CN102266791A - Hydrocracking catalyst and application thereof - Google Patents
Hydrocracking catalyst and application thereof Download PDFInfo
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- CN102266791A CN102266791A CN2010101906937A CN201010190693A CN102266791A CN 102266791 A CN102266791 A CN 102266791A CN 2010101906937 A CN2010101906937 A CN 2010101906937A CN 201010190693 A CN201010190693 A CN 201010190693A CN 102266791 A CN102266791 A CN 102266791A
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Abstract
The invention relates to a hydrocracking catalyst and an application thereof. The catalyst comprises a carrier, at least a metal component selected from VIII group metals, at least a metal component selected from VIB group metals and an assistant agent of boron or fluorine. The carrier comprises a solid acid component and aluminum oxide. The aluminum oxide is characterized in that: the aluminum oxide is the gamma-aluminum oxide transformed from pseudo-boehmite having an index n more than or equal to 1.1 and less than or equal to 2.5, wherein the n is calculated from the following formula, n=D(031)/D(120), the D(031) represents a grain size of a crystal face represented by a (031) peak in a XRD spectrogram of the pseudo-boehmite grains, the D(120) represents a grain size of a crystal face represented by a (120) peak in the XRD spectrogram of the pseudo-boehmite grains, the (031) peak is the peak having a 2theta of 34-43 DEG in the XRD spectrogram, the (120) peak is the peak having a 2theta of 23-33 DEG in the XRD spectrogram, the D is calculated from the following formula, D=K*lambda/(B*cos theta), the lambda is the diffraction wavelength of the target type material, the B is the half peak width of the corrected diffraction peak, the 2theta is the position of the diffraction peak. Compared to the prior art, the hydrocracking property of the catalyst provided by the present invention is improved.
Description
Technical field
The present invention is about a kind of hydrocracking catalyst and application thereof, the hydrocracking catalyst and the application thereof of more specifically saying so and containing auxiliary agent boron or fluorine about a kind of.
Background technology
Under hydrogenation conditions, hydrocarbon oil crude material contacts with catalyst and may comprise: reactions such as hydrodesulfurization, hydrodenitrogeneration, HDM, hydrocracking.Wherein the performance of catalyst plays crucial effect to the upgrading effect of hydrocarbon feed, the selectivity of target product.
With the catalyst that contains the carrier loaded hydrogenation active metals component preparation of porous heat-resistant inorganic oxide (as aluminium oxide), solid acid (as molecular sieve) is the catalyst that is widely used in the hydrocarbon oil hydrogenation cracking.In the prior art, the report of relevant this class catalyst is a lot, for example:
CN 1169458A catalyst for distillate hydro-cracking has following composition: the heavy % of heavy %, tungsten oxide 10-38 of boron 0.5-5.0 heavy %, nickel oxide 2.5-5.0, 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 the 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 with NH3-TPD method mensuration.This catalyst has the selectivity to middle distillate higher than prior art when having good desulfurization, denitrification activity.
CN1054150C discloses a kind of catalyst for hydrocracking diesel oil, and carrier that this catalyst is made up of aluminium oxide, amorphous aluminum silicide and molecular sieve and the hydrogenation active metals that loads on this carrier are formed WO in the 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 a Y zeolite, its infrared total acid content is 0.5-1 mM/gram, and lattice constant is the 2.436-2.444 nanometer.Described aluminium oxide is pore volume 0.8-1.1 milliliter/gram; Surface area 230-400 rice
2The little porous aluminum oxide of/gram.
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 milliliter/gram, 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 the tenor 10-30 of VI B family, the content of VIII family metal oxide are the heavy % of 2-15.
For the hydrocracking catalyst that contains molecular sieve, wherein contained porous heat-resistant inorganic oxide exerts an influence to the dispersity of hydrogenation active metals component and catalyst pores structural property etc., 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 that contains solid acid (comprising silica-alumina and molecular sieve) component, after solid acid and hydrogenation active metals component were determined, the character of the alumina host that its performance and catalyst are contained was relevant.The n value of the boehmite that prior art provides (being generally 0.85-1.05) on the low side, when the boehmite that adopts this type of prepares catalyst, when particularly preparation was used for 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 and application thereof, this catalyst contains carrier, at least a metal component that is selected from VIII family, at least a metal component and auxiliary agent boron or the fluorine that is selected from VI B family, described carrier contains solid acid component and aluminium oxide, it is characterized in that, described aluminium oxide is that a kind of boehmite by 1.1≤n≤2.5 transforms the gama-alumina that obtains, n=D (031)/D (120) wherein, 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 is meant that 2 θ in the XRD spectra are 34-43 ° peak, described 120 peaks are meant that 2 θ in the XRD spectra are 23-33 ° peak, D=K λ/(Bcos θ), λ is the diffraction wavelength of target section bar material, B is the half-peak breadth of corrected diffraction maximum, and 2 θ are the position of diffraction maximum.
The present invention also provides a kind of hydrocarbon oil hydrogenation cracking method, is included under the hydrocracking reaction condition, with hydrocarbon oil crude material oil and hydrocracking 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, compare with the diesel oil hydrogenation modification catalyst that existing method provides, catalyst provided by the invention can make the diesel cetane-number increase rate be significantly improved.
