CN102049281B - Super deep hydrodesulfurization catalyst and preparation method thereof - Google Patents
Super deep hydrodesulfurization catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a super deep hydrodesulfurization catalyst and a preparation method thereof. The catalyst comprises a composite oxide (NixWyOz), MoO3, aluminum oxide, a type-Y molecular sieve. The method comprises: adding a proper amount of water soluble nitride in a Ni, W and Al precipitation process; after gelatin is formed, adding type-Y molecular sieve slurry; aging and beating with MoO3; and forming and activating. When the method is used, the porous structure of the catalyst is improved, more metal active sites are exposed from the surface of the catalyst, the utilization rate of active metals is improved, the type-Y molecular sieve and metals having hydrogenation activity are uniformly and fully contacted and well combined, and the effect of super deep hydrodesulfurization of diesel is achieved. In addition, the aperture and pore capacity of the catalyst are increased, so a Ni-W high-activity center is fully used, it is easier for complex macromolecules to contact the active center, and the effect is more obvious particularly when the catalyst is used for processing distillates with high macromolecule content.
Description
Technical field
The present invention relates to a kind of Hydrobon catalyst and preparation method thereof, particularly a kind of distillate ultra-deep hydrodesulfuration Catalysts and its preparation method that contains Y molecular sieve.
Background technology
Because the burning meeting of sulfur-containing compounds from fuel causes serious harm to world environments and society, so in the standard of the clean fuel formulated of countries in the world, greatly improved the wherein restriction of sulfur content.EPA is down to 15ppm in June, 2006 with the standard of diesel oil sulfur content.In the various desulfur technologies of diesel oil, the most ripe is the hydrodesulfurization technology.The method that realizes deep desulfuration comprises development of new reactor and new catalyst.Dynamics research shows, if the sulfur content of diesel oil is reduced to below the 15ppm from 500ppm, the volume of reactor must increase by three times, and its cost is very high concerning the high-temperature high-voltage reaction device.Therefore, realize that the only method of deep hydrodesulfurizationof of diesel oil is the highly active catalyst of exploitation.
In petroleum distillate, contain the various structures sulfur-containing compound different with molecular weight, comprise mercaptan, thioether, thiophenes.These sulfur-containing compounds can carry out hydrogenation and desulphurization reaction and remove sulphur atom (for example the sulfide of mercaptan, straight chain and ring-type is converted into saturated hydrocarbons or aromatic compound) from raw material under the industrial hydrodesulfurization reaction condition of routine.In deep desulfuration stage (sulfur content is lower than 500 μ g/g) and ultra-deep desulfurization stage (sulfur content is lower than 50 μ g/g), the sulfur-containing compound in the diesel oil distillate is mainly dibenzothiophenes class sulfide.The reactivity of this class sulfide and substituent quantity and position are closely related.4,6-dimethyl Dibenzothiophene class sulfide is generally the most difficult class sulfide that removes, because and sulphur atom next-door neighbour's methyl makes and produced sterically hinderedly between the activated centre of sulphur atom and catalyst, sulphur atom is the activated centre of accessible reaction not, thereby causes reaction rate significantly to descend.Therefore, realize that deep desulfuration must develop dibenzothiophenes and derivative thereof are had highly active catalyst.
In Hydrobon catalyst, generally adopt at present Co-Mo and Ni-Mo as active component, with Al
2O
3Be carrier, adopt the method for dipping, then utilize the process of one or more dryings and roasting to make catalyst.Also carrier material and VIII family and the co-precipitation of vib metal composition can be prepared hydrogenation catalyst.
Bulk phase catalyst refers to that the loaded catalyst that is dispersed on the carrier with active component is relative, not take inactive carrier as carrier.The catalyst major part is made of active component, and the content of active constituent is generally unrestricted, sometimes also claims body catalyst.
