CN102242000B - Processing method of heavy hydrocarbon oil - Google Patents
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Abstract
A processing method of heavy hydrocarbon oil comprises the following steps of: (1) letting the heavy hydrocarbon oil contact with a hydrotreating catalyst in a hydrotreatment reaction unit under the hydrotreatment reaction condition, and separating through a separation unit to obtain a refinery gas, distillate oil whose distillation range is less than or equal to that of diesel oil and distillate oil whose distillation range is greater than that of diesel oil; (2) carrying out at least two dewaxing treatments on the distillate oil, whose distillation range is greater than that of diesel oil and which is obtained from Step (1), in a solvent dewaxing unit under the solvent dewaxing condition, wherein the first dewaxing treatment is conducted to obtain dewaxing oil and a first cerate, and a second solvent dewaxing treatment is conducted on the first cerate in the solvent dewaxing unit to obtain foots oil and a second cerate; (3) letting the foots oil obtained from Step (2) contact with a catalytic dewaxing catalyst in a catalytic dewaxing reaction unit under the catalytic dewaxing reaction condition to obtain foots oil which undergoes catalytic dewaxing; (4) respectively carrying out hydrofining processing on the foots oil which undergoes catalytic dewaxing, the dewaxing oil and the second cerate under hydrofining reaction condition in a hydrofining reaction unit to further obtain HVI III base oil, HVI II base oil and a wax product.
Description
Technical field
The present invention relates to a kind of working method of hydrocarbon ils.The working method that relates in particular a kind of heavy hydrocarbon oil.
Background technology
Adopt the method for the standby lubricant base of multistep Hydrogenation to know in the art.In these class methods, the first step is take hydrogenating desulfurization, nitrogen as purpose mostly, and the while is with open loop or the hydrogenation saturation history of aromatic hydrocarbons.Second step is mainly that to reduce the product pour point be purpose isomerization-visbreaking process or hydrodewaxing process.This kind hydrogenation process has certain requirement to raw material, utilizes the raw material of intermediate base to produce by this kind process the hydroconversion condition that HVI III class base oil need to be very harsh, and yield losses is large.
CN 101074393A discloses a kind of method for preparing lubricant base, the method comprise the dewaxing raw material in the situation that add auxiliary agent through after solvent dewaxing, the sweat oil of pressed oil and second and third section 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, cut out＞300 ℃ of parts do oil base stock, and＜300 ℃ of parts are done solvent oil.The catalyzer that the isomerization-visbreaking part is used is with the dual-function catalyst of precious metal as the hydrogenation dehydrogenation component, is ZAP, SAPO, ZSM and the SSZ dewaxing by molecular sieve catalyzer that is loaded with 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 that production high value added product as much as possible is purpose with the maximized utilization heavy hydrocarbon oil through hydrotreatment, and a kind of working method of new heavy hydrocarbon oil is provided.
The invention provides a kind of working method of heavy hydrocarbon oil, comprise: (1) is under the hydrotreatment reaction conditions, heavy hydrocarbon oil is contacted with hydrotreating catalyst at the hydrotreatment reaction member, through separating unit separate obtain refinery gas, boiling range less than with the distillate that equals diesel oil and the boiling range distillate greater than diesel oil; (2) under solvent dewaxing unit and solvent dewaxing condition, the boiling range that step (1) is obtained once dewaxes greater than the distillate of diesel oil, obtain a kind of pressed oil and a slack wax, slack wax is carried out the secondary solvent dewaxing in the solvent dewaxing unit, obtain a kind of sweat oil and secondary slack wax; (3) under the catalytic dewaxing reaction conditions, the sweat oil that step (2) is obtained contacts with catalytic dewaxing catalyst at the catalytic dewaxing reaction member, obtains a kind of sweat oil through catalytic dewaxing; (4) under hydrofining reaction unit and hydrofining reaction condition, the sweat oil through catalytic dewaxing that (4a) step (3) is obtained contacts with Hydrobon catalyst, obtains a kind of base oil of the HVI of satisfying III standard; The pressed oil that (4b) step (2) is obtained contacts with Hydrobon catalyst, obtains a kind of base oil of the HVI of satisfying II standard; The secondary slack wax that (4c) step (2) is obtained contacts with Hydrobon catalyst, obtains a kind of wax product.
Compare with existing method, method provided by the invention can utilize heavy hydrocarbon oil to produce the product of greater amt, more kinds as much as possible, and for example, synchronous production satisfies base oil and the wax product of HVI II standard, HVI III standard.
Description of drawings
Fig. 1 is the schematic flow sheet of working method that the invention provides a kind of vacuum distillate of method.
Embodiment
According to the working method of heavy hydrocarbon oil provided by the invention, wherein, described heavy hydrocarbon oil refers to an at least part of class hydrocarbon ils that contains lubricating oil distillate.For example, described heavy hydrocarbon oil can be each line vacuum distillate and refining after distillate, as one or more distillates in each line vacuum distillate, solvent treatment vacuum distillate, hydrocracking tail oil, slack wax, sweat oil, Fischer-Tropsch synthesis oil, dewaxing vacuum distillate, can be one or more in frivolous asphalt oil, heavy deasphalted oil.
Colloid, macromole polycyclic aromatic hydrocarbons and sulphur, nitrogen compound and aromatic saturation reaction that the hydrotreatment of described step (1) reacts to remove in raw material are purpose.Wherein, described hydrotreatment reaction conditions make boiling range after separating unit separates greater than the sulphur content in the distillate of diesel oil less than 50 μ g/g, preferably less than 20 μ g/g, further preferably less than 10 μ g/g; Nitrogen content is less than 10 μ g/g, preferably less than 5 μ g/g, further preferably less than 2 μ g/g.
The reaction conditions of described hydrotreatment reaction member generally includes: hydrogen dividing potential drop 4-30MPa, temperature 250-470 ℃, air speed 0.2-2.5h
-1, hydrogen-oil ratio 500-3000v/v.Preferred hydrogen dividing potential drop 8-27MPa, temperature 260-450 ℃, air speed 0.3-2h
-1, hydrogen-oil ratio 700-2500v/v.Further preferred hydrogen dividing potential drop 10-25MPa, temperature 280-420 ℃, air speed 0.4-1.5h
-1, hydrogen-oil ratio 800-2000v/v.
The hydrotreating catalyst that described hydrotreatment reaction member adopts can be commercially available commodity or adopt arbitrarily existing method preparation.
