CN102274732B - Hydrotreating catalyst and application thereof - Google Patents
Hydrotreating catalyst and application thereof Download PDFInfo
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- CN102274732B CN102274732B CN 201010196583 CN201010196583A CN102274732B CN 102274732 B CN102274732 B CN 102274732B CN 201010196583 CN201010196583 CN 201010196583 CN 201010196583 A CN201010196583 A CN 201010196583A CN 102274732 B CN102274732 B CN 102274732B
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Abstract
The invention relates to a hydrotreating catalyst and application thereof. The catalyst contains an aluminum oxide carrier, at least one metal component selected from the VIII group and at least one metal component selected from the VIB group. The hydrotreating catalyst is characterized in that: the carrier is obtained by roasting a pseudoboehmite composite containing P1 and P2, and by taking the total amount of the pseudoboehmite composite as reference, the P2 content in the composite is more than 50 percent by weight, wherein P1 is the pseudoboehmite with n1 being not less than 1.1 and not more than 2.5, and the P2 is the pseudoboehmite with n2 being more than 0.8 and less than 1.1; n (1 or 2) is equal to D (1 or 2) (031)/D(1 or 2) (120), wherein D (1 or 2) (031) indicates the crystal grain dimension of the crystal face represented by the (031) peak in the XRD (X-Ray Diffraction) spectrogram of the P1 or P2 pseudoboehmite crystal grains, the D(1 or 2) (120) indicates the crystal grain dimension of the crystal face represented by the (120) peak in the XRD spectrogram of the P1 or P2 pseudoboehmite crystal grains, D is equal to Klambda/(Bcos theta), lambda is the diffraction wavelength of a target material, B is the halfpeak breadth of the corrected diffraction peak, and 2theta is the position of the diffraction peak. Compared with the traditional hydrotreating catalyst, the catalyst provided by the invention has improved performance.
Description
Technical field
The present invention relates to a kind of hydrotreating catalyst and application thereof.
Background technology
Nitrogen oxide (NO in the motor vehicle discharged tail gas
X) not only form the acid rain in city and outskirts area, also seriously destroy the ozone layer of the earth; Containing multiple being classified as by international research mechanism in the particle in the tail gas (PM) may be the material that makes the human carcinogen; Sulfur-containing compound is also very large on the Exhaust emission impact in the diesel oil, particularly to NO
XWith the generation of PM obvious facilitation is arranged, the oxysulfide (SO that generates during the sulfur-containing compound burning
X) be that the main cause that causes acid rain to form can cause again Vehicle Exhaust Gas Cleaning Catalysts to be poisoned.Aromatic hydrocarbons in the diesel oil also has many adverse effects to its character, and aromatic hydrocarbons can make carbon monoxide, the NO in the vehicle exhaust
XIncrease with the pollutant discharge amount such as PM, aromatic hydrocarbons also can reduce the Cetane number of diesel oil.
In recent years, for satisfying environmental protection to pernicious gas NO in the vehicle exhaust
X, SO
XDeng the requirement of the strict restriction of emission, impel the developing rapidly of the correlation techniques such as hydrotreating catalyst that turns to purpose with the fraction oil of petroleum high-quality.In addition, because petroleum resources day by day reduce, the coal liquefaction technology is developed, and wherein contains more nitrogen-containing compound, oxygenatedchemicals and aromatic hydrocarbons, olefinic material in the coal direct liquefaction oil, need to carry out hydrotreatment equally before using; The alkene and the oxygenatedchemicals that contain in other artificial artificial oil such as coal-based and the natural gas base Fischer-Tropsch synthesis oil also need carry out hydrotreatment before carrying out upgrading.
Hydrotreating catalyst is formed by alumina support load VI B family and metal component of group VIII usually.In general, for take hydrodesulfurization reaction as main course of reaction, the preferred Co-Mo combination of the hydrogenation activity component of catalyst, for being main course of reaction take hydrogenation deoxidation, hydrodenitrogeneration reaction and aromatic hydrogenation reaction, preferred Ni-Mo or Ni-W combination.
For example, CN1169336A discloses a kind of catalyst for hydrorefining distillate oil, it consists of nickel oxide 1-5 % by weight, tungsten oxide 12-35 % by weight, fluorine 1-9 % by weight, all the other are aluminium oxide, this aluminium oxide be by one or more little porous aluminum oxides and one or more macroporous aluminium oxides by 75: 25-50: 50 weight ratio is composited.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of hydrotreating catalyst and application thereof new, that performance is further improved.
The invention provides a kind of hydrotreating catalyst, contain alumina support, at least a VIII family and at least a metal component that is selected from VI B family of being selected from, it is characterized in that, described carrier is obtained through roasting by the boehmite composition that contains P1 and P2, take the total amount of boehmite composition as benchmark, the content of P2 is more than 50 % by weight in the described composition, and 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 present invention also provides a kind of method for hydrotreating hydrocarbon oil, is 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.
Compare with existing hydrogenation catalyst, the performance that the invention provides catalyst improves.
