CN102188991B - Hydrotreating catalyst and application thereof - Google Patents
Hydrotreating catalyst and application thereof Download PDFInfo
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- CN102188991B CN102188991B CN 201010117568 CN201010117568A CN102188991B CN 102188991 B CN102188991 B CN 102188991B CN 201010117568 CN201010117568 CN 201010117568 CN 201010117568 A CN201010117568 A CN 201010117568A CN 102188991 B CN102188991 B CN 102188991B
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Abstract
The invention discloses a hydrotreating catalyst and application thereof. The hydrotreating catalyst contains a carrier, at least one metal component selected from the VIII family and at least one metal component selected from the VIB family, wherein the carrier contains solid acid components and alumina, characterized in that the alumina is the gamma-alumina obtained by converting at least two pseudoboehmites P1 and P2, wherein P1 is the pseudoboehmite meeting 1.1<=n1<= 2.5; P2 is the pseudoboehmite meeting 0.8<n2<1.1, wherein n(1 or 2) is equal to D(1 or 2)(031)/D(1 or 2)(120), D(1 or 2) (031) represents the grain size of a crystal face represented by a (031) peak in the XRD (X-Ray Diffraction) spectrogram of the P1 or P2 pseudoboehmites, and D(1 or 2) (120) represents the grain size of a crystal face represented by a (120) peak in the XRD (X-Ray Diffraction) spectrogram of the P1 or P2 pseudoboehmite crystalline grains; the 031 peak is the peak with the 2theta of 34-43 degrees in the XRD spectrogram, and the 120 peak is the peak with the 2theta of 23-33 degrees in the XRD spectrogram; and D is equal to K lambda/(Bcos theta), wherein lambda is the diffraction wavelength of a target material, B is the halfpeak breadth of a corrected diffraction peak, and 2theta is the position of the diffraction peak. Compared with the prior art, the hydrotreating performance of the catalyst provided by the invention is obviously improved.
Description
Technical field
The present invention is about a kind of hydrotreating catalyst and application thereof.
Background technology
Under hydrogenation conditions, hydrocarbon feed contacts with catalyst and may comprise: the reactions such as hydrodesulfurization, hydrodenitrogeneration, HDM, hydrocracking.Wherein the performance of catalyst is to the upgrading effect of hydrocarbon feed, the effect of selectively playing key of target product.
A class hydrotreating catalyst that is widely used in upgrading hydrocarbon oil with the catalyst that contains the carrier loaded hydrogenation active metals component preparation of porous heat-resistant inorganic oxide (such as aluminium oxide), solid acid (such as molecular sieve).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 fluorine 0.5-5.0 heavy %, nickel oxide 2.5-5.0, all the other are carrier.This carrier is comprised 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 with NH3-TPD method mensuration.This catalyst has selective to middle distillate higher than prior art when having good desulfurization, denitrification activity.
CN1054150C discloses a kind of catalyst for hydrocracking diesel oil, and the carrier that this catalyst is comprised of aluminium oxide, amorphous aluminum silicide and molecular sieve and the hydrogenation active metals that loads on this carrier form 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 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 ml/g; 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 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 are the heavy % of 2-15.
US5,030,780 disclose a kind of saturation process of aromatic compound, the method has been used a kind of catalyst, described catalyst contains the hydrogenation metal that loads on a kind of carrier, described catalyst carrier contains a kind of zeolite and a kind of porous heat-resistant inorganic oxide, particularly contain the heat-resistant inorganic oxide that is dispersed in the silicon-aluminium in the alumina host, described zeolite comprises known nature or artificial synthetic various crystalline silico-alumino zeolites, such as faujasite, modenite, the Erionite zeolite, y-type zeolite, the X-type zeolite, the L zeolite, omega zeolite, the ZSM-4 zeolite, Beta zeolite etc.
For the hydrotreating 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 hydrotreating catalyst of performance and application thereof are provided.
The present inventor finds under study for action, for the hydrotreating 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 Kaolinite Preparation of Catalyst that adopts this type of, during particularly for the preparation of the catalyst of poor-quality diesel-oil by cut fraction oil hydrotreatment, its performance can not finely meet the demands.