Consisting of of described hydrotreating catalyst is conventionally known to one of skill in the art, usually by heat-resistant inorganic oxide carrier (containing or do not contain molecular sieve) with load on cobalt and/or nickel, molybdenum and/or the tungsten on this carrier and contain 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, preferably contain cobalt and/or the nickel of 1-8 % by weight, the molybdenum of 10-35 % by weight and/or tungsten are in element, one or more adjuvant components in the fluorine of 0-6 % by weight, phosphorus and boron, the carrier of equal amount.
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, preferred 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, Y zeolite more preferably, more preferred Y zeolite through the hydrothermal method super stabilizing.
Described hydrotreating catalyst is before using, usually can be under hydrogen exists, carry out prevulcanized with sulphur, hydrogen sulfide or sulfur-bearing raw material at the temperature of 140-370 ℃, this prevulcanized can be carried out also can original position vulcanizing in device outside device, is translated into sulfide type.
Be suitable as hydrotreating catalyst be used 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 give unnecessary details here.
Described hydrotreatment reaction member can comprise one or more hydrotreating reactor.In a concrete embodiment, described hydrotreatment reaction member comprises the reactor of two series connection.In this hydrotreatment reaction member, the reactor that vacuum distillate is entered successively two series connection that are filled with respectively catalyst I and catalyst I I contacts with catalyzer.Wherein, described catalyst I and catalyst I I can be the same or different, and namely they can be a kind of, can be also the combinations of two or more different hydrotreating catalysts.
According to method provided by the invention, when described hydrotreatment reaction member comprises plural hydrotreating reactor, the size of each reactor can be the same or different, in preferred embodiment, the reaction conditions of described the first reactor comprises: hydrogen dividing potential drop 4-30MPa, temperature 250-470 ℃, air speed 0.2-2h
-1, hydrogen-oil ratio 500-3000v/v.Preferred hydrogen dividing potential drop 8-27MPa, temperature 300-450 ℃, air speed 0.3-1.5h
-1, hydrogen-oil ratio 700-2500v/v.Further preferred hydrogen dividing potential drop 10-25MPa, temperature 350-420 ℃, air speed 0.4-1h
-1, hydrogen-oil ratio 800-2000v/v.The reaction conditions of the second reactor comprises: hydrogen dividing potential drop 2-25MPa, temperature 200-400 ℃, air speed 0.4-2.5h
-1, hydrogen-oil ratio 200-1000v/v.Preferred hydrogen dividing potential drop 4-20MPa, temperature 230-350 ℃, air speed 0.6-2h
-1, hydrogen-oil ratio 300-800v/v.Further preferred hydrogen dividing potential drop 6-17MPa, temperature 260-320 ℃, air speed 0.8-1.5h
-1, hydrogen-oil ratio 300-600v/v.For the reaction conditions that makes the second reactor meets the demands, can be connected with interchanger between the first reactor and the second reactor, the material that is flowed out by the first reactor enters the second reactor reaction after the interchanger heat exchange.
According to method provided by the invention, described separating unit can adopt a kind of and several method realization arbitrarily to realize the required purpose that is separated into, and for example, separates by methods such as strippings known in the art and comprises H
2S, NH
3With small molecule hydrocarbon molecule products such as gas or liquefied gas; The product liquid of method after to aforementioned stripping by distillation separates the distillate (greater than the distillate of 350 ℃) that obtains gasoline (boiling range is generally 30 ℃-205 ℃), diesel oil (boiling range is generally 180 ℃-350 ℃) and overweight diesel oil.
According to method provided by the invention, the operational condition of wherein said solvent dewaxing operating unit and method are condition well known in the art and method.Operational condition and then realization by the adjustment solvent dewaxing are-12 ℃ to-15 ℃ through the pour point of a solvent dewaxing gained pressed oil; The pour point of secondary solvent dewaxing gained sweat oil is-12 ℃ to 90 ℃, is preferably 0 ℃ to 80 ℃, more preferably 20 ℃ to 80 ℃.The solvent that wherein adopts is the habitual solvent of solvent dewaxing, for example, adoptable dewaxing solvent is the mixture of ketone, propane or ketone and aromatic hydrocarbons, the mixture of preferred ketone and aromatic hydrocarbons, the mixture of one or more in the preferred butanone of ketone wherein (can be different isomerization body of butanone and composition thereof), acetone, methyl iso-butyl ketone (MIBK), aromatic hydrocarbons is benzene and/or toluene.Preferred solvent is the mixture of ketone and benzene class, as butanone-toluene, Acetone-Benzene, Acetone-Benzene-toluene, butanone-benzene-toluene Mixed Solvent.
In preferred embodiment, the mass ratio of agent (solvent) oil (boiling range is greater than the distillate of diesel oil) of described the first dewaxing section is 0.5-3, is preferably 1-2.5, further preferred 1.2-2.2.The mass ratio of agent (solvent) oil of the second dewaxing section (slack wax that the first dewaxing section obtains) is 0.5-3, is preferably 1-2.5, more preferably 1.3-2.
As technology well known in the art, in " modern lubricating oil processing technique " book, the solvent treatment of lubricating oil distillate and solvent dewaxing have been carried out more describing in detail [water sky moral, " modern lubricating oil processing technique ", Sinopec press in June, 1997 version, p166～p213, p226～p278] quote as a reference here.
According to method provided by the invention, described catalytic dewaxing reaction transforms the straight waxes molecule as purpose under the catalytic hydroprocessing condition.Wherein used catalyst is selected from one or more in catalytic dewaxing use catalyzer well known in the art.For example, contain the catalyzer that molecular sieve, heat-resistant inorganic oxide matrix and hydrogenation metal component with central hole structure consists of.Take the catalyzer total amount as benchmark, the content of the mesoporous molecular sieve in preferred dewaxing catalyst is the 20-80 % by weight, and the content of aluminum oxide is the 15-75 % by weight, and in oxide compound, the content of described hydrogenation metal is the 0.1-5 % by weight.Further the content of preferred described mesoporous molecular sieve is the 30-70 % by weight, and the content of aluminum oxide is the 30-70 % by weight, and in oxide compound, the content of described hydrogenation metal is the 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 with non-one dimension central hole structure of the molecular sieve of the non-one dimension central hole structure of having of zeolite type and 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, preferred ZSM-5.