For example, under identical reaction condition, the invention provides 4 of catalyst, 6-dimethyl Dibenzothiophene hydrodesulfurization activity can improve 7-40% than the catalyst that prior art provides.And for example, in hydrogen dividing potential drop 6.4 MPas, 340 ℃ of reaction temperatures, liquid hourly space velocity (LHSV) 2.0 hours
-1Hydrogenation conditions under, Maoming straight-run diesel oil is carried out hydrotreatment, adopt to the invention provides catalyst C
2Relative hydrodesulfurization activity can improve 65% than contrast medium DC2.
The specific embodiment
According to catalyst provided by the invention, take the total amount of boehmite composition as benchmark, the content of described P2 is preferably more than 60 % by weight; Described P1 is preferably 1.2≤n
1≤ 2.2 boehmite, P2 is preferably 0.85≤n
2≤ 1.05 boehmite.
In a concrete embodiment, the weight ratio of P1 and P2 is 50 in the described composition: 50-5: 95, be preferably 40: 60-5: 95.
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, 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, also can be under the condition of pulp P1 to be mixed with P2 and water being enough to, afterwards after filtration, dry or moist.When adopting any one prior art to mix, those skilled in the art optionally can control the uniformity that described mixing should reach, and the present invention is not particularly limited this.
Described n=D (031)/D (120), wherein, the crystallite dimension of the crystal face of 031 peak representative in the XRD spectra of D (031) expression boehmite crystal grain, the crystallite dimension of the crystal face of 120 peak representatives in the XRD spectra of D (120) expression boehmite crystal grain, described 031 peak refers to that 2 θ in 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.
According to boehmite composition provided by the invention, wherein, described P2 is 0.8＜n
2＜1.1 boehmite can be the boehmite that adopts any one prior art preparation.
The preparation method of the boehmite P1 of described 1.1≤n≤2.5 comprises: aluminum contained compound solution is contacted with acid or alkali carry out precipitation reaction, perhaps organic aluminum contained compound is contacted the reaction that is hydrolyzed with water, obtain hydrated alumina; 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 one of arbitrary 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 in preferred 1.2≤n≤2.2 scopes.
Wherein, the consumption of grain growth conditioning agent is not particularly limited, the consumption of grain growth conditioning agent is the 0.5-10% of organic aluminum contained compound weight to be hydrolyzed, more preferably 1-8.5%, further preferred 5-8.5% in the selective hydrolysis reaction; The consumption of grain growth conditioning agent is the inorganic 0.5-10% that contains al reactant weight in the described precipitation reaction, more preferably 1-8.5%, further preferred 5-8.5%; In the described ageing process, the consumption of grain growth conditioning agent can be preferably 1-8.5% for the 0.5-10% of hydrated alumina weight, further preferred 5-8.5%.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% of inorganic aluminum contained compound weight, in the described hydrolysis, the consumption of described grain growth conditioning agent is the 0.5-10% 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% 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, be preferably polyhydroxy sugar alcohol and carboxylate thereof, be 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 can be two kinds or more of, use after mixing.Described aluminate solution is aluminate solution arbitrarily, such as sodium aluminate solution and/or potassium aluminate solution.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 one or more that are selected from 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 one or more that are selected from ammoniacal liquor, NaOH, the potassium hydroxide; Preferred salt is one or more that are selected from 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 source, 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 is 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 aluminum alkoxide contacts with water 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 ℃.
The embodiment of the boehmite of preparation 1.1≤n≤2.5 may further comprise the steps:
(1) will contain the aluminum contained compound solution of grain growth conditioning agent and aqueous slkali or acid solution parallel type 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 in the existence of grain growth conditioning agent or not, are 7-10,35-98 ℃ under at pH without filtration, aging 0.2-6 hour;
(3) product that filter, washing step (2) obtains;
(4) product that obtains of drying steps (3) obtains the boehmite of 1.1≤n provided by the invention≤2.5.
Described sintering temperature is 550-950 ℃, is preferably 600-850 ℃, roasting time 1-12 hour, is preferably 2-8 hour.
According to catalyst provided by the invention, wherein said carrier optionally can be made into the arbitrarily article shaped of convenient operation, such as sphere, compressing tablet and bar shaped.Described moulding can be carried out according to a conventional method, all can such as methods such as compressing tablet, spin, extrusions.Take the extruded moulding method as example, for guaranteeing carrying out smoothly of moulding, when moulding, usually need in material (being boehmite), introduce auxiliary agent and water etc. herein.For example, described boehmite and 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) are mixed then extrusion molding.Article shaped drying, roasting obtain carrier.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 ℃, 1-8 hour drying time, further preferred baking temperature is 60-150 ℃, and be 2-6 hour drying time.
According to catalyst provided by the invention, described VIII family metal component is preferably cobalt and/or nickel, VI B family metal component is preferably molybdenum and/or tungsten, in oxide and take catalyst as benchmark, the content of described VIII family metal component is the 1-10 % by weight, be preferably the 2-7 % by weight, the content of described VI B family metal component is the 10-45 % by weight, is preferably the 12-40 % by weight.