The specific embodiment
According to catalyst provided by the invention, wherein said aluminium oxide is by 1.1≤n≤2.5, and preferably the boehmite by 1.2≤n≤2.2 transforms the gama-alumina that obtains.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 is meant that 2 θ in the XRD spectra are 34-43 ° peak, described 120 peaks are meant that 2 θ in the XRD spectra are 23-33 ° peak, D=K λ/(Bcos θ), K is the Scherrer constant, λ is the diffraction wavelength of target section bar material, B is the half-peak breadth of this diffraction maximum, and 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 when 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; When 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.With described carrier is benchmark, and the content of aluminium oxide is 5-99.5 weight %, more preferably 20-99 weight % described in preferred embodiment.
The preparation method of the boehmite of described feature with 1.1≤n≤2.5 comprises: aluminum contained compound solution is contacted with acid or alkali carry out precipitation reaction, perhaps organic aluminum contained compound is contacted the reaction that is hydrolyzed with water, obtain hydrated alumina; The above-mentioned hydrated alumina that obtains is worn out, 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 in the presence of the grain growth conditioning agent, carry out, described grain growth 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 or precipitation reaction and aging in any one process in the presence of the grain growth conditioning agent, carry out realizing purpose of the present invention, but under the preferable case, described hydrolysis and ageing process or described precipitation reaction and ageing process are all carried out in the presence of the grain growth conditioning agent, and the n that can make the gained boehmite like this is in preferred 1.2≤n≤2.2 scopes.
Wherein, there is no particular limitation to the consumption of grain growth conditioning agent, the consumption of grain growth conditioning agent is the 0.5-10 weight % that treats organic aluminum contained compound weight of hydrolysis in the selective hydrolysis reaction, 1-8.5 weight % more preferably, further preferred 5-8.5 weight %; The consumption of grain growth conditioning agent is the inorganic 0.5-10 weight % that contains al reactant weight in the described precipitation reaction, 1-8.5 weight % more preferably, further preferred 5-8.5 weight %; In the described ageing process, the consumption of grain growth conditioning agent can be preferably 1-8.5 weight % for the 0.5-10 weight % of hydrated alumina weight, further preferred 5-8.5 weight %.Unless stated otherwise, among the present invention, the consumption of described grain growth conditioning agent is that benchmark calculates with the weight of aluminium oxide corresponding in organic aluminum contained compound, inorganic aluminum contained compound and the hydrated alumina respectively.Also be, in aluminium oxide, in the described precipitation reaction, the consumption of described grain growth conditioning agent is the 0.5-10 weight % of inorganic aluminum contained compound weight, in the described hydrolysis, the consumption of described grain growth conditioning agent is the 0.5-10 weight % of organic aluminum contained compound weight, and in the described ageing process, the consumption of described grain growth conditioning agent is the 0.5-10 weight % of hydrated alumina weight.
Among 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 in D-sorbite, glucose, gluconic acid, gluconate, ribitol, ribonic acid, the ribose hydrochlorate one or more.Described gluconate and ribose hydrochlorate can be their soluble-salt separately, for example, can be in sylvite, sodium salt and the lithium salts one or more.
In boehmite preparation process of the present invention, adding mode to described grain growth conditioning agent is not particularly limited, the grain growth conditioning agent can be added separately, also can be in advance the grain growth conditioning agent be mixed with wherein one or more raw materials, and then the raw material that will contain the grain growth 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, for example can be one or more the aqueous solution in aluminum sulfate, aluminium chloride, the aluminum nitrate.Because price is low, preferably sulfuric acid aluminium, liquor alumini chloridi.Aluminium salt can use separately also and can use two kinds or more of mixing back.Described aluminate solution is an 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 with aluminium oxide.
Described acid can be various Bronsted acids or be acid oxide in aqueous medium, for example, can be in sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetate, citric acid, the oxalic acid one or more, preferred Bronsted acid be selected from one or more in nitric acid, sulfuric acid, the hydrochloric acid.Described carbonic acid can original position produces by feed carbon dioxide in aluminum salt solution and/or aluminate solution.Concentration to described acid solution is not particularly limited, preferred H
+Concentration be the 0.2-2 mol.
Described aqueous slkali can for hydroxide or in aqueous medium hydrolysis make the aqueous solution be the salt of alkalescence, preferred hydroxide is selected from one or more in ammoniacal liquor, NaOH, the 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, the potash.Concentration to described aqueous slkali is not particularly limited, preferred OH
-Concentration be the 0.2-4 mol.When during as alkali, when calculating the consumption of described grain growth conditioning agent, also considering the amount of corresponding aluminium oxide in sodium metaaluminate and/or the potassium metaaluminate with sodium metaaluminate and/or potassium metaaluminate.
Described organic aluminum contained compound can be various can with water generation hydrolysis, producing in the aluminum alkoxide of aqua oxidation aluminum precipitation one or more, for example can be in aluminium isopropoxide, isobutanol aluminum, aluminium isopropoxide, three tert-butoxy aluminium and the isooctanol aluminium one or more.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 boehmite preparation process of the present invention, the described condition of precipitation reaction that makes 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 the reactant or acid.
Condition to described hydrolysis is not particularly limited, as long as water contacts with aluminum alkoxide hydrolysis generation hydrated alumina takes place, and the condition that hydrolysis specifically takes place is conventionally known to one of skill in the art.
Wherein, can in hydrolysis or precipitation reaction obtain slurries that the slurries of hydrated alumina or filter cake after filtering add the water preparation again, add the compound of crystal grain growth regulating effect, also can add aqueous slkali or acid solution and suitably regulate the pH value, under suitable temperature, wear out then to 7-10.Separate then, washing, drying.