US6299760, US6156695, US6537442, US6440888, US6652738 disclose and have contained VIII family/group vib active metal component and be used for bulk phase catalyst of hydrotreatment and preparation method thereof.The preparation of catalyst can be adopted solution route or solid route, and tenor can reach 50wt%-100wt%.Active metal component can be Ni-Mo or Ni-Mo-W.Can contain or not contain adhesive component in the catalyst.Adhesive is mainly used to bonding metal, improves the intensity of catalyst.Because the catalyst metal content of the method preparation is high, often lacks enough interactions between metal and aluminium oxide and can cause catalyst strength poor.Active component part is comprised of a large amount of metals, has some interior metal components and can not be fully utilized and cause loss of activity in forming Ni-Mo or Ni-Mo-W powder process, and this problem can not be by simple bonding the solution.
CN1951561A has proposed a kind of preparation method of hydrotreating catalyst, comprising: (1) coprecipitation generates Ni
xW
yO
zThe composite oxides precursor; (2) Ni
xW
yO
zComposite oxides precursor and MoO
3Making beating mixes, filters; (3) moulding, activation are final catalyst.The catalyst metal content of the method preparation is high, but pore volume and specific area are less, have affected the dispersiveness of high-load reactive metal, do not bring into play fully the activity of high-load metal component.Active metallic content is high can to increase the catalyst cost, the less range of application that affects catalyst of while pore volume, and (such as the hydrocracking prerefining) can not show good catalytic activity during for the treatment of heavy distillate.
Sulfur content is when 500 μ g/g are following in the diesel oil, and sulfur-containing compound all is to have sterically hindered difficulty to remove sulfur containing species.Industrial, common Hydrobon catalyst is just because of being difficult to 4-MDBT (4-MDBT), 4,6-DMDBT (4, the 6-dimethyl Dibenzothiophene) etc. have sterically hindered sulfur-containing compound and transform and can't carry out deep desulfuration, thereby be difficult to obtain in the product sulfur content less than the super clean fuel of 50 μ g/g.In ultra-deep desulfurization, remove 4,6-dimethyl Dibenzothiophene class sulfides, can be saturated by hydrogenation, Methyl transporters, methyl removes and four kinds of reaction paths such as C-C bond fission, make 4, the methyl of next-door neighbour's sulphur atom is distorted, removes and the variation such as transfer in the 6-dimethyl Dibenzothiophene class sulfide, has reduced the sterically hindered of sulphur atom, makes sulphur atom be easy to contact with catalyst active center and carries out desulphurization reaction.Methyl transporters, methyl remove the catalyst that uses with three kinds of reaction path requirements such as C-C bond fission and have certain acidity.Catalyst adds a small amount of molecular sieve when having the strong hydrogenation activity, make catalyst have certain strong acid center, can significantly improve desulfurization, the denitrification activity of catalyst, reaches the purpose of diesel oil distillate ultra-deep desulfurization.
CN1872962A discloses a kind of hydrotreating catalyst that contains molecular sieve, this catalyst is take aluminium oxide and Y zeolite as carrier, supported active metal component nickel, molybdenum and tungsten, namely first with boehmite and Y zeolite mechanical mixture, then extruded moulding, again step impregnation supported active metal component.CN1184843A discloses a kind of catalyst for hydrogenation treatment of diesel oil, also is precursor and the zeolite mixed-forming that has adopted aluminium oxide, and roasting is with the aqueous solution dipping that contains hydrogenation active metals, then drying and roasting.Said method is the method for preparing conventional load type catalyst, is subject to the restriction of carrier hole structure, and the reactive metal load capacity can not be too much, and active the raising is restricted.And the method can not make aluminium oxide and Y zeolite evenly mix, and has affected the interaction between acidic components and the hydrogenation activity component, and then has affected desulfurized effect.
In the standby catalyst of body phase legal system, because active metallic content is higher, taking full advantage of of the active metal component of catalyst is very important.In the prior art, only emphasize the kind of metal and the cooperation effect between content and the different metal, how to allow catalyst have the active metal component of rational pore structure and high-load to play one's part to the full, how to allow acidic components and reactive metal in the catalyst reasonably combine, how to allow when same tenor catalyst have the aspects such as better hydrogenation activity and do not relate to.
