CN103657667A - Preparation method for novel heavy oil hydrogenization demetallization catalyst adopting macroporous structures - Google Patents
Preparation method for novel heavy oil hydrogenization demetallization catalyst adopting macroporous structures Download PDFInfo
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Abstract
The invention discloses a preparation method for a novel heavy oil hydrogenization demetallization catalyst adopting macroporous structures. The preparation method is characterized by particularly comprising the following steps: 1) preparing alumina sol; 2) mixing pitch residue powder with the alumina sol to prepare a catalyst carrier adopting the macroporous structures; 3) impregnating the formed catalyst carrier by a two-step impregnation method adopting isopyknic division to finally obtain the catalyst. The catalyst prepared by the method adopts mesopore structures and the macroporous structures at different proportions; the proportion of the macroporous structures can be adjusted with the amount of pore forming materials of pitch residues. A diffusion experiment shows that the catalyst adopting the macroporous structures in a certain proportion meets mechanism of a heavy oil hydrogenization demetallization reaction, has a relatively high metal accommodation ability, effectively lowers the reaction resistance in the heavy oil hydrogenization demetallization reaction process, improves effective diffusion coefficient of heavy oil in the catalyst, and is suitable for processing heavy oil or residual oil with relatively high metal content.
Description
Technical field
The present invention relates to a kind of preparation method of novel macroporous structure catalyst for heavy oil hydrogenation demetal, this preparation method is suitable for preparing various heavy oil hydrogenating treatment catalysts, is particularly suitable for preparing various catalyst for heavy oil hydrogenation demetal.
Background technology
Along with crude oil heaviness trend obviously, the technology of light materialization of heavy oil is paid close attention to widely.Heavy-oil hydrogenation is an important means of heavy oil lighting, so heavy-oil hydrogenation catalyst is the key of research and development heavy-oil hydrogenation technology.Heavy oil molecules is larger, non-hydrocarbons magazine is higher, and do not gasify under catalytic hydrogenation condition, heavy-oil hydrogenation reaction is usually interior diffusion controlled reaction, in heavy oil, contain a large amount of metals simultaneously, mainly nickel and vanadium, and nickel and vanadium mainly exist with the form of the organic complex of the non-porphyrin of porphyrin, stability is high, be difficult to remove, the mechanism of heavy oil hydrogenation demetal reaction has determined the requirement to catalyst for heavy oil hydrogenation demetal, must possess suitable specific area, pore size distribution and pore structure, could effectively reduce diffusional resistance, improve reaction effect.Therefore, the novel catalyst for heavy oil hydrogenation demetal of the applicable catalyst for heavy oil hydrogenation demetal performance of research and development is extremely urgent.
Heavy oil molecules has complicated three-dimensional structure.Meanwhile, in heavy oil hydrogenation demetal reaction, the metal sulfide removing causes except meeting covers catalyst surface that catalyst eats dishes without rice or wine to stop up, active decline.That catalyst of heavy oil and love usually be take the part of aluminium oxide as carrier or carrier, because heavy oil molecules amount is large, impurity content is higher, therefore General Requirements heavy-oil hydrogenation catalyst has higher pore volume and larger aperture, to reduce the diffusional resistance of heavy oil molecules, therefore the aluminium oxide as catalyst carrier also must have higher pore volume and larger aperture and specific area.Yet the pore volume of catalyst carrier, aperture, specific area and intensity is restriction mutually again.Therefore, as how to prepare active better and the higher heavy-oil hydrogenation catalyst of intensity become the key of heavy-oil hydrogenation technical research.For adapting to the needs of heavy oil hydrogenation demetal process, the preparation of the catalyst carrier of some applicable heavy-oil hydrogenation processes has been in the news.