The invention provides a kind of hydrotreating catalyst, this catalyst contains carrier and at least a VIII of being selected from family and at least a metal component that is selected from group vib, described carrier contains solid acid component and aluminium oxide, it is characterized in that, described aluminium oxide is a kind of gama-alumina that is obtained by at least two kinds of boehmite P1 and P2 conversion, wherein, P1 is 1.1≤n
1≤ 2.5 boehmite, P2 are 0.8＜n
2＜1.1 boehmite; n
(1 or 2)=D
(1 or 2)(031)/D
(1 or 2)(120), described D
(1 or 2)(031) crystallite dimension of the crystal face of (031) peak representative in the XRD spectra of expression P1 or P2 boehmite crystal grain, D
(1 or 2)(120) crystallite dimension of the place crystal face at (120) peak in the XRD spectra of expression P1 or P2 boehmite crystal grain, D=K λ/(Bcos θ), λ is the diffraction wavelength of target shaped material, and 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 method for hydrotreating hydrocarbon oil, is included under the hydrotreatment reaction condition, with 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, compare with the catalyst for hydrogenation treatment of diesel oil that existing method provides, the catalyst that the inventive method provides can make the diesel cetane-number increase rate have a more substantial increase.
The specific embodiment
According to catalyst provided by the invention, wherein said aluminium oxide is a kind of gama-alumina that is obtained by at least two kinds of boehmite P1 and P2 conversion.Wherein, P1 is 1.1≤n
1≤ 2.5 boehmite, P2 are 0.8＜n
1＜1.1 boehmite; n
(1 or 2)=D
(1 or 2)(031)/D
(1 or 2)(120), described D
(1 or 2)(031) crystallite dimension of the crystal face of (031) peak representative in the XRD spectra of expression P1 or P2 boehmite crystal grain, D
(1 or 2)(120) crystallite dimension of the place crystal face at (120) peak in the XRD spectra of expression P1 or P2 boehmite crystal grain.Described 031 peak refers to that 2 θ in the XRD spectra are 34-43 ° peak, described 120 peaks refer to that 2 θ in the XRD spectra are 23-33 ° peak, the D value is obtained by following formula, D=K λ/(Bcos θ), K is the Scherrer constant, λ is the diffraction wavelength of target shaped 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, when calculating D (031), D (031)=K λ/(Bcos θ), wherein B is the half-peak breadth of 031 diffraction maximum, and 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.
Preferred described P1 is 1.2≤n
1≤ 2.2 boehmite, P2 are 0.85≤n
2≤ 1.05 boehmite.Take described carrier as benchmark, the content of aluminium oxide is the 5-99.5 % by weight described in preferred embodiment, more preferably the 20-99 % by weight.
Satisfying under the non-vanishing prerequisite of P1, P2, the present invention is not particularly limited the mixing ratio of described P1 and P2.The consumption of preferred described P1 and P2 makes that the weight ratio of P1 and P2 is 40: 60～95: 5 in mixed boehmite, more preferably 45: 55～80: 20.
According to catalyst provided by the invention, wherein, P2 can be commodity or the boehmite that adopts any one prior art preparation.
Described have 1.1≤n
1The preparation method of the boehmite P1 of≤2.5 feature 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; Hydrated alumina obtained above 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, can make like this n of gained boehmite P1
1At preferred 1.2≤n
1In≤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 % 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 the selective hydrolysis reaction; The consumption of grain growth conditioning agent is the inorganic 0.5-10 % by weight that contains al reactant weight in the described precipitation reaction, more preferably 1-8.5 % by weight, further preferred 5-8.5 % by weight; In the described ageing process, the consumption of grain growth conditioning agent can be preferably the 1-8.5 % by weight for the 0.5-10 % by weight of hydrated alumina weight, further preferred 5-8.5 % by weight.Unless stated otherwise, among the present invention, the consumption of described grain growth conditioning agent respectively in organic aluminum contained compound, inorganic aluminum contained compound and the hydrated alumina weight of corresponding aluminium oxide calculate as benchmark.Also be, in aluminium oxide, in the 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 the 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 the described ageing process, the consumption of described grain growth conditioning agent is the 0.5-10 % by 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 crystal grain at the material of 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 after the two kinds or more of mixing.Described aluminate solution is aluminate solution arbitrarily, such as sodium aluminate solution and/or potassium aluminate.Because its acquisition is easy and price is low, preferred sodium aluminate solution.Aluminate solution also can be used alone or as a mixture.
Concentration to described aluminum salt solution and/or aluminate solution is not particularly limited, and preferably counts the 0.2-1.1 mol/L with aluminium oxide.
Described acid can be various Bronsted acids or be acid oxide in aqueous medium, for example, can be one or more in sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid, the oxalic acid, preferred Bronsted acid be selected from one or more in nitric acid, sulfuric acid, the 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, preferred H
+Concentration be the 0.2-2 mol/L.
