CN102242001B - Method for producing lubricant base oil from foots oil - Google Patents
Method for producing lubricant base oil from foots oil Download PDFInfo
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Abstract
The invention relates to a method for producing lubricant base oil from foots oil. The method for producing the lubricant base oil from the foots oil comprises the following steps: a, preparing foots oil with a reduced pour point through contacting the foots oil with a dewaxing catalyst under conditions of a dewaxing reaction catalysis unit and a dewaxing reaction catalysis process; and b, obtaining the lubricant base oil through contacting the foots oil with the reduced pour point obtained in step a with a hydrofining catalyst under conditions of a hydrofining reaction unit and a hydrofining reaction process and separating, wherein the sulfur content in the foots oil is less than 50 mug/g, and the nitrogen content in the foots oil is less than 10 mug/g.
Description
Technical field
The present invention relates to a kind of method of producing lubricant base.
Background technology
Adopt multistep Hydrogenation to know in the art for the method for lubricant base.In these class methods, the first step is take hydrogenating desulfurization, nitrogen as object mostly, and the while is with open loop or the hydrogenation saturation history of aromatic hydrocarbons.Second step is mainly that to reduce product pour point be that object isomerization-visbreaking process is crossed hydrodewaxing process.
CN 101074393A discloses a kind of method of preparing lubricant base, the method comprise dewaxing raw material in the situation that adding auxiliary agent, after solvent dewaxing, the sweat oil of pressed oil and second and third section of dewaxing is mixed into hydrotreatment-after refining-atmospheric and vacuum distillation-isomerization-visbreaking-hydrofinishing process.Wherein hydrotreatment section catalyzer be industrial for the production of lubricant base or hydrocracking catalyst, be that carrier is W-Ni, Mo-Ni, the W-Mo-Ni catalyzer of sial.The pressure 12-20MPa of hydrotreatment process, temperature is 360-420 ℃, air speed 0.5-1.5h
-1, hydrogen-oil ratio 800-2000v/v.The pressure 12-20MPa for the treatment of process after hydrogenation, temperature is 250-320 ℃, air speed 0.8-1.5h
-1, hydrogen-oil ratio 200-1000v/v.Distillation fraction, cuts out 300 ℃ of parts of > and does oil base stock, and 300 ℃ of parts of < are done solvent oil.The catalyzer that isomerization-visbreaking part is used is the dual-function catalyst using precious metal as hydrogenation dehydrogenation component, for being loaded with ZAP, SAPO, ZSM and the SSZ dewaxing by molecular sieve catalyzer of precious metal.The pressure 10-20MPa of isomerization-visbreaking process, temperature is 300-420 ℃, air speed 0.5-1.5h
-1, hydrogen-oil ratio 500-1600v/v.Hydrofinishing is industrial Hydrobon catalyst, and its saturation conditions is pressure 10-20MPa, and temperature is 220-300 ℃, air speed 0.8-1.5h
-1, hydrogen-oil ratio 100-800v/v.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of new production lubricant base, particularly utilizes sweat oil to produce the method for lubricant base.
The invention provides a kind of sweat oil that utilizes and produce the method for lubricant base, comprising: a), under a catalytic dewaxing reaction member and catalytic dewaxing reaction conditions, sweat oil is contacted with dewaxing catalyst, prepare a kind of depression of pour point sweat oil; B) under hydrofining reaction unit and hydrofining reaction condition, the depression of pour point that step a) is obtained sweat oil contact with Hydrobon catalyst, be isolated to lubricant base, wherein, sulphur content in described sweat oil is less than 50 μ g/g, and nitrogen content is less than 10 μ g/g.
Compared with the conventional method, method lubricant base yield provided by the invention obviously improves.
Accompanying drawing explanation
Fig. 1 is a kind of schematic flow sheet that utilizes wax oil to produce base oil of high viscosity index lubricant that the invention provides method, and this flow process comprises catalytic dewaxing reaction member and hydrofining reaction unit.
Fig. 2 is that another that the invention provides method utilizes wax oil to produce the schematic flow sheet of base oil of high viscosity index lubricant, and this flow process comprises hydrotreatment reaction member, catalytic dewaxing reaction member and hydrofining reaction unit.
Embodiment
According to method provided by the invention, wherein, the sulphur content in described sweat oil is less than 50 μ g/g, is preferably less than 20 μ g/g, is further preferably less than 10 μ g/g, and nitrogen content is less than 10 μ g/g, is preferably less than 5 μ g/g, is further preferably less than 2 μ g/g.
Described sweat oil comprises the whole hydrocarbon products outside the wax product that solvent dewaxing obtains.In prior art, solvent dewaxing can be the dewaxing that the vacuum distillate obtaining through atmospheric and vacuum distillation is carried out, can be also vacuum distillate after hydrotreatment carry out dewaxing.When the raw material of described solvent dewaxing is by the stock oil after hydrotreatment, the sulphur of the sweat oil obtaining thus, nitrogen content can meet aforesaid requirement, can be directly as raw material for the present invention; When although the raw material of described solvent dewaxing is conventional vacuum distillate or process hydrotreatment, but when in product, sulphur, nitrogen content can not meet the demands, sulphur, the nitrogen content of the sweat oil obtaining thus can not meet aforesaid requirement, can adopt any one existing hydroprocessing process to refine it, so that it meets the demands.
