CN102161002B - Catalyst for hydrotreatment and application thereof - Google Patents
Catalyst for hydrotreatment and application thereof Download PDFInfo
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- CN102161002B CN102161002B CN 201010113146 CN201010113146A CN102161002B CN 102161002 B CN102161002 B CN 102161002B CN 201010113146 CN201010113146 CN 201010113146 CN 201010113146 A CN201010113146 A CN 201010113146A CN 102161002 B CN102161002 B CN 102161002B
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Abstract
The invention relates to a catalyst for hydrotreatment, containing the following components: an aluminum oxide carrier, at least one metallic component from VIII group and at least one metallic component from VIB group. The catalyst is characterized in that the aluminum oxide carrier is obtained by mixing, forming and roasting of at least two boehmites P1 and P2, wherein for the P1, n1 is more than or equal to 1.1 and less than or equal to 2.5, and for the P2, n2 is more than 0.8 and less than 1.1, and n (1 or 2) is equal to D (1 or 2) (031)/D (1 or 2) (120); and the D (1 or 2) (031) represents the size of the crystal grain on the crystal face of (031) peak in the XRD spectrogram of the crystal grain of the boehmite P1 or P2, the D (1 or 2) (120) represents the size of the crystal grain on the crystal face of (120) peak in the XRD spectrogram of the crystal grain of the boehmite P1 or P2, the 031 peak is the peak in which 2theta is 34-43 degrees in the XRD spectrogram, the 120 peak is the peak in which 2theta is 23-33 degrees in the XRD spectrogram, D is equal to Klambda/(Bcostheta), lambda is the diffraction wavelength of a target type material, B is half peak width of the corrected diffraction peak, and 2theta is the position of a diffraction peak. Compared with the prior art, the performance of the catalyst provided by the invention is improved obviously.
Description
Technical field
The present invention is about a kind of hydrotreating catalyst and application thereof.
Background technology
Day by day scarcity along with petroleum resources, the contradiction of crude oil heaviness and product lighting is becoming increasingly acute, the countries in the world oil refining enterprise is all mixed refining or is entirely refined catalytic cracking (RFCC) technology of residual oil and the thermal cracking technology such as coking greatly developing, and wherein RFCC technique becomes the most effectively technique of light materialization of heavy oil.But the impurity of high-load in the residual oil has larger impact such as sulphur, nitrogen, metal and carbon residue etc. to the stable operation of RFCC process unit.In order to increase resid feed to the adaptability of RFCC device, as the raw material preprocessing device of RFCC device, taking off percentage of admixture, particularly desulfurization degree, demetallization per and taking off carbon yield of residue fixed-bed hydrotreater beds just seems particularly important.
Alumina support is the carrier of this type of catalyst of preparation, by can reaching the pore structure of optimization of catalysts to the selection of alumina support, and then improves the performance of catalyst.For example:
Patent ZL97115112 discloses a kind of residuum hydrogenating and metal-eliminating catalyst, and this catalyst loads on a kind of large-pore alumina carrier take VIII family and/or group vib metallic element as active component.The pore volume of this carrier is 0.80～1.20ml/g (mercury injection method), and specific area is 110～200m
2/ g can several apertures be 15～20nm, and bulk density is 0.50～0.60g/ml.Method of the present invention is in the boehmite kneading process, adds simultaneously physics expanding agent and chemical enlargement agent, and kneading becomes plastic, extruded moulding, dry, roasting makes carrier, with the spray impregnation method active component is added on the carrier again, and drying, roasting make catalyst.Catalyst of the present invention is applicable to heavy oil, especially the HDM of residual oil and/or hydrodesulfurization.
Patent ZL200310117322 discloses a kind of residuum hydrogenating and metal-eliminating catalyst and preparation method thereof, this catalyst contains a kind of macropore alumina supporter and the molybdenum and/or tungsten and cobalt and/or the nickel that load on this carrier, in oxide and take catalyst as benchmark, described catalyst contains molybdenum and/or the tungsten of 0.5-15 % by weight, 0.3-8 the cobalt of % by weight and/or nickel, the carrier of aequum, it is characterized in that, described carrier contains a kind of halogen, take the carrier total amount as benchmark, this carrier contains the aluminium oxide of 95-99 % by weight, in element, 0.1-5 the halogen of % by weight, its acid amount is less than 0.2 mM/gram.Because the acid of the carrier in the catalyst provided by the invention amount is low, when making it keep higher HDM activity, coke content is low again.