Summary of the invention
For deficiency of the prior art, the invention provides a kind of body phase ultra-deep hydrodesulfuration Catalysts and its preparation method.The method can be improved the catalyst pores structure, metal disperses more even, better its metal component of performance is active, and Y zeolite can be given full play to its acidity, and better cooperate with hydrogenation active metals, reach the effect of Ultra-deep Desulfurization of Diesel Fuels, suit especially in the mink cell focus hydrotreatment, to use.
The bulk phase catalyst major part is made of active metal component, and the content of active metal component is generally unrestricted, but active metallic content is high, will increase the preparation cost of catalyst, and affects pore structure and the intensity of catalyst.And the conventional negative supported catalyst is subject to the restriction of carrier hole structure, and the reactive metal load capacity can not be too much, and active the raising is restricted.The present invention finds by a large amount of experiments, become an amount of water-soluble nitrogen-containing compound of introducing in the glue process at bulk phase catalyst, can regulate the pore structure of catalyst and the distribution of reactive metal, in the situation that be lower than conventional bulk phase catalyst active metallic content, still can reach the activity of conventional bulk phase catalyst, can also increase the intensity of catalyst simultaneously.And add Y zeolite with suitable way, and it is matched with active metal component better, be beneficial to the desulfurization of the sterically hindered large sulfur-containing compound such as 4,6-dimethyl Dibenzothiophene class, and then reach the purpose of ultra-deep desulfurization.
Body phase ultra-deep hydrodesulfuration catalyst of the present invention contains Mo, W, three kinds of metal components of Ni, and wherein W, Ni exist with the composite oxides form: Ni
xW
yO
z, z=x+3y, Mo exists with oxide form: MoO
3Take the weight of catalyst as benchmark, composite oxides Ni
xW
yO
zWith oxide M oO
3Gross weight content be 30%～70%, be preferably 35%～55%, the content of aluminium oxide is 10%～65%, is preferably 30%～60%, the content of Y zeolite is 1%～20%, is preferably 5%～15%.
The character of catalyst of the present invention is as follows: specific area is 150～450m
2/ g, pore volume is 0.20～0.60ml/g, pore-size distribution is as follows: diameter is that the following shared pore volume in hole of 4nm accounts for 10%～35% of total pore volume, diameter is that the shared pore volume in the hole of 4～15nm accounts for 50%～85% of total pore volume, what diameter was that the above pore volume of 15nm accounts for total pore volume is 5%～15%, preferred pore-size distribution is as follows: diameter is that the following shared pore volume in hole of 4nm accounts for 10%～25% of total pore volume, diameter accounts for 60%～80% of total pore volume at the shared pore volume in the hole of 4～15nm, and what diameter was that the above shared pore volume in hole of 15nm accounts for total pore volume is 8%～15%.
In the catalyst of the present invention, composite oxides Ni
xW
yO
zThe ratio of middle x and y is 1: 7～7: 1, is preferably 1: 3～3: 1.Composite oxides Ni
xW
yO
zWith oxide M oO
3Weight ratio be 1: 8～8: 1, be preferably 1: 5～5: 1.
The SiO of Y zeolite used herein
2/ Al
2O
3Mol ratio 10～20, cell parameter are 2.423～2.445nm, infrared acidity 0.2～0.5mmol.This Y zeolite can adopt the synthetic or conventional method modification of existing method and get.
Can also contain one or more in silica, amorphous aluminum silicide, phosphorous oxides, titanium oxide, Zirconium oxide, the boron oxide compound in the catalyst of the present invention, the weight content in catalyst is 0～30%, is preferably 1%～20%.
