CN102950013A - Hydrogenation catalyst with active ingredients distributed non-uniformly and preparation method thereof - Google Patents
Hydrogenation catalyst with active ingredients distributed non-uniformly and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a hydrogenation catalyst with active ingredients distributed non-uniformly. The preparation method comprises the steps of impregnating solution containing VIII group metallic compounds, VIB group metallic compounds and phosphorus compounds and a formed carrier in an open environment to obtain an impregnated carrier and putting the impregnated carrier under the airtight condition. The invention provides the hydrogenation catalyst with active ingredients distributed non-uniformly, which is prepared by the preparation method. The method is simple, is easy to operate and is low in environmental pollution. The prepared catalyst has higher hydrodesulfurization activity.
Description
Technical field
The present invention relates to a kind of preparation method of hydrogenation catalyst of active component non-uniform Distribution and a kind of hydrogenation catalyst of the active component non-uniform Distribution that is prepared by the method.
Background technology
The environmental consciousness that day by day strengthens and more and more stricter environmental regulation force the oil refining circle more to pay attention to the exploitation of Clean Fuel Production technology, and how the production cleaning sulphur oil product of economical rationality has become oil refining circle current and expected future needs one of problem that emphasis solves in the regular period.Exploitation have high activity more and optionally the novel hydrogenation catalyst then be one of most economical method of production clear gusoline.
In catalytic reaction process, according to Reaction controlling step, poisoning and sintering behavior, wearability requirement, and the many factors such as economy of preparation process, need to make special design to the CONCENTRATION DISTRIBUTION of loaded catalyst active component.Press the position that the active component layer distributes in the catalyst granules different, can be divided into Four types: evenly distribute, " eggshell " distributes, and " yolk " distributes and " albumen " (the 199-200 page or leaf in " catalyst carrier preparation and application technology " book of writing referring to Zhu Hongfa (petroleum industry publishing house 2002 May the 1st edition) that distributes.Wherein " yolk " distributes because its active component concentrates on the carrier granular center, and when catalyst contacted noxious material or is subjected to strong corrosion, this distribution ratio was evenly distributed with profit.For example, mink cell focus is carried out the utilization rate that deep processing will be conducive to improve crude oil, reduce environmental pollution.
US4760045 discloses a kind of heavy oil hydrogenating treatment catalyst and preparation method thereof, this catalyst contains porous refractory oxides carrier and at least a periodic table of elements Vb that is selected from that loads on this carrier, the hydrogenation active metals component of VIb and VIII, it is characterized in that, satisfy Cr along the distribution of the described metal concentration in catalyst cross section
1＜Cr
2And R1＞R2, wherein, R1 and R2 represent respectively the ratio apart from r1 and r2 and the distance from the kernel of section to the outer surface from the kernel of section to the respective point, Cr
1＜Cr
2Represent respectively the concentration of the described metal component of described respective point.This catalyst comprises: be enough to make described hydrogenation active metals component satisfy Cr along the concentration of catalyst cross section (radial section) by the method preparation of load hydrogenation active metals on the porous refractory oxides
1＜Cr
2And adopting maceration extract A to flood described carrier under R1＞R2 condition, separation maceration extract A is further with maceration extract B dipping (as required further with maceration extract A dipping), dry and roasting after the separation maceration extract; Wherein, R1 and R2 represent respectively the ratio apart from r1 and r2 and the distance from the center, interface to outer surface from the kernel of section to the respective point, Cr
1＜Cr
2Represent respectively the concentration of the described metal component of described respective point, described solution A is for containing at least a periodic table of elements VB that is selected from, the aqueous solution of the hydrogenation active metals component of VIB and VIII, or a kind of reactive metal and at least a anion that is formed by VIIA family element, ammonium ion, nitrate ion of being selected from of containing, sulfate ion, hydroxide ion, phosphate anion, boric acid is with ion and organic acid mixed solution; Solution B is a kind of water or contains at least a anion that is comprised of VIIA family element that is selected from, the ammonium radical ion, nitrate ion, sulfate ion, hydroxide ion, phosphate anion, boric acid is with ion and the organic acid aqueous solution, described solution B does not contain active metal component, contains described anion in described solution A and B at least a solution.The heavy oil hydrogenating treatment catalyst active component of the method preparation is uneven distribution (yolk type), residual oil being carried out in the hydrotreatment process specific activity component equally distributed hydrotreating catalyst life-span longer, prolonged duration of runs of device.
As everyone knows, metalloporphyrin is easy to catalytic hydrogenation generation demetalization reaction in the residual oil under hydroconversion condition, and its HDM course roughly was divided into for two steps.In the 1st step, an outer shroud double-bond hydrogenation of metalloporphyrin generates metal porphin phenol (dihydro metalloporphyrin); In the 2nd step, metal porphin phenol decomposes, and metal deposition is on catalyst.It is emphasized that the metal of deviating from can be deposited on the catalyst immediately, blocking catalyst duct and pollute that it is mutually active, thus cause the irreversible inactivation of catalyst.Compare for the catalyst of " evenly profile " with reactive metal, when " yolk type uneven distribution type " catalyst is used for the heavy-oil hydrogenation processing reaction, not only show preferably HDM activity, simultaneously be tending towards center migration to catalyst granules by the metal of this catalyst removal, to the appearance metallicity that improves catalyst and keep the activity stability of catalyst favourable.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of simple, easy to operate, environmental pollution is little, and has the preparation method of hydrogenation catalyst of the active component non-uniform Distribution of higher hydrodesulfurization activity.