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, the described known technology that is separated into this area is as the method for filtration or centrifugation or evaporation.
In boehmite preparation process of the present invention, after aging, also comprise the washing and the dry step that often comprise in the preparation boehmite process, described washing and dry method are preparation 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, an embodiment preferred may further comprise the steps:
(1) will contain the aluminum contained compound solution of grain growth conditioning agent and aqueous slkali or acid solution and stream or batch (-type) and join and carry out precipitation reaction in the reaction vessel, obtain the hydrated alumina slurries; Perhaps in deionized water, add the reaction that is hydrolyzed of grain growth conditioning agent and aluminum alkoxide, obtain the hydrated alumina slurries;
(2) filter cake behind the hydrated alumina dope filtration that step (1) is obtained adds in the aluminium oxide slurries that water making beating obtains again again, adds the grain growth conditioning agent, after regulating pH and being 7-10, in 35-98 ℃ of aging 0.2-6 hour; Also the hydrated alumina slurries that above-mentioned steps (1) can be obtained without filter the grain growth conditioning agent exist or not in the presence of be under the 7-10 at pH, in 35-98 ℃ of aging 0.2-6 hour;
(3) product that filter, washing step (2) obtains;
(4) product that obtains of drying steps (3) obtains boehmite provided by the invention.
Boehmite according to the preceding method preparation can be converted into gama-alumina of the present invention through roasting, the method of described roasting and condition are enough to make boehmite to be converted into the method and the condition of gama-alumina for conventional, for example, sintering temperature is 350-950 ℃, be 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 the silica-alumina that is commonly used for the cracking activity component and in the molecular sieve one or more.Wherein, described molecular sieve can be the zeolite with macroporous structure, as zeolite with faujasite, Beta zeolite, omega zeolite structure, it can be zeolite with central hole structure, as have modenite, ZSM-5 zeolite, ZSM-11 zeolite, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-48 zeolite, an isostructural zeolite of ZSM-57 zeolite, can be zeolite also, as have Erionite zeolite, the zeolite structured zeolite of ZSM-34 with small structure.Preferred solid acid component is zeolite molecular sieve with faujasite structure, have the zeolite structured zeolite molecular sieve of Beta, have the ZSM-5 structure zeolite molecular sieve, have the zeolite molecular sieve of mordenite structure and in the silica-alumina one or more.Described zeolite with faujasite structure is preferably y-type zeolite, USY, the rare-earth type overstable gamma zeolite REUSY of further preferred HY zeolite, rare-earth type Y zeolite REY, rare-earth type HY zeolite REHY, overstable gamma zeolite USY, part amorphization wherein, the Y zeolite of titaniferous, phosphorous Y and super steady in HY type zeolite, the dealuminium Y type beta stone one or more of reaching.
Described silica-alumina preferably has the silica-alumina of structure of similar to thin diaspore, and further preferred 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, Q1 are the solid of described silica-alumina
27Chemical shift is the peak area at 60 ± 0.1-0.2ppm place in the Al NMR spectrogram, and Q2 is the solid of described silica-alumina
27Chemical shift is the peak area at 5 ± 0.1-0.2ppm place in the Al NMR spectrogram.
27The chemical shift at each peak and each peak area are that reference is measured with saturated aluminum sulfate aqueous solution on Varian UnityInova 300M type nuclear magnetic resonance spectrometer in the Al NMR spectrogram.
Described silica-alumina can be commercially available commodity or adopt any one prior art for preparing.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 and is used for the present invention.
A kind of preparation method who preferably satisfies the silica-alumina of aforementioned requirement may further comprise the steps:
(1) a kind of solution that contains aluminium salt and a kind of aqueous slkali or acid solution and stream are joined be carried out to the glue reaction in the reaction vessel, reaction condition: the pH value is 6.5-8.5, and temperature is 30-75 ℃;
(2) product that step (1) is generated is at pH 7-8.5, and temperature 30-75 ℃ was worn out 5-120 minute down;
(3) under agitation, a kind of solution of silicon-containing compound is joined in the product that step (2) obtains;
(4) at pH 8-10,80-98 ℃ of product 12-24 hour of descending aging step (3) to obtain;
(5) product that wash, filtration step (4) obtains;
(6) product that obtains of drying steps (5) obtains described silica-alumina.
Wherein, described aluminum contained compound is selected from one or more in aluminum sulfate, sodium metaaluminate, aluminum nitrate, alchlor, aluminum alkoxide, the alkyl aluminum, is preferably in aluminum sulfate, sodium metaaluminate, aluminum nitrate, the alchlor one or more.
Described alkali be hydroxide or in aqueous medium hydrolysis make the aqueous solution be the salt of alkalescence, preferred hydroxide is selected from one or more in ammoniacal liquor, NaOH, the potassium hydroxide; Preferred salt is selected from one or more in carbonic hydroammonium, ammonium carbonate, sodium acid carbonate, sodium carbonate, saleratus, the potash.
Described acid is Bronsted acid or is acid oxide that in aqueous medium preferred Bronsted acid is selected from one or more in nitric acid, sulfuric acid, the hydrochloric acid; Preferred oxide is a carbon dioxide.
The introducing of the solution of described silicon-containing compound is that the solution with silicon-containing compound mixes 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 to contain in the mixed liquor and stream adding reaction vessel of solution with boehmite and water of silicon-containing compound, the concentration of silicon-containing compound solution and consumption make the silica that contains 5-60 weight % in the final silica-alumina, are preferably 10-45 weight %.