Described aqueous slkali can be hydrolyzed for hydroxide or in aqueous medium the salt that makes the aqueous solution be alkalescence, and 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/L.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 the reaction with steeping in water for reconstitution unboiled water solution, in the aluminum alkoxide of generation aqua oxidation aluminum precipitation one or more for example can be one or more in aluminium isopropoxide, isobutanol aluminum, aluminium isopropoxide, three tert-butoxy aluminium and the isooctanol aluminium.Described organic aluminum contained compound and water consumption ratio are not particularly limited, and the preferred water yield is greater than the required amount of stoichiometry.
In 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 occurs, and the concrete condition that hydrolysis occurs 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 to 7-10, then under suitable temperature, wear out.Then separate, 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 such 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 P1 of the present invention, a preferred embodiment 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; The hydrated alumina slurries that also 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.
Described solid acid component can be selected from the silica-alumina that is commonly used for the cracking activity component and one or more in the molecular sieve.
Wherein, described molecular sieve can be the zeolite with macroporous structure, as the zeolite with faujasite, Beta zeolite, omega zeolite structure, it can be the 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 the zeolite with small structure also, as have the zeolite of Erionite zeolite, ZSM-34 zeolite structure.Preferred solid acid component is zeolite molecular sieve with faujasite structure, has the zeolite structured zeolite molecular sieve of Beta, has the zeolite molecular sieve of ZSM-5 structure, the zeolite molecular sieve with mordenite structure and one or more in the silica-alumina.Described zeolite with faujasite structure is preferably y-type zeolite, further USY, the rare-earth type Y zeolite REY of preferred HY zeolite, part amorphization wherein, rare-earth type HY zeolite REHY, overstable gamma zeolite USY, rare-earth type overstable gamma zeolite REUSY, the Y zeolite of titaniferous, phosphorous Y and super steady one or more that reach in HY type zeolite, the dealuminium Y type beta stone.
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.
27Each peak area of chemical shiftsum at each peak is measured take saturated aluminum sulfate aqueous solution as reference 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 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 for the present invention.
The method of an aforesaid silica-alumina of preferred preparation 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 become 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.
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 the oxide that is acidity in aqueous medium, and preferred Bronsted acid is selected from one or more in nitric acid, sulfuric acid, the hydrochloric acid; Preferred oxide is 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 the 5-60 % by weight in the final silica-alumina, are preferably the 10-45 % by weight.
Described silicon-containing compound can be any water-soluble silicon-containing compound and can be hydrolyzed the silicon-containing compound that forms silicon gel, colloidal sol in aqueous medium.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, take described carrier as benchmark, the content of solid acid component is the 0.5-95 % by weight described in preferred embodiment, more preferably the 1-80 % by weight.
According to catalyst provided by the invention, wherein 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, the group vib metal component is molybdenum and/or tungsten.
According to catalyst provided by the invention, take described catalyst as benchmark, described catalyst preferably contains the carrier of 1-90 % by weight, the VIII family metal component of 1-10 % by weight, the group vib metal component of 5-35 % by weight; Further preferred catalyst contains the carrier of 1-85 % by weight, the VIII family metal component of 1.5-5 % by weight, the group vib metal component of 6-30 % by weight.
Catalyst provided by the invention can adopt the usual method preparation of the art, and for example, described preparation method comprises: the preparation carrier, and to this carrier at least a VIII of being selected from family of introducing and at least a metal component that is selected from group vib.
Wherein said carrier is obtained through mixing and roasting by at least two kinds of boehmite P1, P2 and solid acid component.Described mixing can adopt arbitrarily technology well known in the art to carry out.For example, can be in mixer, grinder directly incite somebody to action at least two kinds of boehmite P1, P2 and solid acid component is mixed by the mode that stirs; Can be enough to incite somebody to action at least two kinds of boehmite P1, P2 and solid acid component and water mixing under the condition of pulp, afterwards filtration, drying or moist method are carried out.The consumption of each component in described mixed process is so that in the final carrier, take described carrier as benchmark, the content of aluminium oxide is the 5-99.5 % by weight in preferred embodiment, the content of solid acid component is the 0.5-95 % by weight, further the content of preferential oxidation aluminium is the 20-99 % by weight, and the content of solid acid component is the 1-80 % by 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, such as being microballoon, sphere, tablet or bar shaped etc.This moulding can method routinely be carried out, for example, and with solid acid component, boehmite P1 and P2 mixing, extruded moulding, the dry also method of roasting.When the extrusion molding of carrier, can in carrier, add an amount of 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, the PVOH.Described drying is conventional method, carries out drying as adopting baking oven, mesh-belt kiln and fluid bed, when adopting heating means to carry out drying, preferred baking temperature is 50-200 ℃, 0.3-6 hour drying time, further preferred baking temperature is 60-150 ℃, and be 0.5-2 hour drying time.The method of described roasting and condition are conventional method and the condition that the catalyst carrier preparation is adopted, as adopt mesh-belt kiln, vertical examination stove and converter to carry out roasting, the condition of described roasting is preferably, at 400-900 ℃ roasting temperature 1-12 hour, further preferably 500-750 ℃ roasting temperature 2-8 hour.
