CN101890382B - Hydrodemetallization catalyst and application thereof - Google Patents
Hydrodemetallization catalyst and application thereof Download PDFInfo
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- CN101890382B CN101890382B CN2009102062567A CN200910206256A CN101890382B CN 101890382 B CN101890382 B CN 101890382B CN 2009102062567 A CN2009102062567 A CN 2009102062567A CN 200910206256 A CN200910206256 A CN 200910206256A CN 101890382 B CN101890382 B CN 101890382B
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Abstract
The invention discloses a residual oil hydrodemetallization catalyst and application thereof. The catalyst has the characteristics of large pore volume, large aperture, high porosity, reasonable pore distribution, large outer surface orifice and pore channel penetrability, is particularly used in a residual oil fixed bed hydrogenation method for depositing replaced metal on an overall catalyst bed uniformly, has high metal capacity and improves the utilization rate of pores, so that the catalyst keeps long-term operation and very high desulfurization degree and denitrogenation rate can be achieved at the same time.
Description
Technical field
The present invention relates to a kind of Hydrodemetalation catalyst and application thereof, especially high Hydrodemetalation catalyst and the application in residual hydrocracking technology thereof of holding the metal ability of large pore volume.
Background technology
At present, hydrotreatment remains the most important means of production high-quality, environmental friendliness oil product.The core of hydrotreatment technology is a catalyst, and for heavy ends (for example VGO, the especially residual oil) hydrogenation of oil, the big young pathbreaker of the aperture of catalyst and pore volume directly influences the performance of catalyst activity.
Four sections catalyst gratings of the general employing of residual hydrocracking technology; Specific as follows: the first segment protect agent is used to deviate from the impurity that iron, calcium and sodium etc. are prone to deviate from; Make in its space that is deposited in catalyst; Catalyst generally adopts special-shaped method, the shape high like voidages such as Raschig rings, and weight metal content about 3%～8% in the catalyst.Second section is adopted catalyst for demetalation, is used for deviating from the most of metal impurities of feedstock oil, mainly adopts non-acid macropore alumina supporter, generally has two peak structure, and the catalyst metals weight content is up to about 5%～12%.The 3rd section is adopted desulphurization catalyst mainly to carry out desulphurization reaction, and the aperture is littler than catalyst for demetalation, and acid stronger than catalyst for demetalation, the catalyst metals weight content is up to 8%～15%.The 4th section is adopted denitrification catalyst mainly to carry out denitrification reaction, and acidity is the strongest, and the catalyst metals weight content is up to 12%～25%.It is that to come from the aperture in existing catalysis material duct too little that prior art extensively adopts this grading method; Pore volume is too little; The asphalitine micelle can't be diffused into catalyst granules inside and react; Make the hole of catalyst not bring into play maximal efficiency, only can make the free asphaltene molecules of part get into catalyst granules inside and react, the catalytic reaction that makes impurity mainly is to react at catalyst surface.This shows that existing catalysis material is unfavorable for that the catalysis of residual oil takes off impurity reaction.
The existing employed carrier material of residuum hydrogenating and metal-eliminating catalyst is generally macroporous aluminium oxide and modified product thereof.The preparation method that macroporous aluminium oxide is commonly used has: physics port-creating method, high-temperature roasting method and pH value swing method.The shortcoming of physics port-creating method is that the duct is inhomogeneous, still has the shortcoming of easy blocking.The precursor of physics expanding agent such as usefulness such as US4448896, US4102822 carbon black, starch and activated alumina or aluminium oxide mixes and pinches the aperture that enlarges alumina support, and the consumption of physics expanding agent is more than the aluminium oxide 10wt%, and said method is in the aluminium oxide precursor, to add the physics expanding agent; And the consumption of expanding agent is big; Cause the pore size distribution disperse of aluminium oxide, big bore portion can not form continuous through hole, and the duct is the ink bottle type; The aperture is less, and intensity is relatively poor.
Owing to the aluminium oxide aperture that prior art is used is too little, vanadium in the asphalitine micelle and nickel can't be diffused into inner duct, have caused the asphalitine micelle to react at the catalyst outer surface; Interparticle voidage becomes the main space of holding the precipitated metal thing, after the precipitated metal thing stops up the space, will cause diffusional resistance to strengthen; Quickened the generation of coking, reaction temperature raises, and coking further strengthens; Force device to be stopped work at last, more catalyst changeout.