Described silicon-containing compound can be any water-soluble silicon-containing compound and the silicon-containing compound that can hydrolysis in aqueous medium forms silicon gel, colloidal sol.For example, one or more in the compounds such as waterglass, the hydrosol and esters of silicon acis.
According to catalyst provided by the invention, described carrier mixes described boehmite and solid acid component after roasting obtains by comprising, described mixing can be the simple accumulation that described boehmite and described solid acid component are placed a place, also can be to adopt any one prior art, for example, can be at mixer, directly boehmite is mixed by the mode that stirs with silicon-containing compound in the grinder, can be enough under the condition of pulp boehmite, silicon-containing compound and water mix, and filter afterwards, dry or moist method is mixed.When adopting any one prior art to mix, those skilled in the art optionally can to described mix the uniformity that should reach control, to this present invention to being not particularly limited.Described method of roasting and condition can be that this area prepares examples of such carriers customary way and condition.Preferred roasting condition comprises: sintering temperature is 350-950 ℃, is preferably 450-900 ℃, and roasting time is 1-12 hour, is preferably 2-8 hour.With described carrier is benchmark, and the content of the described solid acid component described in preferred embodiment in the carrier is 0.5-95 weight %, more preferably 1-80 weight %.
According to catalyst provided by the invention, wherein said carrier is looked different the article shaped that require can be made into various easy operatings, for example can enumerate microballoon, sphere, tablet or bar shaped etc.This moulding can method routinely be carried out, for example, with solid acid component and 1.1≤n≤2.5, the method for boehmite mixing, extruded moulding and the roasting of preferred 1.2≤n≤2.2.When the extrusion molding of carrier, can in carrier, add an amount of extrusion aid and/or adhesive, extrusion molding then.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, the poly-ethanol.
According to catalyst provided by the invention, the carrier that in preferred embodiment, contains 50-90 weight %, 60-85 weight % more preferably, in oxide and with described catalyst is benchmark, the VIII family metal component of 1-8 weight %, 1.5-6 weight % more preferably, the group vib metal component of 5-38 weight %, 10-35 weight % more preferably, in element and with described catalyst is benchmark, 0.5-5.0 the boron of weight % or fluorine, the more preferably boron of 1-4.0 weight % or fluorine.
Catalyst provided by the invention can adopt the usual method preparation in present technique field, and for example, described preparation method comprises: the preparation carrier, and at least a VIII family and at least a metal component and boron or the fluorine auxiliary agent that is selected from VI B family of being selected from of this carrier introducing.
In preferred embodiment, described Preparation of catalysts method comprises at first introduces auxiliary agent boron or fluorine in carrier, for example, adopt contain boracic or fluorine compounds the described carrier drying of solution impregnation, the method for roasting prepare boracic or fluorine carrier.The method of described drying and roasting and condition are conventional method and condition, for example, in drying box after 100-130 ℃ of dry 1-8 hour in 400-600 ℃ of roasting 2-6 hour.Afterwards, adopt dipping method to introduce at least a VIII family and at least a metal component of group VIB in the carrier to described containing.For example, can be to contain at least a VIII family and at least a group VIB metallic compound that is selected from is mixed with described boracic of dipping or fluorine carrier behind the mixed solution, can be to contain at least a VIII family and at least aly to be selected from described boracic of dipping or fluorine carrier behind the independent obtain solution of group VIB metallic compound.Described dipping method is a conventional method.Wherein, by to boracic or fluorine compounds solution, the adjusting and the control of the concentration of the solution of metallic components, consumption or carrier consumption can be prepared the described catalyst of specifying content, and this is the understanding easily of those skilled in the art institute.
According to the present invention, after the step of described boracic of the solution impregnation of described employing metallic components or fluorine carrier is finished, carry out steps such as drying, roasting or not roasting.The condition of described drying and roasting all is 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 boron-containing compound can be water miscible as boric acid, boron oxide or borate, also can be non-water-soluble boride, as halogenation boron etc.Fluorochemical can be water miscible as ammonium fluoride, hydrofluoric acid etc.
Described group VIII metal compound is selected from one or more in the soluble compound of these metals, for example, can be in the nitrate, acetate, carbonate, chloride, soluble complexes of these metals one or more.
Said group VIB metallic compound is selected from one or more in the soluble compound of these metals, for example, can be in molybdate, paramolybdate, tungstates, metatungstate, the ethyl metatungstate one or more.
According to catalyst provided by the invention, before using preferably in the presence of hydrogen, under 140-370 ℃ temperature, carry out presulfurization with sulphur, hydrogen sulfide or sulfur-bearing raw material, this presulfurization can be carried out outside device also can original position sulfuration in device, and the active metal component of its load is converted into the metal sulfide component.
In method for hydrogen cracking provided by the invention, there is no particular limitation to described hydrocracking reaction condition, preferred reaction condition comprises: reaction temperature 200-420 ℃, more preferably 220-400 ℃, hydrogen dividing potential drop 2-18 MPa, 2-15 MPa more preferably, liquid hourly space velocity (LHSV) 0.3-10 hour
-1, more preferably 0.3-5 hour
-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 under the hydrocracking reaction condition with in the catalytic reaction dress of the described catalyst device any, for example, the described fixed bed reactors that are reflected at carry out in moving-burden bed reactor or the 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 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 being selected from crude oil, distillate, solvent-refined oil, slack wax, sweat oil, Fischer-Tropsch synthesis oil, liquefied coal coil, frivolous coal tar and the heavy deasphalted oil one or more.Be particularly suitable for the hydrocracking upgrading of diesel oil or poor ignition quality fuel.