CN101612593A has reported the synthetic of a kind of catalyst carrier for hydrgenating heavy oil.This preparation method utilizes decompression residuum de-oiled asphalt residue dry powder for mill template.De-oiled asphalt residue is ground to form to the fine powder of several microns, then, under Action of Surfactant, be distributed in aluminium colloidal sol precursor, template is removed in the aluminium colloidal sol that contains residue template is dry, calcining, finally supports active component.Synthetic catalyst contains abundant macroporous structure, and the volume fraction of its macropore can be adjusted by the consumption of template.The scope of its average pore size of catalyst of preparation is 6.53-9.97nm, and pore volume scope is 0.48-0.75cm
3/ g, the scope of specific area is 255-301m
2/ g.
CN1247772A has reported a kind of preparation method who is applicable to being used as a kind of aluminium oxide of catalyst carrier for hydrgenating heavy oil.The method is that aluminum compound solution and precipitant solution are contacted under 20-55 ℃, pH6-9,30-80 ℃ and carbonate and/bicarbonate ion, ammonium ion and slurries in the mol ratio of aluminium hydroxide be not less than 0.1, the mol ratio of ammonium ion and carbanion and/or bicarbonate ion is greater than under 1 condition aging at least 10 minutes, filter and wash, then by dry and roasting, obtain catalyst carrier for hydrgenating heavy oil.Catalyst carrier pore volume scope prepared by the method is 0.7-0.9 cm
3/ g, average pore size 11-12nm.
CN1830560A has reported heavy-oil hydrogenation catalyst that a kind of macroporous structure parameter can independently regulate and control and preparation method thereof, this catalyst is used organic granular as template in preparation process, after compound with carrier, remove again template, make to leave in catalyst the macropore that aperture is greater than 5nm, and the aperture of catalyst can be realized by changing the average diameter of granular formwork, the volume fraction of macropore can be realized by changing the consumption of granular formwork.Catalyst prepared by the method can significantly improve the performance of catalyst, is applicable to the catalytic hydrogenation process of mink cell focus.For the higher mink cell focus of tenor, applicability is poor.
Comprise and in the above prior art, there is following common feature and a difficult problem: preparation process more complicated, the performance of prepared hydrogenation catalyst mainly comprises aperture, pore volume, specific area and pore size distribution etc. are larger to the dependence of preparation condition and raw materials, and prepared catalyst mechanical strength is poor, simultaneously, feed change and preparation condition can be to prepared catalyst pore volume, aperture, specific area, pore size distribution and mechanical strength exert an influence simultaneously, therefore, the pore structure that wants to adjust by changing a certain parameter catalyst will be very difficult, and preparation method's repeatability is poor, in these technology, the dry and baking modes of catalyst is common drying mode and baking modes, mechanical strength impact on catalyst is larger, and then affected the long-term operation of heavy-oil hydrogenation catalyst.Meanwhile, these heavy-oil hydrogenation catalysts have certain wide in range property, are applicable to hydrocracking, hydrofinishing, rather than for heavy oil hydrogenation demetal reacts the catalyst of making to measure, are not too applicable to heavy oil hydrogenation demetal reaction.
Summary of the invention
The preparation method who the object of this invention is to provide a kind of novel macroporous structure catalyst for heavy oil hydrogenation demetal, this preparation method is on the basis of early-stage Study, directly asphaltic residue is mixed with boehmite direct mechanical, prepare cheap catalyst carrier, add again on this basis extrusion aid and peptizing agent kneading extrusion, Kaolinite Preparation of Catalyst carrier also adopts the drying mode of supercritical fluid extraction to be dried, and can significantly improve the intensity of catalyst, the service life of extending catalyst.
Technical scheme of the present invention: a kind of preparation method of novel macroporous structure catalyst for heavy oil hydrogenation demetal, is characterized in that: it specifically comprises the steps:
1) preparation of aluminium colloidal sol;
2) asphaltic residue powder and aluminium colloidal sol are mixed with to macroporous structure catalyst carrier;
3) catalyst carrier after moulding is adopted to two step infusion process dippings of equal-volume branch; Finally make catalyst.
The preparation of the aluminium colloidal sol of described step 1: take industrial boehmite powder 10g, add extrusion aid and peptizing agent, extrusion aid is that sesbania powder, addition are 1.0 g-3.0g, peptizing agent is that nitric acid or acetic acid, addition are 9.0g-9.5g, mechanical agitation mixes, and obtains homogeneous, stable, transparent aluminium colloidal sol.