Through hole is very important to petroleum catalyst, and particularly the big molecule of residual oil needs big through hole to carry out the deposition of metal, makes catalyst reach maximum appearance metal ability, improves the life cycle of catalyst.Contain vanadium metal and nickel major part in the residual oil and concentrate in the big molecule of asphalitine, the asphaltene molecules diameter is 4-5nm, be present in saturated hydrocarbons and the aromatic hydrocarbons down at the stable of colloid, more than the micelle of formation more than 10nm, maximum reach nm up to a hundred.Residuum hydrogenating and metal-eliminating catalyst begins to inefficacy from running, and from the surface to the center, keeping the through hole of enough 10nm～100nm to make big molecular diffusion of residual oil and metal deposition is the necessary condition of long-term operation.
CN1184078A discloses a kind of preparation method of alumina support.This method adopts and flows into aluminium hydroxide that glue generates as crystal seed, utilizes pH value swing method to make aluminium hydroxide then, and again through extruded moulding, the pore volume that can obtain pore diameter range 10～30nm or 20～60nm accounts for the aluminium oxide of total pore volume more than 70%.During the moulding of pH swing method aluminium oxide, influencing the intensity of carrier and the factor of pore size has two, i.e. peptization acid and pressure, peptization subacidity or pressure all will cause intensity to reduce inadequately, and aperture and pore volume are diminished.The duct is very big between the alumina powder jointed particle of pH swing method, is to come from the pH swing to cause, and has taken out the duct of a lot of 20～60nm between particle; But during with sour peptization; To be dissolved between particle and break, under pressure, the duct will be constructed again; The aperture in duct and pore volume can sharply diminish, so very big contradiction is arranged between pore volume and the intensity.
CN1068975A discloses the preparation method of a kind of low-density, large pore volume, high-strength alumina carrier, is the aluminium colloidal sol that obtains with acid treatment, adds gelling agent, obtains through the method for forming oil column, and specific surface is 120～280m
2/ g, bulk density are 0.18～0.35g/cm
3, pore volume is 1.5～2.0cm
3/ g, average pore size is 30～60nm, crushing strength is 0.5～3.0kgf/ grain, as the dehydrogenation of long-chain alkane catalyst.This method is that the interpolation hexamethylenetetramine is a gelling agent in aluminium colloidal sol; This gelling agent has formed hole and window in aluminium colloidal sol, have aluminium colloidal sol to intercept between hole and the hole, and it is theoretical that the arrangement in hole meets the ball dress; Between the adjacent hole by the window intercommunication; The duct that this ball dress accumulation mode forms is an ink bottle type structure, and the aperture is less, can't make the big molecular diffusion of residual oil get into inner duct.
CN1107102C discloses a kind of HDM and Hydrobon catalyst and preparation method thereof, adopts to add the acidity that carbon black is expanding method and adding boron adjusting carrier.The carrier that this method obtains is a two peak structure; First peak concentrates on about 10nm, and second peak is the duct that stays after carbon black burns, and concentrates on about 200nm-500nm; Mostly the duct that carbon black stays is the ink bottle aperture, and this duct is unfavorable for removing of slag oil asphalt matter micelle.
CN1205314C discloses the preparation method of a kind of heavy oil hydrogenation demetal, desulphurization catalyst; Two kinds of alumina catalyst support employings are compound; Wherein a kind of is the alumina powder of 1100 ℃ of high-temperature roastings, and this method can form the above duct of more 15nm, and the duct has penetrability; But still too little for the asphalitine micelle, be unfavorable for residual oil demetalization reaction.
Summary of the invention
To weak point of the prior art, the invention provides a kind of good to big molecular diffusion performance, hold the impurity ability is strong, metal removal activity is high Hydrodemetalation catalyst and application thereof, the particularly application in residual hydrocracking technology.
Hydrodemetalation catalyst of the present invention comprises alumina-based supports and active metal component, and the character of said catalyst is following: pore volume is 1.3～2.6ml/g, is preferably 1.6～2.3ml/g, and specific surface is 180～450m
2/ g is preferably 200～350m
2/ g, average pore size is 12～30nm, is preferably 15～25nm, porosity is 80%～93%, is preferably 85%～93%; Pore size distribution is following: bore dia is below 20% less than the shared pore volume in the hole of 10nm; Be preferably below 15%; Bore dia is that the shared pore volume in the hole of 10-100nm is 35%～55% of total pore volume; Bore dia is that the shared pore volume in the hole of 100nm-1000nm is 20%～35% of total pore volume, and bore dia is that the above shared pore volume in hole of 1000nm is 16%～35%, is preferably 18%～30%.