Described mesoporous molecular sieve can be that to have minor axis be 4.2-4.8
Major axis is 5.4-7.0
The molecular sieve of one dimension elliptical aperture structure, preferred 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.
one preferred embodiment in, described dewaxing catalyst contains the molecular sieve of 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 that is obtained through roasting by pseudo-boehmite, wherein, described pseudo-boehmite comprises the pseudo-boehmite P1 of a kind of 1.1≤n≤2.5, n=D (031)/D (120) wherein, 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 the peak of 34-43, described 120 peaks refer to that in XRD spectra, 2 θ are the peak of 23-33, D=K λ/(Bcos θ), K is the Scherrer constant, λ is the diffraction wavelength of target shaped material, B is the peak width at half height of diffraction peak, 2 θ are the position of diffraction peak.The n of preferred described pseudo-boehmite P1 satisfies 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 with acid or alkali carry out precipitin reaction, perhaps organic aluminum contained compound is contacted the reaction that is hydrolyzed with water, obtain hydrated aluminum oxide; Carry out hydrated aluminum oxide obtained above 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 carry out under the grain growing conditioning agent exists, described grain growing conditioning agent is for can regulate the material of 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 carry out realizing purpose of the present invention under the grain growing conditioning agent exists, but under preferable case, described hydrolysis reaction and weathering process or described precipitin reaction and weathering process are all carried out under the grain growing conditioning agent exists, and can make like this n of gained pseudo-boehmite in preferred 1.2≤n≤2.2 scopes.
Wherein, there is no particular limitation to the consumption of grain growing conditioning agent, 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 that contains 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 preferably the 1-8.5 % by weight for the 0.5-10 % by weight of hydrated aluminum oxide weight, further preferred 5-8.5 % by weight.Unless stated otherwise, in the present invention, the consumption of described grain growing conditioning agent respectively in organic aluminum contained compound, inorganic aluminum contained compound and the hydrated aluminum oxide weight of corresponding aluminum oxide calculate as benchmark.Be also, 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 crystal grain at the material of 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, the grain growing conditioning agent can be added separately, also can be in advance the grain growing conditioning agent be mixed with wherein one or more raw materials, and then the raw material that will contain the grain growing conditioning agent reacts.
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, can be for example 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 use separately also and can use after two kinds or more of mixing.Described aluminate solution is aluminate solution arbitrarily, as sodium aluminate solution and/or potassium aluminate.Because its acquisition is easy and price is low, preferred 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 counts the 0.2-1.1 mol/L with aluminum oxide.
Described acid can be various protonic acids or be acid oxide compound in water medium, 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, and the concentration of preferred H+ is the 0.2-2 mol/L.
Described alkaline solution can be hydrolyzed for oxyhydroxide or in water medium the salt that makes the aqueous solution be alkalescence, 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, preferred OH
-Concentration be the 0.2-4 mol/L.When during as alkali, when calculating the consumption of described grain growing conditioning agent, also considering the amount of corresponding aluminum oxide in sodium metaaluminate and/or potassium metaaluminate with sodium metaaluminate and/or potassium metaaluminate.
Described organic aluminum contained compound can be various can the reaction with steeping in water for reconstitution unboiled water solution, 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 the preferred 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, preferred 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 making the method for aluminum precipitation by the control of consumption to alkali in reactant or acid.
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 add the compound of crystal grain growth regulating effect in hydrolysis reaction or precipitin reaction obtain slurries that the slurries of hydrated aluminum oxide or filter cake after filtering add the water preparation again, also can add alkaline solution or acid solution suitably to regulate the pH value to 7-10, then carry out aging at suitable temperature.Then separate, washing, drying.
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, the described known technology that is separated into this area is as the method for filtration or centrifugation or evaporation.
In pseudo-boehmite preparation process of the present invention, also comprise the washing and the dry step that often comprise in preparation pseudo-boehmite process after aging, described washing and dry method are preparation 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) will contain the aluminum contained compound solution of grain growing conditioning agent and alkaline solution or acid solution and stream or intermittent type and join and carry out precipitin reaction in reaction vessel, obtain the hydrated aluminum oxide slurries; Perhaps add the reaction that is hydrolyzed of grain growing conditioning agent and aluminum alkoxide in deionized water, obtain the hydrated aluminum oxide slurries;
(2) filter cake after the hydrated aluminum oxide dope filtration that step (1) is obtained adds in the aluminum oxide slurries that water making beating obtains again again, adds the grain growing conditioning agent, after regulating pH and being 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 without filtering in the existence of grain growing conditioning agent or being under 7-10 at pH not, in 35-98 ℃ of aging 0.2-6 hour;
(3) product that filter, washing step (2) obtains;
(4) product that obtains of drying step (3) obtains the pseudo-boehmite of 1.1≤n provided by the invention≤2.5.
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 the 5-20 nanometer, and the pore volume of bore dia 4-10 nanometer is greater than 70% of total pore volume.The gama-alumina that the pseudo-boehmite P1 of further preferred 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 the 6-15 nanometer, and the pore volume of bore dia 4-10 nanometer is greater than 75% of total pore volume.Be this area customary way and condition with the pseudo-boehmite P1 of described 1.1≤n≤2.5 through method and the condition that roasting is converted into gama-alumina, 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 catalyzer provided by the invention, described catalyzer is looked 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 the ordinary method preparation, for example, when the invention provides catalyzer and be bar shaped catalyst, its preparation method comprises: (1) with mesoporous molecular sieve and 1.1≤n≤2.5, pseudo-boehmite mixing, extruded moulding and the roasting of preferred 1.2≤n≤2.2 prepares the complex carrier of mesoporous molecular sieve and aluminum oxide; Wherein, when extrusion moulding, can add appropriate extrusion aid and/or tackiness agent in described mesoporous molecular sieve and pseudo-boehmite mixture, 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; The temperature of described drying 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 the hydrogenation metal component in described complex carrier, dry and roasting; Wherein, the temperature of described drying 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 contains the solution of the compound of described hydrogenation active metals component, afterwards by the method dipping that soaks or spray, dry and roasting.The described compound that contains the 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, preferred P2 is the pseudo-boehmite of 0.8＜n＜1.1, and further preferred P2 is the pseudo-boehmite of 0.85≤n≤1.05.When described composition contained P2, in oxide compound and take the pseudo-boehmite total amount as benchmark, the content of described P2 was not more than 70 % by weight, further preferably was not more than 50 % by weight, more preferably was 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 preparation.
When described pseudo-boehmite comprises pseudo-boehmite P2 except the pseudo-boehmite of 1.1≤n≤2.5, also comprise the step of introducing this pseudo-boehmite in the preparation method of described catalyzer.For example, the method for introducing P2 mixing, extruded moulding and roasting when described step (1) is mixed mesoporous molecular sieve and P1 is introduced.
