CN102247881B - Hydrocracking catalyst containing rare earth-containing aluminum oxide and application thereof - Google Patents
Hydrocracking catalyst containing rare earth-containing aluminum oxide and application thereof Download PDFInfo
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- CN102247881B CN102247881B CN201010177810.6A CN201010177810A CN102247881B CN 102247881 B CN102247881 B CN 102247881B CN 201010177810 A CN201010177810 A CN 201010177810A CN 102247881 B CN102247881 B CN 102247881B
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Abstract
The invention discloses a hydrocracking catalyst containing rare earth-containing aluminum oxide and application thereof. The catalyst comprises a carrier, at least one metal component which is selected from a VIII group and at least one metal component which is selected from a VIB group, wherein the carrier contains the rare earth-containing aluminum oxide and a solid acid component; the catalyst is characterized in that: the rare earth-containing aluminum oxide is obtained by roasting rare earth-containing pseudo-boehmite; based on an oxide and a dry basis of the pseudo-boehmite, the content of added rare earth component in the pseudo-boehmite is 1-15 percent by weight; the pseudo-boehmite is one of which n is greater than or equal to 1.1 and less than or equal to 2.5, wherein n is equal to D(031)/D(120); D(031) expresses the grain size of a crystal face represented by peak (031) in an XRD (X-Ray Diffraction) spectrum of pseudo-boehmite grains; D(120) expresses the grain size of the crystal face represented by peak (120) in the XRD (X-Ray Diffraction) spectrum of the pseudo-boehmite grains; D is equal to K lambda/(Bcos theta); lambda is diffraction wavelength of a target material; B is half band width of corrected diffraction peak; and 2 theta is the position of the diffraction peak. Compared with the prior art, the hydrocracking performance of the catalyst provided by the invention is improved.
Description
Technical field
The present invention is about a kind of hydrocracking catalyst and application thereof.
Background technology
Under hydrogenation conditions, hydrocarbon oil crude material contacts and may comprise with catalyst: the reactions such as hydrodesulfurization, hydrodenitrogeneration, HDM, hydrocracking.Wherein the upgrading effect of the performance of catalyst to hydrocarbon feed, target product selectively play crucial effect.
The catalyst that is widely used in hydrocarbon oil hydrogenation cracking with the catalyst of preparing containing porous heat-resistant inorganic oxide (as aluminium oxide), the carrier loaded hydrogenation active metals component of solid acid (as molecular sieve).In prior art, about the report of this class catalyst a lot, for example:
CN 1169458A catalyst for distillate hydro-cracking has following composition: the heavy % of heavy %, tungsten oxide 10-38 of heavy %, nickel oxide 2.5-5.0 of rare earth 0.5-5.0, all the other are carrier.This carrier is made up of the aluminium oxide of the heavy % of 20-90 and the zeolite of the heavy % of 10-80.Its mesolite is mesopore or the large pore zeolite of acidity value 1.0-2.0 mM/gram, and aluminium oxide is the aluminium oxide of acidity value 0.5-0.8 mM/gram, and the acidity value of described aluminium oxide or zeolite refers to the acidity value of measuring by NH3-TPD method.This catalyst, in having good desulfurization, denitrification activity, has selective to intermediate oil higher compared with prior art.
CN1054150C discloses a kind of catalyst for hydrocracking diesel oil, and the carrier that this catalyst is made up of aluminium oxide, amorphous aluminum silicide and molecular sieve and the hydrogenation active metals loading on this carrier form, WO in catalyst
3content be that the content of 10-30 heavy %, NiO is that the content of the heavy % of 2-15, molecular sieve is that the content of the heavy % of 5-45, aluminium oxide is that the content of the heavy % of 30-70, amorphous aluminum silicide is the heavy % of 5-25, described molecular sieve is Y zeolite, its infrared total acid content is 0.5-1 mM/gram, and lattice constant is 2.436-2.444 nanometer.Described aluminium oxide is pore volume 0.8-1.1 ml/g; Surface area 230-400 rice
2/ gram little porous aluminum oxide.
CN1184843A discloses a kind of catalyst for hydrocracking diesel oil, and consist of aluminium oxide 40-80 heavy %, amorphous aluminum silicide 0-20 heavy %, the molecular sieve 5-30 of this catalyst weigh %, and described molecular sieve is pore volume 0.40-0.52 ml/g, specific surface 750-900 rice
2/ gram, lattice constant 2.420-2.500, the Y zeolite of silica alumina ratio 7-15, the heavy % of group vib tenor 10-30, the content of VIII family metal oxide is the heavy % of 2-15.
For for the hydrocracking catalyst of molecular sieve, wherein dispersity and the catalyst pores structural property etc. of contained porous heat-resistant inorganic oxide to hydrogenation active metals component exerts an influence, and directly has influence on the catalytic performance of catalyst.
Summary of the invention
The technical problem to be solved in the present invention is on the basis of existing technology, and a kind of new, improved hydrocracking catalyst of performance and application thereof are provided.
The present inventor finds under study for action, for the hydrocracking catalyst containing solid acid (comprising silica-alumina and molecular sieve) component, after solid acid and hydrogenation active metals component are determined, the character of its performance alumina host contained with catalyst is relevant.The n value (being generally 0.85-1.05) on the low side of the boehmite that prior art provides, when adopting this type of boehmite Kaolinite Preparation of Catalyst, during particularly for the preparation of the catalyst of poor-quality diesel-oil by cut fraction oil hydrocracking, its performance can not finely meet the demands.
The invention provides a kind of hydrocracking catalyst that contains rare earth metal, this catalyst contains carrier and at least one and is selected from VIII family and at least one and is selected from the metal component of group vib, described carrier contains containing rare earth alumina and solid acid component, it is characterized in that, described is to be obtained through roasting containing rare earth boehmite by one containing rare earth alumina, in oxide and take the butt of described boehmite as benchmark, the content that described boehmite middle rare earth adds component is 1-15 % by weight, described boehmite is the boehmite of 1.1≤n≤2.5, wherein n=D (031)/D (120), the crystallite dimension of the crystal face of (031) peak representative in the XRD spectra of described D (031) expression boehmite crystal grain, the crystallite dimension of the place crystal face at (120) peak in the XRD spectra of D (120) expression 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), λ is the diffraction wavelength of target shaped material, B is the half-peak breadth of corrected diffraction maximum, 2 θ are the position of diffraction maximum.
The present invention also provides a kind of hydrocarbon oil hydrogenation cracking method, is included under hydrocracking reaction condition, by hydrocarbon oil crude material oil and catalyst haptoreaction, it is characterized in that, described catalyst is aforesaid catalyst provided by the invention.