Described step 2 prepare macroporous structure structured catalysis agent carrier: in the aluminium colloidal sol that step 1 is made, add asphaltic residue powder, the weight of asphaltic residue powder accounts for the 10%-30% of boehmite weight, with high speed disperser, be uniformly dispersed, then on banded extruder, kneading is several times repeatedly, to increase uniformity and the intensity of the aluminium colloidal sol that contains asphaltic residue powder, then extruded moulding; The aluminium colloidal sol that contains asphaltic residue powder after moulding is dry at 110 ℃ in supercritical fluid extraction equipment, then, by the dried aluminium colloidal sol that contains asphaltic residue powder roasting 4-7 hour at 500 ℃-550 ℃ in Muffle furnace, obtain catalyst carrier.
The two step infusion process dippings that described step 3 adopts equal-volume to distribute catalyst carrier, concrete steps are as follows: the first step is first flooded Mo: take a certain amount of (NH
4)
6mo
7o
24H
2o, adds a certain amount of water, and the mass concentration that makes ammonium molybdate solution is 35%-50%, after heating melts, join in the catalyst carrier of 10 grams of step 2 preparations, within standing one hour, make the aqueous solution diffuse in catalyst carrier duct, in baking oven, 110 ℃ of dry and roastings in Muffle furnace, make containing M
ocatalyst sample; Second step dipping Ni: by a certain amount of Ni(NO
3)
26H
2o, adds a certain amount of water-soluble solution, and making the mass concentration of nickel nitrate solution is 25%-35%, has added M pre-soaked
ocatalyst sample, within standing one hour, make the aqueous solution diffuse in catalyst carrier duct, drying and roasting under the same terms, makes the catalyst that contains active component molybdenum and nickel.
In the aluminium colloidal sol preparation of described step 1, can also add auxiliary agent, promoter addition is the 5%-10% that accounts for boehmite powder, and auxiliary agent is a kind of or two kinds of mixtures in silica or titanium dioxide.
Described asphaltic residue powder refers to the de-oiled asphalt residue that heavy oil or residual oil obtain through drastic deasphalting.
Described boehmite can replace with the aluminium oxide after the calcining of boehmite predecessor.
The described first step is first flooded in Mo, the M in ammonium molybdate solution
oo
3content is the 4%-30% of catalyst quality; Described second step first floods in Ni, the 1%-6% that the NiO content in nickel nitrate solution is catalyst quality; Described second step dipping Ni can use C
oreplace, that is: Co (NO
3)
26H
2o is Co source, the 1%-10% that in its aqueous solution, CoO content is catalyst quality.
Prepared catalyst is applicable to processing metal content in hydrodesulfurization, hydrodenitrogeneration, HDM or the hydrogenation preprocessing process of more than 60% heavy oil or residual oil.
Being shaped as of institute's extruded moulding is cylindrical, trifolium-shaped or bunge bedstraw herb type.
Advantage of the present invention is: the method is the synthetic catalyst for heavy oil hydrogenation demetal with macroporous structure of pore creating material with cheap asphaltic residue.Owing to synthesizing the pore creating material asphaltic residue of this catalyst, there is certain pore structure, the carrier material boehmite of synthetic catalyst has certain micropore and mesopore simultaneously, add the drying mode with supercritical fluid extraction, the destruction of having avoided pore structure to cause due to traditional drying mode, therefore the catalyst of the method synthesized is when having certain macroporous structure, and its specific area, intensity and pore volume can be lower than traditional catalyst.The catalyst for heavy oil hydrogenation demetal of this macroporous structure can effectively reduce the resistance to mass tranfer of heavy oil hydrogenation demetal reaction, improves the ability that catalyst holds metal, the service life of extending catalyst.
Below in conjunction with specific implementation method, the present invention is described further, but not as the restriction to the scope of the present invention.