Preferably also comprise the step of a reduction before described catalyzer uses, 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, preferred 10-16MPa, further preferred 8-18MP; Temperature of reaction is 250-450 ℃, preferred 310-400 ℃, and further preferred 350 ℃-380 ℃; Volume space velocity 0.3-3h
-1, preferred 0.4-2h
-1, further preferred 0.5-1.5h
-1, hydrogen to oil volume ratio is 100-3000v/v, the further preferred 5-1000v/v of preferred 300-2000v/v.
According to method provided by the invention, in the hydrofining reaction unit of described step (4), described (4a) contacts the sweat oil through catalytic dewaxing that step (3) obtains with Hydrobon catalyst, obtain a kind of base oil of the HVI of satisfying III standard; The pressed oil that (4b) step (2) is obtained contacts with Hydrobon catalyst, obtains a kind of base oil of the HVI of satisfying II standard; The secondary slack wax that (4c) step (2) is obtained contacts with Hydrobon catalyst, obtains a kind of wax product.Can adopt any existing method to realize the reaction purpose of above-mentioned hydrofining reaction unit, described reaction can be that gradation is carried out hydrofining to pressed oil, slack wax or through the sweat oil of catalytic dewaxing in same reactor, also can independently carry out hydrofining to the present invention to pressed oil, slack wax or through the sweat oil of catalytic dewaxing respectively in hydrofining reactor respectively.In adopting respectively independently hydrofining reactor respectively to the present invention to pressed oil, slack wax or when the sweat oil of catalytic dewaxing carried out hydrofining, the catalyzer that different reactor adopts can be the same or different.
Described Hydrobon catalyst can be take the catalyzer of metallic sulfide as the hydrogenation active metals component, these catalyzer are conventionally known to one of skill in the art, usually by heat-resistant inorganic oxide carrier (containing or do not contain molecular sieve) with load on cobalt and/or nickel, molybdenum and/or the tungsten on this carrier and contain 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, preferably contain cobalt and/or the nickel of 1-8 % by weight, the molybdenum of 10-35 % by weight and/or tungsten are in element, one or more adjuvant components in the fluorine of 0-6 % by weight, phosphorus and boron, 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, preferred 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, Y zeolite more preferably, more preferred Y zeolite through the hydrothermal method super stabilizing.
Above-mentioned Hydrobon catalyst is before using, usually can be under hydrogen exists, carry out prevulcanized with sulphur, hydrogen sulfide or sulfur-bearing raw material at the temperature of 140-370 ℃, this prevulcanized can be carried out also can original position vulcanizing in device outside device, is translated into sulfide type.
Described hydrofining reaction condition generally includes: hydrogen dividing potential drop 2-30MPa, temperature 200-400 ℃, air speed 0.2-2.5h
-1, hydrogen-oil ratio 200-2000v/v.Preferred hydrogen dividing potential drop 4-25MPa, temperature 250-350 ℃, air speed 0.4-2h
-1, hydrogen-oil ratio 300-1500v/v.Further preferred hydrogen dividing potential drop 6-20MPa, temperature 280-320 ℃, air speed 0.8-1.5h
-1, hydrogen-oil ratio 300-1000v/v.
Described Hydrobon catalyst can be to take the reducing metal as the catalyzer of hydrogenation active metals, these catalyzer are conventionally known to one of skill in the art, in preferred embodiment, the Hydrobon catalyst that described hydrofining reaction unit adopts contains carrier and loads at least a nickel, platinum and/or the metallic palladium component that is selected from group VIII on this carrier.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 the 0.1-10 % by weight, more is preferably the 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 that adopts in the hydrofining reaction unit and is used for the present invention.Especially the disclosed a kind of metal mold hydrogenation catalyst of CN1510112A being used for having better hydrofining performance when of the present invention, therefore is particularly suitable for the present invention.
These Hydrobon catalysts are before using, and preferably reduction under 150-500 ℃ under hydrogen exists is translated into reduction-state.This method of reducing is ordinary method, and reduction can be carried out outside reactor, also can original position carry out in reactor.
According to method provided by the invention, the generation oil by the hydrofining reaction unit obtains can adopt the method for distillation to do further separation, to obtain the product of required different fractions.For example, obtaining boiling range by distillation is that light lubricant cut, the flow process of 350 ℃-430 ℃ is the middle lubricating oil distillate of 350 ℃-430 ℃, and flow process is the heavy lubricating oil cut greater than 430 ℃.The method of described distillation is known in this field, usually can comprise the operating unit of one or more flash distillations, air distillation and underpressure distillation, to complete desirable separation.
Employing the invention provides method, can directly process each line vacuum distillate, for example, one or more distillates in vacuum distillate, solvent-refined oil, hydrocracking tail oil, slack wax, sweat oil, Fischer-Tropsch synthesis oil, dewaxing vacuum distillate also can be processed one or more in frivolous asphalt oil, heavy deasphalted oil.
The present invention will be described below in conjunction with accompanying drawing 1.
Next step further illustrates the features and advantages of the invention with embodiment, but does not therefore limit the present invention.
The hydrotreating catalyst that uses in the embodiment of the present invention, dewaxing catalyst and hydrogenation catalyst and preparation method thereof are as follows:
1. the catalyzer a that adopts of hydrotreatment reaction member
A1. the hydrotreating catalyst a1 that uses in the embodiment of the present invention for according to the preparation of the example 6 in CN1169336A with fluorine as auxiliary agent, nickel-tungsten is the catalyzer of active constituent loading on alumina supporter, wherein take the 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.
A2. the hydrotreating catalyst a2 that uses in the embodiment of the present invention for according to the preparation of the example 6 in CN1853780A contain citric acid with fluorine, phosphorus as auxiliary agent, nickel-molybdenum-tungsten is that active constituent loading is in the silica-alumina supported catalyst, consisting of after this catalyzer roasting: nickel oxide 5.0 % by weight, molybdenum oxide 4.0 % by weight, Tungsten oxide 99.999 39.1 % by weight, fluorine 3.5 % by weight, phosphorus oxide 2.4 % by weight, surplus are silica-alumina.
2. the catalyzer b that adopts of wax hydroconversion reactions unit
The pseudo-boehmite P2 of pseudo-boehmite P1, the n of the 1.1≤n that uses in the embodiment of the present invention≤2.5＜1.1, preparation method and originate following (agents useful for same in example except specifying, is chemically pure reagent) thereof:
In example, the n value of all pseudo-boehmites adopts XRD method to measure.The 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 the 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) respectively the grain size that goes out (120) of the calculation of parameter take 2 θ as the 23-33 peak go out (031) as D (120), calculation of parameter take 2 θ as the 34-43 peak grain size as D (031), and by formula n=D (031)/D (120) calculates the n value.