Compared with prior art, the invention provides catalyst performance be improved significantly.For example, compared with the diesel oil hydrogenation modification catalyst providing with existing method, catalyst provided by the invention can make diesel cetane-number increase rate be significantly improved.
The specific embodiment
According to catalyst provided by the invention, wherein, describedly add the boehmite of component containing rare earth, in oxide and take the butt of described boehmite as benchmark, the content of described boehmite middle rare earth is 1-15 % by weight, is preferably 1-10 % by weight.Butt described here refers to described boehmite percentage of the ratio of weight before 550 ℃ of roastings weight after 4 hours and roasting under air atmosphere.
Wherein, n=D (031)/D (120), the crystallite dimension of the crystal face of 031 peak representative in the XRD spectra of described D (031) expression boehmite crystal grain, the crystallite dimension of the crystal face of 120 peak representatives in the XRD spectra of D (120) expression 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 Scherrer constant, λ is the diffraction wavelength of target shaped material, B is the half-peak breadth of this diffraction maximum, 2 θ are the position of this diffraction maximum.For different diffraction maximums, the value that B and 2 θ all get peak correspondingly, for example, and while calculating D (031), D (031)=K λ/(Bcos θ), wherein B is the half-peak breadth of 031 diffraction maximum, 2 θ are the position of 031 diffraction maximum; While calculating D (120), D (120)=K λ/(Bcos θ), wherein B is the half-peak breadth of 120 diffraction maximums, 2 θ are the position of 120 diffraction maximums.Take described carrier as benchmark, in described carrier, the content containing rare earth alumina is 5-99.5 % by weight in a preferred embodiment, more preferably 20-99 % by weight, and the content of solid acid component is 0.5-95 % by weight.More preferably 1-80 % by weight.
Be enough to make described rare earth metal to add under the prerequisite that the content of component in described boehmite meets the demands, the introducing method that the present invention adds component to described rare earth metal is not particularly limited.For example, it can be the method introducing of introducing in the process of boehmite of preparing described 1.1≤n≤2.5 containing the compound of rare earth metal, also can be the boehmite of first preparing described 1.1≤n≤2.5, afterwards itself and the method for the compound containing rare earth metal be introduced.The described compound containing rare earth is that those of ordinary skills know, they are the lucium as leading and containing a small amount of other rare earth (as spectrum, neodymium, samarium, yttrium etc.) take La and/or Ce conventionally, can be also the single rare earth that those of ordinary skills know.In this class mixture, the content of La is 5-90 % by weight, is preferably 10-50 % by weight; The content of Ce is 10-95 % by weight, is preferably 50-90 % by weight: other content of rare earth is less than 20 % by weight, is preferably and is less than 10 % by weight.The described compound containing rare earth is generally the described salt containing rare earth, for example, can be containing one or more in the chloride of rare earth, nitrate, oxalates.
The preparation method of the boehmite of the described feature with 1.1≤n≤2.5 comprises: aluminum contained compound solution is contacted and carries out precipitation reaction with acid or alkali, or organic aluminum contained compound is contacted to the reaction that is hydrolyzed with water, obtain hydrated alumina; Hydrated alumina 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 alumina aging in any one process under grain growth conditioning agent exists, carry out, described grain growth 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 or precipitation reaction and aging in any one process under grain growth conditioning agent exists, carry out realizing object of the present invention, but under preferable case, described hydrolysis and ageing process or described precipitation reaction and ageing process are all carried out under grain growth conditioning agent exists, and the n that can make like this gained boehmite is in preferred 1.2≤n≤2.2 scope.
Wherein, to the consumption of grain growth conditioning agent, there is no particular limitation, in selective hydrolysis reaction, the consumption of grain growth 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 precipitation reaction, the consumption of grain growth 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 ageing process, the consumption of grain growth conditioning agent can be the 0.5-10 % by weight of hydrated alumina 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 growth conditioning agent calculates take the weight of aluminium oxide corresponding in organic aluminum contained compound, inorganic aluminum contained compound and hydrated alumina as benchmark respectively.Also be, in aluminium oxide, in described precipitation reaction, the consumption of described grain growth conditioning agent is the 0.5-10 % by weight of inorganic aluminum contained compound weight, in described hydrolysis, the consumption of described grain growth conditioning agent is the 0.5-10 % by weight of organic aluminum contained compound weight, and in described ageing process, the consumption of described grain growth conditioning agent is the 0.5-10 % by weight of hydrated alumina weight.
In the present invention, described grain growth 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, preferred conditioning agent is alditol and carboxylate thereof, is specifically as follows one or more in D-sorbite, 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 boehmite preparation process of the present invention, the mode that adds to described grain growth conditioning agent is not particularly limited, grain growth conditioning agent can be added separately, also can in advance grain growth conditioning agent be mixed with one or more raw materials wherein, and then the raw material that contains grain growth 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 aluminum sulfate, aluminium chloride, aluminum nitrate.Because price is low, preferably sulfuric acid aluminium, liquor alumini chloridi.Aluminium salt can use 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 counts 0.2-1.1 mol/L with aluminium oxide.
Described acid can be various Bronsted acids or in aqueous medium, be acid oxide, 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 Bronsted acid be selected from one or more in nitric acid, sulfuric acid, hydrochloric acid.Described carbonic acid can original position produce by pass into carbon dioxide 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 aqueous slkali can be hydrolyzed and make the aqueous solution be alkaline salt for hydroxide or in aqueous medium, and preferred hydroxide is selected from one or more in ammoniacal liquor, NaOH, potassium hydroxide; Preferred salt is selected from one or more in sodium metaaluminate, potassium metaaluminate, carbonic hydroammonium, ammonium carbonate, sodium acid carbonate, sodium carbonate, saleratus, potash.Concentration to described aqueous slkali is not particularly limited, preferably OH
-concentration be 0.2-4 mol/L.When during as alkali, while calculating the consumption of described grain growth conditioning agent, also considering the amount of corresponding aluminium 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, one or more in the aluminum alkoxide of generation aqua oxidation aluminum precipitation can be for example one or more in aluminium isopropoxide, isobutanol aluminum, aluminium isopropoxide, three tert-butoxy aluminium and isooctanol 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 boehmite preparation process of the present invention, the described condition that makes precipitation 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 making the method for aluminum precipitation by the control of the consumption to alkali in reactant or acid.
Condition to described hydrolysis is not particularly limited, as long as water contacts with aluminum alkoxide, hydrolysis generation hydrated alumina 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 alumina or filter cake after filtering in hydrolysis or precipitation reaction and again add water in the slurries of preparation and added the compound of crystal grain growth regulating effect, also can add aqueous slkali 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 aqueous slkali can be with above-described identical or different.