In one embodiment, described VIII family metal component is nickel, VI B family metal component is molybdenum and tungsten, in oxide and take catalyst as benchmark, the content of described nickel is the 2-7 % by weight, is preferably the 2-5 % by weight, the content of molybdenum is the 1-6 % by weight, be preferably the 1-5 % by weight, the content of tungsten is the 22-35 % by weight, is preferably the 26-33 % by weight.
In another embodiment, described VIII family metal component is nickel, and VI B family metal component is molybdenum, in oxide and take catalyst as benchmark, the content of described nickel is the 2-7 % by weight, is preferably the 2-6 % by weight, the content of molybdenum is the 10-30 % by weight, is preferably the 14-26 % by weight.
The preparation method of described catalyst is conventional method, comprises to described carrier introducing at least a VIII family and at least a metal component that is selected from VI B family of being selected from.
At least a VIII family and at least a method that is selected from the metal component of VI B family of being selected from of described introducing, can be contact with described carrier separately or after being hybridly prepared into solution containing at least a compound that is selected from VIII family and/or at least a metal component that is selected from VI B family, such as the method by flooding.Described dipping method is conventional method.Wherein, by the regulation and control to concentration, consumption or the carrier consumption of metal-containing compound solution, 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 the steps such as drying, roasting or not roasting.The condition of described drying and roasting 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 being selected from contained preferred their soluble compound of at least a compound that is selected from VIII family and at least a metal component that is selected from VI B family, for example, nickel compound containing can be one or more in the complex compound of nickel nitrate, nickel acetate, nickelous carbonate, nickel chloride, soluble nickel.Containing one or more in the soluble compound that molybdenum or tungsten compound be selected from molybdenum or tungsten, 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 phosphorus and or fluorine, in element and take catalyst as benchmark, the content of phosphorus and/or fluorine is not more than 10 % by weight, is preferably the 1-7 % by weight.
When also containing phosphorus and/or fluorine component in the described catalyst, the introducing method of described phosphorus and/or fluorine can be to have arbitrarily method now, as can being that phosphorous and/or fluorine compounds are directly introduced when the preparation shaping carrier; Can be with phosphorous and/or fluorine compounds with contact with described carrier after the compound that contains the hydrogenation active metals component is mixed with mixed solution; Can also be that phosphorus-containing compound and/or fluorine compounds and hydrogenation activity component are incorporated into respectively in the described carrier.When described phosphorus and/or fluorine and hydrogenation active metals are introduced described carrier respectively, preferably at first contact with described carrier and roasting with phosphorous and/or fluorine compounds solution, 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.
Described phosphorus-containing compound is selected from one or more in phosphoric acid, phosphorous acid, phosphate, the phosphite, preferably phosphoric acid or ammonium phosphate salt.Described fluorochemical is selected from ammonium fluoride, hydrogen fluoride, ammonium fluosilicate etc.
Can also contain organic additive in the catalyst provided by the invention, take described catalyst as benchmark, the content of described organic additive is no more than 20 % by weight, further preferably is no more than 15 % by weight.Described organic additive is to be selected from one or more that contain in oxygen or the organic compounds containing nitrogen, and preferred oxygen-containing organic compound is one or more that are selected from Organic Alcohol and the organic acid; Preferred organic compounds containing nitrogen is one or more that are selected from 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 enumerated ethylenediamine, EDTA and ammonium salt thereof etc.
When catalyst of the present invention 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 continue the method with the solution impregnation that contains organic compound and drying afterwards.Described drying can adopt customary way to carry out, and is not particularly limited, and 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 350-550 ℃, is preferably 400-500 ℃, and roasting time is 1-10 hour, is preferably 2-8 hour.
According to the conventional method in this area, the preparation method of hydrogenation catalyst provided by the invention preferably also is included in before the use, in the presence of hydrogen, under 140-370 ℃ temperature, with sulphur, hydrogen sulfide or sulfur-bearing raw material catalyst is carried out presulfurization, this presulfurization can be carried out also can original position vulcanizing in device outside device, thereby catalyst is converted into sulfide type.
According to method for hydrotreating hydrocarbon oil provided by the invention, wherein said hydrotreatment reaction condition is conventional hydrocarbon hydrotreatment reaction condition, for example, described hydrotreatment reaction condition comprises: reaction temperature 200-650 ℃, preferred 300-510 ℃, hydrogen dividing potential drop 2-20 MPa, preferred 3-15 MPa, liquid hourly space velocity (LHSV) 0.1-3 hour
-1, preferred 1-2 hour
-1, hydrogen/oil volume is than being 50-2000, preferred 100-1000.Wherein, can be different depending on the difference of processing feedstock oil or purpose, it is intelligible that this is that those skilled in the art hold.
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 device of described catalyst any, for example, at fixed bed reactors, carries out in moving-burden bed reactor or the fluidized bed reactor.
Catalyst provided by the invention is applicable to hydrocarbon raw material is carried out hydrotreatment, with production high-quality hydrocarbon fraction.Described hydrocarbon raw material can be various mineral oil or artificial oil or their mixed fraction oil, such as straight run gas oil, vacuum gas oil (VGO), metal removal oil, reduced crude, depitching decompression residuum, coker distillate, catalytic treatment distillate oil, shale oil, asphalt sand oil, ICL for Indirect Coal Liquefaction oil, DCL/Direct coal liquefaction wet goods.