The specific embodiment
Synthesizing of embodiment 1, carrier reference
Take industrial boehmite powder 10g, add extrusion aid sesbania powder and peptizing agent, the addition of sesbania powder be within the scope of 2.0 g(1.0 g-3.0g all can), the addition of the rare nitric acid of peptizing agent or spirit of vinegar be within the scope of 9.3g(9.0 g-9.5g all can), mechanical agitation mixes, and obtains homogeneous, stable, transparent aluminium colloidal sol.By aluminium colloidal sol on banded extruder repeatedly kneading several times, to increase uniformity and the intensity of carrier, then extruded moulding.Carrier after moulding is dry at 110 ℃ in supercritical fluid extraction equipment, then, by the roasting 5 hours at 500 ℃-550 ℃ in Muffle furnace of dried carrier, obtain carrier reference Al
2o
3-1, by carrier is carried out to low temperature N
2absorption characterizes, and then recording BET specific area is 369.1 m
2/ g, surveys the same apparatus of specific surface pore structure is analyzed by BET nitrogen adsorption capacity method, recording average pore size is 8.01nm, and pore volume is 0.56 cm
3/ g, the mechanical strength of carrier is 22.3 N/mm, the mensuration of carrier mechanical strength is measured with digital display granule strength.
3) by carrier reference Al
2o
3-1 two step infusion process dippings that adopt equal-volume to distribute; Concrete steps are as follows: the first step is first flooded Mo: take a certain amount of (NH
4)
6mo
7o
24H
2o, adds a certain amount of water, makes the mass concentration of ammonium molybdate solution at 35%-50%, and heating joins carrier reference Al after melting
2o
3in-1, the M in ammonium molybdate solution
oo
3content is 28% of catalyst quality, within standing one hour, makes the aqueous solution diffuse in catalyst carrier duct, and in baking oven, 110 ℃ of dry, roastings, make containing M
osample; Second step dipping Ni: by a certain amount of Ni(NO
3)
26H
2o, NiO is catalyst quality 5%, adds a certain amount of water-soluble solution, making the mass concentration of nickel nitrate solution is 25%-35%, has added M pre-soaked
osample, within standing one hour, make the aqueous solution diffuse in catalyst carrier duct, drying and roasting under the same terms, makes the catalyst (reference) that contains active component molybdenum and nickel, with Ni-Mo/ γ-Al
2o
3-1 represents.Wherein, the NiO content in nickel nitrate solution is catalyst quality 5%.
Embodiment 2
A preparation method for novel macroporous structure catalyst for heavy oil hydrogenation demetal, specifically comprises the steps:
1) aluminium colloidal sol preparation; Take industrial boehmite powder 10g, add extrusion aid and peptizing agent, extrusion aid is that sesbania powder, addition are 2.0 g, and peptizing agent is that nitric acid, addition are 9.3g, and mechanical agitation mixes, and obtains homogeneous, stable, transparent aluminium colloidal sol.
2) asphaltic residue powder and aluminium colloidal sol are mixed with to macroporous structure catalyst carrier; In the aluminium colloidal sol that step 1 is made, add asphaltic residue powder, the weight of asphaltic residue powder accounts for 10% of boehmite weight, with high speed disperser, disperse 5 minutes, be uniformly dispersed, then on banded extruder, kneading is several times repeatedly, (being 5 times here), to increase uniformity and the intensity of the aluminium colloidal sol that contains asphaltic residue powder, then extruded moulding; The aluminium colloidal sol that contains asphaltic residue powder after moulding is dry at 110 ℃ in supercritical fluid extraction equipment, then by the roasting 5 hours at 500 ℃-550 ℃ in Muffle furnace of the dried aluminium colloidal sol that contains asphaltic residue powder, obtain catalyst carrier, the catalyst carrier Al of embodiment 2
2o
3-2 represent.By carrier is carried out to B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature, characterize, the specific area that records carrier is 372.2 m
2/ g, surveys the same apparatus of specific surface pore structure is analyzed by BET nitrogen adsorption capacity method, the average pore size that records carrier is 20.5nm, and pore volume is 0.74 cm
3/ g, mechanical strength is 20.2N.Add its specific area of pore creating material, aperture and the pore volume of asphaltic residue to be obviously greater than the reference of embodiment 1, and intensity still meet the performance requirement of device to heavy-oil hydrogenation catalyst.
