CN102218325B - Hydrotreating catalyst and application thereof - Google Patents
Hydrotreating catalyst and application thereof Download PDFInfo
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- CN102218325B CN102218325B CN 201110006581 CN201110006581A CN102218325B CN 102218325 B CN102218325 B CN 102218325B CN 201110006581 CN201110006581 CN 201110006581 CN 201110006581 A CN201110006581 A CN 201110006581A CN 102218325 B CN102218325 B CN 102218325B
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Abstract
The invention discloses a hydrotreating catalyst and application thereof. The hydrotreating catalyst comprises a forming carrier and hydrogenated active components carried on the carrier; and the hydrotreating catalyst is characterized in that the hydrogenated active metal components include nickel, molybdenum and tungsten; in terms of oxides and by taking the catalyst as the datum, the content of nickel is 2 to 7 percent by weight, the content of molybdenum is 1 to 6 percent by weight, and the content of tungsten is 22 to 35 percent by weight; the forming carrier is formed by treating a formed matter comprising at least one pseudoboehmite P1 with steam, wherein crystallite dimension ratio n of the pseudoboehmite P1 is larger than or equal to 1.1 and smaller than or equal to 2.5, n equalsto D(031)/D(120), D(031) indicates the crystallite dimension of the crystal face represented by a peak 031 in an XRD (X-Ray Diffraction) spectrogram of pseudoboehmite crystalline grains, D(120) indicates the crystallite dimension of the crystal face represented by a peak 120 in the XRD spectrogram of the pseudoboehmite crystalline grains, the peak 031 indicates that 2 Theta in the XRD spectrogramis a peak of 34-43 degrees, the peak 120 indicates that 2 Theta in the XRD spectrogram is a peak of 23-33 degrees, D equals to K Lambda/(Bcos Theta), K is a Scherrer constant, Lambda is the diffraction wavelength of target type materials, B is the half peak width of a diffraction peak, and 2 Theta is the position of the diffraction peak. Compared with the traditional hydrotreating catalyst, the hydrotreating catalyst provided by the invention has an improved performance.
Description
Technical field
The invention relates to a kind of hydrotreating catalyst and application thereof.
Background technology
Nitrogen oxide (NO in the vehicular emission tail gas
X) not only form the acid rain of city and surrounding 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 big to auto-pollution thing discharging influence 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 the motor vehicle vent gas purification catalysis agent to be poisoned again.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 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 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 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 supported V IB family and group VIII metal component usually.In general, for the course of reaction based on hydrodesulfurization reaction, the preferred Co-Mo combination of the hydrogenation activity component of catalyst, for the course of reaction based on hydrogenation deoxidation, hydrodenitrogeneration reaction and aromatic hydrogenation reaction, preferred Ni-Mo or Ni-W combination.
Studies show that,, show better hydrotreatment performance by the catalyst of Ni-Mo-W combined preparation under certain condition.For example, CN 100469443C discloses a kind of for petroleum distillate oil hydrotreating catalysts, this catalyst is made up of nickel oxide, molybdenum oxide, tungsten oxide and aluminium oxide, also contain phosphorus and organic matter, be benchmark with the roasting rear catalyst, each constituent content is respectively: nickel oxide 1-10 weight %, and molybdenum oxide and tungsten oxide weight content sum are greater than 10-50 weight %, phosphorous oxide 1-9 weight %, all the other are silica+aluminium oxide.This catalyst has fraction oil hydrogenation refining performance preferably.
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 shaping carrier and the hydrogenation activity component that loads on this carrier, it is characterized in that, described hydrogenation active metals component is nickel, molybdenum and tungsten, be benchmark in oxide and with the catalyst, the content of described nickel is 2-7 weight %, and the content of molybdenum is 1-6 weight %, the content of tungsten is 22-35 weight %, and described shaping carrier is obtained through steam treatment by the article shaped of the boehmite P1 that comprises at least a 1.1≤n≤2.5; Wherein, n=D (031)/D (120), the crystallite dimension of the crystal face of 031 peak representative in the XRD spectra of described D (031) expression boehmite crystal grain, the crystallite dimension of the 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, D=K λ/(Bcos θ), K is the Scherrer constant, λ is the diffraction wavelength of target section bar material, B is the half-peak breadth of diffraction maximum, and 2 θ are the position of diffraction maximum.