The following examples will the present invention is described further, but not thereby limiting the invention.
Agents useful for same in the example except specifying, is chemically pure reagent.Each constituent content all adopts x-ray fluorescence spectrometry in the catalyst except specifying.
The n value of all boehmites all adopts XRD method to measure in the example of the present invention.The XRD test is carried out 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), the grain size that the calculation of parameter at ° peak goes out (120) take 2 θ as 23-33 respectively is D (031) as D (120), the calculation of parameter at ° peak goes out (031) take 2 θ as 34-43 grain size, and by formula n=D (031)/D (120) calculates the n value.
The boehmite P1 preparation method of employed 1.1≤n≤2.5 is as follows in the embodiment of the invention:
P1-1, 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, filter cake was through 120 ℃ of dryings 24 hours, obtain hydrated alumina P1-1, adopt XRD to characterize, P1-1 has structure of similar to thin diaspore.
Characterizing the n value that calculates P1-1 through XRD lists in the table 1.
P1-2, adopt following method preparation:
To contain 210 gram aluminium oxide/liter, the causticity coefficient is 1.62 high concentration NaAlO
2Solution and deionized water are mixed with Al
2O
3Concentration is 5 liters of the solution of 40 grams per liters, then adds the NaAlO that gluconic acid sodium salt 16.3 grams obtain containing gluconic acid sodium salt
2Then solution be transferred in the one-tenth glue reactor of cumulative volume 8L, and the reactor ratio of height to diameter is 8, bottom band CO
2Gas distributor.The control solution temperature is 25 ± 5 ℃, passes into the CO of concentration 90 volume % from reactor bottom
2Gas becomes the glue reaction, becomes the glue temperature to be controlled at 20-40 ℃, regulates CO
2Gas flow is 15 ± 2 liter/mins of clocks, makes reaction end pH value reach 8.0-8.5 in 4-6 minute, namely stops ventilation, finishes into the glue reaction.With the gained slurries be heated to 70 ℃ aging 4 hours, then filter with vacuum filter, to be filtered complete after, replenish at filter cake and to add 20 liters of deionized waters (temperature 70 C) flush cake about 30 minutes.The qualified filter cake of washing is joined 1.5 liters of deionized water for stirring become slurries, slurries carry out drying with being pumped into spray dryer, obtain hydrated alumina P1-2.XRD characterizes demonstration, and P1-2 has structure of similar to thin diaspore, characterizes the n value that calculates P1-2 through XRD and lists in the table 1.
P1-3, 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 about 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 about 2 minutes of dry materials time, obtains hydrated alumina P1-3 100-110 ℃ of scope after the drying.Adopt XRD to characterize, P1-3 has structure of similar to thin diaspore.The n value that adopts XRD method to calculate P1-3 is listed in the table 1.
The preparation method of the boehmite P2 of employed n＜1.1 is as follows in the embodiment of the invention.
P2-1, adopt following method preparation:
Prepare boehmite P2-1 according to the method for preparing P1-1, 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, finally obtain hydrated alumina P2-1.
XRD characterizes demonstration, and P2-1 has structure of similar to thin diaspore, and the n value that characterizes and calculate P2-1 through XRD is listed in the table 1.
Repeatedly prepare according to the method described above, to obtain enough for the boehmite raw material in the example.
P2-2 is the commercial boehmite SB powder that German Condea company produces.
P2-3 is the commercial boehmite SD powder that Shandong Aluminium Industrial Corp produces.Employing XRD characterizes and calculates the n value of P2-2 and P2-3 powder and lists in the table 1.
Table 1
Embodiment 1
Take by weighing 350 gram boehmite P1-1 and 650 gram boehmite P2-2, after the mixing, being extruded into circumscribed circle diameter with banded extruder is 1.6 millimeters cloverleaf pattern bar, 120 ℃ of dryings 6 hours.Get wherein 300 grams, at 850 ℃, calcination process is 2.0 hours under the blowing air condition, makes carrier S
1, wherein air mass flow is 2.0 standard cubic meter/kilograms. hour.
Take by weighing 100 gram carrier S
1, with 86 milliliters of dippings of the aqueous solution that contain ammonium paramolybdate 3.9 gram, nickel nitrate 28.2 grams and ammonium metatungstate 57.8 grams 2 hours, 120 ℃ of dryings 5 hours were processed 4 hours, and were obtained catalyst C for 180 ℃
1Catalyst C
1Middle MoO
3, NiO and WO
3Weight content be respectively 1.8%, 4.1% and 27.6%.
Embodiment 2
Take by weighing 100 gram carrier S
1Flooded 1 hour with 86 milliliters of the aqueous solution that contains ammonium paramolybdate 8.6 grams, 180 ℃ of dryings 5 hours, continuation was with 83 milliliters of dippings of the aqueous solution of containing nickel nitrate 29.6 gram, ammonium metatungstate 52.8 grams, phosphatase 11 3.5 grams and aminotriacetic acid 11.5 grams 2 hours, 120 ℃ of dryings 5 hours, processed 4 hours, and obtained catalyst C for 200 ℃
2Catalyst C
2Middle MoO
3, NiO, WO
3, P
2O
5Be respectively 3.6%, 3.8%, 22.1%, 4.3% and 5.9% with the weight content of organic additive.