One preferred embodiment in, the preparation method of described carrier comprises:
(1) is being enough under the condition of pulp described 1.1≤n
1≤ 2.5 boehmite P1, n
2＜1.1 boehmite P2, solid acid component and water mix, and afterwards filtration, dry or moist obtains a kind of composition;
(2) with the extrusion molding on banded extruder of step (1) resulting composition;
(3) step (2) gained extrusion molding thing is dry and roasting.
Wherein, be to guarantee carrying out smoothly of extruded moulding, comprise the step of introducing an amount of water, peptizing agent (as be selected from nitric acid, acetic acid and the citric acid one or more), extrusion aid (as being in sesbania powder, the cellulose one or more) in the described composition and mixing in step (2).When extrusion molding, the kind of the consumption of described water and described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, do not repeat them here.Described drying is conventional method, carries out drying as adopting baking oven, mesh-belt kiln and fluid bed, when adopting heating means to carry out drying, preferred baking temperature is 50-200 ℃, 0.3-12 hour drying time, further preferred baking temperature is 60-150 ℃, and be 0.5-8 hour drying time.The method of described roasting and condition are conventional method and the condition that the catalyst carrier preparation is adopted, as adopt mesh-belt kiln, vertical heater and converter to carry out roasting, the condition of described roasting is preferably, at 400-900 ℃ roasting temperature 1-12 hour, further preferably 500-750 ℃ roasting temperature 2-8 hour.
Another preferred embodiment in, the article shaped preparation method of described carrier comprises:
(1) at kneading machine with described 1.1≤n
1≤ 2.5 boehmite P1, n
2＜1.1 boehmite P2 mixes with solid acid component, obtains a kind of composition;
(2) with the extrusion molding on banded extruder of step (1) resulting composition;
(3) step (2) gained extrusion molding thing is dry and roasting.
Wherein, be to guarantee carrying out smoothly of extruded moulding, comprise in step (1) and introduce an amount of water, peptizing agent (as be selected from nitric acid, acetic acid and the citric acid one or more), extrusion aid (as being in sesbania powder, the cellulose one or more).When extrusion molding, the kind of the consumption of described water and described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, do not repeat them here.Described drying is conventional method, carries out drying as adopting baking oven, mesh-belt kiln and fluid bed, when adopting heating means to carry out drying, preferred baking temperature is 50-200 ℃, 0.3-12 hour drying time, further preferred baking temperature is 60-150 ℃, and be 0.5-8 hour drying time.The method of described roasting and condition are conventional method and the condition that the catalyst carrier preparation is adopted, as adopt mesh-belt kiln, vertical heater and converter to carry out roasting, the condition of described roasting is preferably, at 400-900 ℃ roasting temperature 1-12 hour, further preferably 500-750 ℃ roasting temperature 2-8 hour.
The method of at least a group VIII of described introducing and at least a group vib metal component, can be to contact with described carrier after the group vib metallic compound is mixed with mixed solution with at least a being selected from containing at least a group VIII, such as the method by dipping; Can be to contact with described carrier after being selected from the independent obtain solution of group vib metallic compound with at least a containing at least a group VIII, described contact procedure can realize by any method, for example infusion process.Described dipping method can adopt conventional method.According to the present invention, by the regulation and control to concentration, consumption or the carrier consumption of the solution of metallic components, can prepare the described catalyst of specifying content, it is intelligible that this is that those skilled in the art hold.
According to the present invention, after described impregnation steps is finished, optionally can carry out drying, calcination steps.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 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, the ethyl metatungstate.
Can also contain in the catalyst provided by the invention and be selected from one or more the organic compound that contains in oxygen or the organic compounds containing nitrogen, preferred oxygen-containing organic compound is selected from one or more in Organic Alcohol and the organic acid; Preferred organic compounds containing nitrogen is selected from one or more in the 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, in 2-CDTA, citric acid, tartaric acid, the malic acid one or more, organic compounds containing nitrogen can be ethylenediamine, EDTA and ammonium salt thereof.Described organic compound with take the mol ratio of the group VIII of oxide and group vib metal component sum as 0.03-2, be preferably 0.08-1.5.