In a preferred embodiment, described dewaxing catalyst contains the molecular sieve with central hole structure, heat-resistant inorganic oxide matrix and hydrogenation metal component, described heat-resistant inorganic oxide matrix comprises a kind of gama-alumina being obtained through roasting by pseudo-boehmite, wherein, described pseudo-boehmite comprises a kind of pseudo-boehmite P1 of 1.1≤n≤2.5, wherein n=D (031)/D (120), the grain-size of the crystal face of 031 peak representative in the XRD spectra of described D (031) expression pseudo-boehmite crystal grain, the grain-size of the crystal face of 120 peak representatives in the XRD spectra of D (120) expression pseudo-boehmite crystal grain, described 031 peak refers to that in XRD spectra, 2 θ are
peak, described 120 peaks refer to that in XRD spectra, 2 θ are
peak, D=K λ/(Bcos θ), K is Scherrer constant, λ is the diffraction wavelength of target shaped material, the peak width at half height that B is diffraction peak, the position that 2 θ are diffraction peak.The n of preferred described pseudo-boehmite P1 meets 1.2≤n≤2.2.
The preparation method of the pseudo-boehmite of described 1.1≤n≤2.5 comprises: aluminum contained compound solution is contacted and carries out precipitin reaction with acid or alkali, or organic aluminum contained compound is contacted to the reaction that is hydrolyzed with water, obtain hydrated aluminum oxide; Hydrated aluminum oxide obtained above is carried out aging, wherein, described aluminum contained compound solution and acid or alkali contact or described organic aluminum contained compound and water contact and hydrated aluminum oxide aging in any one process under grain growing conditioning agent exists, carry out, described grain growing conditioning agent is the material that can regulate the speed of growth of crystal grain on different crystal faces.
As long as although make hydrolysis reaction or precipitin reaction and aging in one of arbitrary process under grain growing conditioning agent exists, carry out realizing object of the present invention, but under preferable case, described hydrolysis reaction and weathering process or described precipitin reaction and weathering process are all carried out under grain growing conditioning agent exists, and the n that can make like this gained pseudo-boehmite is in preferred 1.2≤n≤2.2 scope.
Wherein, to the consumption of grain growing conditioning agent, there is no particular limitation, in selective hydrolysis reaction, the consumption of grain growing conditioning agent is the 0.5-10 % by weight of organic aluminum contained compound weight to be hydrolyzed, more preferably 1-8.5 % by weight, further preferred 5-8.5 % by weight; In described precipitin reaction, the consumption of grain growing conditioning agent is the inorganic 0.5-10 % by weight containing al reactant weight, more preferably 1-8.5 % by weight, further preferred 5-8.5 % by weight; In described weathering process, the consumption of grain growing conditioning agent can be the 0.5-10 % by weight of hydrated aluminum oxide weight, is preferably 1-8.5 % by weight, further preferred 5-8.5 % by weight.Unless stated otherwise, in the present invention, the consumption of described grain growing conditioning agent calculates take the weight of aluminum oxide corresponding in organic aluminum contained compound, inorganic aluminum contained compound and hydrated aluminum oxide as benchmark respectively.Also be, in aluminum oxide, in described precipitin reaction, the consumption of described grain growing conditioning agent is the 0.5-10 % by weight of inorganic aluminum contained compound weight, in described hydrolysis reaction, the consumption of described grain growing conditioning agent is the 0.5-10 % by weight of organic aluminum contained compound weight, and in described weathering process, the consumption of described grain growing conditioning agent is the 0.5-10 % by weight of hydrated aluminum oxide weight.
In the present invention, described grain growing conditioning agent can be the various materials that can regulate the speed of growth of crystal grain on different crystal faces, particularly can regulate the material of crystal grain in the speed of growth of 120 crystal faces and 031 crystal face, be preferably polyhydric sugar-alcohol and carboxylate salt thereof, be specifically as follows one or more in Sorbitol Powder, glucose, gluconic acid, gluconate, ribitol, ribonic acid, ribose hydrochlorate.Described gluconate and ribose hydrochlorate can be their soluble salt separately, for example, can be one or more in sylvite, sodium salt and lithium salts.
In pseudo-boehmite preparation process of the present invention, the mode that adds to described grain growing conditioning agent is not particularly limited, grain growing conditioning agent can be added separately, also can in advance grain growing conditioning agent be mixed with one or more raw materials wherein, and then the raw material that contains grain growing conditioning agent is reacted.
Wherein, described inorganic aluminum contained compound solution can be various aluminum salt solutions and/or aluminate solution, and described aluminum salt solution can be various aluminum salt solutions, for example, can be one or more the aqueous solution in Tai-Ace S 150, aluminum chloride, aluminum nitrate.Because price is low, preferably sulfuric acid aluminium, liquor alumini chloridi.Aluminium salt can be used separately also and can after two kinds or more of mixing, use.Described aluminate solution is aluminate solution arbitrarily, as sodium aluminate solution and/or potassium aluminate.Because it obtains easy and price is low, preferably sodium aluminate solution.Aluminate solution also can be used alone or as a mixture.
Concentration to described aluminum salt solution and/or aluminate solution is not particularly limited, and preferably with aluminum oxide, counts 0.2-1.1 mol/L.
Described acid can be various protonic acids or in water medium, be acid oxide compound, for example, can be one or more in sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid, oxalic acid, preferred protonic acid be selected from one or more in nitric acid, sulfuric acid, hydrochloric acid.Described carbonic acid can original position produce by pass into carbonic acid gas in aluminum salt solution and/or aluminate solution.Concentration to described acid solution is not particularly limited, preferably H
+concentration be 0.2-2 mol/L.
Described alkaline solution can be hydrolyzed and make the aqueous solution be alkaline salt for oxyhydroxide or in water medium, and preferred oxyhydroxide is selected from one or more in ammoniacal liquor, sodium hydroxide, potassium hydroxide; Preferred salt is selected from one or more in sodium metaaluminate, potassium metaaluminate, bicarbonate of ammonia, volatile salt, sodium bicarbonate, sodium carbonate, saleratus, salt of wormwood.Concentration to described alkaline solution is not particularly limited, preferably OH
-concentration be 0.2-4 mol/L.When during as alkali, while calculating the consumption of described grain growing conditioning agent, also considering the amount of corresponding aluminum oxide in sodium metaaluminate and/or potassium metaaluminate using sodium metaaluminate and/or potassium metaaluminate.