P1-1, adopt following method preparation:
In the retort of 2 liters and stream add 1000 ml concns be 48 gram aluminum oxide/liter aluminum trichloride solution and 300 milliliters contain 200 gram aluminum oxide/liter, the causticity coefficient is 1.58, Sorbitol Powder content is 1.82 grams per liters sodium aluminate solution carries out precipitin reaction, temperature of reaction is during 80 ℃, conditioned reaction logistics capacity make and the pH value is 4.0, reaction time 15 minutes; Adding concentration in the gained slurries is the weak ammonia adjusting slurries pH to 10.0 of 5 % by weight, and be warming up to 80 ℃, aging 3 hours, then filter with vacuum filter, to be filtered complete after, replenish on filter cake and added 20 liters of deionized waters (80 ℃ of temperature) flush cake approximately 30 minutes.The qualified filter cake of washing is joined 1.5 liters of deionized water for stirring become slurries, slurries carry out drying with being pumped into spray-dryer, control the spray-dryer temperature out 100-110 ℃ of scope, approximately 2 minutes dry materials time, obtain hydrated aluminum oxide P1-1 after drying.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, adopt following method preparation:
To contain 210 gram aluminum oxide/liter, the causticity coefficient is 1.62 high density NaAlO
2Solution and deionized water are mixed with Al
2O
3Concentration is 5 liters of the solution of 40 grams per liters, then adds Sunmorl N 60S 16.3 grams to obtain containing the NaAlO of Sunmorl N 60S
2Then solution be transferred in the plastic reactor of cumulative volume 8L, and the 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 the plastic reaction, and the plastic temperature is controlled at 20-40 ℃, regulates CO
2Gas flow is 15 ± 2 liter/mins of clocks, makes reaction end pH value reach 8.0-8.5 in 4-6 minute, namely stops ventilation, finishes the plastic reaction.With the gained slurries be heated to 70 ℃ aging 4 hours, then filter with vacuum filter, to be filtered complete after, replenish on filter cake and added 20 liters of deionized waters (temperature 70 C) flush cake approximately 30 minutes.The qualified filter cake of washing is joined 1.5 liters of deionized water for stirring become slurries, slurries carry out drying 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, characterizes through XRD the n value that calculates P1-2 and lists in table 1.
P2-1, adopt following method preparation:
Method according to P1-1 prepares pseudo-boehmite, and different is, does not contain Sorbitol Powder in sodium aluminate solution, and drying obtains hydrated aluminum oxide P2-1.XRD characterizes demonstration, and P2-1 has structure of similar to thin diaspore, characterizes through XRD the n value that calculates P2-1 and lists 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 the XRD characterizing method to calculate the 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. (the Chang Ling catalyst plant provides with a kind of ZSM-22 molecular sieve, silica alumina ratio 56) mix with pseudo-boehmite P1-1, sesbania powder, add aqueous nitric acid, abundant kneading, then extrude diameter and be the cloverleaf pattern bar of 1.3 millimeters on banded extruder, under 120 ℃ dry 4 hours, then 600 ℃ of roastings 2 hours in air obtained carrier.With carrier with containing Pt (NH
3)
4Cl
2Solution carry out saturated dipping, then under 110 ℃ dry 4 hours, 400 ℃ of roastings were 3 hours in air atmosphere.Then the 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 its composition sees Table 2.Metal content in catalyzer is with the x-ray fluorescence method analysis.
B2. (the Chang Ling catalyst plant provides with a kind of ZSM-22 molecular sieve, silica alumina ratio 120) mix with pseudo-boehmite P1-2, sesbania powder, add aqueous nitric acid, abundant kneading, then extrude diameter and be the butterfly bar of 1.3 millimeters on banded extruder, under 120 ℃ dry 4 hours, then 550 ℃ of roastings 4 hours in air obtained carrier.With carrier with containing Pt (NH
3)
4Cl
2Solution carry out saturated dipping, then under 120 ℃ dry 2 hours, 450 ℃ of roastings were 4 hours in air atmosphere.Then the 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 its composition sees Table 2.
B3. method for preparing catalyst is identical with embodiment 1, and different is that pseudo-boehmite P2-1 is replaced P1-1.Catalyzer after reduction is designated as b3, and its composition sees Table 2.
B4. method for preparing catalyst is identical with embodiment 2, and different is that pseudo-boehmite P2-2 is replaced P1-2.Catalyzer after reduction is designated as b4, and its composition sees Table 2.
Table 2
| Catalyzer | b1 | b2 | b3 | b4 |
| Molecular sieve 1 and content, % | ZSM-22 50.2 | ZSM-22 36.0 | ZSM-22 50.2 | ZSM-22 50.2 |
| P1 and content, % | P1-1 49.0 | P1-2 63.6 | - | - |
| P2 and content, % | - | - | P2-1 49.0 | P2-2 63.6 |
| Pt，％ | 0.8 | 0.4 | 0.8 | 0.4 |
3. the catalyzer c that adopts of hydrofining reaction unit
C1. the Hydrobon catalyst c1 that uses in the embodiment of the present invention according to.Example 6 preparations in CN1853777A, consisting of after its roasting: nickel oxide 3.7 % by weight, Tungsten oxide 99.999 25.0 % by weight, molybdenum oxide 2.0 % by weight, carrier is aluminum oxide.
C2. the Hydrobon catalyst c2 that uses in the embodiment of the present invention is for containing the magnesium auxiliary agent according to the preparation of the example 1 in CN085934A, nickel-tungsten is the catalyzer of active constituent loading on alumina supporter, wherein take the catalyzer total amount as benchmark, in oxide compound, the content of nickel is 3.4 % by weight, the content of tungsten is 32.5 % by weight, and the content of magnesium is 0.7 % by weight, and all the other are aluminum oxide.
C3. the Hydrobon catalyst c 3 that uses in the embodiment of the present invention is according to example 11 preparations 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 described flow process of accompanying drawing 1 oil that processes raw material, wherein, the hydrotreatment reaction member adopts single reactor to carry out.Hydrotreatment reaction member catalyzer is a1, and catalytic dewaxing reaction member catalyzer is b1, and 4a hydrofining reaction unit catalyzer is c3, and 4b hydrofining reaction unit catalyzer is c1, and 4c hydrofining reaction unit catalyzer is c2.