3) by catalyst carrier Al
2o
3-2 two step infusion process dippings that adopt equal-volume to distribute; Concrete steps are as follows: the first step is first flooded Mo: take a certain amount of (NH
4)
6mo
7o
24H
2o, adds a certain amount of water, and the mass concentration that makes ammonium molybdate solution is 35%-50%, after heating melts, joins in the catalyst carrier of 10 grams of step 2 preparations M in ammonium molybdate solution
oo
3content is 28% of catalyst quality, within standing one hour, makes the aqueous solution diffuse in catalyst carrier duct, and in baking oven, 110 ℃ of dry, roastings, make containing M
osample; Second step dipping Ni: by a certain amount of Ni(NO
3)
26H
2o, in nickel nitrate solution, NiO content is catalyst quality 5%, adds a certain amount of water-soluble solution, makes the mass concentration 25%-35% of nickel nitrate solution, has added M pre-soaked
osample, within standing one hour, make the aqueous solution diffuse in catalyst carrier duct, drying and roasting under the same terms, makes catalyst of the present invention, with Ni-Mo/ γ-Al
2o
3-2 represent.
Described asphaltic residue powder refers to the de-oiled asphalt residue that residual oil or heavy oil obtain through drastic deasphalting.
Embodiment 3
A preparation method for novel macroporous structure catalyst for heavy oil hydrogenation demetal, specifically comprises the steps:
1) aluminium colloidal sol preparation; Take industrial boehmite powder 10g, add extrusion aid and peptizing agent, extrusion aid is that sesbania powder, addition are 1.0 g, and peptizing agent is that acetic acid, addition are 9.0g, and mechanical agitation mixes, and obtains homogeneous, stable, transparent aluminium colloidal sol.
2) asphaltic residue powder and aluminium colloidal sol are mixed with to macroporous structure catalyst carrier; In the aluminium colloidal sol that step 1 is made, add asphaltic residue powder, the weight of asphaltic residue powder accounts for 20% of boehmite weight, with high speed disperser, disperse 5 minutes, be uniformly dispersed, then kneading 3 times repeatedly on banded extruder, to increase uniformity and the intensity of the aluminium colloidal sol that contains asphaltic residue powder, then extruded moulding; The aluminium colloidal sol that contains asphaltic residue powder after moulding is dry at 110 ℃ in supercritical fluid extraction equipment, then by the roasting 4 hours at 500 ℃-550 ℃ in Muffle furnace of the dried aluminium colloidal sol that contains asphaltic residue powder, obtain catalyst carrier, the catalyst carrier Al of embodiment 3
2o
3-3 represent.Carrier is through nitrogen absorption under low temperature and pore structure analysis, and the BET specific area that records carrier is 373.5 m
2/ g, average pore size is 22.5nm, pore volume is 0.76 cm
3/ g, mechanical strength is 18.5N.The specific area of carrier, average pore size and pore volume are obviously greater than the reference of embodiment 1.Due to average pore size and pore volume increase, the mechanical strength of leading carrier declines a little.
Step 3 is identical with the step 3 of embodiment 2, makes catalyst of the present invention, with Ni-Mo/ γ-Al
2o
3-3 represent.
Embodiment 4
Embodiment 4 is identical with embodiment 2, and difference is: the addition of extrusion aid is 3.0g, and peptizing agent is that nitric acid, addition are 9.5g, and the weight of asphaltic residue powder accounts for 30% of boehmite, obtains catalyst and carries Al
2o
3-4.Carrier is through nitrogen absorption under low temperature and pore structure analysis, and the BET specific area that records carrier is 375.5 m
2/ g, average pore size is 25.5nm, pore volume is 0.82cm
3/ g, mechanical strength is 15.5N.The specific area of carrier, average pore size and pore volume are obviously greater than the reference of embodiment 1.Due to average pore size and pore volume increase, the mechanical strength of carrier declines a little.Finally make catalyst of the present invention, with Ni-Mo/ γ-Al
2o
3-4 represent.
