CN103657667B - A kind of preparation method of macroporous structure catalyst for heavy oil hydrogenation demetal - Google Patents
A kind of preparation method of macroporous structure catalyst for heavy oil hydrogenation demetal Download PDFInfo
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Abstract
The preparation method who the invention discloses a kind of 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 two step infusion processes of equal-volume branch flood; Finally make catalyst. The prepared catalyst of the method has central hole structure and the macroporous structure of different proportion, and the ratio of macropore can regulate along with the amount of pore creating material asphaltic residue. Diffusion test shows, this catalyst that contains certain proportion macroporous structure meets the mechanism of heavy oil hydrogenation demetal reaction, there is the stronger ability of holding metal, effectively reduce the reaction resistance in heavy oil hydrogenation demetal course of reaction, improve the effective diffusion cofficient of heavy oil in catalyst, be applicable to higher heavy oil or the residual oil of processing metal content.
Description
Technical field
The present invention relates to a kind of preparation method of macroporous structure catalyst for heavy oil hydrogenation demetal, this preparation methodBe suitable for preparing various heavy oil hydrogenating treatment catalysts, be particularly suitable for preparing various heavy oil hydrogenation demetals and urgeAgent.
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 addsHydrogen is an important means of heavy oil lighting, and therefore heavy-oil hydrogenation catalyst is the pass of research and development heavy-oil hydrogenation technologyKey. Heavy oil molecules is larger, and non-hydrocarbons magazine is higher, and does not gasify under catalytic hydrogenation condition, heavy-oil hydrogenationReaction is usually interior diffusion controlled reaction, contains a large amount of metals in heavy oil simultaneously, is mainly nickel and vanadium, andNickel and vanadium mainly exist with the form of the organic complex of the non-porphyrin of porphyrin, and stability is high, is difficult to remove heavy oilThe mechanism of HDM reaction has determined the requirement to catalyst for heavy oil hydrogenation demetal, and it is suitable to possessSpecific area, pore size distribution and pore structure, could effectively reduce diffusional resistance, improves reaction effect. Therefore, grindThe novel catalyst for heavy oil hydrogenation demetal of sending out catalyst for heavy oil hydrogenation demetal performance applicable is extremely urgent.
Heavy oil molecules has complicated three-dimensional structure. Meanwhile, in heavy oil hydrogenation demetal reaction, the gold removingBelong to sulfide and cause except meeting covers catalyst surface that catalyst eats dishes without rice or wine to stop up, active decline. Heavy oil and loveThat catalyst is usually taking aluminium oxide as carrier or a part for carrier, and because heavy oil molecules amount is large, impurity containsMeasure highlyer, therefore General Requirements heavy-oil hydrogenation catalyst has higher pore volume and larger aperture, to reduce heavilyThe diffusional resistance of oil molecule, therefore also must have higher pore volume and as the aluminium oxide of catalyst carrierLarge aperture and specific area. But pore volume, aperture, specific area and the intensity of catalyst carrier are againRestriction mutually. Therefore, as how prepared heavy-oil hydrogenation catalyst better active and that intensity is higher become to attach most importance toThe key of oil hydrogen addition technology research. For adapting to the needs of heavy oil hydrogenation demetal process, some applicable heavy-oil hydrogenationsThe preparation of the catalyst carrier of process has been in the news.
CN101612593A has reported the synthetic of a kind of catalyst carrier for hydrgenating heavy oil. This preparation method utilizes to subtractPress residual oil de-oiled asphalt residue dry powder for mill template. De-oiled asphalt residue is ground to form to the fine powder of several microns, soAfter under Action of Surfactant, be distributed in aluminium colloidal sol precursor, by dry the aluminium colloidal sol that contains residue template,Template is removed in calcining, finally supports active component. Synthetic catalyst contains abundant macroporous structure, its macroporeVolume fraction can adjust by the consumption of template. The scope of its average pore size of catalyst of preparation is6.53-9.97nm, pore volume scope is 0.48-0.75cm3/ g, the scope of specific area is 255-301m2/g。
CN1247772A has reported a kind of preparation that is applicable to a kind of aluminium oxide that is used as catalyst carrier for hydrgenating heavy oilMethod. The method is that aluminum compound solution and precipitant solution are contacted under 20-55 DEG C, pH6-9, at 30-80DEG C and carbonate and/bicarbonate ion, ammonium ion and slurries in the mol ratio of aluminium hydroxide be not less than 0.1, ammoniumThe mol ratio of ion and carbanion and/or bicarbonate ion is greater than under 1 condition aging at least 10 minutes,Filter and wash, then obtain catalyst carrier for hydrgenating heavy oil by dry and roasting. Catalysis prepared by the methodAgent carrier pore volume scope is 0.7-0.9cm3/ g, average pore size 11-12nm.