When 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 impregnated carrier behind the mixed solution, dry method then; And the method that organic compound is mixed with separately impregnated carrier behind the solution.In rear a kind of method, preferred at first introducing contains the solution of other components to flood described carrier, and drying, roasting or not roasting are afterwards again with this carrier of solution impregnation that contains organic compound and dry method.Described drying can adopt customary way to carry out, and there is no particular limitation, is preferably 100-300 ℃ such as baking temperature, is preferably 1-12 hour drying time, and further preferred baking temperature is 100-250 ℃, and be 2-8 hour drying time.The condition of described roasting also is 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, when preparation contains the described catalyst of organic compound, preferably by selecting the introducing amount of described organic compound, and so that in the final catalyst organic compound with take the mol ratio of nickel, molybdenum and the tungsten sum of oxide as 0.03-2.0, be preferably 0.08-1.5.
According to catalyst provided by the invention, can also contain the material that any material that does not affect the catalytic performance that the invention provides catalyst maybe can improve the catalytic performance of catalyst provided by the invention.As introducing in the components such as phosphorus, titanium or silicon one or both, in element and take catalyst as benchmark, the introducing amount of above-mentioned auxiliary agent is the 0-10 % by weight, is preferably the 0.5-5 % by weight.
During one or both components in also containing components such as being selected from phosphorus, titanium or silicon in the described catalyst, the described introducing method that is selected from the components such as phosphorus, titanium or silicon can be method arbitrarily, as can be that compound with auxiliary agent as described in containing directly mixes with solid acid component, boehmite P1, P2, moulding and roasting; Can be the compound that to contain described auxiliary agent and contact with described carrier after the compound that contains the hydrogenation active metals component is mixed with mixed solution; Can also be to contact and roasting with described carrier behind the independent obtain solution of the compound that contains auxiliary agent.When auxiliary agent and hydrogenation active metals are introduced described carrier respectively, preferably at first auxiliary compound solution contacts with described carrier and roasting with containing, contact with the solution of the compound that contains the hydrogenation active metals component more afterwards, for example pass through 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 the conventional method in this area, described hydrotreating catalyst is before using, usually can be 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 another embodiment, the invention still further relates to the application of described catalyst in hydrocarbon oil hydrogenation is processed.Described hydrotreatment is included under hydrogen existence and the hydrotreatment reaction condition, and hydrocarbon oil feed is contacted with aforementioned hydrogenation catalyst of the present invention.
In hydrotreating method provided by the invention, to described hydroconversion condition without any special restriction, can adopt common reaction condition, for example can enumerate reaction temperature 200-420 ℃, more preferably 220-400 ℃, pressure 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 hydrotreatment reaction can be enough to make described feedstock oil to carry out under the hydrotreatment reaction condition with in the catalytic reaction dress of the described catalyst device any, for example, at described fixed bed reactors, carry out in moving-burden bed reactor or the fluidized bed reactor.
Adopt hydrotreating method 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 be 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 hydro-upgrading of diesel oil or poor ignition quality fuel.
The present invention will be further described for following example.
Agents useful for same in the example except specifying, is chemically pure reagent.
The preparation of the boehmite P2 of boehmite P1, the n of employed 1.1≤n≤2.5＜1.1 and source thereof are (except the commodity boehmite in the embodiment of the invention, if when the actual amount of other samples once prepares obtainable amount above following method, can repeat to prepare according to correlation method):
P1-1, adopt following method preparation:
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 be 80 ℃, conditioned reaction logistics capacity so that in and the pH value be 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 % by weight, and be warming up to 80 ℃, aging 3 hours, then filter with vacuum filter, to be filtered complete after, replenish to add 20 liters of deionized waters (80 ℃ of temperature) flush cake approximately 30 minutes at filter cake.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 approximately 2 minutes dry materials time, obtains hydrated alumina P1-1 100-110 ℃ of scope after the drying.Adopt XRD to characterize, P1-1 has structure of similar to thin diaspore.
XRD measures at 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 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 is D (031) as D (120), the calculation of parameter at ° peak goes out (031) take 2 θ as 34-43 grain size, and calculating n=D (031)/D (120), the n value that characterizes, calculates P1-1 through XRD is listed in the table 1.