Embodiment 5, boehmite powder and the direct mixed-forming of auxiliary agent are prepared carrier reference
Embodiment 5 is identical with embodiment 2, difference is: get industrial boehmite powder 10g, add extrusion aid sesbania powder 3g, add a kind of or two kinds of mixtures in auxiliary agent silica or titanium dioxide, addition is the 5%-10% that accounts for boehmite powder, and the addition that adds the rare nitric acid of peptizing agent or spirit of vinegar is 9.3g, then adds asphaltic residue powder, the weight of asphaltic residue powder accounts for 30% of boehmite, obtains catalyst carrier Al
2o
3-5.Carrier is through nitrogen absorption under low temperature and pore structure analysis, and the BET specific area that records carrier is 325.5 m
2/ g, average pore size is 21.5nm, pore volume is 0.72cm
3/ g, mechanical strength is 20.5N.From measurement result, can find out, add after a certain amount of auxiliary agent, the specific area of carrier, average pore size and pore volume are obviously greater than the reference of embodiment 1, and the intensity of carrier is compared with Al
2o
3-4 make moderate progress, and this explanation adds auxiliary agent to be conducive to improve the mechanical strength of carrier.Finally make catalyst of the present invention, with Ni-Mo/ γ-Al
2o
3-5 represent.
Embodiment 6
The reactivity worth of catalyst and mechanical strength
On continous way minisize reaction still, the catalyst of embodiment 1-5 is evaluated, and surveyed its mechanical strength.Raw material oil properties is in Table 1
Table 1 elm refining residual oil character
| Project | Character | Project | Character |
| Density (20 ℃, g/cm 3） | 0.9563 | Carbon, w% | 87.26 |
| Carbon residue, W% | 13.5 | Hydrogen, w% | 11.91 |
| Mean molecule quantity | 738 | Sulphur, w% | 0.25 |
| Viscosity (80 ℃, mm 2/s) | 455.7 | Nitrogen, w% | 0.56 |
| Four component analyses, W% | ? | Iron, μ g/g | 7.2 |
| Saturated minute | 36.8 | Calcium, μ g/g | 16.8 |
| Fragrance minute | 33.4 | Nickel, μ g/g, | 67.5 |
| Colloid | 26.4 | Vanadium, μ g/g | 45.2 |
| Asphalitine | 3.4 | Sodium, μ g/g | 16.9 |
Experiment condition: P=6Mpa; T=360 ℃, reaction feed is elm refining reduced crude, mass space velocity is 2.4h
-1, hydrogen-oil ratio=600:1, loaded catalyst is 3g, and except reactivity worth, the mechanical strength of catalyst has also been measured in experiment, and experimental result is in Table 2.
Hydrogenation reaction result and the mechanical strength of table 2 synthesized catalyst
| Catalyst | De-(nickel+vanadium) rate % | Mechanical strength N/mm |
| Ni-Mo/γ-Al 2O 3-1 | 20.2 | 22.5 |
| Ni-Mo/γ-Al 2O 3-2 | 67.3 | 21.4 |
| Ni-Mo/γ-Al 2O 3-3 | 78.5 | 19.5 |
| Ni-Mo/γ-Al 2O 3-4 | 80.2 | 18.3 |
| Ni-Mo/γ-Al 2O 3-5 | 83.5 | 17.5 |
Embodiment 7
Identical with embodiment 1, difference is: infusion process dipping, second step is with Co (NO
3)
26H
2o is Co source, the same Ni(NO of dosage
3)
26H
2o, the 1%-10% that in its aqueous solution, CoO content is catalyst quality.Make catalyst ginseng sample than using Co-Mo/ γ-Al
2o
3-1 represents.
Embodiment 8
Identical with embodiment 2, difference is: infusion process dipping, second step is with Co (NO
3)
26H
2o is Co source, the same Ni(NO of dosage
3)
26H
2o, the 1%-10% that CoO is catalyst quality.Make catalyst ginseng sample than using Co-Mo/ γ-Al
2o
3-2 represent.