Described organic aluminum contained compound can be various can with water generation hydrolysis reaction, one or more in the aluminum alkoxide of generation aqua oxidation aluminum precipitation can be for example one or more in aluminum isopropylate, isobutanol aluminum, aluminium isopropoxide, three tert-butoxy aluminium and isooctyl alcohol aluminium.Described organic aluminum contained compound and water consumption ratio are not particularly limited, and preferably the water yield is greater than the required amount of stoichiometry.
In pseudo-boehmite preparation process of the present invention, the condition of described precipitin reaction is not particularly limited, preferably pH value is 3-11, more preferably 6-10; Temperature can be 30-90 ℃, is preferably 40-80 ℃.
Wherein, it is conventionally known to one of skill in the art by the control of the consumption to alkali in reactant or acid, making the method for aluminum precipitation.
Condition to described hydrolysis reaction is not particularly limited, as long as water contacts with aluminum alkoxide, hydrolysis reaction generation hydrated aluminum oxide occurs, and the concrete condition that hydrolysis occurs is conventionally known to one of skill in the art.
Wherein, can obtain the slurries of hydrated aluminum oxide or filter cake after filtering in hydrolysis reaction or precipitin reaction and add the compound of crystal grain growth regulating effect in again adding slurries prepared by water, also can add alkaline solution or acid solution suitably to regulate pH value to 7-10, then at suitable temperature, carry out aging.Then separate, wash, be dried.
Described acid solution or alkaline solution can be with above-described identical or different.
Described aging temperature is preferably 35-98 ℃, and digestion time is preferably 0.2-6 hour.
According to method provided by the invention, described in be separated into the known technology of this area, as the method for filtration or centrifugation or evaporation.
In pseudo-boehmite preparation process of the present invention, after aging, also comprise and prepare the washing that often comprises in pseudo-boehmite process and dry step, described washing and dry method are for preparing pseudo-boehmite conventional process.For example, can use oven dry, forced air drying or spray-dired method.Generally speaking, drying temperature can be 100-350 ℃, is preferably 120-300 ℃.
According to the preparation method of pseudo-boehmite of the present invention, a preferred embodiment comprises the following steps:
(1) by containing the aluminum contained compound solution of grain growing conditioning agent and alkaline solution or acid solution and flow or intermittent type joins in reaction vessel and carries out precipitin reaction, obtain hydrated aluminum oxide slurries; Or in deionized water, add the reaction that is hydrolyzed of grain growing conditioning agent and aluminum alkoxide, obtain hydrated aluminum oxide slurries;
(2) filter cake after the hydrated aluminum oxide slurries that step (1) obtained filter adds water more again pulls an oar in the aluminum oxide slurries that obtain, and adds grain growing conditioning agent, after regulating pH to be 7-10, in 35-98 ℃ of aging 0.2-6 hour; The hydrated aluminum oxide slurries that also above-mentioned steps (1) can be obtained are under 7-10 without filtering in the existence of grain growing conditioning agent or not at pH, in 35-98 ℃ of aging 0.2-6 hour;
(3) product filter, washing step (2) obtaining;
(4) product that drying step (3) obtains, obtains the pseudo-boehmite of 1.1≤n≤2.5 provided by the invention.
The gama-alumina that the pseudo-boehmite P1 of described 1.1≤n≤2.5 obtains through roasting has following physico-chemical property, and pore volume is 0.5-1.1 ml/g, and specific surface is 100-400 rice
2/ gram, can several bore dias be 5-20 nanometer, the pore volume of bore dia 4-10 nanometer is greater than 70% of total pore volume.The gama-alumina that further preferably the pseudo-boehmite P1 of described 1.1≤n≤2.5 obtains through roasting has following physico-chemical property, and pore volume is 0.55-0.90 ml/g, and specific surface is 150-350 rice
2/ gram, can several bore dias be 6-15 nanometer, the pore volume of bore dia 4-10 nanometer is greater than 75% of total pore volume.Method and condition that the pseudo-boehmite P1 of described 1.1≤n≤2.5 is converted into gama-alumina through roasting are this area customary way and condition, for example, described condition comprises: the temperature of roasting can be 400-650 ℃, be preferably 450-600 ℃, roasting time is 1-15 hour, is preferably 3-10 hour.
According to the invention provides catalyzer, take catalyzer total amount as benchmark, the content of preferred described mesoporous molecular sieve is 20-80 % by weight, and the content of aluminum oxide is 15-75 % by weight, and in oxide compound, the content of described hydrogenation metal is 0.1-5 % by weight.Further the content of preferred described mesoporous molecular sieve is 30-70 % by weight, and the content of aluminum oxide is 30-70 % by weight, and in oxide compound, the content of described hydrogenation metal is 0.2-1 % by weight.
Described hydrogenation metal is selected from one or more in cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, molybdenum and tungsten, preferred platinum wherein.
Described mesoporous molecular sieve can be the molecular sieve with non-one dimension central hole structure, is selected from one or more in the molecular sieve of the non-one dimension central hole structure of having of zeolite type and the molecular sieve with non-one dimension central hole structure of means of nonzeolitic.The maximum diameter of hole of wherein said mesoporous molecular sieve is preferably 3.6～7.5 dusts, is preferably 3.8～6.5 dusts.For example, the molecular sieve with non-one dimension central hole structure of described zeolite type can be selected from one or more in ZSM-5, ZSM-11, ZSM-35, Beta, mordenite; The molecular sieve with non-one dimension central hole structure of described means of nonzeolitic can be selected from one or more in SAPO-21, SAPO-33, SAPO-35, preferably ZSM-5.