Described aging temperature is preferably 35-98 ℃, and ageing 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 boehmite preparation process of the present invention, after aging, also comprise and prepare the washing that often comprises in boehmite process and dry step, described washing and dry method are for preparing boehmite conventional process.For example, can use oven dry, forced air drying or spray-dired method.Generally speaking, baking temperature can be 100-350 ℃, is preferably 120-300 ℃.
According to the preparation method of boehmite of the present invention, a preferred embodiment comprises the following steps:
(1) by containing the aluminum contained compound solution of grain growth conditioning agent and aqueous slkali or acid solution and flow or batch (-type) joins in reaction vessel and carries out precipitation reaction, obtain hydrated alumina slurries; Or in deionized water, add the reaction that is hydrolyzed of grain growth conditioning agent and aluminum alkoxide, obtain hydrated alumina slurries;
(2) filter cake after the hydrated alumina slurries that step (1) obtained filter again adds water and pulls an oar in the aluminium oxide slurries that obtain, and adds grain growth conditioning agent, after regulating pH to be 7-10, in 35-98 ℃ of aging 0.2-6 hour; The hydrated alumina slurries that also above-mentioned steps (1) can be obtained are under 7-10 without filtering in the existence of grain growth 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 steps (3) obtains, obtains boehmite provided by the invention.
When described rare earth is while introducing in the process of boehmite of described 1.1≤n≤2.5 of preparation, the introducing of described rare earth can be to carry out in step in the preparation process of boehmite described above (1)-(4) any one or several step.For example in rapid (2) afterwards, complete the aging aqueous solution containing the compound of rare earth of introducing afterwards, be fully uniformly mixed, then complete filtration, washing and dry.Also can be step (4) to be obtained to boehmite under the condition that is enough to pulp and the aqueous solution that contains rare earth compound, filter afterwards, be dried.Wherein filtration and drying condition are identical with the above-mentioned method of preparing boehmite.With Re
2o
3meter take the butt of described boehmite as benchmark, the content of described boehmite middle rare earth component is 1-15 % by weight, is preferably the % by weight into 1-10.
Described phosphorous boehmite can be converted into aluminium oxide of the present invention through roasting, the method of described roasting is conventional method, and described roasting condition comprises: sintering temperature is 350-950 ℃, is preferably 450-900 ℃, roasting time is 1-12 hour, is preferably 2-8 hour.
According to catalyst provided by the invention, described solid acid component can be selected from one or more in silica-alumina and the molecular sieve that is commonly used for cracking activity component.Wherein, described molecular sieve can be the zeolite with macroporous structure, as there is the zeolite of faujasite, Beta zeolite, omega zeolite structure, it can be the zeolite with central hole structure, as there is modenite, ZSM-5 zeolite, ZSM-11 zeolite, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-48 zeolite, the isostructural zeolite of ZSM-57 zeolite, also can be the zeolite with small structure, as there is the zeolite of Erionite zeolite, ZSM-34 zeolite structure.Preferred solid acid component is the zeolite molecular sieve with faujasite structure, there is the zeolite structured zeolite molecular sieve of Beta, have ZSM-5 structure zeolite molecular sieve, there are one or more in zeolite molecular sieve and the silica-alumina of mordenite structure.The described zeolite with faujasite structure is preferably y-type zeolite, further preferably one or more in the Y zeolite of USY, the rare-earth type overstable gamma zeolite REUSY of HY zeolite wherein, rare-earth type Y zeolite REY, rare-earth type HY zeolite REHY, overstable gamma zeolite USY, part amorphization, titaniferous, phosphorous Y and super steady and HY type zeolite, dealuminium Y type beta stone.
Described silica-alumina preferably has the silica-alumina of structure of similar to thin diaspore, and they can be commercially available commodity or adopt any one prior art preparation.For example, the Siral series commodity silica-alumina that German Condea company produces has structure of similar to thin diaspore, all can be used as solid acid component for the present invention.
Further preferably N value is 0.1-1, and more preferred N value is the silica-alumina with structure of similar to thin diaspore of 0.2-0.8.Described N=Q1/Q2, the solid that Q1 is described silica-aluminium oxide
27in Al NMR spectrogram, chemical shift is the peak area at 60 ± 0.1-0.2ppm place, the solid that Q2 is described silica-aluminium oxide
27in Al NMR spectrogram, chemical shift is the peak area at 5 ± 0.1-0.2ppm place.
27in AlNMR spectrogram, the each peak area of the chemical shiftsum at each peak is measured take saturated aluminum sulfate aqueous solution as reference on Varian UnityInova 300M type nuclear magnetic resonance spectrometer.
A kind of preparation method of the silica-alumina that preferably meets aforementioned requirement comprises the following steps:
(1) a kind of solution containing aluminium salt and a kind of aqueous slkali or acid solution stream are joined and in reaction vessel, carry out plastic and react, reaction condition: pH value is 6.5-8.5, temperature is 30-75 ℃;
(2) product step (1) being generated is at pH 7-8.5, aging 5-120 minute at temperature 30-75 ℃;
(3) under agitation, a kind of solution of silicon-containing compound is joined in the product that step (2) obtains;
(4) at pH 8-10, the product 12-24 hour that aging step (3) obtains at 80-98 ℃;
(5) product that washing, filtration step (4) obtain;
(6) product that drying steps (5) obtains, obtains described silica-aluminium oxide.
Wherein, described aluminum contained compound is selected from one or more in aluminum sulfate, sodium metaaluminate, aluminum nitrate, alchlor, aluminum alkoxide, alkyl aluminum, is preferably one or more in aluminum sulfate, sodium metaaluminate, aluminum nitrate, alchlor.
Described alkali be hydroxide or in aqueous medium hydrolysis make the aqueous solution be alkaline salt, preferred hydroxide is selected from one or more in ammoniacal liquor, NaOH, potassium hydroxide; Preferred salt is selected from one or more in carbonic hydroammonium, ammonium carbonate, sodium acid carbonate, sodium carbonate, saleratus, potash.
Described acid is Bronsted acid or in aqueous medium, is acid oxide, and preferred Bronsted acid is selected from one or more in nitric acid, sulfuric acid, hydrochloric acid; Preferred oxide is carbon dioxide.
The introducing of the solution of described silicon-containing compound is that the solution of silicon-containing compound is mixed with the mixed liquor of water with prepared boehmite, for example, can be under agitation the solution of silicon-containing compound to be joined in the mixed liquor of boehmite and water, also can be that the solution that contains silicon-containing compound is added in reaction vessel with mixed liquor the stream of boehmite and water, the concentration of silicon-containing compound solution and consumption make the silica that contains 5-60 % by weight in final silica-aluminium oxide, are preferably 10-45 % by weight.