The present invention also provides a kind of method for hydrotreating hydrocarbon oil, is included under the hydrotreatment reaction condition, with hydrocarbon oil crude material oil and catalyst haptoreaction, it is characterized in that described catalyst is aforesaid catalyst provided by the invention.
Compare with existing hydrogenation catalyst, the performance that the invention provides catalyst improves.For example, under identical reaction condition, the hydrodesulfurization activity that the invention provides catalyst can improve 14-24% than the catalyst that prior art provides.
The specific embodiment
According to catalyst provided by the invention, wherein said P1 is preferably the boehmite of 1.2≤n≤2.2.Described n=D (031)/D (120), the crystallite dimension of the crystal face of 031 peak representative in the XRD spectra of described D (031) expression boehmite crystal grain, the crystallite dimension of the crystal face of 120 peak representatives in the XRD spectra of D (120) expression boehmite crystal grain, described 031 peak refers to that 2 θ in 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, and λ is the diffraction wavelength of target section bar material, and B is the half-peak breadth of this diffraction maximum, 2 θ are the position of this diffraction maximum, for different diffraction maximums, the value that B and 2 θ all get peak correspondingly, for example, when calculating D (031), D (031)=K λ/(Bcos θ), wherein B is the half-peak breadth of 031 diffraction maximum, 2 θ are the position of 031 diffraction maximum; When calculating D (120), D (120)=K λ/(Bcos θ), wherein B is the half-peak breadth of 120 diffraction maximums, 2 θ are the position of 120 diffraction maximums.
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; The above-mentioned hydrated alumina that obtains is worn out, wherein, described aluminum contained compound solution and acid or alkali contact or described organic aluminum contained compound and water contact and hydrated alumina aging in any one process in the presence of the grain growth conditioning agent, carry out, described grain growth conditioning agent is for can regulate the material of the speed of growth of crystal grain on different crystal faces.
As long as although make hydrolysis or precipitation reaction and aging in 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 the n of gained boehmite like this 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% that treats organic aluminum contained compound weight of hydrolysis in the selective hydrolysis reaction, more preferably 1-8.5%, further preferred 5-8.5%; 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 is that benchmark calculates with the weight of aluminium oxide corresponding in organic aluminum contained compound, inorganic aluminum contained compound and the hydrated alumina respectively.Also be, in aluminium oxide, in the described precipitation reaction, the consumption of described grain growth conditioning agent is the 0.5-10% 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 use two kinds or more of mixing back.Described aluminate solution is aluminate solution arbitrarily, 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 with aluminium oxide.
Described acid can be various Bronsted acids or be acid oxide in aqueous medium, for example, can be in sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid, the oxalic acid one or more, preferred Bronsted acid be to be selected from nitric acid, sulfuric acid, the hydrochloric acid one or more.Described carbonic acid can original position produces by feed carbon dioxide in aluminum salt solution and/or aluminate solution.Concentration to described acid solution is not particularly limited, and the concentration of preferred H+ is the 0.2-2 mol.
Described aqueous slkali can for hydroxide or in aqueous medium hydrolysis make the aqueous solution be the salt of alkalescence, preferred hydroxide is to be selected from ammoniacal liquor, NaOH, the potassium hydroxide one or more; Preferred salt is to be selected from sodium metaaluminate, potassium metaaluminate, carbonic hydroammonium, ammonium carbonate, sodium acid carbonate, sodium carbonate, saleratus, the potash one or more.Concentration to described aqueous slkali is not particularly limited, preferred OH
-Concentration be the 0.2-4 mol.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 with water generation hydrolysis, producing in the aluminum alkoxide of aqua oxidation aluminum precipitation one or more, for example can be in aluminium isopropoxide, isobutanol aluminum, aluminium isopropoxide, three tert-butoxy aluminium and the isooctanol aluminium one or more.Described organic aluminum contained compound and water consumption ratio are not particularly limited, and the preferred water yield is greater than the required amount of stoichiometry.
In boehmite preparation process of the present invention, the described condition of precipitation reaction that makes is not particularly limited, preferred pH value is 3-11, more preferably 6-10; Temperature 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 takes place, and the condition that hydrolysis specifically takes place is conventionally known to one of skill in the art.
Wherein, can in hydrolysis or precipitation reaction obtain slurries that the slurries of hydrated alumina or filter cake after filtering add the water preparation again, add the compound of crystal grain growth regulating effect, also can add aqueous slkali or acid solution and suitably regulate the pH value to 7-10, under suitable temperature, wear out then.Separate then, washing, drying.