In the prior art, by can be met the hydrogenation catalyst of particular requirement to the selection of alumina support.But, these catalyst being used for the hydrotreatment reaction, when processing the demetalization reaction especially for heavy-oil hydrogenation, but their performance still has very large room for improvement.
Summary of the invention
The technical problem to be solved in the present invention is on the basis of existing technology, and the application of a kind of new, better hydrotreating catalyst of performance and this catalyst is provided.
The invention provides a kind of hydrotreating catalyst, contain alumina support, at least a VIII of being selected from family and at least a metal component that is selected from group vib, it is characterized in that, described alumina support is obtained through mixing, moulding, roasting by the composition that contains P1 and two kinds of boehmites of P2 at least, 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.
The invention provides a kind of method for hydrotreating hydrocarbon oil, be included under the hydrotreatment reaction condition, with hydrocarbon oil crude material and catalyst haptoreaction, it is characterized in that, described catalyst is aforesaid catalyst provided by the invention.
Compared with prior art, the invention provides being prepared through the carrier that mixing, moulding, roasting obtain by the composition that contains P1 and at least two kinds of boehmites of P2 of catalyst, so that this catalyst performance improves.For example, employing meets alumina support that the boehmite composition of requirement of the present invention obtains through roasting and prepares and contain molybdenum oxide 14.5 % by weight, residuum hydrogenating and metal-eliminating, the desulphurization catalyst of cobalt oxide 3.4 % by weight, take nickel content as 15.6ppm, content of vanadium as 38.2ppm, sulfur content as 3.3%, nitrogen content as 0.24%, husky light VRDS is raw material when carrying out activity rating to carbon residue as Maoming of 10.7%, its desulfurization degree is 88.7%, and demetallization per is 67.2.And adopt the preparation of reference carrier contain molybdenum oxide 14.5 % by weight, residuum hydrogenating and metal-eliminating, the desulphurization catalyst of cobalt oxide 3.4 % by weight, when estimating with same materials oil and process conditions, desulfurization degree and demetallization per are respectively 87.8% and 66.8%.
The specific embodiment
According to catalyst provided by the invention, the carrier preparation that wherein said alumina support is obtained through mixing, moulding, roasting by the composition that contains P1 and two kinds of boehmites of P2 at least, 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.Preferred described P1 is 1.2≤n
1≤ 2.2 boehmite, P2 are 0.85≤n
2≤ 1.05 boehmite.
Described composition is mixed to get by P1 and P2, described mixing can be the simple accumulation that described P1 and P2 are placed a place, also can be to adopt any one prior art, for example can in mixer, grinder, directly P1 be mixed by the mode that stirs with P2, can be under the condition of pulp P1 to be mixed with P2 and water being enough to, filter afterwards, dry or moist method mixes.When adopting any one prior art to mix, those skilled in the art optionally can control the uniformity that described mixing should reach, to this present invention to being not particularly limited.
Wherein, optionally can be arbitrarily to the mixing ratio of described P1 and P2, be not particularly limited here.In preferred embodiment, the mixed weight of described P1 and P2 is 40: 60～95: 5 than preferred P1: P2, more preferably 45: 55～80: 20.
Described P2 is 0.8＜n
2＜1.1 boehmite can be to be selected from the boehmite that commercially available commodity also can adopt any one prior art preparation.
Described P1 is 1.1≤n
1The preparation method of≤2.5 boehmite 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.According to catalyst provided by the invention, wherein, P2 is 0.8＜n
2＜1.1 boehmite can be the boehmite that adopts any one prior art preparation.
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 P1 boehmite
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 P1 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 P1 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 P1 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 P1 boehmite 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 P1 boehmite provided by the invention.
Described moulding can be carried out according to a conventional method, all can such as methods such as compressing tablet, spin, extrusions.
One preferred embodiment in, the preparation method of described aluminium oxide shaping carrier comprises:
(1) mixes at the boehmite P2 and the water that are enough under the condition of pulp boehmite P1, the n of described 1.1≤n≤2.5＜1.1, filter afterwards, dry or moist, obtain described 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).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 examination stove and converter to carry out roasting, the condition of described roasting is preferably, at 350-1200 ℃ roasting temperature 1-12 hour, further preferably 500-950 ℃ roasting temperature 2-8 hour.
Another preferred embodiment in, the preparation method of described aluminium oxide shaping carrier comprises:
(1) mixes at the boehmite P2 of kneading machine with boehmite P1, the n of described 1.1≤n≤2.5＜1.1, obtain described 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).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 examination stove and converter to carry out roasting, the condition of described roasting is preferably, at 350-1200 ℃ roasting temperature 1-12 hour, further preferably 500-950 ℃ roasting temperature 2-8 hour.