Described silicon-containing compound can be any water-soluble silicon-containing compound and in aqueous medium, can be hydrolyzed the silicon-containing compound that forms silicon gel, colloidal sol.For example, one or more in the compound such as waterglass, the hydrosol and esters of silicon acis.
According to catalyst provided by the invention, described carrier is by comprising described containing obtaining through roasting after rare earth boehmite and solid acid component mixing, described mixing can be the simple accumulation that is placed in a place containing rare earth boehmite and described solid acid component by described, also can be to adopt any one prior art, for example, can be at mixer, in grinder, directly described boehmite is mixed by the mode stirring with solid acid component, can be by described boehmite under the condition that is enough to pulp, solid acid component and water mix, filter afterwards, dry or moist method is mixed.When adopting any one prior art while mixing, the uniformity that those skilled in the art optionally can should reach described mixing is controlled, to this present invention to being not particularly limited.Sintering temperature is 350-950 ℃, is preferably 450-900 ℃, and roasting time is 1-12 hour, is preferably 2-8 hour.Take described carrier as benchmark, the content of the described solid acid component in described carrier is 0.5-95 % by weight in a preferred embodiment, more preferably 1-80 % by weight.
According to catalyst provided by the invention, wherein said carrier is depending on the different article shaped that require can be made into various easy operatings, for example, can enumerate microballoon, spherical, tablet or bar shaped etc.This moulding can method routinely be carried out, for example, by solid acid component and 1.1≤n≤2.5, the preferably method of described boehmite mixing, extruded moulding the roasting of 1.2≤n≤2.2.In the time of the extrusion molding of carrier, can in carrier, add appropriate extrusion aid and/or adhesive, then extrusion molding.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, starch, polyvinyl alcohol, PVOH.
According to catalyst provided by the invention, described catalyst preferably contains the carrier of 50-90 % by weight, in oxide and take described catalyst as benchmark, and the VIII family metal component of 1-10 % by weight, the group vib metal component of 5-40 % by weight.The carrier that further preferred catalyst contains 60-85 % by weight, the VIII family metal component of 1.5-6 % by weight, the group vib metal component of 10-35 % by weight.
According to catalyst provided by the invention, the described VIII of being selected from family and the metal component that is selected from group vib are not particularly limited, preferred VIII family metal component is cobalt and/or nickel, group vib metal component is molybdenum and/or tungsten.
The preparation method who the invention provides catalyst comprises in described carrier and introduces at least one group VIII and at least one group vib metal component.The method of at least one group VIII of described introducing and at least one group vib metal component is this area conventional process, for example, can be to be selected from after group vib metallic compound is mixed with mixed solution and to contact with described carrier with at least one containing at least one group VIII, as passed through the method for dipping; Can be to contact with described carrier after containing at least one group VIII and at least one being selected from the independent obtain solution of group vib metallic compound, as passed through the method for dipping.Described dipping method is conventional method.Wherein, the regulation and control of concentration, consumption or carrier consumption by the solution to metallic components, can prepare the described catalyst of specifying content, and it is intelligible that this is that those skilled in the art hold.
According to the present invention, after described metal impregnation step completes, optionally can be dried, the step such as roasting or not roasting.Described condition dry and roasting is all conventional, and for example, baking temperature is 100-300 ℃, is preferably 100-280 ℃, and be 1-12 hour drying time, is preferably 2-8 hour; Sintering temperature is 350-550 ℃, is preferably 400-500 ℃, and roasting time is 1-10 hour, is preferably 2-8 hour.
Described group VIII metallic compound is selected from one or more in the soluble compound of these metals, for example, can be one or more in the nitrate, acetate, carbonate, chloride, soluble complexes of these metals.
Said group vib metallic compound is selected from one or more in the soluble compound of these metals, for example, can be one or more in molybdate, paramolybdate, tungstates, metatungstate, ethyl metatungstate.
In catalyst provided by the invention, can also contain one or more the organic compound being selected from containing in oxygen or organic compounds containing nitrogen, preferred oxygen-containing organic compound is selected from one or more in Organic Alcohol and organic acid; Preferred organic compounds containing nitrogen is selected from one or more in organic amine.For example, oxygen-containing organic compound can be enumerated ethylene glycol, glycerine, polyethylene glycol (molecular weight is 200-1500), diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1, one or more in 2-CDTA, citric acid, tartaric acid, malic acid, organic compounds containing nitrogen can be ethylenediamine, EDTA and ammonium salt thereof.Described organic compound with take the group VIII of oxide and the mol ratio of group vib metal component sum as 0.03-2, be preferably 0.08-1.5.
In the time that catalyst of the present invention further contains organic compound, the introducing method of described organic compound can be method arbitrarily, such as enumerating, described organic compound and other components (comprising metal component and adjuvant component etc.) is mixed with to impregnated carrier after mixed solution, dry method then; And organic compound is mixed with separately to the method for impregnated carrier after solution.In a kind of rear method, preferably first introduce carrier described in the solution impregnation that contains other components, dry, roasting or not roasting, afterwards again by this carrier of solution impregnation containing organic compound dry method.Described being dried can adopt customary way to carry out, and to this, there is no particular limitation in the present invention, and such as baking temperature is 100-300 ℃, be 1-12 hour drying time, and preferably baking temperature is 100-250 ℃, and be 2-8 hour drying time.The condition of described roasting is also conventional, and for example described sintering temperature is 250-550 ℃, is preferably 300-500 ℃, and roasting time is 1-10 hour, is preferably 2-8 hour.
According to the present invention, contain organic compound in preparation described catalyst time, preferably by selecting the introduction volume of described organic compound, make in final catalyst organic compound with the mol ratio of nickel, molybdenum and tungsten sum take oxide as 0.03-2.0, be preferably 0.08-1.5.
According to catalyst provided by the invention, can also contain any material that does not affect the catalytic performance that the invention provides catalyst and maybe can improve the material of the catalytic performance of catalyst provided by the invention.As introduced one or both in the components such as phosphorus, titanium or silicon, in element and take catalyst as benchmark, the introduction volume of above-mentioned auxiliary agent is 0-10 % by weight, is preferably 0.5-5 % by weight.