Described acid solution or aqueous slkali can be with above-described identical or different.
Described aging temperature is preferably 35-98 ℃, and ageing time is preferably 0.2-6 hour.
According to method provided by the invention, the described known technology that is separated into this area is as the method for filtration or centrifugation or evaporation.
In boehmite preparation process of the present invention, after aging, also comprise the washing and the dry step that often comprise in the preparation boehmite process, described washing and dry method are preparation boehmite conventional process.For example, can use oven dry, forced air drying or spray-dired method.Generally speaking, baking temperature can be 100-350 ℃, is preferably 120-300 ℃.
According to the preparation method of boehmite of the present invention, an embodiment preferred may further comprise the steps:
(1) will contain the aluminum contained compound solution of grain growth conditioning agent and aqueous slkali or acid solution 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; Also the hydrated alumina slurries that above-mentioned steps (1) can be obtained without filter the grain growth conditioning agent exist or not in the presence of be under the 7-10 at pH, in 35-98 ℃ of aging 0.2-6 hour;
(3) product that filter, washing step (2) obtains;
(4) product that obtains of drying steps (3) obtains the boehmite of 1.1≤n provided by the invention≤2.5.
According to catalyst provided by the invention, wherein said shaping carrier optionally can be made into is convenient to the article shaped of operating arbitrarily, as spherical, compressing tablet and bar shaped.Described moulding can be carried out according to a conventional method, all can as methods such as compressing tablet, spin, extrusions.
The method of described steam treatment and condition are this area customary way and condition, for example, can will comprise that the article shaped of boehmite P1 of at least a 1.1≤n≤2.5 is without the one-step method of directly carrying out steam treatment of roasting, also the article shaped that comprises the boehmite P1 of at least a 1.1≤n≤2.5 at first can be carried out roasting, carry out the two step method of steam treatment afterwards again.The condition of described steam treatment comprises: temperature is 400-800 ℃, be preferably 500-650 ℃, time is 1-10 hour, be preferably 2-6 hour, wherein, described steam is air and mixture of steam, and the mixed proportion of air and steam (volume) is 1: 0.3-15, mixed gas flow be the 0.4-6 standard cubic meter/(kilogram carrier. hour).When the two-step method steam treatment, the condition of described roasting comprises: sintering temperature is 350-700 ℃, is preferably 500 ℃-650 ℃, and roasting time is 1-10 hour, is preferably 2-6 hour.
According to catalyst provided by the invention, wherein, described boehmite can comprise the boehmite P2 except the boehmite of 1.1≤n≤2.5, described P2 is the boehmite of n＜1.1, preferred P2 is the boehmite of 0.8＜n＜1.1, and further preferred P2 is the boehmite of 0.85≤n≤1.05.When described composition contains P2, be benchmark in oxide and with the boehmite total amount, the content of described P2 is not more than 50 weight %, further preferably is not more than 30 weight %, more preferably is not more than 20 weight %.
According to catalyst provided by the invention, wherein, can also contain silica and/or molecular sieve in the described carrier.When described carrier contains silica and/or molecular sieve, be benchmark with described carrier, the content of described silica is not more than 30 weight %, preferably is not more than 25 weight %, and the content of described molecular sieve is not more than 15 weight %, preferably is not more than 12 weight %.
When containing silica and/or molecular sieve in the described shaping carrier, the preparation of described shaping carrier comprises the precursor of described boehmite and silica and/or molecular sieve mixes and the step of moulding.The precursor of described silica is preferably Ludox, described molecular screening one or more in Y zeolite, beta-molecular sieve.Wherein, the preferred HY of described Y zeolite and/or ultra-steady Y molecular sieve (USY).
According to catalyst provided by the invention, be benchmark in oxide and with the catalyst, the content of described nickel is 2-7 weight %, be preferably 2-5 weight %, the content of molybdenum is 1-6 weight %, is preferably 1-5 weight %, the content of tungsten is 22-35 weight %, is preferably 26-33 weight %.
Described Preparation of catalysts method is conventional method, comprises to described carrier introducing nickel, molybdenum and tungsten metal component.
The method of described introducing nickel, molybdenum and tungsten metal component can be to contact with described carrier separately or after being hybridly prepared into solution containing nickel compound, molybdate compound and Tungstenic compound, as the method by dipping.Described dipping method is conventional method.Wherein, by adjusting and the control to concentration, consumption or the carrier consumption of containing metal compound solution, can prepare the described catalyst of specifying content, this is the understanding easily of those skilled in the art institute.