The invention provides a kind of preparation method of hydrogenation catalyst of active component non-uniform Distribution, wherein, the method comprises: will contain the solution of group VIII metallic compound, group vib metallic compound and phosphorus-containing compound and shaping carrier and flood carrier after obtaining flooding under open environment, the carrier behind the described dipping is placed in confined conditions.
The invention provides the hydrogenation catalyst of the active component non-uniform Distribution that a kind of preparation in accordance with the present invention prepares.
Method of the present invention is simple to operation, environmental pollution is little, and the catalyst for preparing has higher hydrodesulfurization activity.
The specific embodiment
The invention provides a kind of preparation method of hydrogenation catalyst of active component non-uniform Distribution, wherein, the method comprises: will contain the solution of group VIII metallic compound, group vib metallic compound and phosphorus-containing compound and shaping carrier and flood carrier after obtaining flooding under open environment, the carrier behind the described dipping is placed in confined conditions.
According to the present invention, can realize goal of the invention of the present invention according to preceding method, optional wider range of described condition of placing in confined conditions, for the present invention, under the preferable case, described condition of placing in confined conditions comprises that the temperature of placement is room temperature-250 ℃, is preferably 40-250 ℃, more preferably 50-180 ℃, more preferably 80-160 ℃; Time is 0.01-48 hour, is preferably 1-48 hour, more preferably 4-48 hour.
According to the present invention, can realize goal of the invention of the present invention according to preceding method, optional wider range of described condition of under open environment, flooding, for the present invention, under the preferable case, described temperature of flooding under open environment is room temperature to 80 ℃, is preferably room temperature to 60 ℃, more preferably room temperature to 50 ℃; Time is 0.01-6 hour, is preferably 0.5-4 hour, more preferably 1-4 hour.
According to of the present invention preferred embodiment a kind of, wherein, described temperature of placing in confined conditions is 50-180 ℃, is preferably 80-160 ℃, and the time is 1-48 hour, is preferably 4-48 hour; Described temperature of flooding under open environment is room temperature to 60 ℃, is preferably room temperature to 50 ℃, and the time is 0.5-4 hour, is preferably 1-4 hour.
Among the present invention, room temperature can for the indoor temperature in each season in throughout the year, be generally 5-40 ℃.
The present inventor finds in research process unexpectedly, the consumption of group vib metallic compound has a great impact the distribution of the active component in the hydrogenation catalyst that finally obtains, the present inventor finds, guarantee the consumption of described group vib metallic compound so that when the group vib tenor is lower than 12% in the hydrogenation catalyst for preparing, when being preferably 3-11%, the active component in the described hydrogenation catalyst is " yolk type " and distributes.Therefore, under the preferable case, take total catalyst weight as benchmark, the consumption of described group vib metallic compound so that in the hydrogenation catalyst for preparing the group vib metal be lower than 12% in the content of oxide, be preferably 3-11%.Described " yolk type " is distributed as definition well known in the art, for example can be referring to (the definition in the 199-200 page or leaf in " catalyst carrier preparation and application technology " book that Zhu Hongfa writes (petroleum industry publishing house 2002 May the 1st edition).
According to the present invention, the consumption of described group VIII metallic compound can be selected in wider scope, under the preferable case, take total catalyst weight as benchmark, the consumption of described group VIII metallic compound so that in the hydrogenation catalyst for preparing the group VIII metal be preferably 0.5-3% take the content of oxide as 0.05-5%.
According to the present invention, the consumption of described phosphorus-containing compound can be selected in wider scope, under the preferable case, take total catalyst weight as benchmark, the consumption of described phosphorus-containing compound so that in the hydrogenation catalyst for preparing phosphorus take the content of oxide as 0.1-10%, be preferably 0.3-8%, more preferably 1-6%.
Without specific (special) requirements, the phosphorus-containing compound of this area routine all can be realized purpose of the present invention to the kind of described phosphorus-containing compound in the present invention, and under the preferable case, described phosphorus-containing compound is one or more in phosphoric acid, phosphorous acid, phosphate and the phosphite; More preferably, described phosphorus-containing compound is one or more in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate and the ammonium dihydrogen phosphate (ADP).
The present invention to the kind of described VII family metallic compound without specific (special) requirements, for example can be for nickel compound containing, cobalt compound, contain ruthenium compound, iron containing compounds, nickel compound containing, rhodium-containing compound, contain palladium compound, contain in the platinum compounds one or more, under the preferable case, in order to make activity of hydrocatalyst of the present invention higher, described group VIII metallic compound is nickel compound containing and/or cobalt compound.
