grades of wherein hydrogenation protecting agent, hydrodemetallation (HDM) agent, hydrogen desulfurization agent is respectively RG-10A, RDM-2, RMS-1, produces by Sinopec catalyzer branch office Chang Ling catalyst plant.The reaction conditions of residual hydrocracking, > 520 DEG C of hydrogenated residue tower bed material yields (taking resid feed as benchmark), character list in table 2.
Solvent deasphalting unit operates:
> 520 DEG C of hydrogenated residue tower bed materials, C3 alkane are entered from the upper and lower of extraction tower respectively, and carry out counter current contact in extraction tower.Operational condition comprises: pressure 4.0MPa, solvent ratio 6.0v/v.The frivolous asphalt oil yield (with > 520 DEG C of hydrogenated residue tower bed materials for benchmark) obtained through extracting, character list in table 3.
Hydrotreatment reaction member operates:
Catalyzer is catalyst I a, Ib and the Ic combination of layering filling, wherein, and Ib: Ic: Ia=5: 15: 80 (volume ratios).
Catalyst I
aaccording to the open method preparation of CN85104438, it consists of: nickel oxide 3 % by weight, Tungsten oxide 99.999 25 % by weight, and fluorine is weight 4%, and surplus is γ-Al
2o
3.
Catalyst I
bprepare according to the embodiment 5 in CN1966616A, wherein hydrogenation active metals component is molybdenum and nickel, is benchmark with oxide basis and with catalyzer, and the content of molybdenum is 4.5 % by weight, and the content of nickel is 1.5 % by weight.
Catalyst I
cprepare according to the embodiment 15 of CN1782033A, wherein hydrogenation active metals component is molybdenum and nickel, is benchmark with oxide basis and with catalyzer, and the content of molybdenum is 13.7 % by weight, and the content of nickel is 3 % by weight.
Reaction conditions and obtain > 500 DEG C of tower bed material yields (with frivolous asphalt oil for benchmark), character list in table 4 through distillation.
Catalytic dewaxing reaction member operates:
The catalyzer DW-a that catalytic dewaxing reaction member adopts
The dewaxing catalyst DW-a used in the embodiment of the present invention be according in CN1382526A example 6 prepare take platinum as the catalyzer of active constituent loading on SAPO-11 molecular sieve/alumina supporter, wherein with catalyzer total amount for benchmark, the content of platinum is 0.3 % by weight, all the other are carrier, take carrier as benchmark, in this carrier, the content of SAPO-11 molecular sieve is 75 % by weight, and all the other are aluminum oxide.
Reaction conditions comprises: temperature 360, pressure 15 MPa, liquid hourly space velocity 0.7 hour
-1, hydrogen to oil volume ratio is 800.Table 5 is listed in through distilling > 500 DEG C of products oil yield (with frivolous asphalt oil for benchmark), character of obtaining.