Stock oil Jingmen subtracts four line distillates, 20 ℃ of density 905.0kg/m
3, 100 ℃ of viscosity 12.63mm
2/ s, sulphur content 0.55w%, nitrogen content 3200 μ gg
-1
The reaction conditions of hydrotreatment reaction member comprises: hydrogen dividing potential drop 15MPa, 375 ℃ of temperature, air speed 0.5h
-1, hydrogen-oil ratio 1000v/v.
Separating unit adopts underpressure distillation, and the boiling range that obtains is listed in table 3 greater than distillate yield, sulphur and the nitrogen content of diesel oil (final boiling point is greater than 350 ℃).
The operational condition of one section solvent dewaxing unit comprises: selected solvent is the mixture of butanone and toluene, and its mixing quality ratio is 50: 50, and the quality agent-oil ratio is 2, and filtration temperature is-25 ℃.Take boiling range greater than the distillate total amount of diesel oil as benchmark, yield dewaxed oil, pour point are listed in table 4.
The operational condition of two sections solvent dewaxing unit comprises: same section dewaxing of selected solvent, and the quality agent-oil ratio is 1.5, filtration temperature is-25 ℃.Take boiling range greater than the distillate total amount of diesel oil as benchmark, sweat oil yield, zero pour, slack wax yield are listed in table 4.
The reaction conditions of catalytic dewaxing reaction member comprises: hydrogen dividing potential drop 12MPa, 370 ℃ of temperature, air speed 0.6h
-1, hydrogen-oil ratio 800v/v.
The reaction conditions of 4a hydrofining reaction unit comprises: hydrogen dividing potential drop 12MPa, 210 ℃ of temperature, air speed 0.8h
-1, hydrogen-oil ratio 500v/v.Take the sweat oil inlet amount as benchmark,＞400 ℃ of lubricating oil distillate base oil yield, viscosity index, pour point, the viscosity of 100 ℃ are listed in table 5.
The reaction conditions of 4b hydrofining reaction unit comprises: hydrogen dividing potential drop 10MPa, 300 ℃ of temperature, air speed 1h
-1, hydrogen-oil ratio 500v/v.Take the pressed oil inlet amount as benchmark, lubricant base yield, viscosity index, pour point, the viscosity of 100 ℃ are listed in table 5.
The reaction conditions of 4c hydrofining reaction unit comprises: hydrogen dividing potential drop 10MPa, 300 ℃ of temperature, air speed 1h
-1, hydrogen-oil ratio 500v/v.The slack wax that obtains take two sections dewaxings is as benchmark, and wax product yield and character are listed in table 5.
Embodiment 2
Except catalytic dewaxing reaction member catalyzer is b3, other are identical with embodiment 1.Wherein, the separating unit flow process is listed in table 3 greater than yield, sulphur and the nitrogen content of the distillate of diesel oil (final boiling point is greater than 350 ℃).Take boiling range greater than the distillate total amount of diesel oil as benchmark, yield dewaxed oil, the pour point of one section solvent dewaxing are listed in table 4, the sweat oil yield of two sections section solvent dewaxings, zero pour, slack wax yield are listed in table 4.Take the sweat oil inlet amount as benchmark, the viscosity of lubricant base yield after 4a hydrofining, viscosity index, pour point and 100 ℃ is listed in table 5.Take the pressed oil inlet amount as benchmark, the viscosity of lubricant base yield after 4b hydrofining, viscosity index, pour point and 100 ℃ is listed in table 5.The slack wax that obtains take two sections dewaxings is as benchmark, and after 4c hydrofining, wax product yield and character are listed in table 5.
Embodiment 3
According to the described flow process of accompanying drawing 1 oil that processes raw material, wherein, the hydrotreatment reaction member adopts in the double-reactor of series connection and carries out.Hydrotreatment reaction member the first reactor catalyzer is a1, the second reactor catalyzer is a2, catalytic dewaxing reaction member catalyzer is b2,4a hydrofining reaction unit catalyzer is c1,4b hydrofining reaction unit catalyzer is c3, and 4c hydrofining reaction unit catalyzer is c2.
Stock oil is with embodiment 1.
The reaction conditions of the first reactor of hydrotreatment reaction member comprises: hydrogen dividing potential drop 15MPa, 365 ℃ of temperature, air speed 0.6h
-1, hydrogen-oil ratio 1000v/v.
The reaction conditions of the second reactor of hydrotreatment reaction member comprises: hydrogen dividing potential drop 15MPa, 280 ℃ of temperature, air speed 1h
-1, hydrogen-oil ratio 1000v/v.
Separating unit adopts underpressure distillation, take total charge raw material oil as benchmark, obtains flow process greater than the distillate of diesel oil (final boiling point is greater than 350 ℃), and its yield, sulphur and nitrogen content are listed in table 3.
The operational condition of one section solvent dewaxing unit comprises: selected solvent is the mixture of butanone and toluene, and its mixing quality ratio is 50: 50, and the quality agent-oil ratio is 2, and filtration temperature is-25 ℃.Take boiling range greater than the distillate total amount of diesel oil as benchmark, yield dewaxed oil, pour point are listed in table 4.
The operational condition of two sections solvent dewaxing unit comprises: same section dewaxing of selected solvent, and the quality agent-oil ratio is 1.5, filtration temperature is-25 ℃.Take boiling range greater than the distillate total amount of diesel oil as benchmark, sweat oil yield, pour point, slack wax yield are listed in table 4.
The reaction conditions of catalytic dewaxing reaction member comprises: hydrogen dividing potential drop 12MPa, 370 ℃ of temperature, air speed 0.7h
-1, hydrogen-oil ratio 1000v/v.
The reaction conditions of 4a hydrofining reaction unit comprises: hydrogen dividing potential drop 12MPa, 300 ℃ of temperature, air speed 1h
-1, hydrogen-oil ratio 500v/v.Take the sweat oil inlet amount as benchmark, the viscosity of lubricant base yield, viscosity index, pour point and 100 ℃ is listed in table 5.
The reaction conditions of 4b hydrofining reaction unit comprises: hydrogen dividing potential drop 10MPa, 200 ℃ of temperature, air speed 1h
-1, hydrogen-oil ratio 500v/v.Take the pressed oil inlet amount as benchmark, the viscosity of lubricant base yield, viscosity index, pour point and 100 ℃ is listed in table 5.