The preparation process of catalyst of the present invention may further comprise the steps:
(1) coprecipitation generates Ni
xW
yO
zThe composite oxides precursor; (2) to Ni
xW
yO
zAdd the Y zeolite slurries in the composite oxides precursor, aging under stirring condition; (3) to step (2) obtain aging after mixture in add MoO
3Making beating mixes, filters, and is then dry; (4) through roll, moulding, activation be final catalyst, wherein step (1) process is as follows: preparation contains the saline mixed solution of Ni, W, Al component, then also flow to add in the retort that water purification is housed simultaneously with the water miscible nitrogen-containing compound aqueous solution, precipitating reagent ammoniacal liquor and become glue, the pH value of slurries is in 7.0～10.0 scopes in the retort, making gelatinous precipitate, namely is composite oxides Ni
xW
yO
zPrecursor; Wherein the addition of water miscible nitrogen-containing compound is with NH
4 +Meter, with the mol ratio of active metal nickel and tungsten total amount be 0.2～2.0, precipitating reagent can working concentration ammoniacal liquor arbitrarily.Described water miscible nitrogen-containing compound can be selected one or more in ammonium citrate, carbonic hydroammonium, ammonium acetate, the ammonium oxalate, is preferably carbonic hydroammonium.
The described preparation of step (1) contains the saline mixed solution of Ni, W, Al component, wherein contain nickel salt and can be in nickelous sulfate, nickel nitrate, the nickel chloride etc. one or more, tungsten salt can be in sodium tungstate, the ammonium metatungstate etc. one or more, contains aluminium ion solution and can be in aluminum nitrate, aluminium chloride, the aluminum sulfate etc. one or more.Becoming the glue temperature is 30～100 ℃, and gelation time is generally 0.5～5.0 hour, is preferably 0.5～3.0 hour.
The described Y zeolite slurries of step (2) are to be to mix in 1: 1～10: 1 by volume with Y zeolite and water, then through grinding, make molecular sieve pulp.The described aging condition of step (2) is under stirring state, and aging temperature is 30～90 ℃, and ageing time 1～5 hour, pH value are 7.0～10.0.
50～150 ℃ of the described baking temperatures of step (3), 0.5～24 hour drying time.
Step (4) is described to roll in the process, can add extrusion aid, described extrusion aid refers to be conducive to the material of extrusion modling, and such as in sesbania powder, carbon black, graphite powder, the citric acid etc. one or more, the consumption of extrusion aid accounts for the 1wt%～10wt% of total material butt.Can or contain with water purification after the moulding and can decompose salt (such as ammonium acetate) solution and wash.
The described activation of step (4) comprises the processes such as dry and roasting.Stripe shape thing drying, roasting obtain final catalyst prod after will washing.Wherein dry and roasting can be adopted this area normal condition, as 50～200 ℃ of dryings 1～48 hour, 450～600 ℃ of roastings 0.5～24 hour, is preferably 1～8 hour.
In the inventive method, add required catalyst promoter and add component in a step that can be in above-mentioned steps or a few step.Auxiliary agent generally comprises one or more among P, F, Ti, Si, B, the Zr etc.The interpolation component is generally one or more in silica, zirconia, clay, sial, titanium oxide, the magnesia etc.
Catalyst shape of the present invention can be sheet, spherical, cylindrical bars and irregular bar (clover, bunge bedstraw herb), preferably cylindrical bars and irregular bar (clover, bunge bedstraw herb) as required.The diameter of catalyst can be 0.8～2.0mm slice and＞the thick bar of 2.5mm.
Catalyst of the present invention has higher hydrodesulfurization activity, can be used for hydrocracking preliminary treatment and diesel oil desulphurization technology, and this catalyst also can be used in other hydrofinishing and the hydroprocessing technique.
The nitrogen-containing compound consumption is wanted suitably when consumption is large, can causes difficulty to the moulding of catalyst, and catalyst strength is caused very large impact in the inventive method.When consumption hour, the pore structure of catalyst is changed little, metal is evenly distributed on catalyst.