Described mesoporous molecular sieve can be to have minor axis to be
major axis is
the molecular sieve of one dimension elliptical aperture structure, preferably one or more in ZSM-22, NU-10, Theta-1, ISI-1, ZSM-23, SAPO-11, SAPO-31, SAPO-41, further preferred ZSM-22.
Described molecular sieve can be commercially available commodity, can be also to adopt any one prior art preparation.
According to catalyzer provided by the invention, described catalyzer is depending on the different forming composition that require can be made into various easy handlings, such as microballoon, spherical, tablet or bar shaped etc.
Catalyzer provided by the invention can adopt ordinary method preparation, for example, when the invention provides catalyzer and be bar shaped catalyst, its preparation method comprises: (1), by mesoporous molecular sieve and 1.1≤n≤2.5, preferably the complex carrier of mesoporous molecular sieve and aluminum oxide is prepared in pseudo-boehmite mixing, extruded moulding the roasting of 1.2≤n≤2.2; Wherein, when extrusion moulding, can in described mesoporous molecular sieve and pseudo-boehmite mixture, add appropriate extrusion aid and/or tackiness agent, then extrusion moulding; The kind of described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, and for example common extrusion aid can be selected from one or more in sesbania powder, methylcellulose gum, starch, polyvinyl alcohol, PVOH; Described dry temperature can be 100-200 ℃, is preferably 120-150 ℃; The temperature of roasting can be 350-650 ℃, is preferably 400-600 ℃, and roasting time is 1-15 hour, is preferably 3-10 hour; (2) adopt the method for dipping to introduce hydrogenation metal component in described complex carrier, dry and roasting; Wherein, described dry temperature can be 100-200 ℃, is preferably 120-150 ℃.The temperature of roasting can be 400-650 ℃, is preferably 450-600 ℃, and roasting time is 1-15 hour, is preferably 3-10 hour.Described dipping method is ordinary method, and for example preparation is containing the solution of the compound of described hydrogenation active metals component, afterwards by the method dipping soaking or spray, dry and roasting.The described compound containing hydrogenation activity component is selected from one or more in these their soluble compounds, for example, can be one or more in the nitrate, acetate, carbonate, muriate, soluble complexes of these metals.
According to catalyzer provided by the invention, wherein, described pseudo-boehmite optionally can also comprise the pseudo-boehmite P2 except the pseudo-boehmite of 1.1≤n≤2.5, described P2 is the pseudo-boehmite of n < 1.1, preferably P2 is the pseudo-boehmite of 0.8 < n < 1.1, the pseudo-boehmite that further preferably P2 is 0.85≤n≤1.05.When described composition contains P2, in oxide compound and take pseudo-boehmite total amount as benchmark, the content of described P2 is not more than 70 % by weight, is further preferably not more than 50 % by weight, is more preferably not more than 30 % by weight.Described P2 is that the pseudo-boehmite of 0.8 < n < 1.1 can be to be selected from the pseudo-boehmite that commercially available commodity also can adopt any one prior art to prepare.
When described pseudo-boehmite comprises the pseudo-boehmite P2 except the pseudo-boehmite of 1.1≤n≤2.5, in the preparation method of described catalyzer, also comprise the step of introducing this pseudo-boehmite.For example, the method for introducing P2 mixing, extruded moulding roasting when described step (1) is mixed mesoporous molecular sieve and P1 is introduced.
The step that preferably also comprises a reduction before described catalyzer is used, described reduction is preferably carried out under hydrogen atmosphere, and reduction temperature is preferably 300～550 ℃, and the recovery time is preferably 2～10 hours.
The reaction conditions of described catalytic dewaxing reaction member generally includes: hydrogen dividing potential drop 1-20MPa, preferably 10-16MPa, further preferred 8-18MP; Temperature of reaction is 250-450 ℃, preferably 310-400 ℃, further preferably 330 ℃-390 ℃; Volume space velocity 0.3-3h
-1, preferably 0.4-2h
-1, further preferred 0.5-1.5h
-1, hydrogen to oil volume ratio is 100-3000v/v, preferably the further preferred 500-1000v/v of 300-2000v/v.
In a preferred embodiment, the sweat oil catalytic dewaxing reaction conditions of described step in b) makes catalytic dewaxing generate oily pour point to be less than-12 ℃, to be preferably less than-15 ℃, be further preferably less than-18 ℃.
According to method provided by the invention, can adopt any existing method performing step hydrofining reaction b).Described hydrofining reaction condition generally includes: hydrogen dividing potential drop 2-30MPa, temperature 130-400 ℃, air speed 0.2-2.5h
-1, hydrogen-oil ratio 200-2000v/v.Preferably hydrogen dividing potential drop 4-25MPa, temperature 160-350 ℃, air speed 0.4-2h
-1, hydrogen-oil ratio 300-1500v/v.Further preferred hydrogen dividing potential drop 6-20MPa, temperature 200-320 ℃, air speed 0.8-1.5h
-1, hydrogen-oil ratio 300-1000v/v.
Wherein, described Hydrobon catalyst can be the catalyzer take metallic sulfide as hydrogenation active metals component, these catalyzer are conventionally known to one of skill in the art, conventionally by heat-resistant inorganic oxide carrier (containing or containing molecular sieve) and load on cobalt on this carrier and/or nickel, molybdenum and/or tungsten and containing or do not contain one or more auxiliary agents that are selected from fluorine, phosphorus or boron and form.Wherein, the content of described each component is conventional content, in oxide compound and take catalyzer as benchmark, the cobalt and/or the nickel that preferably contain 1-8 % by weight, the molybdenum of 10-35 % by weight and/or tungsten, in element, one or more adjuvant components in fluorine, phosphorus and the boron of 0-6 % by weight, the carrier of equal amount.
Heat-resistant inorganic oxide carrier described in Hydrobon catalyst 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.Be preferably aluminum oxide and/or silicon oxide.