The reaction conditions of 4c hydrofining reaction unit comprises: hydrogen dividing potential drop 12MPa, 300 ℃ of temperature, air speed 1h
-1, hydrogen-oil ratio 500v/v.The slack wax that obtains take two sections dewaxings is as benchmark, and wax product yield and character are listed in table 5.
Embodiment 4
Except catalytic dewaxing reaction member catalyzer is b4, other are identical with embodiment 3.Wherein, the separating unit flow process is listed in table 3 greater than yield, sulphur and the nitrogen content of the distillate of diesel oil (final boiling point is greater than 350 ℃).Take boiling range greater than the distillate total amount of diesel oil as benchmark, yield dewaxed oil, the pour point of one section solvent dewaxing are listed in table 4, the sweat oil yield of two sections section solvent dewaxings, zero pour, slack wax yield are listed in table 4.Take the sweat oil inlet amount as benchmark, the viscosity of lubricant base yield after 4a hydrofining, viscosity index, pour point and 100 ℃ is listed in table 5.Take the pressed oil inlet amount as benchmark, the viscosity of lubricant base yield after 4b hydrofining, viscosity index, pour point and 100 ℃ is listed in table 5.The slack wax that obtains take two sections dewaxings is as benchmark, and after 4c hydrofining, wax product yield and character are listed in table 5.
Table 3
| Embodiment | 1 | 2 | 3 | 4 |
| Greater than the yield of the distillate of diesel oil, % by weight | 81.13 | 81.13 | 85.25 | 85.25 |
| Sulphur, μ g/g | 15 | 15 | 11 | 11 |
| Nitrogen, μ g/g | ＜1 | ＜1 | ＜1 | ＜1 |
Table 4
| Embodiment | 1 | 2 | 3 | 4 |
| One section solvent dewaxing | ||||
| Yield dewaxed oil, % by weight | 37.66 | 37.66 | 35.6 | 35.6 |
| The pressed oil pour point, ℃ | -15 | -15 | -15 | -15 |
| Two sections solvent dewaxings | ||||
| The sweat oil yield, % by weight | 41.82 | 41.82 | 47.75 | 47.75 |
| The slack wax yield, % by weight | 20.37 | 20.37 | 19.65 | 19.65 |
| The sweat oil zero pour, ℃ | 60 | 60 | 62 | 62 |
Table 5
| Embodiment | 1 | 2 | 3 | 4 |
| 4a hydrofining | ||||
| Lubricating oil＞400 ℃ base oil yield, % by weight | 72.54 | 70.71 | 71.62 | 70.20 |
| Viscosity index | 127 | 122 | 135 | 120 |
| Pour point, ℃ | -18 | -18 | -15 | -15 |
| The viscosity of 100 ℃, mm 2/s | 8.583 | 8.245 | 8.468 | 8.354 |
| 4b hydrofining | ||||
| The lubricant base yield, % by weight | 99.5 | 99.5 | 99.8 | 99.8 |
| Viscosity index | 92 | 92 | 90 | 90 |
| Pour point, ℃ | -12 | -12 | -12 | -12 |
| The viscosity of 100 ℃, mm 2/s | 15.35 | 15.35 | 14.23 | 14.23 |
| 4c hydrofining | ||||
| The wax product yield, % by weight | 99.2 | 99.2 | 99.3 | 99.3 |
| Oleaginousness/% | 0.47 | 0.47 | 0.48 | 0.48 |
| Fusing point/℃ | 61.4 | 61.4 | 61 | 61 |
| Penetration degree/(0.1mm) | 4 | 4 | 5 | 5 |
For ease of the understanding to each product property, table 6 has provided in China Petrochemical Corp.'s lubricant base consensus standard about HVI II lube base oil standard, table 7 has provided in China Petrochemical Corp.'s lubricant base consensus standard about HVI III lube base oil standard, table 8 has provided full refining wax standard, from result, product obtained by the method for the present invention can satisfy respectively the standard of HVI II, HVI III lube base oil standard and complete concise wax product.
Table 8 full refining wax national standard (GB 446-93)
Claims (24)
1. the working method of a heavy hydrocarbon oil, comprise: (1) is under the hydrotreatment reaction conditions, heavy hydrocarbon oil is contacted with hydrotreating catalyst at the hydrotreatment reaction member, through separating unit separate obtain refinery gas, boiling range less than with the distillate that equals diesel oil and the boiling range distillate greater than diesel oil; (2) under solvent dewaxing unit and solvent dewaxing condition, the boiling range that step (1) is obtained carries out at least twice dewaxing greater than the distillate of diesel oil, wherein, dewaxing for the first time obtains a kind of pressed oil and a slack wax, slack wax is carried out the secondary solvent dewaxing in the solvent dewaxing unit, obtain a kind of sweat oil and secondary slack wax; (3) under the catalytic dewaxing reaction conditions, the sweat oil that step (2) is obtained contacts with catalytic dewaxing catalyst at the catalytic dewaxing reaction member, obtains a kind of sweat oil through catalytic dewaxing; (4) under hydrofining reaction unit and hydrofining reaction condition, the sweat oil through catalytic dewaxing that (4a) step (3) is obtained contacts with Hydrobon catalyst, obtains a kind of base oil of the HVI of satisfying III standard; The pressed oil that (4b) step (2) is obtained contacts with Hydrobon catalyst, obtains a kind of base oil of the HVI of satisfying II standard; The secondary slack wax that (4c) step (2) is obtained contacts with Hydrobon catalyst, obtains a kind of wax product.
2. method according to claim 1, is characterized in that, the hydrotreatment reaction conditions of described step (1) make boiling range after separating unit separates greater than the sulphur content in the distillate of diesel oil less than 50 μ g/g, nitrogen content is less than 10 μ g/g.
3. method according to claim 2, is characterized in that, the hydrotreatment reaction conditions of described step (1) make boiling range after separating unit separates greater than the sulphur content in the distillate of diesel oil less than 20 μ g/g, nitrogen content is less than 5 μ g/g.
4. method according to claim 3, is characterized in that, the hydrotreatment reaction conditions of described step (1) make boiling range after separating unit separates greater than the sulphur content in the distillate of diesel oil less than 10 μ g/g, nitrogen content is less than 2 μ g/g.
5. method according to claim 1, is characterized in that, described hydrotreatment reaction member comprises the reactor of two series connection, and wherein, the reaction conditions of described the first reactor comprises: hydrogen dividing potential drop 4-30MPa, temperature 250-470 ℃, air speed 0.2-2h
-1, hydrogen-oil ratio 500-3000v/v, the reaction conditions of the second reactor comprises: hydrogen dividing potential drop 2-25MPa, temperature 200-400 ℃, air speed 0.4-2.5h
-1, hydrogen-oil ratio 200-1000v/v.