According to catalyst provided by the invention, the usual content that at least a VIII of being selected from family wherein and at least a content that is selected from the metal component of group vib are heavy oil hydrogenating treatment catalyst.In preferred embodiment, preferred VIII family metal component is cobalt and/or nickel, the group vib metal component is molybdenum and/or tungsten, in oxide and take catalyst as benchmark, the content of described VIII family metal component is preferably the 0.5-10 % by weight, 1.5-5 % by weight more preferably, the content of described group vib metal component is preferably the 5-35 % by weight, more preferably the 6-30 % by weight.
Described at least a group vib and at least a group VIII metal component of being selected from is carried under the prerequisite on the described carrier being enough to, the present invention is not particularly limited the method that described group vib, group VIII metal component are carried on the described carrier.For example, can be under the condition that is enough to the nickel that is selected from group VIII of effective dose and/or cobalt metal component be deposited on the described carrier, the solution of described carrier with the compound that contains the nickel that is selected from group VIII containing of effective dose and/or cobalt metal component is contacted, as passing through the methods such as dipping, co-precipitation, preferred infusion process is carried out drying, roasting or not roasting afterwards.The condition of described drying is 80～350 ℃ for the habitual condition of this type of catalyst of preparation such as baking temperature, is preferably 100～300 ℃, and be 1～24 hour drying time, is preferably 2～12 hours.When described catalyst need to carry out roasting, described temperature was preferably 100-700 ℃, and roasting time is 1-6 hour, and further preferred temperature is preferably 200-500 ℃, and roasting time is 2-4 hour.
Described group VIII metallic compound is selected from one or more in the group VIII metal soluble compound, such as in the nitrate of cobalt and/or nickel metal, acetate, soluble carbonate salt, chloride, the soluble complexes one or more.
Described group vib metallic compound is selected from one or more in the group vib metal soluble compound, such as in molybdate, tungstates, metatungstate, the ethyl metatungstate one or more.
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 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 containing components such as being selected from phosphorus or silicon in the described catalyst, its introducing method can be that the compound that will contain described auxiliary agent directly mixes with boehmite, moulding and roasting; Can be the compound that to contain described auxiliary agent and contact with described alumina support after the compound that contains the hydrogenation active metals component is mixed with mixed solution; Can also be to contact and roasting with described alumina support behind the independent obtain solution of the compound that contains auxiliary agent.When auxiliary agent and hydrogenation active metals are introduced described alumina support respectively, preferably at first auxiliary compound solution contacts with described alumina support and roasting with containing, contact with the solution of the compound that contains the hydrogenation active metals component more afterwards, such as by methods such as ion-exchange, dipping, co-precipitation, preferred infusion process, described sintering temperature is 250-600 ℃, is preferably 350-500 ℃, roasting time is 2-8 hour, is preferably 3-6 hour.
According to method provided by the present invention, described hydrotreatment reaction condition is the usual reaction condition of heavy raw oil hydrotreatment, in preferred embodiment, described hydrotreatment reaction condition is: reaction temperature 300-550 ℃, further preferred 330-480 ℃, hydrogen dividing potential drop 4-20 MPa, further preferred 6-18 MPa, volume space velocity 0.1-3 hour
-1, further preferred 0.15-2 hour
-1, hydrogen to oil volume ratio 200-2500, further preferred 300-2000.
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.
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.
Catalyst provided by the invention is applicable to hydrocarbon oil hydrogenation and processes, and carries out hydrotreatment especially for heavy oil, to remove sulphur, nitrogen and metal wherein.In order to provide qualified feedstock oil for subsequent technique (such as catalytic cracking process).
The below will illustrate the present invention by example.Agents useful for same in the example except specifying, is chemically pure reagent.
The boehmite P2 of boehmite P1, the n of employed 1.1≤n≤2.5＜1.1 in the embodiment of the invention, its preparation method and originate as follows:
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 (comprising P1-2a and P1-2b), 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, and drying does not obtain hydrated alumina P1-2a; Through 120 ℃ of dryings 24 hours, obtain hydrated alumina P1-2b, adopt XRD to characterize (characterizing with P1-2a equally through 120 ℃ of dryings 24 hours), P1-2a and P1-2b have structure of similar to thin diaspore.