Embodiment 3
Take by weighing 300 gram boehmite P1-2 and 700 gram boehmite P2-3, after the mixing, being extruded into circumscribed circle diameter with banded extruder is 1.6 millimeters cloverleaf pattern bar, 120 ℃ of dryings 8 hours.Get wherein 300 grams, at 800 ℃, calcination process is 4 hours under the blowing air condition, makes carrier S
2, wherein air mass flow is 1.5 standard cubic meter/kilograms. hour.
Take by weighing 100 gram carrier S
2, 85 milliliters of the aqueous solution with containing 10.7 gram ammonium fluorides flooded 1 hour, 130 ℃ of dryings 5 hours, and 480 ℃ of roastings 3 hours get fluorine-containing carrier, wherein fluorine-containing 5.0 % by weight.
Take by weighing above-mentioned fluorine-containing carrier 100 grams, with 85 milliliters of dippings of the aqueous solution that contain ammonium paramolybdate 4.9 grams, nickel nitrate 23.4 grams, ammonium metatungstate 54.6 grams and phosphoric acid 7.8 grams 2 hours, 120 ℃ of dryings 5 hours were processed 4 hours for 200 ℃.Continuation is with the aqueous solution dipping of 55 milliliters of the aqueous solution that contain glycerine 7.2 gram 1.5 hours, and 165 ℃ of dryings 6 hours obtain catalyst C
3Catalyst C
3Middle MoO
3, NiO, WO
3, F, P
2O
5Be respectively 2.2%, 3.3%, 24.8%, 3.2%, 2.7% and 4.0% with the weight content of organic additive.
Embodiment 4
Take by weighing 250 gram boehmite P1-3 and 750 gram boehmite P2-2, after the mixing, being extruded into circumscribed circle diameter with banded extruder is 1.6 millimeters cloverleaf pattern bar, 120 ℃ of dryings 4 hours.Get wherein 300 grams, at 750 ℃, calcination process is 5 hours under the blowing air condition, makes carrier S
3, wherein air mass flow is 2.0 standard cubic meter/kilograms. hour.
Take by weighing 100 gram carrier S
3, 84 milliliters of the aqueous solution with containing 13.0 gram ammonium fluorides flooded 1 hour, 120 ℃ of dryings 6 hours, and 400 ℃ of roastings 5 hours get fluorine-containing carrier, wherein fluorine-containing 6.0 % by weight.
Take by weighing fluorine-containing carrier 100 grams of this kind, with 84 milliliters of dippings of the aqueous solution that contain ammonium paramolybdate 3.4 gram, nickel nitrate 19.4 grams, ammonium metatungstate 63.9 grams, phosphoric acid 5.3 grams and ethylenediamine tetra-acetic acid 10.0 grams 1 hour, 120 ℃ of dryings 3 hours, 180 ℃ of dryings 4 hours obtain catalyst C
4Catalyst C
4Middle MoO
3, NiO, WO
3, F, P
2O
5Be respectively 1.5%, 2.6%, 28.2%, 3.6%, 1.8% and 5.4% with the weight content of organic additive.
Embodiment 5
Take by weighing 150 gram boehmite P1-1 and 850 gram boehmite P2-3, after the mixing, being extruded into circumscribed circle diameter with banded extruder is 1.4 millimeters cloverleaf pattern bar, 120 ℃ of dryings 4 hours.Get wherein 600 grams, at 700 ℃, calcination process is 6 hours under the blowing air condition, makes carrier S
4, wherein air mass flow is 3.0 standard cubic meter/kilograms. hour.
Take by weighing 100 gram carrier S
4, 83 milliliters of the aqueous solution with containing 15.8 gram ammonium fluorides flooded 2 hours, 100 ℃ of dryings 7 hours, and 450 ℃ of roastings 3 hours get fluorine-containing carrier, and fluorine content is 7.2 % by weight.
Take by weighing above-mentioned fluorine-containing carrier 100 grams, with 82 milliliters of dippings of the aqueous solution that contain ammonium paramolybdate 4.9 grams, nickel nitrate 23.9 grams, ammonium metatungstate 59.1 grams and citric acid 13.3 grams 1.5 hours, 120 ℃ of dryings 5 hours were processed 4 hours, and were obtained catalyst C for 200 ℃
5Catalyst C
5Middle MoO
3, NiO, WO
3, F and organic additive weight content be respectively 2.2%, 3.3%, 26.5%, 4.4% and 6.6%.
Embodiment 6
Take by weighing 100 gram boehmite P1-3 and 900 gram boehmite P2-3, after the mixing, being extruded into circumscribed circle diameter with banded extruder is 1.4 millimeters cloverleaf pattern bar, 120 ℃ of dryings 4 hours.Get wherein 300 grams, at 600 ℃, calcination process is 8 hours under the blowing air condition, makes carrier S
5, wherein air mass flow is 4.0 standard cubic meter/kilograms. hour.