The present invention without specific (special) requirements, for example can be in cobalt nitrate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and the cobaltous sulfate one or more to the kind of described cobalt compound, is preferably in cobalt nitrate, cobalt acetate and the basic cobaltous carbonate one or more.
The present invention without specific (special) requirements, for example can be in nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and the nickelous sulfate one or more to the kind of described nickel compound containing, is preferably in nickel nitrate, nickel acetate and the basic nickel carbonate one or more.
The present invention without specific (special) requirements, is preferably molybdate compound and/or Tungstenic compound to the kind of described group vib metallic compound.
The present invention to the kind of described molybdate compound without specific (special) requirements, for example can be for molybdic acid, molybdenum oxide, molybdate, paramolybdate, contain molybdenum heteropolyacid and contain one or more of molybdenum heteropolyacid salt, be preferably in molybdic acid, molybdenum trioxide, ammonium molybdate, ammonium paramolybdate, phosphomolybdic acid and the P-Mo-Wo acid one or more.
The present invention to the kind of described Tungstenic compound without specific (special) requirements, for example can be in wolframic acid, tungstates, metatungstate, ethyl metatungstate, heteropoly acid containing tungsten and the heteropoly acid containing tungsten salt one or more, be preferably in wolframic acid, ammonium metatungstate, ethyl ammonium metatungstate, phosphotungstic acid and the P-Mo-Wo acid one or more.
Without specific (special) requirements, for example described shaping carrier can be the shaping carrier that is obtained by one or more moulding in heat-resistant inorganic oxide, inorganic silicate and the molecular sieve to the kind of described shaping carrier in the present invention.
The present invention to the kind of described heat-resistant inorganic oxide without specific (special) requirements, can carry out with reference to prior art, for example can be aluminium oxide, silica, titanium oxide, magnesia, silica-alumina, aluminium oxide-magnesia, silica-magnesia, silica-zirconia, silica-thorium oxide, silica-beryllium oxide, silica-titanium oxide, silica-zirconia, the oxidation titania-zirconia, silica-alumina-thorium oxide, silica-alumina-titanium oxide, silica-alumina-magnesia, silica-alumina-zirconia, natural zeolite, in the clay one or more, wherein, be preferably aluminium oxide and/or silica.
The present invention without specific (special) requirements, can be the aluminium oxide of pure gamma phase structure to the structure of described aluminium oxide, also can be the aluminium oxide of transition state duplex grain structure (aluminium oxide of at least a mixed crystal among gamma and delta, the theta).The present invention without specific (special) requirements, for example can be to make through high-temperature roasting the preparation method of the aluminium oxide of described transition state duplex grain structure, and sintering temperature can be 600-1200 ℃, is preferably 700-1100 ℃; Roasting time can be 0.5-12 hour, is preferably 2-8 hour.
The present invention without specific (special) requirements, can be in zeolite or the non-zeolitic molecular sieves one or more to the kind of described molecular sieve.Described zeolite molecular sieve can be in erionite, ZSM-34 zeolite, modenite, ZSM-5 zeolite, ZSM-11 zeolite, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, L zeolite, y-type zeolite, X-type zeolite, ZSM-3 molecular sieve, ZSM-4 molecular sieve, ZSM-18 molecular sieve, ZSM-20 molecular sieve, ZSM-48 zeolite, ZSM-57 zeolite, faujasite, Beta zeolite and the omega zeolite one or more.Described non-zeolite molecular sieve can be in phosphate aluminium molecular sieve, HTS and SAPO (such as the SAPO) molecular sieve one or more.
Among the present invention, described shaping carrier can be cloverleaf pattern, butterfly, cylindrical, hollow cylindrical, quatrefoil, asymmetric quatrefoil, five leaf or spherical.
The method according to this invention, under the preferable case, method of the present invention also comprises the step that the carrier after placing is in confined conditions carried out drying or drying and roasting.
The present invention, can carry out with reference to prior art without specific (special) requirements the condition of described drying, roasting.For example, the temperature of described drying is generally 100-250 ℃, is preferably 120-200 ℃, and the time is 0.5-10 hour, is preferably 2-8 hour; The temperature of roasting is generally 300-700 ℃, is preferably 300-550 ℃, and the time is 0.5-12 hour, is preferably 1-8 hour.
The method according to this invention needs depending on use, and method of the present invention can also be introduced some auxiliary agents in preparation process.The present invention, can carry out with reference to prior art (for example, dipping, kneading, sol-gal process etc.) without specific (special) requirements the ways and means of introducing other auxiliary agent, does not repeat them here.The present invention does not limit especially to the kind of described other auxiliary agent, can select according to actual needs.Usually, can be fluorine and/or boron.The present invention, can carry out with reference to prior art also without specific (special) requirements the amount of introducing described other auxiliary agent, generally can for the 0.01-5 % by weight of total catalyst weight, be preferably the 0.1-5 % by weight.
The present invention to the kind of the described solution that contains group VIII metallic compound, group vib metallic compound and phosphorus-containing compound without specific (special) requirements, can carry out with reference to prior art, be preferably the aqueous solution that contains group VIII metallic compound, group vib metallic compound and phosphorus-containing compound.