Embodiment 9
Identical with embodiment 3, difference is: infusion process dipping, second step is with Co (NO
3)
26H
2o is Co source, the same Ni(NO of dosage
3)
26H
2o, the 1%-10% that CoO is catalyst quality.Make catalyst ginseng sample than using Co-Mo/ γ-Al
2o
3-3 represent.
Embodiment 10
Identical with embodiment 4, difference is: infusion process dipping, second step is with Co (NO
3)
26H
2o is Co source, the same Ni(NO of dosage
3)
26H
2o, the 1%-10% that CoO is catalyst quality.Make catalyst ginseng sample than using Co-Mo/ γ-Al
2o
3-4 represent.
Embodiment 11
Identical with embodiment 5, difference is: infusion process dipping, second step is with Co (NO
3)
26H
2o is Co source, the same Ni(NO of dosage
3)
26H
2o, the 1%-10% that CoO is catalyst quality.Make catalyst ginseng sample than using Co-Mo/ γ-Al
2o
3-5 represent.
Embodiment 12
The reactivity worth of catalyst and mechanical strength
Catalyst to embodiment 7-11 is evaluated, and experiment condition is with embodiment 6, and experimental result is in Table 3.
Hydrogenation reaction result and the mechanical strength of table 3 synthesized catalyst
| Catalyst | De-(nickel+vanadium) rate % | Mechanical strength N/mm |
| Co-Mo／γ- Al 2O 3-1 | 23.5 | 22.7 |
| Co-Mo／γ- Al 2O 3-2 | 70.5 | 22.1 |
| Co-Mo／γ- Al 2O 3-3 | 75.6 | 19.8 |
| Co-Mo／γ- Al 2O 3-4 | 82.5 | 18.5 |
| Co-Mo／γ- Al 2O 3-5 | 85.1 | 17.9 |
From the result of table 2 and table 3, can find out, with heavy petroleum asphalt residue powder, do pore creating material, directly mix with boehmite, and the prepared catalyst for heavy oil hydrogenation demetal of the drying mode that adopts supercritical fluid extraction has higher metal removal activity and good mechanical strength, can meet the particularly performance requirement of ebullated bed to catalyst for heavy oil hydrogenation demetal of industrial differential responses device, and the consumption of pore creating material asphaltic residue is higher, the activity of catalyst is higher, especially add after a certain amount of auxiliary agent, regulated the acid distribution of catalyst, the HDM that has greatly improved prepared catalyst is active.
In above-described embodiment, institute's extruded moulding is shaped as cylindrical, trifolium-shaped or bunge bedstraw herb type; M in embodiment
oo
3for all can within the scope of 4%-30% and the NiO of the catalyst quality 1%-6% that is catalyst quality, the prepared catalyst of the present invention is applicable in hydrodesulfurization, hydrodenitrogeneration, HDM or the hydrogenation preprocessing process of heavy oil that processing metal content is higher or residual oil, is especially applicable to tenor at more than 60% heavy oil or residual oil.
Claims (10)
1. a preparation method for novel macroporous structure catalyst for heavy oil hydrogenation demetal, is characterized in that: it specifically comprises the steps:
1) preparation of aluminium colloidal sol;
2) asphaltic residue powder and aluminium colloidal sol are mixed with to macroporous structure catalyst carrier;
3) catalyst carrier after moulding is adopted to two step infusion process dippings of equal-volume branch; Finally make catalyst.
2. the preparation method of a kind of novel macroporous structure catalyst for heavy oil hydrogenation demetal according to claim 1, it is characterized in that: the preparation of the aluminium colloidal sol of described step 1: take industrial boehmite powder 10g, add extrusion aid and peptizing agent, extrusion aid is that sesbania powder, addition are 1.0 g-3.0g, peptizing agent is that nitric acid or acetic acid, addition are 9.0g-9.5g, mechanical agitation mixes, and obtains homogeneous, stable, transparent aluminium colloidal sol.