Table 1 stock oil character
| Stock oil | |
| Density (20 DEG C)/gcm -3 | 0.965 |
| 100 DEG C of kinematic viscosity/mm 2·s -1 | 43.10 |
| Carbon residue/% | 9.81 |
| Sulphur content/% | 3.5 |
| Nitrogen content/% | 0.36 |
| Bituminous matter/% | 3.6 |
Table 2 residual hydrogenation result
| Reaction conditions | |
| Hydrogen dividing potential drop/MPa | 13.0 |
| Volume space velocity/h-1 | 0.25 |
| Temperature of reaction/DEG C | 380 |
| > 520 DEG C of hydrogenated residue heavy tower bed material character | |
| Yield/% | 85 |
| Density (20 DEG C)/gcm -3 | 0.945 |
| 100 DEG C of kinematic viscosity/mm 2·s -1 | 36 |
| Carbon residue/% | 3.9 |
| Sulphur content/% | 0.3 |
| Nitrogen content/% | 0.16 |
The frivolous asphalt oil character of table 3
| The trade mark | Frivolous asphalt oil |
| Yield/% | 50 |
| Density (20 DEG C)/gcm -3 | 0.9176 |
| Kinematic viscosity/mm 2·s -1 | |
| 100℃ | 32.78 |
| Colourity/number | 8.0 |
| Condensation point/DEG C | 56 |
| Carbon residue/% | 0.71 |
| Sulphur content/% | 0.25 |
| Nitrogen content/% | 0.14 |
| Acid number/mgKOHg -1 | 0.42 |
| Wax content/% | 21.9 |
Table 4 frivolous asphalt oil hydrogenation result
| Reaction conditions | |
| Hydrogen dividing potential drop/MPa | 15.0 |
| Volume space velocity/h-1 | 0.4 |
| Temperature of reaction/DEG C | 365 |
| > 500 DEG C of hydrogenated oil heavy tower bed material character | |
| Yield/% | 87 |
| Density (20 DEG C)/gcm -3 | 0.876 |
| 100 DEG C of kinematic viscosity/mm 2·s -1 | 28 |
| Sulphur content/μ g/g | 30 |
| Nitrogen content/μ g/g | 5 |
Table 5 hydrogenation-pressed oil character
| Catalytic dewaxing oil yield, character | |
| Yield/% | 75 |
| Density (20 DEG C)/gcm -3 | 0.8892 |
| Kinematic viscosity/mm 2·s -1 | |
| 100℃ | 30.95 |
| 40℃ | 471.4 |
| Viscosity index | 95 |
| Colourity/number | 1.0 |
| Pour point/DEG C | -15 |
| Flash-point (opening)/DEG C | 290 |
| Rotary oxygen bomb/min | 265 |
Comparative example 1
Save residual hydrocracking reaction member according to the flow process of embodiment 1, adopt this flow process to produce bright stock.Solvent deasphalting unit, hydrotreatment reaction member are identical with embodiment with the operation of catalytic dewaxing unit.Wherein, frivolous asphalt oil yield (being as the criterion with resid feed), character list in 5, and table 6 is listed in dewaxing processed oil yield (with frivolous asphalt oil for benchmark), character.
The frivolous asphalt oil character of table 5
| Frivolous asphalt oil | |
| Yield/% | 20 |
| Density (20 DEG C)/gcm -3 | 0.9187 |
| Kinematic viscosity/mm 2·s -1 | |
| 100℃ | 33.55 |
| Colourity/number | 8.0 |
| Condensation point/DEG C | 58 |
| Carbon residue/% | 0.75 |
| Sulphur content/% | 0.45 |
| Nitrogen content/% | 0.25 |
| Acid number/mgKOHg -1 | 0.46 |
| Wax content/% | 22 |
Table 6 hydrogenation-pressed oil character
| Catalytic dewaxing oil yield, character | |
| Yield/% | 75 |
| Density (20 DEG C)/gcm -3 | 0.8897 |
| Kinematic viscosity/mm 2·s -1 | |
| 100℃ | 31.24 |
| 40℃ | 491.5 |
| Viscosity index | 93 |
| Colourity/number | 1.0 |
| Pour point/DEG C | -15 |
| Flash-point (opening)/DEG C | 295 |
| Rotary oxygen bomb/min | 244 |
The national standard of part bright stock product lists in table 7.Relatively can see, by the bright stock product that the invention provides method and reference method and all can be met 120SB standard, but the yield of the inventive method significantly improves.