P1-2, adopt following method preparation:
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 % by 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 filter after 55 ℃ of lower wearing out 60 minutes, filter cake washs 2 times with the deionized water making beating, through 120 ℃ of dryings 24 hours, obtain hydrated alumina P1-2, adopt XRD to characterize, P1-2 has structure of similar to thin diaspore, and the n value that calculates P1-2 is listed in (the XRD characterizing method is with embodiment 1) in the table 1.
P2-1, adopt following method preparation:
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 P2-1.Method according to embodiment 1 adopts XRD to characterize, and P2-1 has structure of similar to thin diaspore, and the n value that characterizes, calculates P2-1 through XRD is listed in (the XRD characterizing method is with embodiment 1) in the table 1.
P2-2, adopt following method preparation:
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 P2-2.Method according to embodiment 1 adopts XRD to characterize, and P2-2 has structure of similar to thin diaspore, and the n value that characterizes, calculates P2-2 through XRD is listed in (the XRD characterizing method is with embodiment 1) in the table 1.
P2-3 is the commodity boehmite (SD powder) that Shandong Aluminum Plant produces, and the n value that characterizes, calculates P2-3 through XRD is listed in (the XRD characterizing method is with embodiment 1) in the table 1.
P2-4 is the commodity boehmite (Yantai powder) that Yantai aluminium manufacturer produces, and the n value that characterizes, calculates P2-4 through XRD is listed in (the XRD characterizing method is with embodiment 1) in the table 1.
Table 1
* take the commercial SB powder of Condea company as benchmark, record the degree of crystallinity of each sample.
Embodiment 1-8 illustrates catalyst provided by the invention and preparation thereof.
Embodiment 1
With the P1-1 (butt is 70 heavy %) of 139.3 grams and the P2-1 (butt is 70 heavy %) and 93.3 gram Y zeolite (catalyst Chang Ling branch company products of 46.4 grams, 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.Carrier forms as shown in table 2.
Get carrier Z1 100 grams, contain WO with 90 milliliters
3413 grams per liters, the ammonium metatungstate of NiO 63.5 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.Take catalyst as benchmark, the composition after the roasting of C1 catalyst is as shown in table 3.
Embodiment 2
P1-1 and 65 gram P2-2 (butt is 70 heavy %) and 93.3 gram Y zeolite (catalyst Chang Ling branch company products with 120.7 grams, 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.Carrier forms as shown in table 2.
Get carrier Z2 100 grams, contain WO with 90 milliliters
3413 grams per liters, the ammonium metatungstate of NiO 63.5 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.Take catalyst as benchmark, the composition after the roasting of C2 catalyst is as shown in table 3.
Embodiment 3
P1-1 and 74.3 gram P2-3 (butt is 70 heavy %) and 93.3 gram Y zeolite (catalyst Chang Ling branch company products with 111.4 grams, 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.Carrier forms as shown in table 2.
Get carrier Z3 100 grams, contain WO with 90 milliliters
3413 grams per liters, the ammonium metatungstate of NiO 63.5 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.Take catalyst as benchmark, the composition after the roasting of C3 catalyst is as shown in table 3.
Embodiment 4
P1-2 (butt is 70 heavy %) and 83.6 gram P2-4 (butt is 70 heavy %) and 93.3 gram Y zeolite (catalyst Chang Ling branch company products with 102.1 grams, 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.Carrier forms as shown in table 2.
Get carrier Z4 100 grams, contain WO with 90 milliliters
3413 grams per liters, the ammonium metatungstate of NiO 63.5 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.Take catalyst as benchmark, the composition after the roasting of C4 catalyst is as shown in table 3.
Embodiment 5
P1-2 and 59.7 gram P2-1 and 13.5 gram Y zeolite (catalyst Chang Ling branch company products with 211.7 grams, 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 Z5.Carrier forms as shown in table 2.
Get carrier Z5 100 grams, 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 roastings 3 hours obtained catalyst C5.Take catalyst as benchmark, the composition after the roasting of C5 catalyst is as shown in table 3.
Embodiment 6
P1-2 and 34.3 gram P2-3 and 160 gram Y zeolite (catalyst Chang Ling branch company products with 80 grams, 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 Z6.Carrier forms as shown in table 2.
Get carrier Z6 100 grams, 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 dipping of ammonium metatungstate, nickel nitrate, ammonium molybdate and the citric acid of citric acid 182.6 grams per liters 1 hour, in 120 ℃ of oven dry 2 hours, 180 ℃ were continued dry 3 hours, and obtained catalyst C6.Take catalyst as benchmark, the composition after the roasting of C6 catalyst is as shown in table 3.