When containing molecular sieve in described Hydrobon catalyst, one or more in zeolite or non-zeolitic molecular sieves of described molecular screening, preferably bore dia is the molecular sieve of 0.6-0.8 nanometer, as be selected from one or more in L zeolite, y-type zeolite, X-type zeolite, Beta zeolite, mordenite, ZSM-3, ZSM-4, ZSM-18, ZSM-20, SAPO-5, more preferably Y zeolite, the more preferred Y zeolite through hydrothermal method super stabilizing.
Above-mentioned Hydrobon catalyst is before being used, conventionally can be under hydrogen exists, at the temperature of 140-370 ℃, with sulphur, hydrogen sulfide or sulfur-bearing raw material, carry out prevulcanized, this prevulcanized can be carried out outward also can in device, original position vulcanizing at device, is translated into sulfide type.
Described Hydrobon catalyst can be the catalyzer as hydrogenation active metals take reducing metal, these catalyzer are conventionally known to one of skill in the art, in a preferred embodiment, the Hydrobon catalyst that described hydrofining reaction unit adopts contains carrier and loads at least one on this carrier the nickel, platinum and/or the metallic palladium component that are selected from group VIII.One or more in the optional self-alumina of described carrier, 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.In metal and take catalyzer as benchmark, the content of described group VIII metal is preferably 0.1-10 % by weight, is more preferably 0.1-5 % by weight.For example, CN1510112A discloses a kind of metal mold hydrogenation catalyst, CN1245204 discloses a kind of bimetal hydrogenation catalyst etc., all has good hydrofining performance, all can be used as the Hydrobon catalyst adopting in hydrofining reaction unit for the present invention.Especially the disclosed a kind of metal mold hydrogenation catalyst of CN1510112A, when of the present invention, has better hydrofining performance, is therefore particularly suitable for the present invention.
These Hydrobon catalysts are before being used, and preferably reduction at 150-500 ℃ under hydrogen exists, is translated into reduction-state.This method of reducing is ordinary method, and reduction can be carried out outward at reactor, also can in reactor, original position carry out.
According to method provided by the invention, the generation oil being obtained by hydrofining reaction unit, can adopt the method for distillation to do further separation, to obtain the product of required different fractions.For example, by distillation, obtaining boiling range is that light lubricant cut, the flow process of 350 ℃-430 ℃ is the middle lubricating oil distillate of 350 ℃-430 ℃, and flow process is to be greater than the heavy lubricating oil cut of 430 ℃.The method of described distillation is known in this field, conventionally can comprise the operating unit of one or more flash distillations, air distillation and underpressure distillation, to complete desirable separation.
When the sulphur in described sweat oil, nitrogen content can not meet of the present invention requirement, in the inventive method, can comprise the step of a hydrotreatment, by this processing, described sweat oil is met the demands.The method of described hydrotreatment is the usual method in this area, and its reaction conditions generally includes: hydrogen dividing potential drop 4-30MPa, temperature 250-470 ℃, air speed 0.2-2.5h
-1, hydrogen-oil ratio 200-3000v/v.Preferably hydrogen dividing potential drop 8-27MPa, temperature 260-450 ℃, air speed 0.3-2h
-1, hydrogen-oil ratio 300-2000v/v.Further preferred hydrogen dividing potential drop 10-25MPa, temperature 280-350 ℃, air speed 0.4-1.5h
-1, hydrogen-oil ratio 400-1000v/v.
Consisting of of described hydrotreating catalyst is conventionally known to one of skill in the art, conventionally by heat-resistant inorganic oxide carrier (containing or containing molecular sieve) and load on cobalt on this carrier and/or nickel, molybdenum and/or tungsten and containing or do not contain one or more auxiliary agents that are selected from fluorine, phosphorus or boron and form.Wherein, the content of described each component is conventional content, in oxide compound and take catalyzer as benchmark, the cobalt and/or the nickel that preferably contain 1-8 % by weight, the molybdenum of 10-35 % by weight and/or tungsten, in element, one or more adjuvant components in fluorine, phosphorus and the boron of 0-6 % by weight, the carrier of equal amount.They can be commercially available commodity or adopt any existing method preparation.
Heat-resistant inorganic oxide carrier described in hydrotreating catalyst 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.Be preferably aluminum oxide and/or silicon oxide.
When containing molecular sieve in described hydrotreating catalyst, one or more in zeolite or non-zeolitic molecular sieves of described molecular screening, preferably bore dia is the molecular sieve of 0.6-0.8 nanometer, as be selected from one or more in L zeolite, y-type zeolite, X-type zeolite, Beta zeolite, mordenite, ZSM-3, ZSM-4, ZSM-18, ZSM-20, SAPO-5, more preferably Y zeolite, the more preferred Y zeolite through hydrothermal method super stabilizing.
Described hydrotreating catalyst is before being used, conventionally can be under hydrogen exists, at the temperature of 140-370 ℃, with sulphur, hydrogen sulfide or sulfur-bearing raw material, carry out prevulcanized, this prevulcanized can be carried out outward also can in device, original position vulcanizing at device, is translated into sulfide type.
Be suitable as hydrotreating catalyst for example of the present invention as, the disclosed a kind of Hydrobon catalyst of CN1085934A, the disclosed a kind of Hydrobon catalyst of CN1105053A, the disclosed a kind of Hydrobon catalyst of CN1169336A, the disclosed a kind of hydrotreating catalyst of CN1803283A, and CN1853780A, CN1853777A, CN1853781A, CN1853782A, CN1840618A, CN1872960A, CN1872959A disclose serial hydrogenation catalyst etc.About composition of above-mentioned catalyzer and preparation method thereof, all on the books in above-mentioned patent documentation, do not repeat here.
With embodiment, further illustrate the features and advantages of the invention below, but therefore do not limit the present invention.