Table 7
Claims (20)
1. produce the method for bright stock for one kind, comprise: (1) is under a residual hydrocracking reaction member and residual hydrocracking reaction conditions, by hydrogen, residual oil raw material and catalyst for hydrotreatment of residual oil contact reacts, being isolated to a kind of boiling range is residual oil after the hydrogenation of more than 470 DEG C; (2) under a Solvent deasphalting unit and solvent deasphalting conditions, the boiling range obtained step (1) is that the residual oil after more than 470 DEG C hydrogenation carries out solvent treatment, obtains the residual oil after a kind of solvent treatment; (3) under a hydrotreatment reaction member and hydrotreatment reaction conditions, the residual oil after the solvent treatment obtain hydrogen, step (2) and hydrotreating catalyst contact reacts, obtain the solvent-refined oil after a kind of hydrotreatment; (4) under a catalytic dewaxing reaction member and catalytic dewaxing reaction conditions, solvent-refined oil after the hydrotreatment obtain step (3) carries out catalytic dewaxing reaction, be isolated to bright stock product oil, wherein, described step (3) comprises and catalyst I with hydrotreating catalyst
athe catalyst I of layered arrangement
b, described layering makes described stock oil in hydrotreatment reaction zone 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.
2. method according to claim 1, is characterized in that, through the separation described in step (1), obtaining a kind of boiling range is residual oil after the hydrogenation of more than 500 DEG C.
3. method according to claim 1, is characterized in that, the hydrotreatment reaction conditions of described step (1) comprising: temperature 330 ~ 450 DEG C, hydrogen dividing potential drop 6 ~ 20MPa, volume space velocity 0.2 ~ 1.5h
-1, hydrogen to oil volume ratio 500 ~ 1500: 1; The hydrotreatment reaction conditions of described step (3) comprising: temperature 330 ~ 420 DEG C, hydrogen dividing potential drop 6 ~ 20MPa, volume space velocity 0.3 ~ 2h
-1, hydrogen to oil volume ratio 500 ~ 1500: 1; The catalytic dewaxing reaction conditions of described step (4) comprising: hydrogen dividing potential drop 1-20MPa, and temperature is 250-400 DEG C, volume space velocity 0.3-3h during liquid
-1, hydrogen to oil volume ratio is 100-3000: 1.
4. method according to claim 3, is characterized in that, the hydrotreatment reaction conditions of described step (1) comprising: temperature 350 ~ 430 DEG C, hydrogen dividing potential drop 8 ~ 18MPa, volume space velocity 0.3 ~ 1.2h
-1, hydrogen to oil volume ratio 600 ~ 1200: 1; The hydrotreatment reaction conditions of described step (3) comprising: temperature 350 ~ 400 DEG C, hydrogen dividing potential drop 8 ~ 18MPa, volume space velocity 0.4 ~ 1.2h
-1, hydrogen to oil volume ratio 600 ~ 1200: 1; The catalytic dewaxing reaction conditions of described step (4) comprising: hydrogen dividing potential drop 4-18MPa, and temperature is 280-390 DEG C, volume space velocity 0.4-2h during liquid
-1, hydrogen to oil volume ratio is 200-2000: 1.
5. method according to claim 1, it is characterized in that, described solvent deasphalting conditions comprises: solvent and boiling range are the residual oil volume ratio after more than 470 DEG C hydrogenation is 2 ~ 10: 1, extraction tower head temperature 20 ~ 150 DEG C, pressure 2 ~ 6MPa, described solvent is selected from one or more in C3-C7 alkane or alkene, condensate oil, light naphthar, gasoline.
6. method according to claim 5, it is characterized in that, described solvent deasphalting conditions comprises: solvent and boiling range are the residual oil volume ratio after more than 470 DEG C hydrogenation is 3 ~ 8: 1, extraction tower head temperature 30 ~ 120 DEG C, pressure 3 ~ 5MPa, described solvent is the mixed solvent of one or more in propane, propylene, butane and pentane.
7. method according to claim 1, is characterized in that, described I
acontaining the carrier being 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, containing or not containing being selected from fluorine, in boron and phosphorus one or more adjuvant components and containing or not containing organic additive, take catalyzer as benchmark, be 1 ~ 5 % by weight with the content of the nickel of oxide basis and/or cobalt, the content of molybdenum and/or tungsten is 12 ~ 35 % by weight, fluorine is selected from element, in boron and phosphorus, the content of one or more adjuvant components is 0 ~ 9 % by weight, described organism with the mol ratio of the hydrogenation active metals component sum of oxide basis for 0-2.