Following example will the present invention will be further described.
Agents useful for same in the example except that specifying, is chemically pure reagent.
Embodiment 1
The present embodiment explanation is fit to preparation the present invention boehmite of carrier and preparation method thereof.
In one 2 liters retort and stream add 1000 ml concns be 48 gram aluminium oxide/liter aluminum trichloride solution and 300 milliliters contain 200 gram aluminium oxide/liter, the causticity coefficient is 1.58, D-sorbite content is 1.82 grams per liters sodium aluminate solution carries out precipitation reaction, reaction temperature 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 aqua ammonia adjusting slurries pH to 10.0 of 5 weight %, and be warming up to 80 ℃, aging 3 hours, filter with vacuum filter then, behind to be filtered the finishing, on filter cake, replenished adding 20 liters of deionized waters (80 ℃ of temperature) flush cake about 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 spray dryer outlet temperature about 2 minutes of dry materials time, obtains hydrated alumina P1 100-110 ℃ of scope after the drying.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 the Scherrer formula: (D is a crystallite dimension to D=K λ/(Bcos θ), λ is the diffraction wavelength of target section bar material, B is the half-peak breadth of corrected diffraction maximum, 2 θ are the position of diffraction maximum) be that grain size that the calculation of parameter at 23-33 ° of peak goes out (120) is D (120), is that the grain size that the calculation of parameter at 34-43 ° of peak goes out (031) is D (031) with 2 θ with 2 θ respectively, and calculate n=D (031)/D (120), characterize the n value that calculates P1 through XRD and list in the table 1.
Embodiment 2
This embodiment is used for explanation and the invention provides boehmite and preparation method thereof.
In one 2 liters retort and stream add 600 ml concns be 96 gram aluminium oxide/liter, wherein contain the aluminum sulfate solution of 3.6 gram ribitol and the ammonia spirit that concentration is 8 weight % and carry 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, adding proper ammonia in slurries, to make the pH value of slurries be 8.5, slurries filtered after under 55 ℃ aging 60 minutes, filter cake washs 2 times with the deionized water making beating, filter cake was through 120 ℃ of dryings 24 hours, 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 the Scherrer formula: (D is a crystallite dimension to D=K λ/(Bcos θ), λ is the diffraction wavelength of target section bar material, B is the half-peak breadth of corrected diffraction maximum, 2 θ are the position of diffraction maximum) be that grain size that the calculation of parameter at 23-33 ° of peak goes out (120) is D (120), is that the grain size that the calculation of parameter at 34-43 ° of peak goes out (031) is D (031) with 2 θ with 2 θ respectively, and calculate n=D (031)/D (120), characterize the n value that calculates P2 through XRD and list in the table 1.
Comparative Examples 1
This Comparative Examples explanation preparation reference catalyst boehmite of carrier and preparation method thereof.
Method according to embodiment 1 prepares boehmite, and different is, aluminum sulfate solution change into concentration be 48 gram aluminium oxide/liter aluminum trichloride solution, and do not contain D-sorbite in the sodium aluminate solution, obtain hydrated alumina DP1.Method according to embodiment 1 adopts XRD to characterize, and DP1 has structure of similar to thin diaspore, characterizes the n value that calculates DP1 through XRD and lists in the table 1.
Comparative Examples 2
Method according to embodiment 2 prepares boehmite, and different is, the aluminum sulfate solution that contains ribitol by concentration be 96 gram aluminium oxide/liter aluminum sulfate solution replace, also be not contain ribitol in the aluminum sulfate solution, obtain hydrated alumina DP2.Method according to embodiment 1 adopts XRD to characterize, and DP2 has structure of similar to thin diaspore, characterizes the n value that calculates DP2 through XRD and lists in the table 1.
Table 1
From the result of table 1 as can be seen, adopt the boehmite of method preparation provided by the invention to have the feature of 1.1≤n≤2.5, preferred 1.2≤n≤2.2, and adopt the method for prior art and the n value of the various boehmites that are obtained commercially at present all less than 1.1.
Embodiment 3～10 explanations Catalysts and its preparation method provided by the invention.
Embodiment 3
The boehmite that the laboratory of 185.7 grams is synthetic (butt 70 heavy %) P1 and 93.3 gram Y zeolite (catalyst Chang Ling branch company of China Petrochemical Industry products, lattice constant 24.53 dusts, butt 75 heavy %) mix, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, wet bar was in 120 ℃ of oven dry 3 hours, 600 ℃ of roastings 4 hours obtain carrier Z1.Get carrier Z1150 gram, flooded 1 hour with the BAS of 133 milliliters of boracic 19.3 grams per liters, 120 ℃ of oven dry, 500 ℃ of roastings 4 hours obtain boracic carrier ZF1.
Get carrier ZF1100 gram, contain WO with 88 milliliters
3422 grams per liters, the ammonium metatungstate of NiO 64.9 grams per liters and nickel nitrate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 3 hours obtained catalyst C1, and the composition after the C1 roasting is listed in table 2.The hydrogenation active metals components contents adopts X fluorescence spectrometry (down together).