List in the table 1 according to carrying out the n value that XRD characterized, calculated P1-2a and P1-2b with aforementioned P1-1 same procedure.
P2-1, adopt following method preparation:
Method according to P1-1 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.Adopt XRD to characterize according to the method for embodiment 1, P2-1 has structure of similar to thin diaspore, lists in the table 1 according to carrying out the n value that XRD characterized, calculated P2-1 with aforementioned P1-1 same procedure.
P2-2 (comprising P2-2a and P2-2b), adopt following method preparation:
Method according to P1-2 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, drying does not obtain hydrated alumina P2-2a; Through 120 ℃ of dryings 24 hours, obtain hydrated alumina P2-2b.Adopt XRD to characterize (characterizing with P2-2a equally through 120 ℃ of dryings 24 hours) according to the method for embodiment 1, P2-2a and P2-2b have structure of similar to thin diaspore, list in the table 1 according to carrying out the n value that XRD characterized, calculated P2-2a and P2-2b with aforementioned P1-1 same procedure.
P2-3 is the commodity boehmite (SD powder) that Shandong Aluminum Plant produces, according to aforementioned P1-1 same procedure carry out XRD characterize,, the n value that calculates P2-3 lists in the table 1.
P2-4, for the permanent brightness chemical industry in Yantai Co., Ltd produce commodity boehmite (Yantai powder), list in the table 1 according to carrying out the n value that XRD characterized, calculated P2-4 with aforementioned P1-1 same procedure.
Table 1
* take the commercial SB powder of Condea company as benchmark, record the degree of crystallinity of each sample.
Embodiment 1～5 explanation is suitable for preparing the boehmite that the invention provides catalyst, carrier and preparation method thereof.
Embodiment 1
(1) boehmite composition:
P1-1, two kinds of boehmites of P2-3 are fed intake by 60: 40 butt weight ratio and mixed 20 minutes at kneading machine, obtain the invention provides composition Z P-1.
(2) alumina support:
Get first composition Z P-1600 gram, the sesbania powder that adds 20 grams mixes, do at room temperature concentration with this mixture and 520 milliliters and be 1% aqueous solution of nitric acid, mix, continuing kneading at double screw banded extruder afterwards is plastic, and is extruded into the butterfly bar of 1.1 millimeters of φ, wet bar is through 120 ℃ of dryings after 4 hours, in 600 ℃ of roastings 3 hours, obtain carrier Z1, carrier Z1 character is shown in Table 2.
The boehmite of reference example 1～5 explanation reference, aluminium oxide shaping carrier and preparation method thereof.
Reference example 1
(1) boehmite composition:
P2-1, two kinds of boehmites of P2-3 are fed intake by 60: 40 butt weight ratio and mixed 20 minutes at kneading machine, obtain contrast composition DZP-1 is provided.
(2) alumina support:
Get first composition DZP-1600 gram, the sesbania powder that adds 20 grams mixes, at room temperature be 1% aqueous solution of nitric acid again with the concentration of this mixture and 520 milliliters, mix, continuing kneading at double screw banded extruder afterwards is plastic, and is extruded into the butterfly bar of 1.1 millimeters of φ, wet bar is through 120 ℃ of dryings after 4 hours, in 600 ℃ of roastings 3 hours, obtain carrier DZ1, carrier DZ1 character is shown in Table 2.
Embodiment 2
(1) boehmite composition:
P1-1, two kinds of boehmites of P2-3 by 60: 40 butt weight ratio, 500 grams that feed intake, are added respectively in 1500 ml deionized water totally, continue to stir 15 minutes after being stirred to pulp, then overanxious, obtain composition Z P-2 provided by the invention
(2) alumina support:
Get composition Z P-2600 gram, after double screw banded extruder continuation kneading is plastic, be extruded into the butterfly bar of 1.1 millimeters of φ, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains carrier Z2 through 120 ℃ of dryings, and carrier Z2 character is shown in Table 2.
Reference example 2
(1) boehmite composition:
P2-3, two kinds of boehmites of P2-1 by 40: 60 butt weight ratio, 500 grams that feed intake, are added respectively in 1500 ml deionized water totally, continue to stir 15 minutes after being stirred to pulp, then overanxious, obtain Comparative composition DZP-2
(2) aluminium oxide:
Get composition DZP-2600 gram, after double screw banded extruder continuation kneading is plastic, be extruded into the butterfly bar of 1.1 millimeters of φ, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains carrier DZ2 through 120 ℃ of dryings, and carrier DZ2 character is shown in Table 2.