3. the preparation method of a kind of novel macroporous structure catalyst for heavy oil hydrogenation demetal according to claim 1, it is characterized in that: described step 2 prepare macroporous structure structured catalysis agent carrier: in the aluminium colloidal sol that step 1 is made, add asphaltic residue powder, the weight of asphaltic residue powder accounts for the 10%-30% of boehmite weight, with high speed disperser, be uniformly dispersed, then on banded extruder, kneading is several times repeatedly, to increase uniformity and the intensity of the aluminium colloidal sol that contains asphaltic residue powder, then extruded moulding; The aluminium colloidal sol that contains asphaltic residue powder after moulding is dry at 110 ℃ in supercritical fluid extraction equipment, then, by the dried aluminium colloidal sol that contains asphaltic residue powder roasting 4-7 hour at 500 ℃-550 ℃ in Muffle furnace, obtain catalyst carrier.
4. the preparation method of a kind of novel macroporous structure catalyst for heavy oil hydrogenation demetal according to claim 1, it is characterized in that: the two step infusion process dippings that described step 3 adopts equal-volume to distribute catalyst carrier, concrete steps are as follows: the first step is first flooded Mo: take a certain amount of (NH
4)
6mo
7o
24H
2o, adds a certain amount of water, and the mass concentration that makes ammonium molybdate solution is 35%-50%, after heating melts, join in the catalyst carrier of 10 grams of step 2 preparations, within standing one hour, make the aqueous solution diffuse in catalyst carrier duct, in baking oven, 110 ℃ of dry and roastings in Muffle furnace, make containing M
ocatalyst sample; Second step dipping Ni: by a certain amount of Ni(NO
3)
26H
2o, adds a certain amount of water-soluble solution, and making the mass concentration of nickel nitrate solution is 25%-35%, has added M pre-soaked
ocatalyst sample, within standing one hour, make the aqueous solution diffuse in catalyst carrier duct, drying and roasting under the same terms, makes the catalyst that contains active component molybdenum and nickel.
5. the preparation method of a kind of novel macroporous structure catalyst for heavy oil hydrogenation demetal according to claim 2, it is characterized in that: in the aluminium colloidal sol preparation of described step 1, can also add auxiliary agent, promoter addition is the 5%-10% that accounts for boehmite powder, and auxiliary agent is a kind of or two kinds of mixtures in silica or titanium dioxide.
6. according to the preparation method of a kind of novel macroporous structure catalyst for heavy oil hydrogenation demetal described in claim 1 or 3, it is characterized in that: described asphaltic residue powder refers to the de-oiled asphalt residue that heavy oil or residual oil obtain through drastic deasphalting.
7. according to the preparation method of a kind of novel macroporous structure catalyst for heavy oil hydrogenation demetal described in claim 2 or 3, it is characterized in that: described boehmite can replace with the aluminium oxide after the calcining of boehmite predecessor.
8. the preparation method of a kind of novel macroporous structure catalyst for heavy oil hydrogenation demetal according to claim 4, is characterized in that: the described first step is first flooded in Mo, the M in ammonium molybdate solution
oo
3content is the 4%-30% of catalyst quality; Described second step first floods in Ni, the 1%-6% that the NiO content in nickel nitrate solution is catalyst quality; Described second step dipping Ni can use C
oreplace, that is: Co (NO
3)
26H
2o is Co source, the 1%-10% that in its aqueous solution, CoO content is catalyst quality.
9. the preparation method of a kind of novel macroporous structure catalyst for heavy oil hydrogenation demetal according to claim 1, is characterized in that: prepared catalyst is applicable to processing metal content in hydrodesulfurization, hydrodenitrogeneration, HDM or the hydrogenation preprocessing process of more than 60% heavy oil or residual oil.
10. the preparation method of a kind of novel macroporous structure catalyst for heavy oil hydrogenation demetal according to claim 3, is characterized in that: being shaped as of institute's extruded moulding is cylindrical, trifolium-shaped or bunge bedstraw herb type.
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| CN111632627A (en) * | 2020-05-18 | 2020-09-08 | 上海国惠环保科技集团有限公司 | Preparation method of structural auxiliary for molding |
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