Composition after the described roasting is meant that catalyst is formed (down together) in the sample of 550 ℃ of roastings after 4 hours under air atmosphere.
Embodiment 4
Boehmite P2 that the laboratory of 185.7 grams is synthetic (butt 70 heavy %) and 93.3 gram Y zeolite (catalyst Chang Ling branch company of China Petrochemical Industry products, lattice constant 24.53 dusts, butt 75 heavy %) mix, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, wet bar was in 120 ℃ of oven dry 3 hours, 600 ℃ of roastings 4 hours obtain carrier Z2.Get carrier Z2150 gram, flooded 1 hour with the BAS of 155 milliliters of boracic 16.7 grams per liters, 120 ℃ of oven dry, 500 ℃ of roastings 4 hours obtain boracic carrier ZF2.
Get carrier ZF2100 gram, contain WO with 103 milliliters
3360.5 grams per liter, the ammonium metatungstate of NiO 55.4 grams per liters and nickel nitrate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 3 hours obtained catalyst C2, and the composition after the C2 roasting is listed in table 2.
Comparative Examples 3
Boehmite DP1 that the laboratory of 185.7 grams is synthetic (butt 70 heavy %) and 93.3 gram Y zeolite (catalyst Chang Ling branch company of China Petrochemical Industry products, lattice constant 24.53 dusts, butt 75 heavy %) mix, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, wet bar was in 120 ℃ of oven dry 3 hours, 600 ℃ of roastings 4 hours obtain carrier Z3.Get carrier Z3150 gram, flooded 1 hour with the BAS of 155 milliliters of boracic 16.7 grams per liters, 120 ℃ of oven dry, 500 ℃ of roastings 4 hours obtain boracic carrier ZF3.
Get carrier ZF3100 gram, contain WO with 103 milliliters
3360.5 grams per liter, the ammonium metatungstate of NiO 55.4 grams per liters and nickel nitrate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 3 hours obtained catalyst C3, and the composition after the C3 roasting is listed in table 2.
Comparative Examples 4
Boehmite DP2 that the laboratory of 185.7 grams is synthetic (butt 70 heavy %) and 93.3 gram Y zeolite (catalyst Chang Ling branch company of China Petrochemical Industry products, lattice constant 24.53 dusts, butt 75 heavy %) mix, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, wet bar was in 120 ℃ of oven dry 3 hours, 600 ℃ of roastings 4 hours obtain carrier Z4.Get carrier Z4150 gram, with the borated amine solution impregnation of 155 milliliters of boracic 16.7 grams per liters 1 hour, 120 ℃ of oven dry, 500 ℃ of roastings 4 hours obtain boracic carrier ZF4.
Get carrier ZF4100 gram, contain WO with 103 milliliters
3360.5 grams per liter, the ammonium metatungstate of NiO 55.4 grams per liters and nickel nitrate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 3 hours obtained catalyst C4, and the composition after the C4 roasting is listed in table 2.
Comparative Examples 5
Boehmite DP2 that the laboratory of 185.7 grams is synthetic (butt 70 heavy %) and 93.3 gram Y zeolite (catalyst Chang Ling branch company of China Petrochemical Industry products, lattice constant 24.53 dusts, butt 75 heavy %) mix, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, wet bar was in 120 ℃ of oven dry 3 hours, 600 ℃ of roastings 4 hours obtain carrier Z5.Get carrier Z5150 gram, flooded 1 hour with the BAS of 155 milliliters of boracic 16.7 grams per liters, 120 ℃ of oven dry, 500 ℃ of roastings 4 hours obtain boracic carrier ZF5.
Get carrier ZF5100 gram, contain WO with 103 milliliters
3360.5 grams per liter, the ammonium metatungstate of NiO 55.4 grams per liters, nickel nitrate and 12.95 gram citric acid mixed solutions dippings 1 hour, in 120 ℃ of oven dry 2 hours, 150 ℃ of dryings 3 hours obtained catalyst C5.Wherein, organic compound be 0.3 in the nickel of oxide and the mol ratio of tungsten sum, the composition after the C5 roasting is listed in table 2.
Embodiment 5
Boehmite P1 that the laboratory of 245.5 grams is synthetic and 13.5 gram Y zeolite (catalyst Chang Ling branch company of China Petrochemical Industry products, lattice constant 24.59 dusts, butt 74 heavy %) mix, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, wet bar was in 120 ℃ of oven dry 3 hours, 600 ℃ of roastings 4 hours obtain carrier Z6.Get carrier Z6150 gram, flooded 1 hour with the BAS of 128 milliliters of boracic 17.0 grams per liters, 120 ℃ of oven dry, 480 ℃ of roastings 4 hours obtain boracic carrier ZF6.
Get carrier ZF6100 gram, contain WO with 85 milliliters
3478.8 grams per liter, NiO 54.7 grams per liters, the mixed solution of ammonium metatungstate, nickel nitrate and the ethylene glycol of ethylene glycol 162.3 grams per liters dipping 1 hour, in 120 ℃ of oven dry 2 hours, 150 ℃ of dryings 3 hours obtained catalyst C6.Wherein, organic compound be 0.20 in the nickel of oxide and the mol ratio of tungsten sum, form after the C6 roasting and list in table 2.