When in described catalyst, also contain in components such as being selected from phosphorus, titanium or silicon one or both components time, the described introducing method that is selected from the components such as phosphorus, titanium or silicon is conventional method, as can be by containing as described in auxiliary agent compound directly and solid acid component, 1.1≤n≤2.5, preferably boehmite mixing, moulding the roasting of 1.2≤n≤2.2; Can be to contact with described carrier after the compound that contains described auxiliary agent is mixed with to mixed solution with the compound that contains hydrogenation active metals component; Can also be after independent the compound that contains auxiliary agent obtain solution, to contact with described carrier and roasting.In the time that auxiliary agent and hydrogenation active metals are introduced described carrier respectively, preferably first with containing, auxiliary compound solution contacts with described carrier and roasting, contact with the solution of the compound that contains hydrogenation active metals component more afterwards, for example, by the method for dipping, described sintering temperature is 250-600 ℃, be preferably 350-500 ℃, roasting time is 2-8 hour, is preferably 3-6 hour.
According to catalyst provided by the invention, use before preferably hydrogen exist under, at the temperature of 140-370 ℃, carry out presulfurization with sulphur, hydrogen sulfide or sulfur-bearing raw material, this presulfurization can be carried out outward also can in device, original position vulcanizing at device, and the active metal component of its load is converted into metal sulfide component.
In method for hydrogen cracking provided by the invention, to described hydrocracking reaction condition, there is no particular limitation, preferred reaction condition comprises: reaction temperature 200-420 ℃, 220-400 ℃ more preferably, hydrogen dividing potential drop 2-18 MPa, 2-15 MPa more preferably, liquid hourly space velocity (LHSV) 0.3-10 hour
-1, 0.3-5 hour more preferably
-1, hydrogen to oil volume ratio 50-5000,50-4000 more preferably.
The device of described hydrocracking reaction can be enough to make described feedstock oil to carry out in device with the catalytic dress that reacts of described catalyst under hydrocracking reaction condition any, for example, described reaction, at fixed bed reactors, is carried out in moving-burden bed reactor or fluidized bed reactor.
Adopt method for hydrogen cracking provided by the invention can directly process all kinds of hydrocarbon oil crude materials, so that it is carried out to hydro-upgrading or hydrocracking.Described hydrocarbon oil crude material can be various heavy mineral oils or artificial oil or their mixed fraction oil, such as be selected from crude oil, distillate, solvent-refined oil, slack wax, sweat oil, Fischer-Tropsch synthesis oil, liquefied coal coil, frivolous coal tar and heavy deasphalted oil one or more.Be particularly suitable for the hydrocracking upgrading of diesel oil or poor ignition quality fuel.
The present invention will be further described for example below.
Agents useful for same in example, except special instruction, is chemically pure reagent.
Embodiment 1
The present embodiment explanation is applicable to boehmite of preparation the present invention carrier and preparation method thereof.
In the retort of 2 liters and stream add 1000 ml concns be 48 grams of aluminium oxide/liter aluminum trichloride solution and 300 milliliters containing 200 grams of aluminium oxide/liter, causticity coefficient is 1.58, D-sorbite content is 1.82 grams per liters sodium aluminate solution carries out precipitation reaction, reaction temperature 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 aqua 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, 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 outlet temperature 100-110 ℃ of scope, approximately 2 minutes dry materials time, after being dried, obtain hydrated alumina P1.Adopt XRD to characterize, P1 has structure of similar to thin diaspore.
XRD measures on SIMENS D5005 type X-ray diffractometer, CuK α radiation, and 44 kilovolts, 40 milliamperes, sweep speed is 2 °/minute.According to Scherrer formula: (D is crystallite dimension to D=K λ/(Bcos θ), λ is the diffraction wavelength of target shaped material, B is the half-peak breadth of corrected diffraction maximum, 2 θ are the position of diffraction maximum) calculation of parameter at ° peak goes out (120) take 2 θ as 23-33 respectively grain size as D (120), the calculation of parameter at ° peak goes out (031) take 2 θ as 34-43 grain size be D (031), and calculating n=D (031)/D (120), the n value that calculates P1 through XRD sign is listed in table 1.
Embodiment 2
The present embodiment explanation is applicable to boehmite of preparation the present invention carrier and preparation method thereof.
In the retort of 2 liters and stream add 600 ml concns be 96 grams of aluminium oxide/liter, the ammonia spirit that is wherein 8 % by weight containing the aluminum sulfate solution of 3.6 grams of ribitol and concentration carries out precipitation reaction, reaction temperature is 40 ℃, reaction time is 10 minutes, it is 7 that the flow of control ammonia spirit makes the pH of reaction system, after precipitation reaction finishes, in slurries, adding proper ammonia to make the pH value of slurries is 8.5, slurries filter after aging 60 minutes at 55 ℃, deionized water making beating washing 2 times for filter cake, filter cake is dried 24 hours through 120 ℃, obtain hydrated alumina P2, adopt XRD to characterize, P2 has structure of similar to thin diaspore.
XRD measures on SIMENS D5005 type X-ray diffractometer, CuK α radiation, and 44 kilovolts, 40 milliamperes, sweep speed is 2 °/minute.According to Scherrer formula: (D is crystallite dimension to D=K λ/(Bcos θ), λ is the diffraction wavelength of target shaped material, B is the half-peak breadth of corrected diffraction maximum, 2 θ are the position of diffraction maximum) calculation of parameter at ° peak goes out (120) take 2 θ as 23-33 respectively grain size as D (120), the calculation of parameter at ° peak goes out (031) take 2 θ as 34-43 grain size be D (031), and calculating n=D (031)/D (120), the n value that calculates P2 through XRD sign is listed in table 1.
Comparative example 1
This comparative example explanation preparation reference catalyst boehmite of carrier and preparation method thereof.
Method according to embodiment 1 is prepared boehmite, different, aluminum sulfate solution change into concentration be 48 grams of aluminium oxide/liter aluminum trichloride solution, and in sodium aluminate solution containing D-sorbite, obtain hydrated alumina DP1.Adopt XRD to characterize according to the method for embodiment 1, DP1 has structure of similar to thin diaspore, and the n value that calculates DP1 through XRD sign is listed in table 1.
Comparative example 2
This comparative example explanation preparation reference catalyst boehmite of carrier and preparation method thereof.
Method according to embodiment 2 is prepared boehmite, different, containing the aluminum sulfate solution of ribitol by concentration be 96 grams of aluminium oxide/liter aluminum sulfate solution replace, be also in aluminum sulfate solution containing ribitol, obtain hydrated alumina DP2.Adopt XRD to characterize according to the method for embodiment 1, DP2 has structure of similar to thin diaspore, and the n value that calculates DP2 through XRD sign is listed in table 1.
Table 1
From the results shown in Table 1, the boehmite that adopts method provided by the invention to prepare has the feature of 1.1≤n≤2.5, preferably 1.2≤n≤2.2, and adopt the method for prior art and the n value of the various boehmites that are obtained commercially to be at present all less than 1.1.
Embodiment 3～10 explanation Catalysts and its preparation method provided by the invention.