Embodiment 3
(1) boehmite:
P1-2, two kinds of boehmites of P2-4 are fed intake by 50: 50 butt weight ratio and mixed 20 minutes at kneading machine, obtain the invention provides composition Z P-3.
(2) aluminium oxide
Get first composition Z P-3600 gram, the sesbania powder that adds 20 grams mixes, at room temperature be 1% aqueous solution of nitric acid again with the concentration of this mixture and 660 milliliters, mix, continuing kneading at double screw banded extruder afterwards is plastic, and is extruded into the butterfly bar of 1.1 millimeters of φ, wet bar is through 120 ℃ of dryings after 4 hours, in 900 ℃ of roastings 3 hours, obtain carrier Z3, carrier Z3 character is shown in Table 2.
Comparative Examples 3
(1) boehmite:
P2-2, two kinds of boehmites of P2-4 are fed intake by 50: 50 butt weight ratio and mixed 20 minutes at kneading machine, obtain Comparative composition DZP-3.
(2) aluminium oxide:
Get first composition DZP-3600 gram, the sesbania powder that adds 20 grams mixes, at room temperature be 1% aqueous solution of nitric acid again with the concentration of this mixture and 660 milliliters, mix, continuing kneading at double screw banded extruder afterwards is plastic, and is extruded into the butterfly bar of 1.1 millimeters of φ, wet bar is through 120 ℃ of dryings after 4 hours, in 900 ℃ of roastings 3 hours, obtain carrier DZ3, carrier DZ3 character is shown in Table 2.
Embodiment 4
(1) boehmite:
P1-1, two kinds of boehmites of P2-3 are fed intake by 70: 30 butt weight ratio and mixed 20 minutes at kneading machine, obtain the invention provides composition Z P-4.
(2) aluminium oxide:
Get first composition Z P-4600 gram, the sesbania powder that adds 20 grams mixes, at room temperature be 1% aqueous solution of nitric acid again with the concentration of this mixture and 520 milliliters, mix, continuing kneading at double screw banded extruder afterwards is plastic, and is extruded into the butterfly bar of 1.1 millimeters of φ, wet bar is through 120 ℃ of dryings after 4 hours, in 600 ℃ of roastings 3 hours, obtain carrier Z4, carrier Z4 character is shown in Table 2.
Comparative Examples 4
(1) boehmite:
P2-1, two kinds of boehmites of P2-3 are fed intake by 70: 30 butt weight ratio and mixed 20 minutes at kneading machine, obtain Comparative composition DZP-4.
(2) aluminium oxide:
Get first composition DZP-4600 gram, the sesbania powder that adds 20 grams mixes, at room temperature be 1% aqueous solution of nitric acid again with the concentration of this mixture and 520 milliliters, mix, continuing kneading at double screw banded extruder afterwards is plastic, and is extruded into the butterfly bar of 1.1 millimeters of φ, wet bar is through 120 ℃ of dryings after 4 hours, in 600 ℃ of roastings 3 hours, obtain carrier DZ4, carrier DZ4 character is shown in Table 2.
Embodiment 5
(1) boehmite:
P1-1, two kinds of boehmites of P2-3 are fed intake by 60: 40 butt weight ratio and mixed 20 minutes at kneading machine, obtain the invention provides composition Z P-5.
(2) aluminium oxide:
Get first composition Z P-5600 gram, the sesbania powder that adds 20 grams mixes, at room temperature be 1% aqueous solution of nitric acid again with the concentration of this mixture and 520 milliliters, mix, continuing kneading at double screw banded extruder afterwards is plastic, and is extruded into the butterfly bar of 1.3 millimeters of φ, wet bar is through 120 ℃ of dryings after 4 hours, in 600 ℃ of roastings 3 hours, obtain carrier Z5, carrier Z5 character is shown in Table 2.
Comparative Examples 5
(1) boehmite:
P2-1, two kinds of boehmites of P2-3 are fed intake by 60: 40 butt weight ratio and mixed 20 minutes at kneading machine, obtain Comparative composition DZP-5.
(2) aluminium oxide:
Get first composition DZP-5600 gram, the sesbania powder that adds 20 grams mixes, at room temperature be 1% aqueous solution of nitric acid again with the concentration of this mixture and 520 milliliters, mix, continuing kneading at double screw banded extruder afterwards is plastic, and is extruded into the butterfly bar of 1.3 millimeters of φ, wet bar is through 120 ℃ of dryings after 4 hours, in 600 ℃ of roastings 3 hours, obtain carrier DZ5, carrier DZ5 character is shown in Table 2.