Embodiment 6
Boehmite P2 that the laboratory of 114.3 grams is synthetic and 160 gram Y zeolite (catalyst Chang Ling branch company of China Petrochemical Industry products, lattice constant 24.57 dusts, butt 75 heavy %) mix, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, wet bar was in 120 ℃ of oven dry 3 hours, 600 ℃ of roastings 4 hours obtain carrier Z7.Get carrier Z7150 gram, flooded 1 hour with the BAS of 130 milliliters of boracic 17.1 grams per liters, 120 ℃ of oven dry, 450 ℃ of roastings 4 hours obtain boracic carrier ZF7.
Get carrier ZF7100 gram, contain WO with 87 milliliters
3458.4 grams per liter, NiO 47.5 grams per liters, MoO
342.4 grams per liter, the mixed aqueous solution of ammonium metatungstate, nickel nitrate, ammonium molybdate and the citric acid of citric acid 182.6 grams per liters dipping 1 hour, in 120 ℃ of oven dry 2 hours, 180 ℃ of roastings 3 hours obtained catalyst C7.Wherein, organic compound is 0.36 with mol ratio in nickel, molybdenum and the tungsten sum of oxide, forms after the C7 roasting and lists in table 2.
Embodiment 7
The boehmite P1 that the laboratory of 185.7 grams is synthetic, 38.5 gram N values are 0.4 silica-alumina (catalyst Chang Ling branch company of China Petrochemical Industry product, butt 78 heavy %) with 53.3 gram Y zeolite (catalyst Chang Ling branch company of China Petrochemical Industry products, lattice constant 24.53 dusts, butt 75 heavy %) mix, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, wet bar is in 120 ℃ of oven dry 3 hours, and 600 ℃ of roastings 4 hours obtain carrier Z8.Get carrier Z8150 gram, flooded 1 hour with the BAS of 131 milliliters of boracic 26.5 grams per liters, 120 ℃ of oven dry, 500 ℃ of roastings 4 hours obtain boracic carrier ZF8.
Get carrier ZF8100 gram, contain WO with 87 milliliters
3399.1 grams per liter, the ammonium metatungstate of NiO 47.9 grams per liters and nickel nitrate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 3 hours obtained catalyst C8, form after the C8 roasting and list in table 2.
Embodiment 8
The boehmite P1 that the laboratory of 85.7 grams is synthetic, 76.9 gram N values are 0.6 silica-alumina (catalyst Chang Ling branch company of China Petrochemical Industry product, butt 78 heavy %) with 106.7 gram Y zeolite (catalyst Chang Ling branch company of China Petrochemical Industry products, lattice constant 24.53 dusts, butt 75 heavy %) mix, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, wet bar is in 120 ℃ of oven dry 3 hours, and 600 ℃ of roastings 4 hours obtain carrier Z9.Get carrier Z9150 gram, flooded 1 hour with the BAS of 131 milliliters of boracic 40.8 grams per liters, 120 ℃ of oven dry, 470 ℃ of roastings 4 hours obtain boracic carrier ZF9.
Get carrier ZF9100 gram, contain WO with 87 milliliters
3513.1 grams per liter, the ammonium metatungstate of NiO 47.9 grams per liters and nickel nitrate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 3 hours obtained catalyst C9, form after the C9 roasting and list in table 2.
Embodiment 9
The boehmite P1 that the laboratory of 85.7 grams is synthetic, 76.9 gram N values are 0.6 silica-alumina (catalyst Chang Ling branch company of China Petrochemical Industry product, butt 78 heavy %) with 106.7 gram Y zeolite (catalyst Chang Ling branch company of China Petrochemical Industry products, lattice constant 24.53 dusts, butt 75 heavy %) mix, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, wet bar is in 120 ℃ of oven dry 3 hours, and 600 ℃ of roastings 4 hours obtain carrier Z10.Get carrier Z10150 gram, flooded 1 hour with the ammonium fluoride solution of 131 milliliters of fluorine-containing 30.6 grams per liters, 120 ℃ of oven dry, 470 ℃ of roastings 4 hours obtain fluorine-containing carrier ZF10.
Get carrier ZF10100 gram, contain WO with 87 milliliters
3513.1 grams per liter, the ammonium metatungstate of NiO 47.9 grams per liters and nickel nitrate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 3 hours obtained catalyst C10, form after the C10 roasting and list in table 2.
Table 2
Embodiment 10-11
Following example illustrates method provided by the invention and effect thereof.
With density is 0.9058 gram per centimeter
3, sulfur content is that 3800ppm, nitrogen content are 501ppm, and Cetane number is that 28.7 catalytic cracking diesel oil is a raw material, estimates the performance of catalyst C1 provided by the invention, C2 on 30 milliliters of fixed bed devices, and the catalyst loading amount is 20 milliliters.Before advancing feedstock oil catalyst is carried out presulfurization, conditions of vulcanization is: 110 ℃ were vulcanized 2 hours, and 300 ℃ were vulcanized 4 hours, and sulfurized oil is the kerosene that contains 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 Examples 6-8
According to the performance of example 10 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 | 10 | 11 | Comparative Examples 6 | Comparative Examples 7 | Comparative Examples 8 |
| Catalyst | C?1 | C2 | C3 | C4 | C5 |
| The Cetane number value added | 11.5 | 10.3 | 8.4 | 9.0 | 9.6 |
| Diesel yield, % | ＞95 | ＞95 | ＞95 | ＞95 | ＞95 |
The result that table 3 provides shows, compares with existing catalyst, and diesel cetane-number is had bigger increase rate.