Embodiment 3
By boehmite the P1 synthetic laboratory of 300 grams, join containing Re
2o
3in its total amount of rare earth of the RECl3 of 27.1 grams per liters, the weight percentage of each composition is: Ce
2o
363 % by weight, La
2o
325%, Pr
6o
1112.1 % by weight, Nd
2o
35.0 % by weight, Sm
2o
30.5 % by weight, other 4.4 % by weight, lower with) 330 milliliters of the aqueous solution, be fully uniformly mixed.Flood 2 hours, be dried 3 hours at 120 ℃, then 280 roasting 3 hours, obtains the boehmite PR1 containing rare earth.
By the boehmite synthetic laboratory of 185.7 grams (the heavy % of butt 70) PR1 and 93.3 grams of Y zeolite (China Petrochemical Industry's catalyst Chang Ling branch company products, lattice constant 24.53 dusts, the heavy % of butt 75) mix, be extruded into circumscribed circle diameter and be the trilobal bar of 1.6 millimeters, wet bar is dried 3 hours in 120 ℃, 600 ℃ of roastings 4 hours, obtain carrier Z1.
Get 100 grams of carrier Z1, with 88 milliliters containing WO
3422 grams per liters, the ammonium metatungstate of NiO 64.9 grams per liters and nickel nitrate mixed solution dipping 1 hour, dries 2 hours in 120 ℃, and 450 ℃ of roastings 3 hours, obtain catalyst C, and the composition after C1 roasting is listed in table 2.WO
3, NiO and Re
2o
3the content of component adopts X-fluorescence method to measure (lower same).
Composition after described roasting, refer under air atmosphere catalyst in 550 ℃ of roastings the sample composition after 4 hours (lower with).
Embodiment 4
By boehmite the P2 synthetic laboratory of 300 grams, join containing Re
2o
3the RECl of 27.1 grams per liters
3330 milliliters of the aqueous solution, are fully uniformly mixed.Flood 2 hours, be dried 3 hours at 120 ℃, then 280 roasting 3 hours, obtains the boehmite containing rare earth, obtains the boehmite PR2 containing rare earth.
By the PR2 of 185.7 grams (the heavy % of butt 70) and 93.3 grams of Y zeolite (China Petrochemical Industry's catalyst Chang Ling branch company products, lattice constant 24.53 dusts, the heavy % of butt 75) mix, be extruded into circumscribed circle diameter and be the trilobal bar of 1.6 millimeters, wet bar is dried 3 hours in 120 ℃, 600 ℃ of roastings 4 hours, obtain carrier Z2.
Get carrier Z2100 gram, with 103 milliliters containing WO
3360.5 grams per liters, the ammonium metatungstate of NiO 55.4 grams per liters and nickel nitrate mixed solution dipping 1 hour, dries 2 hours in 120 ℃, and 450 ℃ of roastings 3 hours, obtain catalyst C2, and the composition after C2 roasting is listed in table 2.
Comparative example 3
By boehmite the DP1 synthetic laboratory of 300 grams, join containing Re
2o
3the RECl of 27.1 grams per liters
3330 milliliters of the aqueous solution, are fully uniformly mixed.Flood 2 hours, be dried 3 hours at 120 ℃, then 280 roasting 3 hours, obtains the boehmite DPR1 containing rare earth.
By the DPR1 of 185.7 grams (the heavy % of butt 70) and 93.3 grams of Y zeolite (China Petrochemical Industry's catalyst Chang Ling branch company products, lattice constant 24.53 dusts, the heavy % of butt 75) mix, be extruded into circumscribed circle diameter and be the trilobal bar of 1.6 millimeters, wet bar is dried 3 hours in 120 ℃, 600 ℃ of roastings 4 hours, obtain carrier Z3.
Get 100 grams of carrier Z3, with 103 milliliters containing WO
3360.5 grams per liters, the ammonium metatungstate of NiO 55.4 grams per liters and nickel nitrate mixed solution dipping 1 hour, dries 2 hours in 120 ℃, and 450 ℃ of roastings 3 hours, obtain catalyst C3, and the composition after C3 roasting is listed in table 2.
Comparative example 4
By boehmite the DP2 synthetic laboratory of 300 grams, join containing Re
2o
3the RECl of 27.1 grams per liters
3330 milliliters of the aqueous solution, are fully uniformly mixed.Flood 2 hours, be dried 3 hours at 120 ℃, then 280 roasting 3 hours, obtains the boehmite DPR2 containing rare earth.
By the DPR2 of 185.7 grams (the heavy % of butt 70) and 93.3 grams of Y zeolite (China Petrochemical Industry's catalyst Chang Ling branch company products, lattice constant 24.53 dusts, the heavy % of butt 75) mix, be extruded into circumscribed circle diameter and be the trilobal bar of 1.6 millimeters, wet bar is dried 3 hours in 120 ℃, 600 ℃ of roastings 4 hours, obtain carrier Z4.
Get 100 grams of carrier Z4, with 103 milliliters containing WO
3360.5 grams per liters, the ammonium metatungstate of NiO 55.4 grams per liters and nickel nitrate mixed solution dipping 1 hour, dries 2 hours in 120 ℃, and 450 ℃ of roastings 3 hours, obtain catalyst C4, and the composition after C4 roasting is listed in table 2.
Comparative example 5
By boehmite the DP2 synthetic laboratory of 300 grams, join containing Re
2o
3the RECl of 27.1 grams per liters
3330 milliliters of the aqueous solution, are fully uniformly mixed.Flood 2 hours, be dried 3 hours at 120 ℃, then 280 roasting 3 hours, obtains the boehmite DPR2 containing rare earth.
By the DPR2 of 185.7 grams (the heavy % of butt 70) and 93.3 grams of Y zeolite (China Petrochemical Industry's catalyst Chang Ling branch company products, lattice constant 24.53 dusts, the heavy % of butt 75) mix, be extruded into circumscribed circle diameter and be the trilobal bar of 1.6 millimeters, wet bar is dried 3 hours in 120 ℃, 600 ℃ of roastings 4 hours, obtain carrier Z5.
Get 100 grams of carrier Z5, with 103 milliliters containing WO
3360.5 grams per liters, ammonium metatungstate, nickel nitrate and 12.95 grams of citric acid mixed solutions of NiO 55.4 grams per liters flood 1 hour, and in 120 ℃ of oven dry 2 hours, 150 ℃ were dried 3 hours, obtain catalyst C5.Wherein, organic compound with take the nickel of oxide and the mol ratio of tungsten sum the composition after 0.3, C5 roasting list in table 2.