Table 2
Embodiment 6～11 explanation catalyst provided by the invention and preparation preparation thereof
Embodiment 6
Get carrier Z1200 gram, contain MoO with 170 milliliters
3208 grams per liters, the ammonium molybdate of CoO 48.7 grams per liters and cobalt nitrate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 420 ℃ of roastings 3 hours obtained catalyst C1.Take the gross weight of catalyst as benchmark, adopt x-ray fluorescence method to measure molybdenum oxide among the catalyst C1 and the content (concrete grammar is seen Petrochemical Engineering Analysis method RIPP133-90) of cobalt oxide, measurement result is as shown in table 3.
Comparative Examples 6～11 explanation reference catalyst and preparations thereof.
Comparative Examples 6
Get carrier DZ1200 gram, contain MoO with 170 milliliters
3208 grams per liters, the ammonium molybdate of CoO 48.7 grams per liters and cobalt nitrate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 420 ℃ of roastings 3 hours obtained catalyst DC1.Measure molybdenum oxide among the catalyst DC1 and the content of cobalt oxide according to the mode identical with embodiment 6, the result is as shown in table 3.
Embodiment 7
Get carrier Z2200 gram, contain MoO with 170 milliliters
3206 grams per liters, the ammonium molybdate of NiO 45 grams per liters and nickel nitrate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 420 ℃ of roastings 3 hours obtained catalyst C2.Measure molybdenum oxide among the catalyst C2 and the content of nickel oxide according to the mode identical with embodiment 6, the result is as shown in table 3.
Comparative Examples 7
Get carrier DZ2200 gram, contain MoO with 170 milliliters
3206 grams per liters, the ammonium molybdate of NiO 45 grams per liters and nickel nitrate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 420 ℃ of roastings 3 hours obtained catalyst DC2.Measure molybdenum oxide among the catalyst DC2 and the content of nickel oxide according to the mode identical with embodiment 6, the result is as shown in table 3.
Embodiment 8
Get carrier Z3200 gram, contain MoO with 200 milliliters
385 grams per liters, the ammonium molybdate of NiO 26 grams per liters and nickel nitrate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 420 ℃ of roastings 3 hours obtained catalyst C3.Measure molybdenum oxide among the catalyst C3 and the content of nickel oxide according to the mode identical with embodiment 6, the result is as shown in table 3.
Comparative Examples 8
Get carrier DZ3200 gram, contain MoO with 200 milliliters
385 grams per liters, the ammonium molybdate of NiO 26 grams per liters and nickel nitrate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 420 ℃ of roastings 3 hours obtained catalyst DC3.Measure molybdenum oxide among the catalyst DC3 and the content of nickel oxide according to the mode identical with embodiment 6, the result is as shown in table 3.
Embodiment 9
Get carrier Z4200 gram, contain MoO with 170 milliliters
3154 grams per liters, the ammonium molybdate of CoO 37 grams per liters and cobalt nitrate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 420 ℃ of roastings 3 hours obtained catalyst C4.Measure molybdenum oxide among the catalyst C4 and the content of cobalt oxide according to the mode identical with embodiment 6, the result is as shown in table 3.
Comparative Examples 9
Get carrier DZ4200 gram, contain MoO with 170 milliliters
3154 grams per liters, the ammonium molybdate of CoO 37 grams per liters and cobalt nitrate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 420 ℃ of roastings 3 hours obtained catalyst DC4.Measure molybdenum oxide among the catalyst DC4 and the content of cobalt oxide according to the mode identical with embodiment 6, the result is as shown in table 3.
Embodiment 10
Get carrier Z5200 gram, contain WO with 170 milliliters
3477 grams per liters, the ammonium metatungstate of NiO 49.4 grams per liters and nickel nitrate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 420 ℃ of roastings 3 hours obtained catalyst C5.Measure tungsten oxide among the catalyst C5 and the content of nickel oxide according to the mode identical with embodiment 6, the result is as shown in table 3.
Comparative Examples 10
Get carrier DZ5200 gram, contain WO with 170 milliliters
3477 grams per liters, the ammonium metatungstate of NiO 49.4 grams per liters and nickel nitrate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 420 ℃ of roastings 3 hours obtained catalyst DC5.Measure tungsten oxide among the catalyst DC5 and the content of nickel oxide according to the mode identical with embodiment 6, the result is as shown in table 3.