Take by weighing 100 gram carrier S
5, with 82 milliliters of dippings of the aqueous solution that contain ammonium paramolybdate 6.3 gram, nickel nitrate 25.5 grams, ammonium metatungstate 62.0 grams, phosphatase 11 1.0 grams and citric acid 12.8 grams 1 hour, 120 ℃ of dryings 3 hours, 170 ℃ of dryings 6 hours obtain catalyst C
6Catalyst C
6Middle MoO
3, NiO, WO
3, P
2O
5Be respectively 2.6%, 3.3%, 25.8%, 3.4% and 5.9% with the weight content of organic additive.
Embodiment 7
Take by weighing 350 gram boehmite P1-1 and 650 gram boehmite P2-3, after the mixing, being extruded into circumscribed circle diameter with banded extruder is 1.6 millimeters cloverleaf pattern bar, 120 ℃ of dryings 6 hours.Get wherein 300 grams, at 600 ℃, calcination process is 5.0 hours under the blowing air condition, makes carrier S
6, wherein air mass flow is 2.0 standard cubic meter/kilograms. hour.
Take by weighing S
6Carrier 100 gram flooded 1 hour with 85 milliliters of the aqueous solution that contains nickel nitrate 15.5 grams and ammonium paramolybdate 32.2 grams, 120 ℃ of dryings 6 hours, and 450 ℃ of roastings 4 hours obtain catalyst C
7Catalyst C
7Middle NiO and MoO
3Weight content is respectively 3.0% and 20.0%.
Embodiment 8
Take by weighing S
2Carrier 100 grams, with 85 milliliters of dippings of the aqueous solution that contain nickel nitrate 20.6 gram, ammonium paramolybdate 34.8 grams and phosphatase 11 1.4 grams 1.5 hours, 120 ℃ of dryings 5 hours were processed 4 hours for 380 ℃, then with 55 milliliters of the aqueous solution dipping that contains 6.3 gram glycerine 2 hours, 140 ℃ of dryings obtained catalyst C in 5 hours
8Catalyst C
8Middle NiO, MoO
3, P
2O
5Be respectively 3.5%, 19.1% with the organic additive weight content, 4.8% and 4.3%.
Embodiment 9
Take by weighing S
3Carrier 100 gram, with 84 milliliters of dippings of the aqueous solution that contain nickel nitrate 26.6 grams, ammonium paramolybdate 32.8 grams, phosphatase 11 0.2 gram and ethylenediamine tetra-acetic acid 8.8 grams 1 hour, 120 ℃ of dryings 3 hours, 170 ℃ of dryings 6 hours obtain catalyst C
9Catalyst C
9Middle NiO, MoO
3, P
2O
5Be respectively 4.1%, 16.1%, 3.8% and 5.4% with the weight content of organic additive.
Embodiment 10
Take by weighing S
4Carrier 100 gram, with 83 milliliters of dippings of the aqueous solution that contain basic nickel carbonate 8.9 grams, molybdenum trioxide 32.9 grams, phosphoric acid 8.4 grams and tartaric acid 8.9 grams 1 hour, 170 ℃ of dryings 6 hours obtained catalyst C
10Catalyst C
10Middle NiO, MoO
3, P
2O
5Be respectively 3.2%, 21.2%, 3.3% and 5.7% with the weight content of organic additive.
Embodiment 11
Take by weighing S
5Carrier 100 gram, with 82 milliliters of dippings of the aqueous solution that contain basic nickel carbonate 10.6 grams, molybdenum trioxide 29.7 grams and phosphatase 79 .2 gram 1 hour, 120 ℃ of dryings 3 hours, 450 ℃ of roastings 4 hours.With 57 milliliters of dippings of the aqueous solution of containing citric acid 10.8 gram 1.5 hours, 180 ℃ of dryings obtained catalyst C in 3 hours again
11Catalyst C
11Middle NiO, MoO
3, P
2O
5Be respectively 3.9%, 19.6%, 3.7% and 6.5% with the weight content of organic additive.
Comparative Examples 1
Take by weighing 350 gram boehmite P2-1 and 650 gram boehmite P2-3, after the mixing, being extruded into circumscribed circle diameter with banded extruder is 1.6 millimeters cloverleaf pattern bar, 120 ℃ of dryings 6 hours.Get wherein 300 grams, at 600 ℃, calcination process is 5.0 hours under the blowing air condition, makes carrier DS
1, wherein air mass flow is 2.0 standard cubic meter/kilograms. hour.
Take by weighing DS
1Carrier 100 gram flooded 1 hour with 81 milliliters of the aqueous solution that contains nickel nitrate 15.5 grams and ammonium paramolybdate 32.2 grams, 120 ℃ of dryings 6 hours, and 450 ℃ of roastings 4 hours obtain reference catalyst DC1.NiO and MoO among the DC1
3Weight content is respectively 3.0% and 20.0%.
Comparative Examples 2
The method of the Kaolinite Preparation of Catalyst M that provides according to CN1169336A prepares reference catalyst DC2.Contain nickel oxide 2.3 % by weight, tungsten oxide 22.0 % by weight, fluorine 4.1 % by weight among the DC2.