Embodiment 5
By boehmite the P1 synthetic laboratory of 300 grams, join containing La
2o
3la (the NO of 30.4 grams per liters
3)
3.6H
2330 milliliters of O (is produced from Beijing Chemical Plant, and the analyzes pure) aqueous solution, are fully uniformly mixed.Flood 2 hours, be dried 2 hours at 120 ℃, then 250 roasting 3 hours, obtains the boehmite PR3 containing lanthanum.
By the PR3 of 245.5 grams (the heavy % of butt 70) and 13.5 grams of Y zeolite (China Petrochemical Industry's catalyst Chang Ling branch company products, lattice constant 24.59 dusts, the heavy % of butt 74) mix, be extruded into circumscribed circle diameter and be the trilobal bar of 1.6 millimeters, wet bar is dried 3 hours in 120 ℃, 600 ℃ of roastings 4 hours, obtain carrier Z6.
Get 100 grams of carrier Z6, with 85 milliliters containing WO
3478.8 grams per liters, NiO 54.7 grams per liters, the mixed solution dipping of ammonium metatungstate, nickel nitrate and the ethylene glycol of ethylene glycol 162.3 grams per liters 1 hour, in 120 ℃ of oven dry 2 hours, 150 ℃ were dried 3 hours, obtain catalyst C6.Wherein, organic compound with take the nickel of oxide and the mol ratio of tungsten sum the composition after 0.20, C6 roasting list in table 2.
Embodiment 6
By boehmite the P2 synthetic laboratory of 300 grams, join containing Ce
2o
3(the NH of 83.9 grams per liters
4)
2ce (NO
3)
6330 milliliters of (is produced from Beijing Chemical Plant, and analyzes pure) aqueous solution, are fully uniformly mixed.Flood 2 hours, be dried 2 hours at 120 ℃, then 250 roasting 3 hours, obtains the boehmite PR4 containing lanthanum.
By the PR4 of 114.3 grams (the heavy % of butt 70) and 160 grams of Y zeolite (China Petrochemical Industry's catalyst Chang Ling branch company products, lattice constant 24.57 dusts, the heavy % of butt 75) mix, be extruded into circumscribed circle diameter and be the trilobal bar of 1.6 millimeters, wet bar is dried 3 hours in 120 ℃, 600 ℃ of roastings 4 hours, obtain carrier Z7.
Get 100 grams of carrier Z7, with 87 milliliters containing WO
3458.4 grams per liters, NiO 47.5 grams per liters, MoO
342.4 grams per liters, the mixed aqueous solution dipping of ammonium metatungstate, nickel nitrate, ammonium molybdate and the citric acid of citric acid 182.6 grams per liters 1 hour, dries 2 hours in 120 ℃, and 180 ℃ of roastings 3 hours, obtain catalyst C7.Wherein, organic compound with mol ratio take nickel, molybdenum and the tungsten sum of oxide the composition after 0.36, C7 roasting list in table 2.
Embodiment 7
By boehmite the P1 synthetic laboratory of 300 grams, join containing Re
2o
3the RECl of 68.0 grams per liters
3330 milliliters of the aqueous solution, are fully uniformly mixed.Flood 3 hours, be dried 3 hours at 120 ℃, then 260 roasting 3 hours, obtains the boehmite PR5 containing rare earth.
By the PR5 of 185.7 grams (the heavy % of butt 70), 38.5 grams of silica-alumina (China Petrochemical Industry's catalyst Chang Ling branch company products that N value is 0.4, the heavy % of butt 78) and 53.3 grams of Y zeolite (China Petrochemical Industry's catalyst Chang Ling branch company products, lattice constant 24.53 dusts, the heavy % of butt 75) mix, be extruded into circumscribed circle diameter and be the trilobal bar of 1.6 millimeters, wet bar is dried 3 hours in 120 ℃, and 600 ℃ of roastings 4 hours, obtain carrier Z8.
Get 100 grams of carrier Z8, with 87 milliliters containing WO
3399.1 grams per liters, the ammonium metatungstate of NiO 47.9 grams per liters and nickel nitrate mixed solution dipping 1 hour, dries 2 hours in 120 ℃, and 450 ℃ of roastings 3 hours, obtain catalyst C8, and the composition after C8 roasting is listed in table 2.
Embodiment 8
By boehmite the P1 synthetic laboratory of 300 grams, join containing Re
2o
3103.1 the RECl of grams per liter
3330 milliliters of the aqueous solution, are fully uniformly mixed.Flood 3 hours, be dried 3 hours at 120 ℃, then 250 roasting 3 hours, obtains the boehmite PR6 containing rare earth.
By the PR6 of 85.7 grams (the heavy % of butt 70), 76.9 grams of silica-alumina (China Petrochemical Industry's catalyst Chang Ling branch company products that N value is 0.6, the heavy % of butt 78) and 106.7 grams of Y zeolite (China Petrochemical Industry's catalyst Chang Ling branch company products, lattice constant 24.53 dusts, the heavy % of butt 75) mix, be extruded into circumscribed circle diameter and be the trilobal bar of 1.6 millimeters, wet bar is dried 3 hours in 120 ℃, and 600 ℃ of roastings 4 hours, obtain carrier Z9.
Get 100 grams of carrier Z9, with 87 milliliters containing WO
3513.1 grams per liters, the ammonium metatungstate of NiO 47.9 grams per liters and nickel nitrate mixed solution dipping 1 hour, dries 2 hours in 120 ℃, and 450 ℃ of roastings 3 hours, obtain catalyst C9, and the composition after C9 roasting is listed in table 2.
Table 2
Example 9-10
Example below illustrates method provided by the invention and effect thereof.
Take density as 0.9058 gram per centimeter
3, sulfur content is that 3800ppm, nitrogen content are 501ppm, and the catalytic cracking diesel oil that Cetane number is 28.7 is raw material, evaluates the performance of catalyst C1 provided by the invention, C2 on 30 milliliters of fixed bed devices, and catalyst loading amount is 20 milliliters.Before entering feedstock oil, catalyst is carried out to presulfurization, conditions of vulcanization is: 110 ℃ are vulcanized 2 hours, and 300 ℃ are vulcanized 4 hours, and sulfurized oil is the kerosene containing 6 heavy % carbon disulfide.Reaction condition is: 360 ℃ of temperature, hydrogen dividing potential drop 6.4MPa, liquid hourly space velocity (LHSV) 1.3 hours
-1, hydrogen to oil volume ratio 600.Analyze the Cetane number that generates diesel oil, the results are shown in Table 3.
Comparative example 6-8
According to the performance of example 9 the same terms evaluate catalysts C3, C4 and C5.Analyze the Cetane number that generates diesel oil, the results are shown in Table 3.