6. method according to claim 5, is characterized in that, the reaction conditions of described the first reactor comprises: hydrogen dividing potential drop 10-25MPa, temperature 350-420 ℃, air speed 0.4-1h
-1, hydrogen-oil ratio 800-2000v/v, the reaction conditions of the second reactor comprises: hydrogen dividing potential drop 4-20MPa, temperature 230-350 ℃, air speed 0.6-2h
-1, hydrogen-oil ratio 300-800v/v.
7. according to claim 5 or 6 described methods, is characterized in that, the reaction conditions of described the second reactor comprises: hydrogen dividing potential drop 6-17MPa, temperature 260-320 ℃, air speed 0.8-1.5h
-1, hydrogen-oil ratio 300-600v/v.
8. method according to claim 1, is characterized in that, the operational condition of described solvent dewaxing operating unit makes the pour point through a solvent dewaxing gained pressed oil be-12 ℃ to-15 ℃; The pour point of secondary solvent dewaxing gained sweat oil is-12 ℃ to 90 ℃.
9. method according to claim 8, is characterized in that, it is 0 ℃ to 80 ℃ that described secondary solvent dewaxing makes the pour point of gained sweat oil.
10. method according to claim 9, is characterized in that, it is 20 ℃ to 80 ℃ that described secondary solvent dewaxing makes the pour point of gained sweat oil.
11. method according to claim 1, it is characterized in that, described dewaxing catalyst contains the molecular sieve of 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 that is obtained through roasting by pseudo-boehmite, wherein, described pseudo-boehmite comprises the pseudo-boehmite P1 of a kind of 1.1≤n≤2.5, n=D (031)/D (120) wherein, 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 λ/(Bcos θ), K is the Scherrer constant, λ is the diffraction wavelength of target shaped material, B is the peak width at half height of diffraction peak, 2 θ are the position of diffraction peak.
12. method according to claim 11 is characterized in that, the n of described pseudo-boehmite P1 satisfies 1.2≤n≤2.2.
13. method according to claim 11 is characterized in that, take the 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 in oxide compound, the content of hydrogenation metal is the heavy % of 0.1-5.
14. method according to claim 13 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 in oxide compound, the content of described hydrogenation metal is the heavy % of 0.2-1.
15. according to claim 11,13, the 14 described methods of any one, it is characterized in that one or more in the preferred cobalt of described hydrogenation metal component, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, molybdenum and tungsten.
16. method according to claim 15 is characterized in that, described hydrogenation metal is platinum.
17. method according to claim 11, it is characterized in that, described mesoporous molecular sieve is selected from one or more in ZSM-5, ZSM-11, ZSM-35, Beta, mordenite, SAPO-21, SAPO-33, SAPO-35, ZSM-22, Nu-10, Theta-1, ISI-1, ZSM-23, SAPO-11, SAPO-31, SAPO-41.
18. method according to claim 17 is characterized in that, described mesoporous molecular sieve is ZSM-5 and/or ZSM-22.
19. method according to claim 11 is characterized in that, contains the pseudo-boehmite P2 of 0.8＜n＜1.1 in described pseudo-boehmite, in oxide compound and take the pseudo-boehmite total amount as benchmark, the content of described P2 is not more than 70 % by weight.
20. method according to claim 19 is characterized in that, described P2 is the pseudo-boehmite of 0.85≤n≤1.05, and in oxide compound and take the pseudo-boehmite total amount as benchmark, the content of described P2 is not more than 50 % by weight.
21. method according to claim 20 is characterized in that, in oxide compound and take the pseudo-boehmite total amount as benchmark, the content of described P2 is not more than 30 % by weight.
22. method according to claim 1 is characterized in that, the reaction conditions of described catalytic dewaxing reaction member generally includes: hydrogen dividing potential drop 1-20MPa, temperature of reaction is 250-450 ℃, volume space velocity 0.3-3h
-1, hydrogen to oil volume ratio is 100-3000v/v.
23. method according to claim 22 is characterized in that, the reaction conditions of described catalytic dewaxing reaction member generally includes: hydrogen dividing potential drop 10-16MPa, temperature of reaction is 310-400 ℃, volume space velocity 0.4-2h
-1, hydrogen to oil volume ratio is 300-2000v/v.
24. method according to claim 23 is characterized in that, the reaction conditions of described catalytic dewaxing reaction member generally includes: hydrogen dividing potential drop 10-16MPa, and temperature of reaction is 350 ℃-380 ℃, volume space velocity is 0.5-1.5h
-1, hydrogen to oil volume ratio is 500-1000v/v.
25. method according to claim 1 is characterized in that, described hydrofining reaction condition generally includes: hydrogen dividing potential drop 2-30MPa, temperature 200-400 ℃, air speed 0.2-2.5h
-1, hydrogen-oil ratio 200-2000v/v.
26. method according to claim 25 is characterized in that, described hydrofining reaction condition generally includes: hydrogen dividing potential drop 4-25MPa, temperature 250-350 ℃, air speed 0.4-2h
-1, hydrogen-oil ratio 300-1500v/v.
27. method according to claim 26 is characterized in that, described hydrofining reaction condition generally includes: hydrogen dividing potential drop 6-20MPa, temperature 280-320 ℃, air speed 0.8-1.5h
-1, hydrogen-oil ratio 300-1000v/v.
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| GB2257156A (en) * | 1991-06-25 | 1993-01-06 | Exxon Research Engineering Co | Process for producing bright stock from deasphalted resid and heavy distillate |
| CN1221020A (en) * | 1997-12-23 | 1999-06-30 | 中国石油化工总公司 | Method of hydrogenation conversion for masrolar D |
| CN101463273A (en) * | 2007-12-20 | 2009-06-24 | 中国石油化工股份有限公司 | Production method of aeroplane oil base oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB2257156A (en) * | 1991-06-25 | 1993-01-06 | Exxon Research Engineering Co | Process for producing bright stock from deasphalted resid and heavy distillate |
| CN1221020A (en) * | 1997-12-23 | 1999-06-30 | 中国石油化工总公司 | Method of hydrogenation conversion for masrolar D |
| CN101463273A (en) * | 2007-12-20 | 2009-06-24 | 中国石油化工股份有限公司 | Production method of aeroplane oil base oil |
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