Embodiment 11
Get carrier Z5, with the ammonium fluoride solution of 170 milliliters of fluorine-containing 72 grams per liters dipping 1 hour, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 3 hours obtained catalyst fluorine bar F6.
Get catalyst fluorine bar F6200 gram, contain WO with 160 milliliters
3507 grams per liters, the ammonium metatungstate of NiO 52 grams per liters and nickel nitrate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 420 ℃ of roastings 3 hours obtained catalyst C6.Measure tungsten oxide among the catalyst C6 and the content of nickel oxide according to the mode identical with embodiment 6, the result is as shown in table 3.
Comparative Examples 11
Get carrier DZ5, with the ammonium fluoride solution of 170 milliliters of fluorine-containing 72 grams per liters dipping 1 hour, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 3 hours obtained catalyst fluorine bar DF6.
Get catalyst fluorine bar DF6200 gram, contain WO with 160 milliliters
3507 grams per liters, the ammonium metatungstate of NiO 52 grams per liters and nickel nitrate mixed solution dipping 1 hour, in 120 ℃ of oven dry 2 hours, 420 ℃ of roastings 3 hours obtained catalyst DC6.Measure tungsten oxide among the catalyst DC6 and the content of nickel oxide according to the mode identical with embodiment 6, the result is as shown in table 3.
Table 3
Embodiment 12-17 explanation the invention provides application and the effect thereof of catalyst.
Embodiment 12-13
The desulfurization performance of difference evaluate catalysts C1, C4 in fixed bed reactors.
Feedstock oil: feedstock oil is that nickel content is that 15.6ppm, content of vanadium are that 38.2ppm, sulfur content are 3.3%, nitrogen content is 0.24%, carbon residue is 10.7% the husky light VRDS in Maoming.
Reaction condition: the particle that respectively catalyst C1, C4 the is broken into diameter 2-3 millimeter reactor of packing into.380 ℃ of reaction temperatures, hydrogen dividing potential drop 14 MPas, air speed 0.5h
-1, hydrogen-oil ratio 700 (volume).
Product analysis: the content (instrument is the U.S. PE-5300 of PE company type plasma quantometer, and concrete grammar is seen Petrochemical Engineering Analysis method RIPP124-90) of nickel and vanadium in the oil after employing inductive coupling plasma emission spectrograph (ICP-AES) mensuration is processed.Use coulometry to measure the content (concrete grammar is seen Petrochemical Engineering Analysis method RIPP62-90) of sulphur and nitrogen.
Calculate respectively total removal efficiency of impurity (sulphur or metal) according to following formula:
The results are shown in table 4.
Embodiment 14
Evaluate catalysts C2's takes off the carbon residue performance in fixed bed reactors.
Feedstock oil: feedstock oil is that nickel content is that 15.6ppm, content of vanadium are that 38.2ppm, sulfur content are 3.3%, nitrogen content is 0.24%, carbon residue is 10.7% the husky light VRDS in Maoming.
Reaction condition: the particle that catalyst C2 the is broken into diameter 2-3 millimeter reactor of packing into.380 ℃ of reaction temperatures, hydrogen dividing potential drop 14 MPas, air speed 0.5h
-1, hydrogen-oil ratio 700.
Product analysis: adopt carbon residue content in the oil after the oil product Conradson method is measured processing (instrument is the U.S. MCRT-160 of ALCOR company type trace carbon residue analyzer, and concrete grammar is seen GB/T17144).
Calculate respectively total removal efficiency of impurity (carbon residue) according to following formula:
The results are shown in table 4.
Embodiment 15
The demetalization performance of evaluate catalysts C3 in fixed bed reactors.
Feedstock oil: feedstock oil is that nickel content is that 29.3ppm, content of vanadium are that 83ppm, sulfur content are 4.7%, nitrogen content is 0.3%, carbon residue is 15.1% the normal slag of Kuwait.
Reaction condition: the particle that catalyst C3 the is broken into diameter 2-3 millimeter reactor of packing into.380 ℃ of reaction temperatures, hydrogen dividing potential drop 14 MPas, air speed 0.6h
-1, hydrogen-oil ratio 700 (volume).
Product analysis: the content (instrument is the U.S. PE-5300 of PE company type plasma quantometer, and concrete grammar is seen Petrochemical Engineering Analysis method RIPP124-90) of nickel and vanadium in the oil after employing inductive coupling plasma emission spectrograph (ICP-AES) mensuration is processed
Calculate respectively total removal efficiency of impurity (metal) according to following formula:
The results are shown in table 4.