Hydrotreating catalyst, dewaxing catalyst and hydrogenation catalyst of in the embodiment of the present invention, using and preparation method thereof are as follows:
1. the catalyzer a of hydrotreatment reaction use
A1. the hydrotreating catalyst a1 using in the embodiment of the present invention be according to the example 6 in CN1169336A, prepare take fluorine as auxiliary agent, nickel-tungsten is the catalyzer of active constituent loading on alumina supporter, wherein take catalyzer total amount as benchmark, in oxide compound, the content of nickel is 2.3 % by weight, and the content of tungsten is 22 % by weight, in element, the content of fluorine is 4 % by weight, and all the other are aluminum oxide.
2. the catalyzer b that wax hydroconversion reactions is used
The pseudo-boehmite P1 of 1.1≤n≤2.5 of using in the embodiment of the present invention, the pseudo-boehmite P2 of n < 1.1, following (the agents useful for same in example in preparation method and source thereof, except special instruction, be chemically pure reagent):
In example, the n value of all pseudo-boehmites adopts XRD method to measure.XRD test is carried out on SIMENSD5005 type X-ray diffractometer, CuK α radiation, and 44 kilovolts, 40 milliamperes, sweep velocity is 2/ minute.According to Scherrer formula: (D is grain-size to D=K λ/(Bcos θ), λ is the diffraction wavelength of target shaped material, B is the peak width at half height of corrected diffraction peak, 2 θ are the position of diffraction peak) grain size that goes out respectively (120) take 2 θ as the calculation of parameter at 23-33 peak is as D (120), the grain size that goes out (031) take 2 θ as the calculation of parameter at 34-43 peak are D (031), and calculates n value by formula n=D (031)/D (120).
P1-1, adopts following method preparation:
In the retort of 2 liters and stream add 1000 ml concns be 48 grams of aluminum oxide/liter aluminum trichloride solution and 300 milliliters containing 200 grams of aluminum oxide/liter, causticity coefficient is 1.58, Sorbitol Powder content is 1.82 grams per liters sodium aluminate solution carries out precipitin reaction, temperature of reaction be 80 ℃, regulate reactant flow make in and pH value be 4.0, reaction time 15 minutes; In gained slurries, adding concentration is the weak ammonia adjusting slurries pH to 10.0 of 5 % by weight, and be warming up to 80 ℃, aging 3 hours, then with vacuum filter, filter, to be filtered complete after, on filter cake supplement add 20 liters of deionized waters (80 ℃ of temperature) flush cake approximately 30 minutes.The qualified filter cake of washing is joined to 1.5 liters of deionized water for stirring and become slurries, slurries are dried with being pumped into spray-dryer, control spray-dryer temperature out 100-110 ℃ of scope, approximately 2 minutes dry materials time, after being dried, obtain hydrated aluminum oxide P1-1.Adopt XRD to characterize, P1-1 has structure of similar to thin diaspore.The n value that adopts XRD method to calculate P1-1 is listed in table 1.
P1-2, adopts following method preparation:
By containing 210 grams of aluminum oxide/liter, the causticity coefficient high density NaAlO that is 1.62
2solution and deionized water are mixed with Al
2o
3concentration is 5 liters of the solution of 40 grams per liters, then adds 16.3 grams of Sunmorl N 60Ss to obtain the NaAlO containing Sunmorl N 60S
2solution, is then transferred in the plastic reactor of cumulative volume 8L, and reactor aspect ratio is 8, bottom band CO
2gas distributor.Controlling solution temperature is 25 ± 5 ℃, passes into the CO of concentration 90 volume % from reactor bottom
2gas carries out plastic reaction, and plastic temperature is controlled at 20-40 ℃, regulates CO
2gas flow is 15 ± 2 liters/min, makes reaction end pH value reach 8.0-8.5 in 4-6 minute, stops ventilation, finishes plastic reaction.By gained slurries be heated to 70 ℃ aging 4 hours, then with vacuum filter, filter, to be filtered complete after, on filter cake supplement add 20 liters of deionized waters (temperature 70 C) flush cake approximately 30 minutes.The qualified filter cake of washing is joined to 1.5 liters of deionized water for stirring and become slurries, slurries are dried with being pumped into spray-dryer, obtain hydrated aluminum oxide P1-2.XRD characterizes demonstration, and P1-2 has structure of similar to thin diaspore, and the n value that calculates P1-2 through XRD sign is listed in table 1.
P2-1, adopts following method preparation:
Method according to P1-1 is prepared pseudo-boehmite, different, and in sodium aluminate solution, not containing Sorbitol Powder, drying obtains hydrated aluminum oxide P2-1.XRD characterizes demonstration, and P2-1 has structure of similar to thin diaspore, and the n value that calculates P2-1 through XRD sign is listed in table 1.
P2-2, is the business pseudo-boehmite SB powder that German Condea company aluminium alcoholates hydrolysis method is produced, and the n value that adopts XRD characterizing method to calculate P2-2 powder is listed in table 1.
Repeatedly prepare according to the method described above, to obtain enough for the pseudo-boehmite raw material in example.
Table 1
* take the degree of crystallinity of the business SB powder of Condea company as 100%.
B1. by a kind of ZSM-22 molecular sieve, (Chang Ling catalyst plant provides, silica alumina ratio 56) mix with pseudo-boehmite P1-1, sesbania powder, add aqueous nitric acid, fully kneading, then on banded extruder, extrude diameter and be the cloverleaf pattern bar of 1.3 millimeters, at 120 ℃ dry 4 hours, then 600 ℃ of roastings 2 hours in air, obtained carrier.By carrier with containing Pt (NH
3)
4cl
2solution carry out saturated dipping, then at 110 ℃ dry 4 hours, 400 ℃ of roastings 3 hours in air atmosphere.Then gained catalyzer is reduced, reduction temperature is 350 ℃, and the recovery time is 4 hours, and hydrogen pressure is 0.1 MPa.Catalyzer after reduction is designated as b1, and it forms in Table 2.Metal content in catalyzer is with x-ray fluorescence method analysis.