The present invention to the method for preparing the described solution that contains group VIII metallic compound and group vib metallic compound without specific (special) requirements, can carry out with reference to prior art, according to of the present invention preferred embodiment a kind of, preparing the described method that contains the solution of group VIII metallic compound, group vib metallic compound and phosphorus-containing compound can be prepared as follows: with nickeliferous (and/or cobalt) compound, contain molybdenum (and/or tungsten) compound and join in the aqueous solution of phosphorus-containing compound, add thermal agitation and form the aqueous solution.
The present invention without specific (special) requirements, can be the various impregnation methods of prior art to the mode of described dipping, for example can be spray dipping, saturated dipping or excessive liquid dipping.
Under the preferable case, the carrier after adopting saturated dipping method to realize when flooding under open environment, only needing will flood behind dipping is directly transferred to heat in the closed container and is got final product.When adopting excessive dipping method to realize under open environment, flooding, only need at the carrier that leaches with funnel behind the dipping after excessive maceration extract obtains flooding, the carrier after will flooding is again transferred to closed container and is heated and get final product.
Among the present invention, the consumption of described solution can be selected according to the method for concrete dipping, and those skilled in the art all can know this, for example, when described dipping was incipient impregnation, the consumption of described solution was the saturated water adsorptive value of carrier, gives unnecessary details no longer one by one at this.
The invention provides the hydrogenation catalyst of the active component non-uniform Distribution that a kind of preparation in accordance with the present invention prepares, according to well known to a person skilled in the art definition, while is according to the distribution trend of the active component of hydrogenation catalyst of the present invention, under the preferable case, the active component in the hydrogenation catalyst of active component non-uniform Distribution of the present invention is " yolk type " and distributes.Generally speaking, described " yolk type " distribution catalyst refers to: " yolk type " factor sigma may of catalyst is a class catalyst of 0≤σ＜0.95.Wherein, " yolk type " factor sigma may is that metal component is at the ratio of concentration with the concentration of center of catalyst granules outer surface; Catalyst granules outer surface concentration refers in the SEM-EDX characterization result mean value along near 20 the numerical point counting rates carrier outer surface radially; Catalyst granules center concentration refers in the SEM-EDX characterization result mean value of 20 numerical point counting rates along about the carrier central point radially.
Radially the counting rate of every bit is mutually corresponding with this tenor along carrier in the SEM-EDX characterization result, and the size of counting rate reflects this tenor height, but does not represent the real content of this metal.Degree of irregularity when the σ value represents the distribution form of active component on the catalyst and quantitatively uneven distribution is described.
Among the present invention, under the preferable case, described group vib metal is 0.4-0.8 at the ratio of the concentration of catalyst granules outer surface and the concentration of center, more preferably 0.4-0.6; Described group VIII metal is 0.3-0.8, more preferably 0.3-0.6 at the ratio of the concentration of catalyst granules outer surface and the concentration of center.
According to the conventional method in this area, catalyst provided by the invention is before using, usually can be in the presence of hydrogen, under 140-370 ℃ temperature, carry out presulfurization with sulphur, hydrogen sulfide or other sulfur-bearing raw material, described presulfurization can carry out also can carrying out the original position sulfuration in device outside device, be translated into sulfide type, all can carry out with reference to prior art this, the present invention does not repeat them here without specific (special) requirements.
The catalytic reaction process that the hydrogenation catalyst that the method according to this invention prepares can be applicable to easily to make catalyst contact poisoning or is subjected to strong corrosion, for example, be applicable to heavy hydrocarbon feedstocks, comprise that the raw materials such as crude oil, reduced crude, decompression residuum carry out the hydrotreatment reaction, are specially adapted to heavy-oil hydrogenation and process (demetalization reaction, desulphurization reaction etc.).
Following example will further specify the present invention, but not thereby limiting the invention.
Among the embodiment, the butt quality refers in the quality of 600 ℃ of roastings after 4 hours.
Among the embodiment, as not specifying, employed reagent is AR.
Specify among the embodiment as not, all adopt the method for incipient impregnation to flood.
Among the present invention, the catalyst elements composition adopts x-ray fluorescence spectrometry with catalyst 550 ℃ of roastings after 4 hours.In addition, adopt SEM-EDX to measure the hydrogenation active metals component along the carrier radial distribution, and by characterization result calculate metal component at particle appearance place the ratio with center concentration, characterization result sees Table 1 and table 2.
Among the present invention, σ
MMiddle σ represents metal component at the ratio of catalyst granules outer surface with the concentration of center, and M represents the kind of metal component, for example σ
MoThe expression metal molybdenum is at the ratio of catalyst granules outer surface with the concentration of center.
Embodiment 1-11 is used for illustrating hydrogenation catalyst of active component non-uniform Distribution provided by the invention and preparation method thereof.