CN1830560A reported heavy-oil hydrogenation catalyst that a kind of macroporous structure parameter can independently regulate and control andPreparation method, this catalyst uses organic granular as template in preparation process, removes after compound with carrier againTemplate, makes to leave in catalyst the macropore that aperture is greater than 5nm, and the aperture of catalyst can be by changing granule dieThe average diameter of plate realizes, and the volume fraction of macropore can be realized by the consumption that changes granular formwork. This sideThe standby catalyst of legal system can significantly improve the performance of catalyst, is applicable to the catalytic hydrogenation process of mink cell focus. ForThe mink cell focus that tenor is higher, applicability is poor.
In the prior art the above, there is following common feature and a difficult problem: preparation process is more multipleAssorted, the performance of prepared hydrogenation catalyst mainly comprises that aperture, pore volume, specific area and pore size distribution etc. are rightThe dependence of preparation condition and raw materials is larger, and prepared catalyst mechanical strength is poor, meanwhile,Feed change and preparation condition can be to the pore volume of prepared catalyst, aperture, specific area, pore size distribution and machinesTool intensity exerts an influence simultaneously, therefore, wants by changing pore structure that a certain parameter adjusts catalyst by non-Normal difficulty, and preparation method's repeatability is poor, and in these technology, the dry and baking modes of catalyst is generalLogical drying mode and baking modes, larger on the mechanical strength impact of catalyst, and then affected heavy-oil hydrogenationThe long-term operation of catalyst. Meanwhile, these heavy-oil hydrogenation catalysts have certain wide in range property, are applicable to addHydrogen cracking, hydrofinishing, instead of for heavy oil hydrogenation demetal reacts the catalyst of making to measure, not too applicableReact in heavy oil hydrogenation demetal.
Summary of the invention
The object of this invention is to provide a kind of preparation method of macroporous structure catalyst for heavy oil hydrogenation demetal, this systemPreparation Method is on the basis of early-stage Study, directly asphaltic residue is mixed to system with boehmite direct mechanicalStandby cheap catalyst carrier, adds extrusion aid and peptizing agent kneading extrusion on this basis again, preparation catalysisAgent 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 macroporous structure catalyst for heavy oil hydrogenation demetal, itsFeature is: 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 two step infusion processes of equal-volume substep flood; Finally make catalyst.
Described step 1) the preparation of aluminium colloidal sol: take industrial boehmite powder 10g, add extrusion aid andPeptizing agent, extrusion aid is that sesbania powder, addition are 1.0g-3.0g, peptizing agent is nitric acid or acetic acid, addsAmount is for 9.0g-9.5g, and mechanical agitation mixes, and obtains homogeneous, stable, transparent aluminium colloidal sol.
Described step 2) prepare macroporous structure catalyst carrier: by step 1) add drop in the aluminium colloidal sol that makesBlue or green residue powder, the 10%-30% that the weight of asphaltic residue powder accounts for boehmite weight, uses high speed disperserBe uniformly dispersed, then on banded extruder repeatedly kneading several times, to increase the aluminium colloidal sol that contains asphaltic residue powderUniformity and intensity, then extruded moulding; By the aluminium colloidal sol that contains asphaltic residue powder after moulding overcriticalDry at 110 DEG C in fluid extraction device, then by the dried aluminium colloidal sol that contains asphaltic residue powder horseNot roasting 4-7 hour at 500 DEG C-550 DEG C in stove, obtains catalyst carrier.