Claims (17)
1. hydrocracking catalyst, this catalyst contains carrier, at least a metal component that is selected from VIII family, at least a metal component and auxiliary agent boron or the fluorine that is selected from group vib, wherein, described carrier contains solid acid component and aluminium oxide, it is characterized in that, described aluminium oxide is that a kind of boehmite by 1.1≤n≤2.5 transforms the gama-alumina that obtains, n=D (031)/D (120) wherein, 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 is meant that 2 θ in the XRD spectra are 34-43 ° peak, described 120 peaks are meant that 2 θ in the XRD spectra are 23-33 ° peak, D=K λ/(Bcos θ), λ is the diffraction wavelength of target section bar material, B is the half-peak breadth of corrected diffraction maximum, and 2 θ are the position of diffraction maximum.
2. catalyst according to claim 1 is characterized in that, described aluminium oxide is that a kind of boehmite by 1.2≤n≤2.2 transforms the gama-alumina that obtains.
3. catalyst according to claim 1 is characterized in that, is benchmark with described carrier, and the content of aluminium oxide is 5-99.5 weight % in the described carrier, and the content of solid acid component is 0.5-95 weight %.
4. catalyst according to claim 3 is characterized in that, is benchmark with described carrier, and the content of aluminium oxide is 20-99 weight % in the described carrier, and the content of solid acid component is 1-80 weight %.
5. catalyst according to claim 1, it is characterized in that, with described catalyst is benchmark, described catalyst contains the carrier of 50-90 weight %, in simple substance, boron or the fluorine of 0.5-5 weight % are in oxide, the VIII family metal component of 1-8 weight %, the VI B family metal component of 5-38 weight %.
6. catalyst according to claim 5, it is characterized in that, with described catalyst is benchmark, described catalyst preferably contains the carrier of 60-85 weight %, in simple substance, boron or the fluorine of 1-4 weight % are in oxide, 1.5-6 the VIII family metal component of weight %, the VI B family metal component of 10-35 weight %.
7. according to claim 1,3 or 4 described catalyst, it is characterized in that described solid acid component is selected from one or more in silica-alumina and the molecular sieve.
8. catalyst according to claim 7 is characterized in that, described solid acid component is selected from one or more in zeolite molecular sieve with faujasite structure, Beta, ZSM-5, the mordenite molecular sieve.
9. catalyst according to claim 8 is characterized in that, described molecular screening is from the y-type zeolite molecular sieve with faujasite structure.
10. catalyst according to claim 9, it is characterized in that described y-type zeolite molecular screening 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.
11. catalyst according to claim 8 is characterized in that, described solid acid component is a 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 N value with silica-alumina of structure of similar to thin diaspore is 0.1-1, and described N=Q1/Q2, Q1 are the solid of described silica-alumina
27Chemical shift is the peak area at 60 ± 0.1-0.2ppm place in the Al NMR spectrogram, and Q2 is the solid of described silica-alumina
27Chemical shift is the peak area at 5 ± 0.1-0.2ppm place in the Al NMR spectrogram.
27The chemical shift at each peak and each peak area are that reference is measured with saturated aluminum sulfate aqueous solution on VarianUnityInova 300M type nuclear magnetic resonance spectrometer in the Al NMR spectrogram.
14. catalyst according to claim 13 is characterized in that, described N value with silica-alumina of structure of similar to thin diaspore is 0.2-0.8.
15. catalyst according to claim 1, it is characterized in that, described catalyst contains one or more the organic matter that is selected from organic alcohol, organic acid, the organic amine, described organic compound be 0.03-2 in the group VIII of oxide and the mol ratio of group vib metal component sum.
16. catalyst according to claim 15, it is characterized in that, described organic alcohol is selected from ethylene glycol, glycerine, polyethylene glycol (molecular weight is 200-1500), diethylene glycol, butanediol, organic acid is selected from acetate, 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 be 0.08-1.5 in the group VIII of oxide and the mol ratio of group vib metal component sum.
17. a hydrocarbon oil hydrogenation cracking method is included under the hydrocracking reaction condition, with hydrocarbon ils and catalyst haptoreaction, it is characterized in that, described catalyst is any described catalyst of claim 1-16.
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| 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 |
| EP1826178A1 (en) * | 2004-11-22 | 2007-08-29 | Idemitsu Kosan Co., Ltd. | Iron-containing crystalline aluminosilicate, hydrocracking catalyst comprising the aluminosilicate, and method of hydrocracking with the catalyst |
| CN101332430A (en) * | 2007-06-27 | 2008-12-31 | 中国石油化工股份有限公司 | Heavy oil hydrogenating treatment catalyst and preparation method thereof |
| CN101618326A (en) * | 2008-06-30 | 2010-01-06 | 中国石油化工股份有限公司 | Heavy oil hydrogenation processing catalyst and method for preparing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1826178A1 (en) * | 2004-11-22 | 2007-08-29 | Idemitsu Kosan Co., Ltd. | Iron-containing crystalline aluminosilicate, hydrocracking catalyst comprising the aluminosilicate, and method of hydrocracking with the catalyst |
| 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 |
| CN101332430A (en) * | 2007-06-27 | 2008-12-31 | 中国石油化工股份有限公司 | Heavy oil hydrogenating treatment catalyst and preparation method thereof |
| CN101618326A (en) * | 2008-06-30 | 2010-01-06 | 中国石油化工股份有限公司 | Heavy oil hydrogenation processing catalyst and method for preparing same |
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