Embodiment 1
Take by weighing 10000 gram aluminium hydrate powder (butt 70 % by weight, available from Chang Ling catalyst branch company of China Petrochemical Industry) usefulness banded extruder (manufacturer: South China Science ﹠ Engineering University's science and technology industry head factory, model: F-26 (III)) being extruded into circumscribed circle diameter is 1.4 millimeters cloverleaf pattern bar, then 120 ℃ of dryings 4 hours, 600 ℃ of roastings 4 hours, obtain carrier S 1, the aluminium oxide that characterizes in this carrier through X-ray diffraction is gama-alumina.
With 16.6 gram molybdenum trioxides, 5.8 gram basic cobaltous carbonates (Co content is 45 % by weight) join and contain 5.4 gram phosphoric acid (mass fraction 85%) aqueous solution, and the heating stirring and dissolving is settled to 220 milliliters;
Take by weighing 200 gram carrier S 1, in the 1000mL beaker, 220 milliliters of mentioned solutions of this carrier S 1 usefulness were flooded 2 hours in 5 ℃ of room temperatures, the carrier after then will flooding is transferred in the autoclave of stainless steel band polytetrafluoro liner, and is airtight through 85 ℃ of heating 48 hours.After being down to room temperature the high pressure kettle cover is opened, through 200 ℃ of dryings 4 hours, obtained catalyst C1, the SEM-EDX measurement result shows that its active metal component is uneven distribution, is " yolk " profile.In oxide, catalyst C1 lists in the table 1 at the composition of 550 ℃ of roastings after 4 hours.
Embodiment 2
With 16.6 gram molybdenum trioxides, 5.8 gram basic cobaltous carbonates (Co content is 45 % by weight) join and contain 5.4 gram phosphoric acid (mass fraction 85%) aqueous solution, and the heating stirring and dissolving is settled to 220 milliliters;
Take by weighing 200 gram carrier S 1, in the 1000mL beaker, 220 milliliters of mentioned solutions of this carrier S 1 usefulness were flooded 2 hours in 20 ℃ of room temperatures, the carrier after then will flooding is transferred in the autoclave of stainless steel band polytetrafluoro liner, and is airtight through 100 ℃ of heating 4 hours.After being down to room temperature the high pressure kettle cover is opened, then through 120 ℃ of dryings 4 hours, roasting was 3 hours in 450 ℃ of air, obtains catalyst C2, and the SEM-EDX measurement result shows that its active metal component is uneven distribution, is " yolk " profile.In oxide, catalyst C2 lists in the table 1 at the composition of 550 ℃ of roastings after 4 hours.
Embodiment 3
The aluminium hydrate powder (butt 70 % by weight) and 2596 of 10000 gram Chang Ling catalyst branch companies is restrained Ludox (available from Haiyang Chemical Plant, Qingdao, contain silica 30 % by weight) and 108 the gram TS-1 molecular sieves (available from Chang Ling catalyst branch company of China Petrochemical Industry) mix, being extruded into circumscribed circle diameter with banded extruder is 1.4 millimeters cylindrical bar, then 120 ℃ of dryings 4 hours, 600 ℃ of roastings 6 hours obtain carrier S 2.
With 16.6 gram molybdenum trioxides, 5.8 gram basic cobaltous carbonates (Co content is 45wt%) join and contain 5.4 gram phosphoric acid (mass fraction 85%) aqueous solution, and the heating stirring and dissolving is settled to 220 milliliters;
Take by weighing 200 gram carrier S 2, in the 1000mL beaker, 220 milliliters of mentioned solutions of these carrier S 2 usefulness were flooded 2 hours in 30 ℃ of room temperatures, the carrier after then will flooding is transferred in the autoclave of stainless steel band polytetrafluoro liner, and is airtight through 90 ℃ of heating 24 hours.After being down to room temperature the high pressure kettle cover is opened, then obtained catalyst C3 in 4 hours through 180 ℃ of dryings, the SEM-EDX measurement result shows that its active metal component is uneven distribution, is " yolk " profile.In oxide, catalyst C3 lists in the table 1 at the composition of 550 ℃ of roastings after 4 hours.
Embodiment 4
Take by weighing 10000 gram aluminium hydrate powder (butt 70 % by weight, available from Chang Ling catalyst branch company of China Petrochemical Industry) usefulness banded extruder (manufacturer: South China Science ﹠ Engineering University's science and technology industry head factory, model: F-26 (III)) being extruded into circumscribed circle diameter is 1.6 millimeters cloverleaf pattern bar, then 120 ℃ of dryings 4 hours, 930 ℃ of roastings 4 hours, obtain carrier S 3, the aluminium oxide that characterizes in this carrier through X-ray diffraction is the mixed crystal phase alumina of δ, θ, mainly take the δ crystalline phase as main.