Described step 3) catalyst carrier is adopted to two step infusion processes dippings of equal-volume substep, concrete steps asUnder: the first step is first flooded Mo: take a certain amount of (NH4)6Mo7O2·4H2O, adds a certain amount of water,The mass concentration that makes ammonium molybdate solution is 35%-50%, and heating joins 10 grams of steps 2 after melting) preparationCatalyst carrier in, leave standstill and within one hour, make the aqueous solution diffuse in catalyst carrier duct, in baking oven 110 DEG CBe dried and roasting in Muffle furnace, make containing MOCatalyst sample; Second step dipping Ni: by a certain amount of Ni(NO3)2·6H2O, adds a certain amount of water-soluble solution, and the mass concentration that makes nickel nitrate solution is 25%-35%,Add M pre-soakedOCatalyst sample, leave standstill within one hour, make the aqueous solution diffuse into catalyst carrier ductIn, drying and roasting under the same terms, makes the catalyst that contains active component molybdenum and nickel.
Described step 1) aluminium colloidal sol preparation in can also add auxiliary agent, promoter addition is for accounting for boehmiteThe 5%-10% of powder, 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 solutionOO3Content is catalyst quality4%-30%; Described second step first floods in Ni, and the NiO content in nickel nitrate solution is catalyst quality1%-6%; Described second step dipping Ni can use COReplace i.e.: Co (NO3)2·6H2O is Co source, and it is water-solubleThe 1%-10% that in liquid, CoO content is catalyst quality.
It is de-that prepared catalyst is applicable to the hydrogenation of the heavy oil of processing metal content more than 60% or residual oilIn sulphur, hydrodenitrogeneration, HDM or hydrogenation preprocessing process.
Being shaped as of described extruded moulding is cylindrical, trifolium-shaped or bunge bedstraw herb type.
Advantage of the present invention is: to be that pore creating material is synthetic with cheap asphaltic residue have a macroporous structure to the methodCatalyst for heavy oil hydrogenation demetal. Because the pore creating material asphaltic residue of synthetic this catalyst has certain hole knotStructure, the carrier material boehmite of synthetic catalyst has certain micropore and mesopore simultaneously, adds with superThe drying mode of supercritical fluid extraction, the destruction of having avoided pore structure to cause due to traditional drying mode, because ofThe catalyst of this method synthesized in thering is certain macroporous structure, its specific area, intensity and holeRong Buhui is lower than traditional catalyst. The catalyst for heavy oil hydrogenation demetal of this macroporous structure can effectively reduce heavilyThe resistance to mass tranfer of oil HDM reaction, improves the ability that catalyst holds metal, the use of extending catalystLife-span.
Below in conjunction with specific implementation method, the present invention is described further, but not as to the invention process modelThe restriction of enclosing.
Detailed description of the invention
Synthesizing of embodiment 1, carrier reference
Take industrial boehmite powder 10g, add extrusion aid sesbania powder and peptizing agent, the addition of sesbania powderFor 2.0g (within the scope of 1.0g-3.0g all can), the addition of the rare nitric acid of peptizing agent or spirit of vinegar be 9.3g(within the scope of 9.0g-9.5g all can), mechanical agitation mixes, and obtains homogeneous, stable, transparent aluminium is moltenGlue. By aluminium colloidal sol on banded extruder repeatedly kneading several times, to increase uniformity and the intensity of carrier, then extrusionMoulding. Carrier after moulding is dry at 110 DEG C in supercritical fluid extraction equipment, then by driedCarrier is roasting 5 hours at 500 DEG C-550 DEG C in Muffle furnace, obtains carrier reference Al2O3-1, by rightCarrier carries out low temperature N2Absorption characterizes, and then recording BET specific area is 369.1m2/ g, uses BET nitrogenAdsorption capacity method is surveyed the same apparatus of specific surface pore structure is analyzed, and recording average pore size is 8.01nm, holeHold for 0.56cm3/ g, the mechanical strength of carrier is 22.3N/mm, the digital display for mensuration of carrier mechanical strengthGrain intensity is measured.
3) by carrier reference Al2O3-1 adopts two step infusion process dippings of equal-volume substep; Concrete steps asUnder: the first step is first flooded Mo: take a certain amount of (NH4)6Mo7O2·4H2O, adds a certain amount of water,Make the mass concentration of ammonium molybdate solution at 35%-50%, heating joins carrier reference after melting Al2O3In-1, the M in ammonium molybdate solutionOO3Content is 28% of catalyst quality, leaves standstill and makes water-soluble in one hourLiquid diffuses in catalyst carrier duct, and in baking oven, 110 DEG C of dry, roastings, make containing MOSample; SecondStep dipping Ni: by a certain amount of Ni (NO3)2·6H2O, NiO is catalyst quality 5%, adds certain water gagingDissolve, making the mass concentration of nickel nitrate solution is 25%-35%, has added M pre-soakedOSample, leave standstillWithin one hour, make the aqueous solution diffuse in catalyst carrier duct, drying and roasting under the same terms, makes and contains activityThe catalyst (reference) of component molybdenum and nickel, with Ni-Mo/ γ-Al2O3-1 represents. Wherein, in nickel nitrate solutionNiO content is 5% of catalyst quality.