Embodiment 7
Be that 0.4 silica alumina (butt is 70 heavy %) restrains Y zeolite (catalyst Chang Ling branch company products with 53.3 with the P1-2 of 111.4 grams and 74.3 gram P2-3,38.5 gram N values, 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 Z7.Carrier forms as shown in table 2.
Get carrier Z7 100 grams, 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 C7.Take catalyst as benchmark, the composition after the roasting of C7 catalyst is as shown in table 3.
Embodiment 8
Be that 0.6 silica alumina (butt is 70 heavy %) restrains Y zeolite (catalyst Chang Ling branch company products with 106.7 with the P1-2 of 51.4 grams and 34.3 gram P2-3,76.9 gram N values, 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 Z8.Carrier forms as shown in table 2.
Get carrier Z8 100 grams, 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 C8.Take catalyst as benchmark, the composition after the roasting of C8 catalyst is as shown in table 3.
Comparative Examples 1
This Comparative Examples explanation reference catalyst and preparation thereof.
P2-1 (butt is 70 heavy %) and 83.6 gram P2-4 (butt is 70 heavy %) and 93.3 gram Y zeolite (catalyst Chang Ling branch company products with 102.1 grams, 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 D1.Carrier forms as shown in table 2.
Get carrier D1 100 grams, contain WO with 90 milliliters
3413 grams per liters, the ammonium metatungstate of NiO 63.5 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 DC1.Take catalyst as benchmark, the composition after the roasting of DC1 catalyst is as shown in table 3.
Table 2
| 5 | Z5 | P1-2：74.1 P2-1：20.9 | 78/22 | 5 | / |
| 6 | Z6 | P1-2：28 P2-3：12 | 70/30 | 60 | / |
| 7 | Z7 | P1-2：39 P2-3：26 | 60/40 | 20 | 15 |
| 8 | Z8 | P1-2：18 P2-3：12 | 60/40 | 40 | 30 |
| Comparative Examples 1 | D1 | P2-1：35.75 P2-4：29.25 | 55/45 | 35 | / |
Table 3
Example 9-13
Following example explanation the invention provides method and effect thereof.
Take density as 0.9168 gram per centimeter
3, sulfur content is that 3800ppm, nitrogen content are 501ppm, and Cetane number is that 27.4 catalytic cracking diesel oil is raw material, estimates the performance of catalyst C1 provided by the invention, C2, C3, C4 and C5 at 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, the results are shown in Table 4.
Comparative Examples 2
Estimate reference catalyst DC1 performance according to embodiment 9 appreciation conditions, the results are shown in Table 4.
Table 4
| Example | 9 | 10 | 11 | 12 | 13 |
| Catalyst | C1 | C2 | C3 | C4 | DC1 |
| The Cetane number value added | 12.3 | 11.9 | 11.2 | 10.9 | 9.8 |
| Diesel yield, % | ＞95 | ＞95 | ＞95 | ＞95 | ＞95 |
The result that table 4 provides shows, compares with existing catalyst, and Catalyst And Method provided by the invention has larger increase rate to diesel cetane-number.
Claims (19)
1. hydrotreating catalyst, this catalyst contains carrier and at least a VIII of being selected from family and at least a metal component that is selected from group vib, described carrier contains solid acid component and aluminium oxide, it is characterized in that, described aluminium oxide is a kind of gama-alumina that is obtained by at least two kinds of boehmite P1 and P2 conversion, wherein, P1 is 1.1≤n
1≤ 2.5 boehmite, P2 are 0.8＜n
2＜1.1 boehmite; n
(1 or 2)=D
(1 or 2)(031)/D
(1 or 2)(120), described D
(1 or 2)(031) crystallite dimension of the crystal face of (031) peak representative in the XRD spectra of expression P1 or P2 boehmite crystal grain, D
(1 or 2)(120) crystallite dimension of the place crystal face at (120) peak in the XRD spectra of expression P1 or P2 boehmite crystal grain, described 031 peak refers to that 2 θ in the XRD spectra are 34-43 ° peak, described 120 peaks refer to that 2 θ in the XRD spectra are 23-33 ° peak, D=K λ/(Bcos θ), λ is the diffraction wavelength of target shaped 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 P1 is 1.2≤n
1≤ 2.2 boehmite, P2 are 0.85≤n
2≤ 1.05 boehmite.
3. catalyst according to claim 1 is characterized in that, the consumption of described P1 and P2 makes that the weight ratio of P1 and P2 is 40: 60～95: 5 in mixed boehmite.