With 16.6 gram molybdenum trioxides, 6.6 gram basic nickel carbonates (Ni content is 41 % by weight) join in the aqueous solution that contains 5.5 gram phosphoric acid (mass fraction 85%), and the heating stirring and dissolving is settled to 220 milliliters;
Take by weighing 200 gram carrier S 3, in the 1000mL beaker, 220 milliliters of mentioned solutions of these carrier S 3 usefulness were flooded 2 hours in 10 ℃ of room temperatures, the carrier after then will flooding is transferred in the autoclave of stainless steel band polytetrafluoro liner, and is airtight through 96 ℃ of heating 18 hours.After being down to room temperature the high pressure kettle cover is opened, then through 120 ℃ of dryings 4 hours, roasting was 5 hours in 430 ℃ of air, obtains catalyst C4, and the SEM-EDX measurement result shows that its active metal component is uneven distribution, is " yolk " profile.In oxide, catalyst C4 lists in the table 1 at the composition of 550 ℃ of roastings after 4 hours.
Embodiment 5
With 16.6 gram molybdenum trioxides, 3.1 gram basic cobaltous carbonate (Co content is 45 % by weight), 3.2 gram basic nickel carbonate (Ni content is 41 % by weight) joins in the aqueous solution that contains 5.5 gram phosphoric acid (mass fraction 85%), the heating stirring and dissolving is settled to 220 milliliters;
Take by weighing 200 gram carrier S 3, in the 1000mL beaker, with 220 milliliters of mentioned solutions of these carrier S 3 usefulness in 36 ℃ of impregnated carriers of room temperature 2 hours, then the carrier after will flooding is transferred in the autoclave of stainless steel band polytetrafluoro liner, airtight through 160 ℃ of heating 6 hours, after being down to room temperature the high pressure kettle cover is opened, then through 120 ℃ of dryings 4 hours, roasting is 4 hours in 400 ℃ of air, obtain catalyst C5, the SEM-EDX measurement result shows that its active metal component is uneven distribution, is " yolk " profile.In oxide, catalyst C5 lists in the table 1 at the composition of 550 ℃ of roastings after 4 hours.
Embodiment 6
With 8.3 gram molybdenum trioxides, 2.1 gram basic cobaltous carbonate (Co content is 45 % by weight), 1.2 gram basic nickel carbonate (Ni content is 41 % by weight) joins in the aqueous solution that contains 6.25 gram phosphoric acid (mass fraction 85%), the heating stirring and dissolving is settled to 220 milliliters;
Take by weighing 200 gram carrier S 3, in the 1000mL beaker, 220 milliliters of mentioned solutions of these carrier S 3 usefulness were flooded 2 hours in 20 ℃ of room temperatures, and the carrier after then will flooding is transferred in the autoclave of stainless steel band polytetrafluoro liner, and is airtight through 140 ℃ of heating 10 hours, after being down to room temperature the high pressure kettle cover is opened, then through 120 ℃ of dryings 4 hours, roasting was 4 hours in 420 ℃ of air, obtains catalyst C6, the SEM-EDX measurement result shows that its active metal component is uneven distribution, is " yolk " profile.In oxide, catalyst C6 lists in the table 1 at the composition of 550 ℃ of roastings after 4 hours.
Embodiment 7
With 24.9 gram molybdenum trioxides, 8.7 gram basic cobaltous carbonate (Co content is 45 % by weight), 1.5 gram basic nickel carbonate (Ni content is 41 % by weight) joins in the aqueous solution that contains 8.1 gram phosphoric acid (mass fraction 85%), the heating stirring and dissolving is settled to 220 milliliters;
Take by weighing 200 gram carrier S 3, in the 1000mL beaker, in 50 ℃ of dippings 2 hours, the carrier after then will flood was transferred in the autoclave of stainless steel band polytetrafluoro liner with 220 milliliters of mentioned solutions of these carrier S 3 usefulness, airtightly heated 10 hours through 130 ℃, after being down to room temperature the high pressure kettle cover is opened, then through 120 ℃ of dryings 4 hours, roasting was 4 hours in 420 ℃ of air, obtains catalyst C7, the SEM-EDX measurement result shows that its active metal component is uneven distribution, is " yolk " profile.In oxide, catalyst C7 lists in the table 1 at the composition of 550 ℃ of roastings after 4 hours.
Embodiment 8
With 16.6 gram molybdenum trioxides, 5.8 gram basic cobaltous carbonates (Co content is 45 % by weight) join and contain 5.4 gram phosphoric acid (mass fraction 85%) aqueous solution, and the heating stirring and dissolving is settled to 220 milliliters;
Take by weighing 200 gram carrier S 3, in the 1000mL beaker, 220 milliliters of mentioned solutions of these carrier S 3 usefulness were flooded 2 hours in 20 ℃ of room temperatures, the carrier after then will flooding is transferred in the autoclave of stainless steel band polytetrafluoro liner, and is airtight through 150 ℃ of heating 24 hours.After being down to room temperature the high pressure kettle cover is opened, continuation 120 ℃ of dryings 4 hours in baking oven, then 400 ℃ of lower roastings 4 hours under air atmosphere obtain catalyst C8, the SEM-EDX measurement result shows that its active metal component is uneven distribution, is " yolk " profile.In oxide, catalyst C8 lists in the table 2 at the composition of 550 ℃ of roastings after 4 hours.