Embodiment 2
A preparation method for 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, help crowdedAgent is that sesbania powder, addition are 2.0g, and peptizing agent is that nitric acid, addition are 9.3g, and mechanical agitation mixes,Obtain homogeneous, stable, transparent aluminium colloidal sol.
2) asphaltic residue powder and aluminium colloidal sol are mixed with to macroporous structure catalyst carrier; By step 1) makeAluminium colloidal sol in add asphaltic residue powder, the weight of asphaltic residue powder accounts for 10% of boehmite weight,With high speed disperser dispersion 5 minutes, be uniformly dispersed, then on banded extruder, kneading several times, (is 5 here repeatedlyInferior), to increase uniformity and the intensity of the aluminium colloidal sol that contains asphaltic residue powder, then extruded moulding; To becomeThe aluminium colloidal sol that contains asphaltic residue powder after type is dry at 110 DEG C in supercritical fluid extraction equipment, thenBy the roasting 5 hours at 500 DEG C-550 DEG C in Muffle furnace of the dried aluminium colloidal sol that contains asphaltic residue powder,Obtain catalyst carrier, the catalyst carrier Al of embodiment 22O3-2 represent. Low by carrier being carried out to BETTemperature nitrogen adsorption method characterizes, and the specific area that records carrier is 372.2m2/ g, by BET nitrogen adsorption capacity methodSurvey the same apparatus of specific surface pore structure is analyzed, the average pore size that records carrier is 20.5nm, and pore volume is0.74cm3/ g, mechanical strength is 20.2N. Add its specific area of pore creating material, aperture and the pore volume of asphaltic residueObviously be greater than the reference of embodiment 1, and intensity still meet device to the performance of heavy-oil hydrogenation catalyst wantAsk.
3) by catalyst carrier Al2O3-2 adopt two step infusion process dippings of equal-volume substep; Concrete steps are as follows:The first step is first flooded Mo: take a certain amount of (NH4)6Mo7O2·4H2O, adds a certain amount of water, makesThe mass concentration of ammonium molybdate solution is 35%-50%, and heating joins catalysis prepared by 10 grams of steps 2 after meltingIn agent carrier, M in ammonium molybdate solutionOO3Content is 28% of catalyst quality, leaves standstill and within one hour, makes the aqueous solutionDiffuse in catalyst carrier duct, in baking oven, 110 DEG C of dry, roastings, make containing MOSample; Second stepDipping Ni: by a certain amount of Ni (NO3)2·6H2O, in nickel nitrate solution, NiO content is catalyst quality5%, add a certain amount of water-soluble solution, make the mass concentration 25%-35% of nickel nitrate solution, add pre-soakedMOSample, leave standstill and within one hour, make the aqueous solution diffuse in catalyst carrier duct, dry roasting under the same termsBurn, make catalyst of the present invention, with Ni-Mo/ γ-Al2O3-2 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 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, help crowdedAgent is that sesbania powder, addition are 1.0g, and peptizing agent is that acetic acid, addition are 9.0g, and mechanical agitation mixes,Obtain homogeneous, stable, transparent aluminium colloidal sol.
2) asphaltic residue powder and aluminium colloidal sol are mixed with to macroporous structure catalyst carrier; By step 1) makeAluminium colloidal sol in add asphaltic residue powder, the weight of asphaltic residue powder accounts for 20% of boehmite weight,Disperse 5 minutes with high speed disperser, be uniformly dispersed, then kneading 3 times repeatedly on banded extruder, contains to increaseUniformity and the intensity of the aluminium colloidal sol of asphaltic residue powder, then extruded moulding; By after moulding to contain pitch residualThe aluminium colloidal sol at ground-slag end is dry at 110 DEG C in supercritical fluid extraction equipment, then by the dried drop that containsThe aluminium colloidal sol of blue or green residue powder is roasting 4 hours at 500 DEG C-550 DEG C in Muffle furnace, obtains catalyst carrier,The catalyst carrier Al of embodiment 32O3-3 represent. Carrier, through nitrogen absorption under low temperature and pore structure analysis, recordsThe BET specific area of carrier is 373.5m2/ g, average pore size is 22.5nm, pore volume is 0.76cm3/ g, machineTool intensity is 18.5N. Specific area, average pore size and the pore volume of carrier is 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-Al2O3-3Represent.