The present invention is by becoming an amount of water-soluble nitrogen-containing compound of adding in the glue process at bulk phase catalyst, make in the glue thing except forming precipitation of hydroxide, also contain an amount of basic salt precipitation, make it in roasting process, emit a certain amount of gas, under the percussion of gas, not only improved the pore structure of catalyst, but also make more metal active position be exposed to the surface of catalyst, improved the utilization rate of reactive metal, simultaneously also for more reactive metal and the interactional chance of acidic components molecular sieve are provided.In the situation that same metal content, activity in the situation that catalyst hydrogenation activity is suitable, can reduce conventional bulk phase catalyst reactive metal consumption apparently higher than conventional bulk phase catalyst, reduces the catalyst preparation cost.Simultaneously, because in the inventive method, Y zeolite is to join Ni with the slurries form
xW
yO
zIn the composite oxides precursor, so not only make Y zeolite and hydrogenation active metals evenly, contact fully, avoided kneading method to add the caused molecular sieve of molecular sieve shortcoming pockety, but also make Y zeolite give full play to its acidity, and can better cooperate with hydrogenation active metals, reach the effect of Ultra-deep Desulfurization of Diesel Fuels.And the increase of bulk phase catalyst of the present invention aperture and pore volume, Ni-W high activity center is fully utilized, complicated macrostructure molecule more easily contacts the activated centre, and especially effect is more obvious when processing the more distillate of large molecule content.
The specific embodiment
Further specify the solution of the present invention and effect below by specific embodiment.The percentage composition that relates to is weight percentage.Specific surface area of catalyst adopts the BET method to measure, and pore volume is determination of nitrogen adsorption, and intensity adopts the side pressure method to measure.
Embodiment 1
Add 1000ml water in the dissolving tank and concentration is 10.9g/cm
3376 milliliters of liquor alumini chloridis, nickel chloride 39g and ammonium metatungstate 36.5g dissolving, be mixed with mixed solution.Get 160g carbonic hydroammonium and be made into the aqueous solution that molar concentration is 2.5mol/l.Then mixed solution, ammonium bicarbonate aqueous solution, precipitating reagent 10% ammoniacal liquor also flow simultaneously to add and become glue in the retort that water purification is housed, and one-tenth glue pH value is 8.0, and one-tenth glue temperature is 60 ℃.After the cemented into bundles, (character of Y zeolite is as follows: SiO to add 8 gram Y zeolite slurries
2/ Al
2O
3Mol ratio 18, cell parameter are 2.440nm, infrared acidity 0.35mmol), aging 2 hours.Filter after aging, filter cake adds 600ml water purification and 8.3g molybdenum trioxide, and making beating stirs, and filters, the filter cake that obtains was 80 ℃ of dryings 5 hours, then extruded moulding, with water purification washing 3 times, wet bar was 120 ℃ of dryings 5 hours, 500 ℃ of roastings 4 hours, obtain final catalyst A, composition and main character see Table 1, and pore size distribution sees Table 2.
Embodiment 2
According to the method for embodiment 1, press the constituent content proportioning of catalyst B in the table 2, in dissolving tank, add aluminium chloride, nickel chloride, ammonium metatungstate, phosphoric acid, waterglass, be mixed with mixed solution.Get 100g carbonic hydroammonium and be made into the solution that molar concentration is 2.0mol/l.Then mixed solution, ammonium bicarbonate aqueous solution, precipitating reagent 20% ammoniacal liquor also flow simultaneously to add and become glue in the retort that water purification is housed, and one-tenth glue pH value is 9.0, and one-tenth glue temperature is 80 ℃.After the cemented into bundles, add 5 gram Y zeolite slurries (character is with embodiment 1), aging 3 hours, filter after aging, filter cake adds 600ml water purification and 6.2g molybdenum trioxide, and making beating stirs, filter, the filter cake that obtains is at 70 ℃ of dryings 7 hours, then extruded moulding, with water purification washing 2 times, wet bar 550 ℃ of roastings 3 hours, obtains final catalyst B 100 ℃ of dryings 8 hours, composition and main character see Table 1, and pore size distribution sees Table 2.