Embodiment 9
Method according to embodiment 8 prepares hydrogenation catalyst, and different is, airtightly obtains catalyst C9 by 200 ℃ of heating 24 hours, and the SEM-EDX measurement result shows that its active metal component is uneven distribution, is " yolk " profile.In oxide, catalyst C9 lists in the table 2 at the composition of 550 ℃ of roastings after 4 hours.
Embodiment 10
Method according to embodiment 8 prepares hydrogenation catalyst, and different is, airtightly places 48 hours by 10 ℃, obtains catalyst C10, and the SEM-EDX measurement result shows that its active metal component is uneven distribution, is " yolk " profile.In oxide, catalyst C10 lists in the table 2 at the composition of 550 ℃ of roastings after 4 hours.
Embodiment 11
Method according to embodiment 7 prepares hydrogenation catalyst, and different is, changes consumption and makes in the hydrogenation catalyst for preparing in oxide, makes MoO
3Content be increased to 15.60%, obtain hydrogenation catalyst C11, the SEM-EDX measurement result is listed in the table 2, the result shows that its active metal component is for " eggshell " type uneven distribution.
Comparative Examples 1
With 16.6 gram molybdenum trioxides, 5.8 gram basic cobaltous carbonates (Co content is 45 % by weight) join in the aqueous solution that contains 5.4 gram phosphoric acid (mass fraction 85%), and the heating stirring and dissolving is settled to 220 milliliters;
Take by weighing carrier S 3200 grams, in the 1000mL beaker, with the above-mentioned solution impregnation of these carrier S 3 usefulness 2 hours, 120 ℃ of dryings are 4 hours in baking oven, then 400 ℃ of lower roastings 4 hours under air atmosphere obtain catalyst D1, and the SEM-EDX measurement result shows that its active metal component is evenly to distribute substantially, in oxide, catalyst D1 lists in the table 2 at the composition of 550 ℃ of roastings after 4 hours.
Comparative Examples 2
Method according to embodiment among the CN101439289A 2 prepares hydrogenation catalyst, and different is with urea and aqueous ammonia to replace phosphoric acid in the preparation maceration extract process;
Take by weighing 16.6 gram molybdenum trioxides and 5.8 gram basic cobaltous carbonates (Co content is 45 % by weight) join and make its dissolving in the ammoniacal liquor, then add 2.0 gram urea, to be made into maceration extract for subsequent use for 220 milliliters of constant volumes after the dissolving evenly; Take by weighing 200 gram alumina support S3, flood according to the method for incipient impregnation.The catalyst that dipping is good is dried under infrared lamp, pack in the airtight crystallizing kettle, put into 150 ℃ of reactions of baking oven 24 hours, then the lid of crystallizing kettle is opened, was continued in baking oven 120 ℃ of dryings 4 hours, with the catalyst that reacted under air atmosphere 400 ℃ of lower roastings 4 hours, namely obtain catalyst D2, the SEM-EDX measurement result is listed in the table 2, and the result shows its active metal component cobalt-based, and this is evenly distribution, and the content of molybdenum species outer surface is a little more than the center.
Comparative Examples 3
Press the method for the embodiment 2 of CN1289647A, adopt unsaturated spray and the method for natural air drying prepares the catalyst that active metal component is Mo, Co.Take by weighing 200 grams, water absorption rate is S3 carrier (δ-Al of 1.10 ml/gs
2O
3), be 0.70 according to pickup and saturated absorption solution amount volume ratio, spray contain 20.24 the gram ammonium molybdates (contain MoO
3Be 82 % by weight) and 154 milliliters of the ammonia spirits of 13.17 gram cobalt nitrates (containing CoO is 25.2 % by weight).Homogenizing is after 7 minutes in spraying equipment, natural air drying.Roasting 3 hours in 530 ℃ of air makes catalyst D3 after air-dry.The SEM-EDX measurement result shows that its active metal component is uneven distribution, is " yolk " profile.In oxide, catalyst D3 lists in the table 2 at the composition of 550 ℃ of roastings after 4 hours.
EXPERIMENTAL EXAMPLE 1-11
Hydrodesulfurization performance for the hydrogenation catalyst that active component non-uniform Distribution provided by the invention is described.
With vanadyl-2,3,7,8,12,13,17,18-octaethylporphyrin (vanadium porphyrin) is as the model compound of HDM, dibenzothiophenes is the hydrodesulfurization model compound, the two is dissolved in the reaction raw materials (content of vanadium 16 μ g/g, sulfur content 10000 μ g/g) that thiacyclohexane is estimated as hydrogenation, in the small fixed high-pressure reactor, the good catalyst C1-C11 of presulfurization is carried out the hydrodesulfurization activity evaluation.Reaction condition is: the hydrogen dividing potential drop is 7MPa, and reaction temperature is 280 ℃, and hydrogen to oil volume ratio is 900, volume space velocity 80h
-1Reacting took a sample after 12 hours analyzes.Generate sulfur content in the oil after adopting the microcoulomb constant sulphur appliance to measure hydrogenation reaction.Wherein, hydrodesulfurization activity is calculated as follows:
A=ln[100/ (100-X)], X is the desulfurization degree of dibenzothiophenes in the formula, and the hydrodesulfurization activity of getting comparative catalyst D2 is 100, and then the relative hydrodesulfurization activity of other catalyst can be represented by the formula: relative activity=(A
QT/ A
D2) * 100%.A in the formula
QTBe the activity of other catalyst, A
D2Activity for reference catalyst.The results are shown in table 1 and table 2.