Embodiment 4
Embodiment 4 is identical with embodiment 2, and difference is: the addition of extrusion aid is 3.0g, and peptizing agent is nitreAcid, addition are 9.5g, and the weight of asphaltic residue powder accounts for 30% of boehmite, obtains catalyst and carriesAl2O3-4. Carrier is through nitrogen absorption under low temperature and pore structure analysis, and the BET specific area that records carrier is 375.5m2/ g, average pore size is 25.5nm, pore volume is 0.82cm3/ g, mechanical strength is 15.5N. The specific surface of carrierLong-pending, average pore size and pore volume are obviously greater than the reference of embodiment 1. Due to average pore size and pore volume increase, carryThe mechanical strength of body declines a little. Finally make catalyst of the present invention, with Ni-Mo/ γ-Al2O3-4 represent.
Embodiment 5, boehmite powder and the direct mixed-forming of auxiliary agent are prepared carrier reference
Embodiment 5 is identical with embodiment 2, and difference is: get industrial boehmite powder 10g, add extrusion aidSesbania powder 3g, adds a kind of or two kinds of mixtures in auxiliary agent silica or titanium dioxide, and addition isAccount for the 5%-10% of boehmite powder, the addition that adds the rare nitric acid of peptizing agent or spirit of vinegar is 9.3g, thenAdd asphaltic residue powder, the weight of asphaltic residue powder accounts for 30% of boehmite, obtains catalyst carrierAl2O3-5. Carrier is through nitrogen absorption under low temperature and pore structure analysis, and the BET specific area that records carrier is 325.5m2/ g, average pore size is 21.5nm, pore volume is 0.72cm3/ g, mechanical strength is 20.5N. Can from measurement resultTo 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 enforcementThe reference of example 1, the intensity of carrier is compared with Al2O3-4 make moderate progress, and this explanation adds auxiliary agent to be conducive to improve carrierMechanical strength. Finally make catalyst of the present invention, with Ni-Mo/ γ-Al2O3-5 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 DEG C, g/cm3) | 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 DEG C, mm2/s) | 455.7 | Nitrogen, w% | 0.56 |
| Four component analyses, W% | Iron, μ g/g | 7.2 | |
| Saturated point | 36.8 | Calcium, μ g/g | 16.8 |
| Fragrance point | 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 DEG C, reaction feed is elm refining reduced crude, mass space velocity is 2.4h-1,Hydrogen-oil ratio=600:1, loaded catalyst is 3g, except reactivity worth, the machine of catalyst has also been measured in experimentTool intensity, 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-Al2O3-1 | 20.2 | 22.5 |
| Ni-Mo/γ-Al2O3-2 | 67.3 | 21.4 |
| Ni-Mo/γ-Al2O3-3 | 78.5 | 19.5 |
| Ni-Mo/γ-Al2O3-4 | 80.2 | 18.3 |
| Ni-Mo/γ-Al2O3-5 | 83.5 | 17.5 |
Embodiment 7
Identical with embodiment 1, difference is: infusion process dipping, second step is with Co (NO3)2·6H2O isCo source, the same to Ni (NO of dosage3)2·6H2O, the 1%-10% that in its aqueous solution, CoO content is catalyst quality.Make catalyst ginseng sample than using Co-Mo/ γ-Al2O3-1 represents.
Embodiment 8
Identical with embodiment 2, difference is: infusion process dipping, second step is with Co (NO3)2·6H2O isCo source, the same to Ni (NO of dosage3)2·6H2O, the 1%-10% that CoO is catalyst quality. Make catalystGinseng sample is than using Co-Mo/ γ-Al2O3-2 represent.
Embodiment 9
Identical with embodiment 3, difference is: infusion process dipping, second step is with Co (NO3)2·6H2O isCo source, the same to Ni (NO of dosage3)2·6H2O, the 1%-10% that CoO is catalyst quality. Make catalystGinseng sample is than using Co-Mo/ γ-Al2O3-3 represent.