Embodiment 12-22
Embodiment 12-22 explanation the inventive method provides the application performance of catalyst.
The catalyst activity evaluation is carried out at the continuous-flow high-pressure micro-device.Catalyst carries out first presulfurization to be processed.Conditions of vulcanization: sulfurized oil is the cyclohexane that contains carbon disulfide 5 % by weight, 360 ℃ of curing temperatures, and the hydrogen dividing potential drop is 4.14MPa.Vulcanize after 3 hours, pass into and contain the n-decane solution that 4,6-dimethyl Dibenzothiophene is 0.45 % by weight, also contain a small amount of sulfur-bearing and nitrogen-containing compound in this reaction raw materials, the catalyst loading amount is 0.15g, and reaction temperature is 300 ℃, and the hydrogen dividing potential drop is 4.14MPa.Reaction is carried out taking a sample after t hour, then adopts gas-chromatography (GC) methods analyst 4,6-dimethyl Dibenzothiophene residual concentration C
t4,6-dimethyl Dibenzothiophene hydrodesulfurization reaction is processed by first order reaction, and reaction rate constant is calculated by following method.
When at first calculating reacting time is t 4,6-dimethyl Dibenzothiophene desulfurization conversion ratio x:
x＝(C
0-C
t)/C
0
C in the formula
0Be when beginning reaction 4,6-dimethyl Dibenzothiophene concentration (C
0Be 0.45%), C
tWhen being t (be sample time, for different catalysts, keep identical reaction time t) for the reaction time 4,6-dimethyl Dibenzothiophene concentration.
4,6-dimethyl Dibenzothiophene desulphurization reaction speed constant is:
k＝1/t.Ln(1/(1-x))
The relative hydrodesulfurization activity of catalyst in the recently expression of the reaction rate constant on this catalyst with reaction rate constant on the Comparative Examples catalyst, the results are shown in Table 2 with 4,6-dimethyl Dibenzothiophene.
Comparative Examples 3
Application and the performance thereof of this Comparative Examples explanation reference catalyst.Adopt with embodiment 12 same procedure and estimate the DC1 catalyst, measure its reaction rate constant k, and to define its relative hydrodesulfurization activity be 100%.The results are shown in table 2.
Table 2
| Embodiment | Catalyst | Relative hydrodesulfurization activity/the % of catalyst |
| 12 | C 1 | 115 |
| 13 | C 2 | 140 |
| 14 | C 3 | 135 |
| 15 | C 4 | 138 |
| 16 | C 5 | 128 |
| 17 | C 6 | 120 |
| 18 | C 7 | 107 |
| 19 | C 8 | 120 |
| 20 | C 9 | 121 |
| 21 | C 10 | 123 |
| 22 | C 11 | 117 |
| Contrast medium 3 | DC1 | 100 |
By data declaration in the table 2, has higher hydrodesulfurization activity by catalyst provided by the invention.
Embodiment 23
Present embodiment further specifies application and the performance thereof that the invention provides catalyst.Reaction is carried out at 200 milliliters of hydrogenation plants, and feedstock oil is Maoming straight-run diesel oil of sulfur-bearing 0.97 % by weight.Before formal charging, with the kerosene that contains carbon disulfide 2 % by weight catalyst is vulcanized first.Conditions of vulcanization is: pressure 3.2 MPas, 300 ℃ of temperature, 25 hours time, sulfurized oil charging air speed 2 hours
-1, hydrogen/oil volume was cut afterwards raw material and is reacted than 300: 1, and reaction temperature is 340 ℃, and the hydrogen dividing potential drop is 6.4 MPas, and liquid hourly space velocity (LHSV) is 2 hours
-1, hydrogen/oil volume ratio is 300: 1.It is generally acknowledged that diesel hydrogenation for removal sulphur is 1.65 order reactions, reaction rate constant k
1Computing formula is:
C in the formula
p, C
fBe respectively sulfur content in product and the raw material, LHSV is the reactant liquor hourly space velocity.
The relative hydrodesulfurization activity of catalyst in the recently expression of the reaction rate constant on this catalyst with reaction rate constant on the Comparative Examples catalyst, the results are shown in Table 3 by diesel oil.
Comparative Examples 4
Application and the performance thereof of this Comparative Examples explanation reference catalyst.Adopt with embodiment 23 same procedure and estimate the DC2 catalyst, measure its reaction rate constant k
1, and to define its relative hydrodesulfurization activity be 100%.The results are shown in table 3
Table 3
| Embodiment | Catalyst | Relative hydrodesulfurization activity/the % of catalyst |
| 24 | C 2 | 165 |
| Contrast medium 4 | DC2 | 100 |
By data declaration in the table 3, by catalyst C provided by the invention
2Relative hydrodesulfurization activity improved 65% than contrast medium DC2.