According to the present invention, after described impregnation steps is finished, optionally can carry out 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 nickel compound containing is selected from one or more in the solubility nickel compound containing, for example, can be in the complex compound of nickel nitrate, nickel acetate, nickelous carbonate, nickel chloride, soluble nickel one or more.
Saidly containing in the soluble compound that molybdenum or tungsten compound be selected from molybdenum or tungsten one or more, for example, can be in molybdate, paramolybdate, tungstates, metatungstate, the ethyl metatungstate one or more.
Can also contain phosphorus in the catalyst provided by the invention, with P
2O
5Meter and be benchmark with the catalyst, the content of described phosphorus is no more than 7 weight %, is preferably to be no more than 5 weight %.
When also containing phosphorus component in the described catalyst, the introducing method of described phosphorus can be to have method arbitrarily now, as can being that phosphorus-containing compound is directly introduced during shaping carrier in preparation; Can be with phosphorus-containing compound 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 hydrogenation activity component are incorporated into respectively in the described carrier.When described phosphorus and hydrogenation active metals are introduced described carrier respectively, preferably at first contact with described carrier and roasting with phosphorus-containing compound 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.
Can also contain organic additive in the catalyst provided by the invention, be benchmark with described catalyst, and the content of described organic additive is no more than 20 weight %, further preferably is no more than 15 weight %.Described organic additive is to be selected to contain in oxygen or the organic compounds containing nitrogen one or more, and preferred oxygen-containing organic compound is to be selected from organic pure and mild organic acid one or more; Preferred organic compounds containing nitrogen is to be selected from the organic amine one or more.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.
When catalyst of the present invention further contains organic compound, the introducing method of described organic compound can be arbitrary method, 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 impregnated carrier behind the solution separately.In a kind of method in back, 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, hydrogenization catalyst preparation method 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 oil hydrogenation processing 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, look the difference of the feedstock oil of handling or purpose can be different, this is the understanding easily of those skilled in the art institute.
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.
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, 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 adopts x-ray fluorescence spectrometry except specifying in the catalyst.
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 section bar material, B is the half-peak breadth of corrected diffraction maximum, 2 θ are the position of diffraction maximum) be that grain size that the calculation of parameter at 23-33 ° of peak goes out (120) is D (120), is that the grain size that the calculation of parameter at 34-43 ° of peak goes out (031) is D (031) with 2 θ with 2 θ respectively, and 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 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, the pH value that adds proper ammonia adjusting slurries in slurries again is 8.5, slurries filtered after under 55 ℃ aging 60 minutes, filter cake washs 2 times with the deionized water making beating, filter cake obtains hydrated alumina P1-1 through 120 ℃ of dryings 24 hours.
XRD characterizes and shows that P1-1 has structure of similar to thin diaspore, calculates the n value of P1-1, 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, adds the NaAlO that gluconic acid sodium salt 16.3 grams obtain containing gluconic acid sodium salt then
2Solution is transferred in the one-tenth glue reactor of cumulative volume 8L then, and the reactor ratio of height to diameter is 8, bottom band CO
2Gas distributor.The control solution temperature is 25 ± 5 ℃, feeds the CO of concentration 90 volume % from reactor bottom
2Gas becomes the glue reaction, becomes the control of glue temperature at 20-40 ℃, regulates CO
2Gas flow is 15 ± 2 liters/minute, makes reaction end pH value reach 8.0-8.5 in 4-6 minute, namely stops ventilation, finishes into the glue reaction.With aging 4 hours of gained slurries heat temperature raising to 70 ℃, filter with vacuum filter then, to be filtered intact after, replenish at filter cake and to add 20 liters of deionized waters (70 ℃ of temperature) flush cake about 30 minutes.The qualified filter cake of washing is joined 1.5 liters of deionized water for stirring become slurries, slurries carry out drying with being pumped into spray dryer, obtain hydrated alumina P1-2.
XRD characterizes and shows that P1-2 has structure of similar to thin diaspore, calculates the n value of P1-2, 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 is during 80 ℃, conditioned reaction logistics capacity make and the pH value is 4.0, reaction time 15 minutes; Adding concentration in the gained slurries is the weak aqua ammonia adjusting slurries pH to 10.0 of 5 weight %, and be warming up to 80 ℃, aging 3 hours, filter with vacuum filter then, behind to be filtered the finishing, replenished adding 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.