Embodiment 10
Identical with embodiment 4, difference is: infusion process dipping, second step is with Co (NO3)2·6H2O isCo source, the same to Ni (NO of dosage3)2·6H2O, the 1%-10% that CoO is catalyst quality. Make catalystGinseng sample is than using Co-Mo/ γ-Al2O3-4 represent.
Embodiment 11
Identical with embodiment 5, difference is: infusion process dipping, second step is with Co (NO3)2·6H2O isCo source, the same to Ni (NO of dosage3)2·6H2O, the 1%-10% that CoO is catalyst quality. Make catalystGinseng sample is than using Co-Mo/ γ-Al2O3-5 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-Al2O3-1 | 23.5 | 22.7 |
| Co-Mo/γ-Al2O3-2 | 70.5 | 22.1 |
| Co-Mo/γ-Al2O3-3 | 75.6 | 19.8 |
| Co-Mo/γ-Al2O3-4 | 82.5 | 18.5 |
| Co-Mo/γ-Al2O3-5 | 85.1 | 17.9 |
Can find out from the result of table 2 and table 3, do pore creating material with heavy petroleum asphalt residue powder, with boehmiteDirectly mix, and adopt the prepared catalyst for heavy oil hydrogenation demetal tool of drying mode of supercritical fluid extractionThere are higher metal removal activity and good mechanical strength, can meet industrial differential responses device particularlyThe performance requirement of ebullated bed to catalyst for heavy oil hydrogenation demetal, and the consumption of pore creating material asphaltic residue is higher,The activity of catalyst is higher, especially adds after a certain amount of auxiliary agent, has regulated the acid distribution of catalyst, largeImprove greatly the HDM activity of prepared catalyst.
In above-described embodiment, institute's extruded moulding is shaped as cylindrical, trifolium-shaped or bunge bedstraw herb type; In embodimentMOO3For within the scope of 4%-30% and the NiO of the catalyst quality 1%-6% that is catalyst quality all can, thisInvent prepared catalyst and be applicable to heavy oil that processing metal content is higher or hydrodesulfurization, the hydrogenation of residual oilIn denitrogenation, HDM or hydrogenation preprocessing process, be especially applicable to the heavy oil of tenor more than 60%Or residual oil.
Claims (6)
1. a preparation method for macroporous structure catalyst for heavy oil hydrogenation demetal, is characterized in that: it specifically comprise asLower step:
1) preparation of aluminium colloidal sol; Described step 1) the preparation of aluminium colloidal sol: take industrial boehmite powder 10g,Add extrusion aid and peptizing agent, extrusion aid is that sesbania powder, addition are 1.0g-3.0g, peptizing agent be nitric acid orPerson's acetic acid, addition are 9.0g-9.5g, and mechanical agitation mixes, and obtain homogeneous, stable, transparent aluminium is moltenGlue;
2) asphaltic residue powder and aluminium colloidal sol are mixed with to macroporous structure catalyst carrier; Described step 2) preparationMacroporous structure catalyst carrier: by step 1) add asphaltic residue powder, asphaltic residue in the aluminium colloidal sol that makesThe weight of powder accounts for the 10%-30% of boehmite weight, is uniformly dispersed with high speed disperser, then in extrusionOn machine, kneading several times, to increase uniformity and the intensity of the aluminium colloidal sol that contains asphaltic residue powder, is then squeezed repeatedlyBar moulding; By the aluminium colloidal sol that contains asphaltic residue powder after moulding in supercritical fluid extraction equipment 110 DEG CLower dry, then by the dried aluminium colloidal sol that contains asphaltic residue powder in Muffle furnace at 500 DEG C-550 DEG CRoasting 4-7 hour, obtains catalyst carrier;
3) catalyst carrier after moulding is adopted two step infusion processes of equal-volume substep flood; Finally make catalyst;Described step 3) adopt two step infusion processes of equal-volume substep to flood catalyst carrier, concrete steps are as follows:The first step is first flooded Mo: take a certain amount of (NH4)6Mo7O2·4H2O, adds a certain amount of water, makesThe mass concentration of ammonium molybdate solution is 35%-50%, and heating joins 10 grams of steps 2 after melting) urging of preparingIn agent carrier, leave standstill and within one hour, make the aqueous solution diffuse in catalyst carrier duct, in baking oven, 110 DEG C are driedAnd roasting in Muffle furnace, make containing MOCatalyst sample; Second step dipping Ni: by a certain amount of Ni (NO3)2·6H2O, adds a certain amount of water-soluble solution, and making the mass concentration of nickel nitrate solution is 25%-35%, adds in advanceFlood MOCatalyst sample, leave standstill within one hour, make the aqueous solution diffuse in catalyst carrier duct, identicalDrying and roasting under condition, makes the catalyst that contains active component molybdenum and nickel.