Embodiment 3
According to the method for embodiment 1, press the constituent content proportioning of catalyst C in the table 1, in retort, add nickel nitrate, ammonium metatungstate, aluminium chloride, zirconium oxychloride, be mixed with mixed solution.Get the 120g ammonium oxalate and be made into the solution that molar concentration is 1.8mol/l.Then mixed solution, the ammonium oxalate aqueous solution, precipitating reagent 12% ammoniacal liquor also flow simultaneously to add and become glue in the retort that water purification is housed, and one-tenth glue pH value is 10.0, and one-tenth glue temperature is 60 ℃.After the cemented into bundles, add 10 gram Y zeolite slurries, aging 2 hours, filter after aging, filter cake adds 600ml water purification and 6.2g molybdenum trioxide, and making beating stirs, filter, the filter cake that obtains is 120 ℃ of dryings 1 hour, extruded moulding then, and wet bar was 130 ℃ of dryings 3 hours, 600 ℃ of roastings 3 hours, obtain final catalyst C, composition and main character see Table 1, and pore size distribution sees Table 2.
Embodiment 4
According to the method for embodiment 1, press the constituent content proportioning of catalyst D in the table 1, in retort, add nickel nitrate, ammonium metatungstate, aluminium chloride, phosphoric acid, be mixed with mixed solution.Get the 140g ammonium citrate and be made into the solution that molar concentration is 2.5mol/l.Then mixed solution, the ammonium oxalate aqueous solution, precipitating reagent 12% ammoniacal liquor also flow simultaneously to add and become glue in the retort that water purification is housed, and one-tenth glue pH value is 9.0, and one-tenth glue temperature is 65 ℃.After the cemented into bundles, add 12 gram Y zeolite slurries, aging 3 hours, filter after aging, filter cake adds 600ml water purification and 8.3g molybdenum trioxide, and making beating stirs, filter, the filter cake that obtains is 120 ℃ of dryings 1 hour, extruded moulding then, and wet bar was 130 ℃ of dryings 3 hours, 600 ℃ of roastings 3 hours, obtain final catalyst C, composition and main character see Table 1, and pore size distribution sees Table 2.
Comparative example 1
According to the method for embodiment 1, wherein do not add ammonium bicarbonate aqueous solution, preparation reference agent E.Catalyst property sees Table 1, and pore size distribution sees Table 2.
Comparative example 2
According to the method for embodiment 1, wherein do not add Y zeolite, preparation reference agent F.Catalyst property sees Table 1, and pore size distribution sees Table 2.
Composition and the character of table 1 embodiment and comparative example gained catalyst
| Catalyst | A | B | C | D | E | F |
| Catalyst forms, % | ||||||
| WO 3 | 34 | 28 | 30 | 32 | 34 | 34 |
| NiO | 13 | 12 | 14 | 12 | 13 | 13 |
| MoO 3 | 8 | 10 | 6 | 8 | 8 | 8 |
| Y zeolite | 8 | 5 | 10 | 12 | 8 | 0 |
| Al 2O 3 | 37 | 42 | 38 | 34 | 37 | 45 |
| Other | Nothing | SiO 2/2.0 P/1.0 | ZrO 2/2.0 | P/2.0 | Nothing | Nothing |
| Physico-chemical property: | ||||||
| Pore volume, cm 3/g | 0.231 | 0.223 | 0.228 | 0.234 | 0.198 | 0.229 |
| Specific area, m 2/g | 211 | 223 | 225 | 230 | 182 | 209 |
| Intensity, N/mm | 16.7 | 16.1 | 15.6 | 15.1 | 17.5 | 15.5 |
Table 2 catalyst pores distributes
Embodiment 5
The present embodiment is estimated catalyst hydrogenation desulphurization reaction performance.