XRD characterizes and shows that P1-3 has structure of similar to thin diaspore, calculates the n value of P1-3, lists 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.Last filter cake drying obtains hydrated alumina P2-1.
XRD characterizes and shows that P2-1 has structure of similar to thin diaspore, calculates the n value of P2-1, lists in the table 1.
P2-2, adopt following method preparation:
Prepare boehmite P2-2 according to the method for preparing P1-3, different is, aluminum trichloride solution change into concentration be 48 gram aluminium oxide/liter aluminum sulfate solution, and do not contain D-sorbite in the sodium aluminate solution.Last filter cake drying obtains hydrated alumina P2-2.
XRD characterizes and shows that P2-2 has structure of similar to thin diaspore, calculates the n value of P2-2, lists in the table 1.
Repeatedly preparation according to the method described above is to obtain enough for the boehmite raw material that uses in the example.
Table 1
Embodiment 1
Take by weighing 1000 gram boehmite P1-1, being extruded into circumscribed circle diameter with banded extruder is 1.6 millimeters cloverleaf pattern bar, 120 ℃ of dryings 6 hours.Getting wherein 300 grams, with the one-step method method for steam treatment, is 1: 0.6 in the volume ratio of air and steam, and gas flow is 1.2 standard cubic meter/kilograms. hour, temperature is processing 3 hours under 600 ℃ of conditions, makes carrier S
1
Take by weighing S
1Carrier 100 gram, with 88 milliliters of dippings of the aqueous solution that contain ammonium paramolybdate 4.9 grams, nickel nitrate 21.9 grams, ammonium metatungstate 52.1 grams, phosphatase 79 .2 gram 2 hours, 120 ℃ of dryings 5 hours, 450 ℃ of roastings 4 hours.Then with 83 milliliters of the aqueous solution dipping that contains 6.6 gram glycerine 1 hour, 130 ℃ of dryings 6 hours obtain catalyst C
1Catalyst C
1Middle MoO
3, NiO, WO
3And P
2O
5Be respectively 2.4%, 3.4%, 25.9%, 3.5% and 4.0% with the weight content of organic additive.
Embodiment 2
Take by weighing 500 gram boehmite P1-2,500 gram boehmite P2-1, being extruded into circumscribed circle diameter with banded extruder is 1.6 millimeters cloverleaf pattern bar, 120 ℃ of dryings 8 hours.Getting wherein 300 grams, with the one-step method method for steam treatment, is 1: 0.8 in the volume ratio of air and steam, and gas flow is 1.4 standard cubic meter/kilograms. hour, temperature is processing 4 hours under 580 ℃ of conditions, makes carrier S
2
Take by weighing S
2Carrier 100 gram, with 88 milliliters of dippings of the aqueous solution that contains ammonium paramolybdate 7.0 grams 1 hour, 180 ℃ of dryings 6 hours.Continuation is with 87 milliliters of dippings of the aqueous solution of containing nickel nitrate 27.9 gram, ammonium metatungstate 45.8 grams, phosphatase 79 .6 gram and aminotriacetic acid 12.9 grams 2 hours, and 120 ℃ of dryings 5.5 hours are handled for 200 ℃ and obtained catalyst C in 4 hours
2Catalyst C
2Middle MoO
3, NiO, WO
3, P
2O
5Be respectively 3.0%, 3.8%, 20.3%, 3.2% and 7.0% with the weight content of organic additive.
Embodiment 3
Take by weighing 800 gram boehmite P1-3,200 gram boehmite P2-2, being extruded into circumscribed circle diameter with banded extruder is 1.6 millimeters cloverleaf pattern bar, 120 ℃ of dryings 4 hours.Getting wherein 300 grams, with the one-step method method for steam treatment, is 1: 1 in the volume ratio of air and steam, and gas flow is 1.6 standard cubic meter/kilograms. hour, temperature is processing 6 hours under 560 ℃ of conditions, makes carrier S
3
Take by weighing S
3Carrier 100 gram, with 86 milliliters of dippings of the aqueous solution that contain ammonium paramolybdate 6.4 grams, nickel nitrate 25.0 grams, ammonium metatungstate 48.2 grams and phosphatase 11 0.7 gram 1 hour, 120 ℃ of dryings 3 hours, 400 ℃ of roastings 6 hours.Flooded 2.5 hours with the aqueous solution that contains malic acid 6.2 grams, 200 ℃ of dryings obtained catalyst C in 3 hours again
3Catalyst C
3Middle MoO
3, NiO, WO
3, P
2O
5Be respectively 3.2%, 3.8%, 24.1%, 4.0% and 3.8% with the weight content of organic additive.