B2. by a kind of ZSM-22 molecular sieve, (Chang Ling catalyst plant provides, silica alumina ratio 120) mix with pseudo-boehmite P1-2, sesbania powder, add aqueous nitric acid, fully kneading, then on banded extruder, extrude diameter and be the butterfly bar of 1.3 millimeters, at 120 ℃ dry 4 hours, then 550 ℃ of roastings 4 hours in air, obtained carrier.By carrier with containing Pt (NH
3)
4cl
2solution carry out saturated dipping, then at 120 ℃ dry 2 hours, 450 ℃ of roastings 4 hours in air atmosphere.Then gained catalyzer is reduced, reduction temperature is 400 ℃, and the recovery time is 4 hours, and hydrogen pressure is 0.1 MPa.Catalyzer after reduction is designated as b2, and it forms in Table 2.
B3. method for preparing catalyst is identical with embodiment 1, and different is that pseudo-boehmite P2-1 is replaced to P1-1.Catalyzer after reduction is designated as b3, and it forms in Table 2.
B4. method for preparing catalyst is identical with embodiment 2, and different is that pseudo-boehmite P2-2 is replaced to P1-2.Catalyzer after reduction is designated as b4, and it forms in Table 2.
Table 2
3. the catalyzer c that hydrofining reaction is used
The Hydrobon catalyst c using in the embodiment of the present invention is prepared according to the example 11 in CN1510112A, and wherein, the content of platinum is 0.22 % by weight, and the content of metallic palladium is 0.43 % by weight.
Embodiment 1
According to the oily raw material that processes raw material of the flow process described in accompanying drawing 1, raw material is for subtracting four line sweat oil A, and character is listed in table 1.Catalytic dewaxing unit catalyzer is all b1 mutually with embodiment 1, hydrofining unit catalyzer c.
The reaction conditions of catalytic dewaxing reaction member comprises: hydrogen dividing potential drop 12MPa, 350 ℃ of temperature, air speed 1h
-1, hydrogen-oil ratio 700v/v.
The reaction conditions of hydrofining reaction unit comprises: hydrogen dividing potential drop 12MPa, 210 ℃ of temperature, air speed 1h
-1, hydrogen-oil ratio 500v/v.Be greater than 400 ℃ of lubricating oil distillate base oil yield, character and list in table 4.
Embodiment 2
Except catalytic dewaxing section catalyzer adopts b2, other conditions are identical with embodiment 2.It is greater than 400 ℃ of lubricating oil distillate yields, character and lists in table 4.
Embodiment 3
Except catalytic dewaxing section catalyzer adopts b3, other conditions are identical with embodiment 2.It is greater than 400 ℃ of lubricating oil distillate yields, character and lists in table 4.
Comparative example 1
Except raw material adopts intermediate base, subtract four line sweat oil B, other are identical with embodiment 2.It is greater than 400 ℃ of lubricating oil distillate base oil yield, character and lists in table 4.
Embodiment 4
According to the oil that processes raw material of the flow process described in accompanying drawing 2, wherein, hydrotreatment reaction member adopts fixed-bed reactor.Hydrotreatment reaction member catalyzer is a1, and catalytic dewaxing reaction member catalyzer is b1, and hydrofining reaction unit catalyzer is c.
Stock oil subtracts four line sweat oil B for certain intermediate base, and its character is listed in table 3.
The reaction conditions of hydrotreatment reaction member comprises: hydrogen dividing potential drop 10MPa, 350 ℃ of temperature, air speed 0.7h
-1, hydrogen-oil ratio 1000v/v.
The reaction conditions of catalytic dewaxing reaction member comprises: hydrogen dividing potential drop 12MPa, 350 ℃ of temperature, air speed 1h
-1, hydrogen-oil ratio 700v/v.
The reaction conditions of hydrofining reaction unit comprises: hydrogen dividing potential drop 12MPa, 210 ℃ of temperature, air speed 1h
-1, hydrogen-oil ratio 500v/v.> 400 ℃ of lubricating oil distillate base oil yield, character are listed in table 4.
Table 3
Table 4
For ease of the understanding to each product property, table 5 has provided in China Petrochemical Corp.'s lubricant base consensus standard about HVI II lube base oil standard, table 6 has provided in China Petrochemical Corp.'s lubricant base consensus standard about HVI III lube base oil standard, from result, product obtained by the method for the present invention can meet respectively HVI II, HVI III lube base oil standard.
Claims (21)
1. utilize sweat oil to produce the method for lubricant base, comprising: a), under a catalytic dewaxing reaction member and catalytic dewaxing reaction conditions, sweat oil is contacted with dewaxing catalyst, prepare a kind of depression of pour point sweat oil, b) under hydrofining reaction unit and hydrofining reaction condition, the depression of pour point that step a) is obtained sweat oil contact with Hydrobon catalyst, be isolated to lubricant base, wherein, sulphur content in described sweat oil is less than 50 μ g/g, and nitrogen content is less than 10 μ g/g, wherein, described dewaxing catalyst contains the molecular sieve with central hole structure, heat-resistant inorganic oxide matrix and hydrogenation metal component, it is characterized in that, described heat-resistant inorganic oxide matrix comprises a kind of gama-alumina being obtained through roasting by pseudo-boehmite, wherein, described pseudo-boehmite comprises a kind of pseudo-boehmite P1 of 1.1≤n≤2.5, wherein n=D (031)/D (120), the grain-size of the crystal face of 031 peak representative in the XRD spectra of described D (031) expression pseudo-boehmite crystal grain, the grain-size of the crystal face of 120 peak representatives in the XRD spectra of D (120) expression pseudo-boehmite crystal grain, described 031 peak refers to that 2 θ in XRD spectra are the peak of 34-43 °, described 120 peaks refer to that 2 θ in XRD spectra are the peak of 23-33 °, D=K enters/(Bcos θ), K is Scherrer constant, enter the diffraction wavelength for target shaped material, B is the peak width at half height of diffraction peak, 2 θ are the position of diffraction peak.