In order to further specify the ultra-deep hydrodesulfuration ability of catalyst of the present invention, adopt catalyst A of the present invention, C and Comparative Examples catalyst E, F, carry out comparative evaluation's test at the 200ml small hydrogenation device, test raw material is Maoming mixed diesel.The raw material main character sees Table 3, and catalyst activity is estimated process conditions and evaluation result sees Table 4.Adopt gas chromatography-atomic emission detector device (GC-AED) to detect hydrofined oil medium sulphide content type, the results are shown in Table 5.
Can find out from the evaluation test result, adopt the catalyst of method preparation of the present invention, has higher Hydrogenation, especially shown more obvious removal effect to having sterically hindered sulfide, have excellent hydrogenation and desulphurizing ability, can be used in the hydrodesulfurization reaction, be particularly useful for producing in the ultra-deep desulfurization reaction of super clean diesel.
Table 3 feedstock oil main character
| Project | Analysis result |
| Density (20 ℃), g/cm 3 | 0.8614 |
| The boiling range scope, ℃ | 178-373 |
| S，μg/g | 12200 |
| N，μg/g | 288 |
| Cetane number | 46.5 |
Table 4 catalyst hydrogenation desulphurization reaction process conditions and evaluation result
The content of different sulfide in table 5 hydrofined oil
| Catalyst | A | C | E | F |
| Sulfur content in the hydrofined oil, μ g/g | 9 | 12 | 56 | 63 |
| C 1-DBT，μg/g | 0 | 0 | 0 | 0 |
| 4-BMDBT，μg/g | 0 | 0 | 8.6 | 9.3 |
| 6-BMDBT，μg/g | 0 | 0 | 9.5 | 11.4 |
| 4，6-BMDBT，μg/g | 1.2 | 1.6 | 26.3 | 27.5 |
| 2，4，6-BMDBT，μg/g | 7.8 | 10.4 | 11.6 | 14.8 |
Claims (15)
1. a body phase ultra-deep hydrodesulfuration catalyst contains Mo, W, three kinds of metal components of Ni, and wherein W, Ni exist with the composite oxides form: Ni
xW
yO
z, z=x+3y, Mo exists with oxide form: MoO
3Take the weight of catalyst as benchmark, catalyst forms and comprises: composite oxides Ni
xW
yO
zWith oxide M oO
3Gross weight content be 30%～70%, the content of aluminium oxide is 10%～65%, the content of Y zeolite is 1%～20%; The character of described catalyst is as follows: specific area is 150～450m
2/ g, pore volume is 0.20～0.60mL/g, pore-size distribution is as follows: diameter accounts for 10%～35% of total pore volume less than the shared pore volume in the hole of 4nm, diameter is that the shared pore volume in the hole of 4～15nm accounts for 50%～85% of total pore volume, and what diameter accounted for total pore volume greater than the shared pore volume in the hole of 15nm is 5%～15%.
2. according to catalyst claimed in claim 1, it is characterized in that, take the weight of catalyst as benchmark, composite oxides Ni
xW
yO
zWith oxide M oO
3Gross weight content be 35%～55%, the content of aluminium oxide is 30%～60%, the content of Y zeolite is 5%～15%.
3. according to catalyst claimed in claim 1, it is characterized in that described composite oxides Ni
xW
yO
zThe ratio of middle x and y is 1: 7～7: 1, composite oxides Ni
xW
yO
zWith oxide M oO
3Weight ratio be 1: 8～8: 1.
4. according to catalyst claimed in claim 1, the pore-size distribution that it is characterized in that described catalyst is as follows: diameter accounts for 10%～25% of total pore volume less than the shared pore volume in the hole of 4nm, diameter accounts for 60%～80% of total pore volume at the shared pore volume in the hole of 4～15nm, and what diameter accounted for total pore volume greater than the shared pore volume in the hole of 15nm is 8%～15%.
5. according to catalyst claimed in claim 1, it is characterized in that containing in the described catalyst one or more in silica, amorphous aluminum silicide, phosphorous oxides, titanium oxide, Zirconium oxide, the boron oxide compound, the weight content in catalyst is 1%～20%.