Embodiment 4
Take by weighing 900 gram boehmite P1-1 (butt is 0.7), 109.4 gram beta-molecular sieve (Chang Ling catalyst plant industrial products, butt is 0.72) and 315 the gram silicon oxide-containings be the Ludox (Qingdao wave silica-gel desiccant factory industrial products) of 25 weight %, being extruded into circumscribed circle diameter with banded extruder is 1.6 millimeters cloverleaf pattern bar, 120 ℃ of dryings 4 hours.Getting wherein 600 grams, is 1: 1 in the volume ratio of air and steam, and gas flow is 1.6 standard cubic meter/kilograms. hour, temperature is processing 3 hours under 600 ℃ of conditions, makes carrier S 4.Getting the S4 vehicle group as calculated becomes: aluminium oxide 80.0 weight %, silica 10.0 weight %, beta-molecular sieve 10.0 weight %.
Take by weighing S
4Carrier 100 gram, with 86 milliliters of dippings of the aqueous solution that contain ammonium paramolybdate 4.4 grams, nickel nitrate 33.9 grams, ammonium metatungstate 71.9 grams and phosphatase 11 1.0 grams 1.5 hours, 120 ℃ of dryings 5 hours were handled 4 hours, and were obtained catalyst C for 200 ℃
4Catalyst C
4Middle MoO
3, NiO, WO
3And P
2O
5Weight content is respectively 1.8%, 4.3%, and 29.9% and 3.4%.
Embodiment 5
Take by weighing S
4Carrier 100 gram, with 86 milliliters of dippings of the aqueous solution that contain ammonium paramolybdate 6.3 grams, nickel nitrate 30.1 grams, ammonium metatungstate 68.2 grams and citric acid 21.4 grams 2 hours, 200 ℃ of dryings 10 hours.Obtain catalyst C
5Catalyst C
5Middle MoO
3, NiO, WO
3Be respectively 2.5%, 3.7% with the weight content of organic additive, 27.5% and 10.6%.
Embodiment 6
Take by weighing S
4Carrier 100 gram, with 86 milliliters of dippings of the aqueous solution that contain ammonium paramolybdate 4.0 grams, nickel nitrate 21.2 grams, ammonium metatungstate 59.3 grams and phosphoric acid 7.3 grams 3 hours, 150 ℃ of dryings 10 hours.Again with 83 milliliters of dippings of the aqueous solution of containing ethanedioic acid tetraacethyl 15.9 gram 2 hours, 120 ℃ of dryings 5 hours were handled 4 hours, and were obtained catalyst C for 200 ℃
6Catalyst C
6Middle MoO
3, NiO, WO
3And P
2O
5Be respectively 1.7%, 2.8%, 25.5%, 2.4% and 8.4% with the weight content of organic additive.
Embodiment 7
Take by weighing 900 gram boehmite P1-2 (butt is 0.7), 57.5 gram HY molecular sieve (Chang Ling catalyst plant industrial products, butt is 0.73) and 560 the gram silicon oxide-containings be the Ludox (Qingdao wave silica-gel desiccant factory industrial products) of 30 weight %, being extruded into circumscribed circle diameter with banded extruder is 1.6 millimeters cloverleaf pattern bar, 120 ℃ of dryings 5 hours.Getting wherein 300 grams, is 1: 1.5 in the volume ratio of air and steam, and gas flow is 1.2 standard cubic meter/kilograms. hour, temperature is processing 6 hours under 560 ℃ of conditions, makes carrier S
5Get S as calculated
5Vehicle group becomes: aluminium oxide 75.0 weight %, silica 20.0 weight %, HY molecular sieve 5.0 weight %.
Take by weighing S
5Carrier 100 gram, with 86 milliliters of dippings of the aqueous solution that contain ammonium paramolybdate 5.9 grams, nickel nitrate 24.1 grams, ammonium metatungstate 54.7 grams, phosphoric acid 6.7 grams and citric acid 12.9 grams 1 hour, 120 ℃ of dryings 3 hours, 170 ℃ of dryings 6 hours obtain catalyst C
7Catalyst C
7Middle MoO
3, NiO, WO
3, P
2O
5Be respectively 2.6%, 3.3%, 24.2%, 2.2% and 7.0% with the weight content of organic additive.