2. method according to claim 1, is characterized in that, the sulphur content in described sweat oil is less than 50 μ g/g, and nitrogen content is less than 10 μ g/g.
3. method according to claim 2, is characterized in that, the sulphur content in described sweat oil is less than 20 μ g/g, and nitrogen content is less than 5 μ g/g.
4. method according to claim 3, is characterized in that, the sulphur content in described sweat oil is less than 10 μ g/g, and nitrogen content is less than 2 μ g/g.
5. method according to claim 1, is characterized in that, the n of described pseudo-boehmite P1 is 1.2≤n≤2.2.
6. method according to claim 1, is characterized in that, take catalyzer total amount as benchmark, the content of described mesoporous molecular sieve is the heavy % of 20-80, and the content of aluminum oxide is the heavy % of 15-75, and the content of hydrogenation metal is the heavy % of 0.1-5.
7. method according to claim 6, is characterized in that, the content of described mesoporous molecular sieve is the heavy % of 30-70, and the content of aluminum oxide is the heavy % of 30-70, and the content of described hydrogenation metal is the heavy %. of 0.2-1
8. according to the method described in claim 1,6,7, it is characterized in that one or more in the described preferred cobalt of hydrogenation active metals component, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, molybdenum and tungsten.
9. method according to claim 8, is characterized in that, described hydrogenation metal is platinum.
10. method according to claim 1, it is characterized in that one or more in ZSM-5, ZSM-11, ZSM-35, Beta, mordenite, SAP0-21, SAP0-33, SAP0-35, ZSM-22, Nu-10, Theta-1, ISI-1, ZSM-23, SAP0-11, SAP0-31, SAP0-41 of described molecular screening.
11. methods according to claim 10, is characterized in that, described molecular sieve is ZSM-5 and/or ZSM-22.
12. methods according to claim 1, is characterized in that, the reaction conditions of described catalytic dewaxing reaction member generally includes: hydrogen dividing potential drop 1-30MPa, temperature of reaction is 250-450 ℃, volume space velocity 0.3-3h
-1, hydrogen to oil volume ratio is 100-3000v/v.
13. methods according to claim 12, is characterized in that, the reaction conditions of described catalytic dewaxing reaction member generally includes: hydrogen dividing potential drop 10-25MPa, temperature of reaction is 310-420 ℃, volume space velocity 0.4-2h
-1, hydrogen to oil volume ratio is 300-2000v/v.
14. methods according to claim 13, is characterized in that, the reaction conditions of described catalytic dewaxing reaction member generally includes: hydrogen dividing potential drop 8-20MP, and temperature of reaction is 330 ℃-390 ℃, volume space velocity is 0.5-1.5h
-1, hydrogen to oil volume ratio is 500-1000v/v.
15. methods according to claim 1, is characterized in that, described hydrofining reaction condition generally includes: hydrogen dividing potential drop 4-25MPa, temperature 160-350 ℃, air speed 0.4-2h
-1, hydrogen-oil ratio 300-1500v/v.
16. methods according to claim 15, is characterized in that, described hydrofining reaction condition generally includes: hydrogen dividing potential drop 6-20MPa, temperature 200-320 ℃, air speed 0.8-1.5h
-1, hydrogen-oil ratio 300-1000v/v.
17. methods according to claim 1, it is characterized in that, described method comprises the step of a hydrotreatment reaction, and the sulphur content in the sweat oil after the hydrotreatment that described hydrotreatment reaction conditions makes to be isolated to is less than 50 μ g/g, and nitrogen content is less than 10 μ g/g.
18. methods according to claim 17, is characterized in that, the sulphur content in the sweat oil after the hydrotreatment that described hydrotreatment reaction conditions makes to be isolated to is less than 20 μ g/g, and nitrogen content is less than 5 μ g/g.
19. methods according to claim 18, is characterized in that, the sulphur content in the sweat oil after the hydrotreatment that described hydrotreatment reaction conditions makes to be isolated to is less than 10 μ g/g, and nitrogen content is less than 2 μ g/g.
20. methods according to claim 17, is characterized in that, the reaction conditions of described hydrotreatment reaction comprises: hydrogen dividing potential drop 8-27MPa, temperature 260-450 ℃, air speed 0.3-2h
-1, hydrogen-oil ratio 300-2000v/v.
21. methods according to claim 20, is characterized in that, the reaction conditions of described hydrotreatment reaction generally includes: hydrogen dividing potential drop 10-25MPa, temperature 280-350 ℃, air speed 0.4-1.5h
-1, hydrogen-oil ratio 400-1000v/v.
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| CN1362479A (en) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | ZSM molecular sieve-containing catalyst and its prepn |
| CN1676585A (en) * | 2004-03-31 | 2005-10-05 | 中国石油化工股份有限公司 | Method for preparing lubricating oil base oil |
| CN1966620A (en) * | 2005-11-16 | 2007-05-23 | 中国石油化工股份有限公司 | Catalytic dewaxing catalyst |
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| CN1362479A (en) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | ZSM molecular sieve-containing catalyst and its prepn |
| CN1676585A (en) * | 2004-03-31 | 2005-10-05 | 中国石油化工股份有限公司 | Method for preparing lubricating oil base oil |
| CN1966620A (en) * | 2005-11-16 | 2007-05-23 | 中国石油化工股份有限公司 | Catalytic dewaxing catalyst |
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