6. the preparation method of the arbitrary described catalyst of claim 1～4 may further comprise the steps: (1) coprecipitation generation Ni
xW
yO
zThe composite oxides precursor; (2) to Ni
xW
yO
zAdd the Y zeolite slurries in the composite oxides precursor, aging under stirring condition; (3) to step (2) obtain aging after mixture in add MoO
3Making beating mixes, filters, and is then dry; (4) through roll, moulding, activation be final catalyst, wherein step (1) process is as follows: preparation contains the saline mixed solution of Ni, W, Al component, then also flow to add in the retort that water purification is housed simultaneously with the water miscible nitrogen-containing compound aqueous solution, precipitating reagent ammoniacal liquor and become glue, the pH value of slurries is in 7.0～10.0 scopes in the retort, making gelatinous precipitate, namely is composite oxides Ni
xW
yO
zPrecursor; Wherein the addition of water miscible nitrogen-containing compound is with NH
4 +Meter, with the mol ratio of active metal nickel and tungsten total amount be 0.2～2.0.
7. in accordance with the method for claim 6, it is characterized in that described water miscible nitrogen-containing compound is one or more in ammonium citrate, carbonic hydroammonium, ammonium acetate and the ammonium oxalate.
8. in accordance with the method for claim 6, it is characterized in that described water miscible nitrogen-containing compound is carbonic hydroammonium.
9. in accordance with the method for claim 6, it is characterized in that the described preparation of step (1) contains the saline mixed solution of Ni, W, Al component, wherein contain nickel salt and be in nickelous sulfate, nickel nitrate, the nickel chloride one or more, tungsten salt is one or both in sodium tungstate, the ammonium metatungstate, contains aluminium salt and be in aluminum nitrate, aluminium chloride, the aluminum sulfate one or more; Becoming the glue temperature is 30～100 ℃, and gelation time is 0.5～5.0 hour.
10. in accordance with the method for claim 6, it is characterized in that the described Y zeolite slurries of step (2) are is to mix in 1: 1～10: 1 with Y zeolite and water by volume, then through grinding, makes molecular sieve pulp.
11. in accordance with the method for claim 6, it is characterized in that the described aging condition of step (2) under stirring state, aging temperature is 30～90 ℃, and ageing time 1～5 hour, pH value are 7.0～10.0.
12. in accordance with the method for claim 6, it is characterized in that 50～150 ℃ of the described baking temperatures of step (3), 0.5～24 hour drying time.
13. in accordance with the method for claim 6, it is characterized in that described in the step (4) after the moulding, wash with water purification or the aqueous solution that contains ammonium acetate.
14. in accordance with the method for claim 6, it is characterized in that the described activation of step (4) comprises drying and roasting, condition is as follows: 50～200 ℃ of dryings 1～48 hour, 450～600 ℃ of roastings 0.5～24 hour.
15. in accordance with the method for claim 6, it is characterized in that adding required catalyst promoter and adding component in step in above-mentioned steps or a few step; Auxiliary agent comprises one or more among P, F, Ti, Si, B, the Zr; The interpolation component is one or more in silica, zirconia, clay, sial, titanium oxide, the magnesia.
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| CN108067246A (en) * | 2016-11-16 | 2018-05-25 | 中国石油天然气股份有限公司 | A kind of preparation method of body phase hydrogenation catalyst |
| CN113578299B (en) * | 2020-04-30 | 2023-11-10 | 中国石油化工股份有限公司 | Silicon-aluminum-zirconium composite oxide, catalytic cracking catalyst, and preparation methods and applications thereof |
| US11826738B2 (en) * | 2020-07-27 | 2023-11-28 | Uop Llc | High activity and high distillate yield hydrocracking catalysts with intimate interaction between unsupported metal oxide and zeolite |
| CN114433204B (en) * | 2020-10-19 | 2023-09-01 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
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