Embodiment 8
Take by weighing 900 gram boehmite P1-3,73.6 gram USY molecular sieve (Chang Ling catalyst plant industrial products, butt is 0.74) and 95.2 gram silica gel (Qingdao wave silica-gel desiccant factory industrial products, butt is 0.98), being extruded into circumscribed circle diameter with banded extruder is 1.6 millimeters cloverleaf pattern bar, 120 ℃ of dryings 4 hours.Getting wherein 300 grams, is 1: 2 in the volume ratio of air and steam, and gas flow is 1.0 cubic metres/kilogram. hour, temperature is processing 4 hours under 580 ℃ of conditions, makes carrier S
6Get S as calculated
6Vehicle group becomes: aluminium oxide 81.0 weight %, silica 12.0 weight %, USY molecular sieve 7.0 weight %.
Take by weighing S
6Carrier 100 gram, with 86 milliliters of dippings of the aqueous solution that contains ammonium paramolybdate 12.3 grams 1 hour, 150 ℃ of dryings 8 hours.Again with 84 milliliters of dippings of the aqueous solution of containing nickel nitrate 19.5 gram, ammonium metatungstate 41.2 grams and phosphoric acid 7.5, malic acid 9.7 grams 2 hours, 180 ℃ of dryings 4 hours obtain catalyst C
8Catalyst C
8Middle MoO
3, NiO, WO
3, P
2O
5Be respectively 5.7%, 2.8%, 19.2%, 2.6% and 5.5% with the weight content of organic additive.
Comparative Examples 1
The method that provides according to CN 100469443C prepares reference agent 1.
Take by weighing 2000 gram aluminium hydrate powder (Chang Ling branch company catalyst plant industrial products dry glue powders, butt is 0.71) and 1039 grams contain the Ludox (Haiyang Chemical Plant, Qingdao's industrial products) of silica 30 weight %, mixing the back, to be extruded into circumscribed circle diameter with banded extruder be 1.4 millimeters butterfly bar, wet bar was in 120 ℃ of dryings 4 hours, under 600 ℃ of conditions during roasting 3, make carrier, getting silica content as calculated is 18.0 weight %.
Take by weighing carrier 200 grams, flooded above-mentioned carriers 3 hours for 176 milliliters with the aqueous solution that contains ammonium paramolybdate 8.0 grams, phosphatase 11 2.2 grams, 120 ℃ of dryings 4 hours, 220 ℃ of dryings are 4 hours again, flooded this carrier 3 hours for 170 milliliters with the aqueous solution that contains nickel nitrate 114.5 grams, ammonium metatungstate 197.5 grams, phosphoric acid 282 grams afterwards, 120 ℃ of dryings 4 hours, 240 ℃ of dryings 4 hours obtain contrast medium 1.MoO in the contrast medium 1 after roasting
3, NiO, WO
3, P
2O
5Weight content be respectively 1.5%, 6.7%, 39.5% and 5.8%.
Embodiment 9～17
The catalyst activity evaluation method that embodiment 9～17 explanation the inventive method provide.
The catalyst activity evaluation is carried out at the continuous-flow high-pressure micro-device.Catalyst carries out presulfurization earlier to be handled.Conditions of vulcanization: sulfurized oil is for containing CS
2Be the cyclohexane of 5 weight %, 360 ℃ of curing temperatures, the hydrogen dividing potential drop is 4.14MPa.Vulcanize after 3 hours, feeding contains the n-decane solution that 4,6-dimethyl Dibenzothiophene is 0.45 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, dilutes with 1.0g quartz sand, reaction temperature is 300 ℃, and the hydrogen dividing potential drop is 4.14MPa.Reaction is carried out taking a sample after t hour, adopts gas-chromatography (GC) methods analyst 4 then, 6-dimethyl Dibenzothiophene residual concentration C
t4,6-dimethyl Dibenzothiophene hydrodesulfurization reaction is handled 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 with the reaction rate constant of 4,6-dimethyl Dibenzothiophene on this catalyst with react at the Comparative Examples catalyst
Speed constantRecently the expression, the results are shown in Table 2.