Experiment Comparative Examples 1-3
The hydrodesulfurization performance of this Comparative Examples explanation Comparative Examples catalyst.Adopt the catalyst D1-D3 of the method evaluation Comparative Examples 1-3 identical with EXPERIMENTAL EXAMPLE 1-11, the results are shown in Table 2.
Table 1
Table 2
Can be illustrated by the result in table 1 and the table 2, the metal component of catalyst provided by the invention all is uneven distribution; And compare with the comparative catalyst, in the presence of vanadium porphin compounds, catalyst provided by the invention can keep higher hydrodesulfurization activity, has better activity stability.
Claims (15)
1. the preparation method of the hydrogenation catalyst of an active component non-uniform Distribution, wherein, the method comprises: will contain the solution of group VIII metallic compound, group vib metallic compound and phosphorus-containing compound and shaping carrier and flood carrier after obtaining flooding under open environment, the carrier behind the described dipping is placed in confined conditions.
2. preparation method according to claim 1, wherein, described condition of placing in confined conditions comprises that temperature is room temperature to 250 ℃, the time is 0.01-60 hour.
3. preparation method according to claim 2, wherein, described temperature of placing in confined conditions is 50-180 ℃, the time is 1-48 hour; Described temperature of flooding under open environment is room temperature to 80 ℃, and the time is 0.01-6 hour.
4. the described preparation method of any one according to claim 1-3, wherein, take total catalyst weight as benchmark, the consumption of described group vib metallic compound so that in the hydrogenation catalyst for preparing the group vib metal be lower than 12% in the content of oxide.
5. preparation method according to claim 4, wherein, take total catalyst weight as benchmark, the consumption of described group vib metallic compound so that in the hydrogenation catalyst for preparing the group vib metal take the content of oxide as 3-11%.
6. the described preparation method of any one according to claim 1-3, wherein, take total catalyst weight as benchmark, the consumption of described group VIII metallic compound so that in the hydrogenation catalyst for preparing the group VIII metal take the content of oxide as 0.05-5%.
7. the described preparation method of any one according to claim 1-3, wherein, take total catalyst weight as benchmark, the consumption of described phosphorus-containing compound so that in the hydrogenation catalyst for preparing phosphorus take the content of oxide as 0.1-10%.
8. the described preparation method of any one according to claim 1-3, wherein, described phosphorus-containing compound is one or more in phosphoric acid, phosphorous acid, phosphate and the phosphite.
9. the described preparation method of any one according to claim 1-3, wherein, described group VIII metallic compound is nickel compound containing and/or cobalt compound.
10. the described preparation method of any one according to claim 1-3, wherein, described group vib metallic compound is molybdate compound and/or Tungstenic compound.
11. the described preparation method of any one according to claim 1-3, wherein, described shaping carrier is obtained by one or more moulding in heat-resistant inorganic oxide, inorganic silicate and the molecular sieve.
12. the described preparation method of any one according to claim 1-3, wherein, the method also comprises the step that the carrier after placing is in confined conditions carried out drying or drying and roasting.
13. preparation method according to claim 12, wherein, the temperature of described drying is 100-250 ℃, and the time is 0.5-10 hour; The temperature of roasting is 300-700 ℃, and the time is 0.5-12 hour.
14. the hydrogenation catalyst of the active component non-uniform Distribution that is prepared by the described preparation method of any one among the claim 1-13.
15. hydrogenation catalyst according to claim 14, wherein, active component is the distribution of yolk type in the described hydrogenation catalyst.
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| CN101152631A (en) * | 2006-09-29 | 2008-04-02 | 中国石油化工股份有限公司 | Selective hydrogenation desulfurizing catalyzer and method of producing the same |
| CN101376110A (en) * | 2007-08-27 | 2009-03-04 | 中国石油化工股份有限公司 | Preparation of hydrogenation catalyst |
| CN101927169A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with active metal component concentration in gradient increase and distribution and preparation method thereof |
| CN101927176A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Hydrogenation catalyst showing gradient increase and distribution of concentration of active metal and acid additive and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101152631A (en) * | 2006-09-29 | 2008-04-02 | 中国石油化工股份有限公司 | Selective hydrogenation desulfurizing catalyzer and method of producing the same |
| CN101376110A (en) * | 2007-08-27 | 2009-03-04 | 中国石油化工股份有限公司 | Preparation of hydrogenation catalyst |
| CN101927169A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with active metal component concentration in gradient increase and distribution and preparation method thereof |
| CN101927176A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Hydrogenation catalyst showing gradient increase and distribution of concentration of active metal and acid additive and preparation method thereof |
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