4. catalyst according to claim 3 is characterized in that, the consumption of described P1 and P2 makes that the weight ratio of P1 and P2 is 45: 55～80: 20 in mixed boehmite.
5. catalyst according to claim 1 is characterized in that, take described carrier as benchmark, the content of aluminium oxide is the 5-99.5 % by weight in the described carrier, and the content of solid acid component is the 0.5-95 % by weight.
6. catalyst according to claim 5 is characterized in that, take described carrier as benchmark, the content of aluminium oxide is the 20-99 % by weight in the described carrier, and the content of solid acid component is the 1-80 % by weight.
7. catalyst according to claim 1 is characterized in that, in oxide and take catalyst as benchmark, described catalyst contains the VIII family metal component of 1-10 % by weight, the group vib metal component of 5-40 % by weight.
8. catalyst according to claim 7 is characterized in that, in oxide and take catalyst as benchmark, described catalyst contains the VIII family metal component of 1.5-6 % by weight, the group vib metal component of 10-35 % by weight.
9. according to claim 1,5 or 6 described catalyst, it is characterized in that, described solid acid component is selected from one or more in silica-alumina and the molecular sieve.
10. catalyst according to claim 9 is characterized in that, described solid acid component is selected from one or more in the molecular sieve.
11. catalyst according to claim 10 is characterized in that, described solid acid component is selected from y-type zeolite.
12. catalyst according to claim 11, it is characterized in that, described Y zeolite is selected from the Y zeolite of Y zeolite, the titaniferous of HY, Rare Earth Y, rare earth HY zeolite, super steady Y, hyperastable Y-type RE zeolite, unformedization of part, one or more among the phosphorous Y.
13. catalyst according to claim 9 is characterized in that, described solid acid component is silica-alumina.
14. catalyst according to claim 13 is characterized in that, described silica-alumina is the silica-alumina with structure of similar to thin diaspore.
15. catalyst according to claim 14 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 60.1ppm-60.2ppm place in the Al NMR spectrogram, and Q2 is the solid of described silica-alumina
27Chemical shift is the peak area at 5.1ppm-5.2ppm place in the Al NMR spectrogram;
27Each 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 in the Al NMR spectrogram.
16. catalyst according to claim 15 is characterized in that, described N value with silica-alumina of structure of similar to thin diaspore is 0.2-0.8.
17. 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 with take the mol ratio of the group VIII of oxide and 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 ethylene glycol, glycerine, molecular weight is the polyethylene glycol of 200-1500, diethylene glycol, in the butanediol one or more, organic acid is selected from acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1, the 2-CDTA, citric acid, tartaric acid, in the malic acid one or more, organic amine is selected from ethylenediamine, in EDTA and the ammonium salt thereof one or more, described organic compound with take the mol ratio of the group VIII of oxide and group vib metal component sum as 0.08-1.5.
19. a method for hydrotreating hydrocarbon oil is included under the hydrotreatment reaction condition hydrocarbon ils and catalyst haptoreaction, it is characterized in that, described catalyst is the described catalyst of claim 1-18 any one.
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| CN105013498B (en) * | 2014-02-20 | 2017-08-22 | 中国石油化工股份有限公司 | A kind of hydrotreating catalyst and its application |
| CN105013521B (en) * | 2014-02-20 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and its application |
| TWI630269B (en) * | 2014-02-20 | 2018-07-21 | 中國石油化工科技開發有限公司 | Hydrocracking catalyst and use thereof |
| CN106268917B (en) * | 2015-05-18 | 2019-01-08 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and its application |
| CN106268931B (en) * | 2015-05-18 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and its application containing composite molecular screen |
| CN106268922B (en) * | 2015-05-18 | 2019-01-08 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and its application |
| CN106268930B (en) * | 2015-05-18 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst of the molecular sieve containing Beta and its application |
| CN106268965B (en) * | 2015-05-18 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst of the molecular sieve containing Beta and its application |
| CN106268724B (en) * | 2015-05-18 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and its application containing Y type molecular sieve |
| CN106554815B (en) * | 2015-09-30 | 2019-11-15 | 中国石油化工股份有限公司 | A method of cleaning diesel oil is produced by high-sulfur nitrogen poor ignition quality fuel |
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| CN1647857A (en) * | 2004-01-19 | 2005-08-03 | 中国石油化工股份有限公司 | Macroporous aluminium oxide carrier and its preparing method |
| 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 |
| CN101450327A (en) * | 2007-11-29 | 2009-06-10 | 南化集团研究院 | Process for preparing alumina carrier |
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