Claims (17)
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, in oxide and take catalyst as benchmark, the content of described VIII family metal component is the 1-10 % by weight, the content of described group vib metal component is the 10-45 % by weight, it is characterized in that, described carrier is obtained through roasting by the boehmite composition that contains P1 and P2, take the total amount of boehmite composition as benchmark, the content of P2 is more than 50 % by weight in the described composition, 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, take the total amount of boehmite composition as benchmark, the content of described P2 is more than 60 % by weight; 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 weight ratio of P1 and P2 is 50 in the described composition: 50-5: 95.
4. catalyst according to claim 3 is characterized in that, the weight ratio of P1 and P2 is 40 in the described composition: 60-5: 95.
5. catalyst according to claim 1 is characterized in that, described sintering temperature is 550-950 ℃, roasting time 1-12 hour.
6. catalyst according to claim 5 is characterized in that, described sintering temperature is 600-850 ℃, roasting time 2-8 hour.
7. catalyst according to claim 1 is characterized in that, described VIII family metal component is cobalt and/or nickel, and the group vib metal component is molybdenum and/or tungsten.
8. catalyst according to claim 1 is characterized in that, the content of described VIII family metal component is the 2-7 % by weight, and the content of described group vib metal component is the 12-40 % by weight.
9. according to claim 1 or 7 described catalyst, it is characterized in that, described VIII family metal component is nickel, the group vib metal component is molybdenum and tungsten, in oxide and take catalyst as benchmark, the content of described nickel is the 2-7 % by weight, and the content of molybdenum is the 1-6 % by weight, and the content of tungsten is the 22-35 % by weight.
10. catalyst according to claim 9 is characterized in that, in oxide and take catalyst as benchmark, the content of described nickel is the 2-5 % by weight, and the content of molybdenum is the 1-5 % by weight, and the content of tungsten is the 26-33 % by weight.
11. according to claim 1 or 7 described catalyst, it is characterized in that described VIII family metal component is nickel, the group vib metal component is molybdenum, and in oxide and take catalyst as benchmark, the content of described nickel is the 2-7 % by weight, and the content of molybdenum is the 10-30 % by weight.
12. catalyst according to claim 11 is characterized in that, in oxide and take catalyst as benchmark, the content of described nickel is the 2-6 % by weight, and the content of molybdenum is the 14-26 % by weight.
13. catalyst according to claim 1 is characterized in that, described catalyst contains phosphorus and/or fluorine, and in element and take catalyst as benchmark, the content of phosphorus and/or fluorine is no more than 10 % by weight.
14. catalyst according to claim 13 is characterized in that, in element and take catalyst as benchmark, the content of phosphorus and/or fluorine is the 1-7 % by weight.
15. catalyst according to claim 1 is characterized in that, contains organic additive in the described catalyst, take described catalyst as benchmark, the content of described organic additive is no more than 20 % by weight.
16. catalyst according to claim 15 is characterized in that, take described catalyst as benchmark, the content of described organic additive is no more than 15 % by weight.
17. a method for hydrotreating hydrocarbon oil is included under the hydrotreatment reaction condition,, it is characterized in that the catalyst that described catalyst provides for claim 1-16 any one with hydrocarbon oil crude material and catalyst haptoreaction.
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| CN110038620B (en) * | 2018-01-16 | 2021-12-07 | 中国石油化工股份有限公司 | Process for preparing hydrocracking catalyst |
| CN113562752B (en) * | 2020-04-28 | 2023-05-05 | 中国石油化工股份有限公司 | Phosphorus-containing pseudo-boehmite, preparation method thereof, phosphorus-containing alumina and application thereof |
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|---|---|---|---|---|
| CN1169336A (en) * | 1996-06-28 | 1998-01-07 | 中国石油化工总公司 | Refined catalyst made by distillate added with hydrogen and preparation thereof |
| US6231750B1 (en) * | 1998-06-25 | 2001-05-15 | Institut Francais Du Petrole | Hydrocracking catalyst comprising a beta zeolite and a group VB element |
| CN1470609A (en) * | 2003-07-01 | 2004-01-28 | 中国石油天然气集团公司 | Catalyst for deep hydrogenation of distillate and its preparing method |
| CN101200654A (en) * | 2006-12-13 | 2008-06-18 | 中国石油化工股份有限公司 | Hydrotreatment catalyst |
| CN102161002A (en) * | 2010-02-24 | 2011-08-24 | 中国石油化工股份有限公司 | Catalyst for hydrotreatment and application thereof |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1169336A (en) * | 1996-06-28 | 1998-01-07 | 中国石油化工总公司 | Refined catalyst made by distillate added with hydrogen and preparation thereof |
| US6231750B1 (en) * | 1998-06-25 | 2001-05-15 | Institut Francais Du Petrole | Hydrocracking catalyst comprising a beta zeolite and a group VB element |
| CN1470609A (en) * | 2003-07-01 | 2004-01-28 | 中国石油天然气集团公司 | Catalyst for deep hydrogenation of distillate and its preparing method |
| CN101200654A (en) * | 2006-12-13 | 2008-06-18 | 中国石油化工股份有限公司 | Hydrotreatment catalyst |
| CN102161002A (en) * | 2010-02-24 | 2011-08-24 | 中国石油化工股份有限公司 | Catalyst for hydrotreatment and application thereof |
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