2. the preparation method of a kind of macroporous structure catalyst for heavy oil hydrogenation demetal according to claim 1, its spyLevy and be: described step 1) aluminium colloidal sol preparation in can also add auxiliary agent, promoter addition is for accounting for the thin water aluminium of planThe 5%-10% of stone flour, auxiliary agent is a kind of or two kinds of mixtures in silica or titanium dioxide.
3. the preparation method of a kind of macroporous structure catalyst for heavy oil hydrogenation demetal according to claim 1, its spyLevy and be: described asphaltic residue powder refers to the de-oiled asphalt residue that heavy oil or residual oil obtain through drastic deasphalting.
4. the preparation method of a kind of macroporous structure catalyst for heavy oil hydrogenation demetal according to claim 1, its spyLevy and be: described boehmite can replace with the aluminium oxide after the calcining of boehmite predecessor.
5. the preparation method of a kind of macroporous structure catalyst for heavy oil hydrogenation demetal according to claim 1, its spyLevy and be: the described first step is first flooded in Mo, the M in ammonium molybdate solutionOO3Content is catalyst quality4%-30%; Described second step first floods in Ni, and the NiO content in nickel nitrate solution is catalyst quality1%-6%; Described second step dipping Ni can use COReplace i.e.: Co (NO3)2·6H2O is Co source, and it is water-solubleThe 1%-10% that in liquid, CoO content is catalyst quality.
6. the preparation method of a kind of macroporous structure catalyst for heavy oil hydrogenation demetal according to claim 1, itsFeature is: being shaped as of described extruded moulding is cylindrical, trifolium-shaped or bunge bedstraw herb type.
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| CN105195118A (en) * | 2015-10-12 | 2015-12-30 | 常州新日催化剂有限公司 | Macroporous structure titanium oxide desulfurization catalyst and preparation method thereof |
| CN108421548B (en) * | 2017-02-15 | 2020-06-16 | 中国石油化工股份有限公司 | Hydrogenation protection catalyst, preparation method thereof and heavy oil hydrotreating method |
| CN108421561B (en) * | 2017-02-15 | 2020-06-16 | 中国石油化工股份有限公司 | Heavy oil hydrogenation catalyst, preparation method thereof and heavy oil hydrogenation treatment method |
| CN108786833B (en) * | 2017-05-02 | 2020-09-11 | 中国石油化工股份有限公司 | Heavy oil hydrogenation catalyst and preparation method thereof |
| CN113042021B (en) * | 2019-12-27 | 2023-05-26 | 中国石油化工股份有限公司 | Ebullated bed hydrogenation catalyst and preparation method thereof |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1831090A (en) * | 2005-03-11 | 2006-09-13 | 石油大学(北京) | Macropore catalytic cracking catalyst synthesized by granular formwork method |
| CN101450313A (en) * | 2007-12-05 | 2009-06-10 | 中国石油天然气股份有限公司 | Preparation method of macropore heavy-oil hydrogenation catalyst |
| CN101612593A (en) * | 2008-06-27 | 2009-12-30 | 中国石油大学(北京) | Method for preparing macroporous heavy oil hydrogenation catalyst by using petroleum residue as template |
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| CN1831090A (en) * | 2005-03-11 | 2006-09-13 | 石油大学(北京) | Macropore catalytic cracking catalyst synthesized by granular formwork method |
| CN101450313A (en) * | 2007-12-05 | 2009-06-10 | 中国石油天然气股份有限公司 | Preparation method of macropore heavy-oil hydrogenation catalyst |
| CN101612593A (en) * | 2008-06-27 | 2009-12-30 | 中国石油大学(北京) | Method for preparing macroporous heavy oil hydrogenation catalyst by using petroleum residue as template |
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