Table 2
| Example | Catalyst | Relative hydrodesulfurization activity/the % of catalyst |
| 9 | C 1 | 118 |
| 10 | C 2 | 114 |
| 11 | C 3 | 116 |
| 12 | C 4 | 115 |
| 13 | C 5 | 117 |
| 14 | C 6 | 121 |
| 15 | C 7 | 123 |
| 16 | C 8 | 124 |
| 17 | Contrast medium 1 | 100 |
By data declaration in the table 2, has higher hydrodesulfurization activity by catalyst provided by the invention.
Claims (13)
1. hydrotreating catalyst, contain shaping carrier and the hydrogenation active metals component that loads on this carrier, it is characterized in that, described hydrogenation active metals component is nickel, molybdenum and tungsten, be benchmark in oxide and with the catalyst, the content of described nickel is 2-7 weight %, and the content of molybdenum is 1-6 weight %, the content of tungsten is 22-35 weight %, and described shaping carrier is obtained through steam treatment by the article shaped of the boehmite P1 that comprises at least a 1.1≤n≤2.5; Wherein, n=D (031)/D (120), the crystallite dimension of the crystal face of 031 peak representative in the XRD spectra of described D (031) expression boehmite crystal grain, the crystallite dimension of the 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, D=K λ/(Bcos θ), K is the Scherrer constant, λ is the diffraction wavelength of target section bar material, B is the half-peak breadth of diffraction maximum, and 2 θ are the position of diffraction maximum.
2. catalyst according to claim 1 is characterized in that, described P1 is the boehmite of 1.2≤n≤2.2.
3. catalyst according to claim 1 is characterized in that, is benchmark in oxide and with the catalyst, and the content of described nickel is 2-5 weight %, and the content of molybdenum is 1-5 weight %, and the content of tungsten is 26-33 weight %.
4. catalyst according to claim 1, it is characterized in that, comprising n＜1.1 boehmite P2 in the article shaped of the described boehmite P1 that comprises at least a 1.1≤n≤2.5, is benchmark with the boehmite total amount, and the content of described P2 is not more than 50 weight %.
5. catalyst according to claim 4 is characterized in that, is benchmark with the boehmite total amount, and the content of described P2 is not more than 30 weight %.
6. catalyst according to claim 5 is characterized in that, is benchmark with the boehmite total amount, and the content of described P2 is not more than 20 weight %.
7. catalyst according to claim 1 is characterized in that, contains silica and/or molecular sieve in the described shaping carrier, is benchmark with described carrier, and the content of described silica is not more than 30 weight %, and the content of described molecular sieve is not more than 15 weight %.
8. catalyst according to claim 7 is characterized in that, is benchmark with described carrier, and the content of described silica is not more than 25 weight %, and the content of described molecular sieve is not more than 12 weight %.
9. catalyst according to claim 1 is characterized in that, described catalyst contains phosphorus, with P
2O
5Meter and be benchmark with the catalyst, the content of described phosphorus is no more than 7 weight %.
10. catalyst according to claim 9 is characterized in that, with P
2O
5Meter and be benchmark with the catalyst, the content of described phosphorus is no more than 5 weight %.
11. catalyst according to claim 1 is characterized in that, contains organic additive in the described catalyst, is benchmark with described catalyst, the content of described organic additive is no more than 20 weight %.
12. catalyst according to claim 11 is characterized in that, is benchmark with described catalyst, the content of described organic additive is no more than 15 weight %.
13. 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 any catalyst that provides of claim 1-12 is provided described catalyst.
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| CN1714927A (en) * | 2004-06-29 | 2006-01-04 | 中国石油化工股份有限公司 | Silicon oxide-aluminium oxide and its preparing method |
| CN1723082A (en) * | 2002-11-08 | 2006-01-18 | 切夫里昂美国公司 | Method for preparing a highly homogeneous amorphous silica-alumina composition |
| CN1763153A (en) * | 2005-10-24 | 2006-04-26 | 长春惠工催化剂有限责任公司 | High activity catalyst for hydrogenation refining of Vaseline and preparation method and uses thereof |
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| CN1723082A (en) * | 2002-11-08 | 2006-01-18 | 切夫里昂美国公司 | Method for preparing a highly homogeneous amorphous silica-alumina composition |
| CN1714927A (en) * | 2004-06-29 | 2006-01-04 | 中国石油化工股份有限公司 | Silicon oxide-aluminium oxide and its preparing method |
| CN1763153A (en) * | 2005-10-24 | 2006-04-26 | 长春惠工催化剂有限责任公司 | High activity catalyst for hydrogenation refining of Vaseline and preparation method and uses thereof |
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