Table 3
| Example | 9 | 10 | 11 | 12 | 13 |
| Catalyst | C1 | C2 | C3 | C4 | C5 |
| Cetane number value added | 11.3 | 10.1 | 8.2 | 8.9 | 9.3 |
| Diesel yield, % | ＞95 | ＞95 | ＞95 | ＞95 | ＞95 |
The result that table 3 provides shows, compared with existing catalyst, diesel cetane-number to be had to larger increase rate.
Claims (19)
1. the hydrocracking catalyst containing containing rare earth metal aluminium oxide, this catalyst contains carrier and at least one and is selected from VIII family and at least one and is selected from the metal component of group vib, described carrier contains containing rare earth alumina and solid acid component, it is characterized in that, described is to be obtained through roasting containing rare earth boehmite by one containing rare earth alumina, in oxide and take the butt of described boehmite as benchmark, the content that described boehmite middle rare earth adds component is 1-15 % by weight, described boehmite is the boehmite of 1.1≤n≤2.5, wherein n=D (031)/D (120), the crystallite dimension of the crystal face of (031) peak representative in the XRD spectra of described D (031) expression boehmite crystal grain, the crystallite dimension of the place crystal face at (120) peak in the XRD spectra of D (120) expression 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), λ is the diffraction wavelength of target shaped material, B is the half-peak breadth of corrected diffraction maximum, 2 θ are the position of diffraction maximum.
2. catalyst according to claim 1, is characterized in that, described containing satisfied 1.2≤n≤2.2 of rare earth boehmite, with Re
20
3meter take the butt of described boehmite as benchmark, the content of described boehmite middle rare earth is 1-10 % by weight.
3. catalyst according to claim 1, is characterized in that, take described carrier as benchmark, the content containing rare earth alumina in described carrier is 5-99.5 % by weight, and the content of solid acid component is 0.5-95 % by weight.
4. catalyst according to claim 3, is characterized in that, take described carrier as benchmark, the content that contains the aluminium oxide of rare earth in described carrier is 20-99 % by weight, and the content of solid acid component is 1-80 % by weight.
5. catalyst according to claim 1, is characterized in that, take described catalyst as benchmark, and the carrier that described catalyst contains 50-90 % by weight, the VIII family metal component of 1-10 % by weight, the group vib metal component of 5-40 % by weight.
6. catalyst according to claim 5, is characterized in that, take described catalyst as benchmark, and the carrier that described catalyst contains 60-85 % by weight, the VIII family metal component of 1.5-6 % by weight, the group vib metal component of 10-35 % by weight.
7. according to the catalyst described in claim 1,3 or 4, it is characterized in that, described solid acid component is selected from one or more in silica-alumina and molecular sieve.
8. catalyst according to claim 7, is characterized in that, described solid acid component is selected from one or more in molecular sieve.
9. catalyst according to claim 8, is characterized in that, described molecular screening is from y-type zeolite molecular sieve.
10. catalyst according to claim 9, it is characterized in that one or more in the Y zeolite of the Y zeolite of HY, Rare Earth Y, rare earth HY zeolite, super steady Y, hyperastable Y-type RE zeolite, part amorphization, titaniferous, phosphorous Y of described y-type zeolite molecular screening.
11. catalyst according to claim 7, is characterized in that, described solid acid component is silica-alumina.
12. catalyst according to claim 11, is characterized in that, described silica-alumina is the silica-alumina with structure of similar to thin diaspore.
13. catalyst according to claim 12, is characterized in that, described in there is structure of similar to thin diaspore the N value of silica-alumina for 0.1-1, described N=Q1/Q2, the solid that Q1 is described silica-alumina
27in A1NMR spectrogram, chemical shift is the peak area at 60 ± 0.1-0.2ppm place, the solid that Q2 is described silica-alumina
27in A1NMR spectrogram, chemical shift is the peak area at 5 ± 0.1-0.2ppm place.
27in Al NMR spectrogram, the each peak area of chemical shiftsum at each peak is measured take saturated aluminum sulfate aqueous solution as reference on Varian UnityInova300M type nuclear magnetic resonance spectrometer.
14. catalyst according to claim 13, is characterized in that, described in there is structure of similar to thin diaspore the N value of silica-alumina for 0.2-0.8.
15. catalyst according to claim 1, is characterized in that, the condition of described roasting comprises: sintering temperature is 350-950 ℃, and roasting time is 1-12 hour.
16. catalyst according to claim 15, is characterized in that, described roasting condition comprises: sintering temperature is 450-900 ℃, and roasting time is 2-8 hour.
17. catalyst according to claim 1, it is characterized in that, described catalyst contains one or more the organic matter being selected from Organic Alcohol, organic acid, organic amine, described organic compound with take the group VIII of oxide and the mol ratio of group vib metal component sum as 0.03-2.
18. catalyst according to claim 17, it is characterized in that, described Organic Alcohol is selected from polyethylene glycol, diethylene glycol, the butanediol that ethylene glycol, glycerine, molecular weight are 200-1500, organic acid is selected from acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2-CDTA, citric acid, tartaric acid, malic acid, machine amine is selected from ethylenediamine, EDTA and ammonium salt thereof, described organic compound with take the group VIII of oxide and the mol ratio of group vib metal component sum as 0.08-1.5.
19. 1 kinds of hydrocarbon oil hydrogenation cracking methods, are included under hydrocracking reaction condition, by hydrocarbon ils and catalyst haptoreaction, it is characterized in that, described catalyst is the catalyst described in claim 1-18 any one.
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| CN1299857A (en) * | 1999-12-13 | 2001-06-20 | 中国石油化工集团公司 | Petroleum hydrocarbon cracking catalyst and its preparation |
| EP1415712A1 (en) * | 2002-10-30 | 2004-05-06 | Institut Francais Du Petrole | Catalyst and process for the hydrocracking of hydrocarbon feedstocks |
| CN1803996A (en) * | 2005-01-14 | 2006-07-19 | 中国石油化工股份有限公司 | Diesel oil hydrotreating catalyst and method for preparing the same |
| CN101088610A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Prepn process of hydroprocessing catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1299857A (en) * | 1999-12-13 | 2001-06-20 | 中国石油化工集团公司 | Petroleum hydrocarbon cracking catalyst and its preparation |
| EP1415712A1 (en) * | 2002-10-30 | 2004-05-06 | Institut Francais Du Petrole | Catalyst and process for the hydrocracking of hydrocarbon feedstocks |
| CN1803996A (en) * | 2005-01-14 | 2006-07-19 | 中国石油化工股份有限公司 | Diesel oil hydrotreating catalyst and method for preparing the same |
| CN101088610A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Prepn process of hydroprocessing catalyst |
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