8. method according to claim 7, is characterized in that, described catalyzer is by γ-Al
2o
3support tungsten and nickel oxide and auxiliary agent fluorine formed, it forms (weight): nickel oxide 1 ~ 5%, Tungsten oxide 99.999 12 ~ 35%, and fluorine is 1 ~ 9%, and surplus is γ-Al
2o
3.
9. method according to claim 7, it is characterized in that, fluorine-containing, the phosphorus hydrogenation catalyst of described catalyzer to be a kind of with silica-alumina be 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, fluorine 1-10 % by weight, phosphorus oxide 0.5-8 % by weight, surplus is silica-alumina; Or the hydrogenation catalyst of containing fluorin of to be a kind of with silica-alumina be 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, fluorine 1-10 % by weight, and surplus is carrier; Or hydrogenation catalyst of containing phosphor and the preparation thereof of to be a kind of with silica-alumina be 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.
10. method according to claim 9, is characterized in that, described catalyzer contains and is selected from containing one or more in oxygen or nitrogenous organism, described organism with the mol ratio of the nickel of oxide basis, molybdenum and tungsten sum for 0.03-2.
11. methods 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, described organism with the mol ratio of the nickel of oxide basis, molybdenum and tungsten sum for 0.08-1.5.
12. methods according to claim 7, it is characterized in that, fluorine-containing, the phosphorus hydrogenation catalyst of described catalyzer to be a kind of with aluminum oxide be 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 0.5-8 % by weight, fluorine 1-10 % by weight, surplus is aluminum oxide; Or the hydrogenation catalyst of containing fluorin of to be a kind of with aluminum oxide be carrier, 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; Or the hydrogenation catalyst of containing phosphor of to be a kind of with aluminum oxide be carrier, nickel oxide 1-10 % by weight is consisted of after this catalyzer roasting, 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, with oxide basis, the mol ratio of tungsten and molybdenum is greater than 2.6 to 30.
13. methods according to claim 12, is characterized in that, described catalyzer contains and is selected from containing one or more in oxygen or nitrogenous organism, described organism with the mol ratio of the nickel of oxide basis, molybdenum and tungsten sum for 0.03-2.
14. methods according to claim 13, 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, described organism with the mol ratio of the nickel of oxide basis, molybdenum and tungsten sum for 0.08-1.5.
15. methods according to claim 1, is characterized in that, by volume and with described catalyst I
afor benchmark, catalyst I
bcontent be 5-30%.
16. methods according to claim 15, is characterized in that, by volume and with described catalyst I
afor benchmark, catalyst I
bcontent be 6-15%.
17. methods according to claim 1, 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%.
18. methods according to claim 17, is characterized in that, by volume and with described catalyst I
afor benchmark, described catalyst I
ccontent be 5-40%.
19. methods according to claim 18, is characterized in that, by volume and with described catalyst I
afor benchmark, described catalyst I
ccontent be 10-30%.
20. methods according to claim 1, is characterized in that, comprise the step of a post-refining after described step (4).
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| CN110607191B (en) * | 2018-06-15 | 2021-11-12 | 中国石油化工股份有限公司 | Combined process for hydrotreatment of residual oil and production of bright stock |
| CN112251256B (en) * | 2019-07-22 | 2022-03-11 | 中国石油化工股份有限公司 | Combined process for hydrotreatment of residual oil and production of bright stock and aromatic base mineral oil |
| CN115678611B (en) * | 2021-07-28 | 2024-03-22 | 中国石油天然气股份有限公司 | Method for producing bright stock from vacuum residuum |
| CN116987527B (en) * | 2023-09-25 | 2024-03-26 | 中石油克拉玛依石化有限责任公司 | Lubricating oil isomerism raw material with high viscosity index and preparation method thereof |
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| CN1154130A (en) * | 1994-08-01 | 1997-07-09 | 切夫里昂美国公司 | Lubricating oil production with VI-selective catalyst |
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