Embodiment 16-17
The desulfurization of evaluate catalysts C5, C6, nitrogen removal performance in fixed bed reactors.
Feedstock oil: feedstock oil is that sulfur content is 9700ppm, and nitrogen content is the straight bavin in Maoming of 97ppm.
Reaction condition: the particle that respectively catalyst C5, C6 the is broken into diameter 2-3 millimeter reactor of packing into.Reaction condition is: 325 ℃ of reaction temperatures, hydrogen dividing potential drop 6.4 MPas, air speed 2h
-1, hydrogen-oil ratio 300.
Product analysis: adopt sulfur content (instrument is THERMO company's T S-3000 UV suLfur anaLyzer, and concrete grammar is seen industry standard SH-T0689) in the oil after ultraviolet fluorescence method is measured processing; Adopt nitrogen content (instrument is the EA3100 chemiluminescence azotometer of Jena company, and concrete grammar is seen industry standard SH-T0657) in the oil after chemiluminescence determination is processed.
Calculate respectively total removal efficiency of impurity (sulphur, nitrogen) according to following formula:
The results are shown in table 4.
Comparative Examples 12-17
The performance of reference aluminium oxide shaping carrier Kaolinite Preparation of Catalyst is described.
Every impurity removal performance according to method evaluation catalyst DC1～DC6 of embodiment 12-17 the results are shown in Table 4.
Table 4
Can be seen by table 4 result, in poor residuum hydrotreatment process by desulphurizing activated, the metal removal activity that the invention provides the alumina preparation catalyst and take off carbon residue and will obviously be better than reference catalyst, in the diesel oil hydrogenation processing procedure, the desulfurization, the denitrification activity that the invention provides catalyst also are higher than reference catalyst.
Claims (6)
1. hydrotreating catalyst, contain alumina support, at least a VIII of being selected from family and at least a metal component that is selected from group vib, it is characterized in that, described alumina support is obtained through mixing, moulding, roasting by the composition that contains P1 and two kinds of boehmites of P2 at least, wherein, the weight ratio of P1 and P2 is 40: 60～95: 5 in the described composition, and 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. boehmite composition according to claim 1 is characterized in that, the weight ratio of P1 and P2 is 45: 55～80: 20 in the described composition.
4. catalyst according to claim 1, it is characterized in that, described VIII family metal component is cobalt and/or nickel, the group vib metal component is molybdenum and/or tungsten, in oxide and take catalyst as benchmark, the content of described VIII family metal component is the 0.5-10 % by weight, and the content of described group vib metal component is the 5-35 % by weight.
5. catalyst according to claim 4 is characterized in that, the content of described VIII family metal component is the 1.5-5 % by weight, and the content of described group vib metal component is the 6-30 % by weight.
6. a 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 the described catalyst of claim 1-5 any one.
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| CN102274730B (en) * | 2010-06-10 | 2013-03-27 | 中国石油化工股份有限公司 | Hydrotreating catalyst and application thereof |
| CN102274732B (en) * | 2010-06-10 | 2013-03-27 | 中国石油化工股份有限公司 | Hydrotreating catalyst and application thereof |
| CN103773487B (en) * | 2012-10-25 | 2015-10-28 | 中国石油化工股份有限公司 | A kind of method for hydrogen cracking of catalytic cracking diesel oil |
| CN103773489B (en) * | 2012-10-25 | 2016-03-02 | 中国石油化工股份有限公司 | A kind of method of hydrotreating processing high nitrogen, high aromatic hydrocarbons poor ignition quality fuel raw material |
| CN103773469B (en) * | 2012-10-25 | 2016-08-24 | 中国石油化工股份有限公司 | A kind of method of hydrotreating being produced high-value product by catalytic cracking diesel oil |
| 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 |
| CN104971732B (en) * | 2014-04-09 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and its application |
| CN106140310B (en) * | 2015-03-30 | 2019-06-14 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and hydrogenation method for hydrocarbon oils |
| CN110201691B (en) * | 2019-06-25 | 2022-05-06 | 中化泉州石化有限公司 | Residual oil hydrodemetallization desulfurization catalyst and preparation method thereof |
| CN113559887B (en) * | 2020-04-28 | 2023-05-05 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method and application thereof |
| CN113559895B (en) * | 2020-04-28 | 2023-05-05 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst, hydrogenation catalyst and application |
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| CN1206037A (en) * | 1997-07-22 | 1999-01-27 | 中国石油化工总公司 | Residuum hydrogenating and metal-eliminating catalyst |
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