The said porosity of the present invention is the porosity of the particle inner duct that records with mercury injection method.
The bulk density of Hydrodemetalation catalyst of the present invention is 0.32～0.50.
Described alumina-based supports is meant that key component is the carrier of aluminium oxide, can also contain conventional adjuvant component, such as in silica, titanium oxide, the phosphorous oxide etc. one or more.The weight of auxiliary agent accounts for 0～10% of alumina-based supports, is preferably 2%～10%.Alumina weight content is preferably in more than 95% more than 90% in the described alumina-based supports.
The weight content of described alumina-based supports in Hydrodemetalation catalyst is 86%～96%.
The infrared acidity of described Hydrodemetalation catalyst is 0.40～0.65mmol/g.
Contain the rod-like nano oxide in the described alumina-based supports, described rod-like nano oxide is aluminium oxide or the aluminium oxide that contains auxiliary agent, and the diameter of this rod-like nano oxide is 50nm～500nm, preferred 80nm～300nm, and length is 2～10 times of diameter.Described rod-like nano oxide is piled into tower structure in disorder in alumina-based supports, make alumina-based supports form large pore volume, the large aperture, and macropore duct connectivity is good, and the aperture is bigger, helps macromolecular diffusion.The weight content of described rod-like nano oxide in alumina-based supports is 30%～100%, is preferably 60%～90%.
In the described alumina-based supports, can also contain the component of being introduced by adhesive, its content accounts for below 50% of carrying alumina body weight, is preferably 0%～40%, such as little porous aluminum oxide and/or macroporous aluminium oxide.
The active metal component that described active metal component can adopt conventional residuum hydrogenating and metal-eliminating catalyst to adopt; Be generally group vib metal and/or group VIII metal; The group vib metal generally is selected from least a among Mo and the W, and the group VIII metal generally is selected from least a among Co and the Ni.Weight with catalyst is benchmark, and the content of reactive metal oxides is 4.0%～14.0%, and the content that is preferably the group vib metal oxide is 3.5%～12.0%, and the content of group VIII metal oxide is 0.5%～4.0%.
The crushing strength of described Hydrodemetalation catalyst is 6～80N/mm, is preferably 8～40N/mm.
The preparation method of Hydrodemetalation catalyst of the present invention is to process alumina-based supports earlier, adopts infusion process supported active metal component then, and wherein the preparation method of alumina-based supports comprises the steps:
(1) preparation of nano-aluminum hydroxide gel,
(2) the nano-aluminum hydroxide gel of step (1) gained is after drying, and moulding again through drying and roasting, obtains alumina-based supports of the present invention;
The introducing mode of auxiliary agent can adopt conventional method in the wherein said alumina-based supports; Such as: in step (1) preparation gel aluminum hydroxide process, introduce; Like CN 200510046480.6 disclosed methods, perhaps the preceding precursor form with auxiliary agent of moulding is mixed and is pinched introducing in step (2).
The described nano-aluminum hydroxide gel of step (1) is to adopt the preparation of the ultra solubilising micelle of fused salt method, and is such as the CN200510046481.0 disclosed method, specific as follows:
A, hydrocarbon component and VB value are mixed less than 1 surfactant;
B, nano-aluminum hydroxide gel are made by following a kind of method at least:
Method one: the inorganic aluminate of fusion slowly joins in the mixture of steps A gained, is mixed to form even colloid; Add precipitating reagent then, under 50～120 ℃ of temperature, be neutralized into glue, aging then, obtain the nano-aluminum hydroxide gel;
Method two: the inorganic aluminate of fusion is slowly added in the mixture of steps A gained, be mixed to and form even colloid; In confined conditions, below the ammonia critical-temperature, be generally the critical-temperature of 30 ℃～ammonia, add precipitating reagent liquefied ammonia, under 30～200 ℃ of temperature, be neutralized into glue, aging then, obtain the nano-aluminum hydroxide gel;
Method three: use precipitating reagent and inorganic aluminate to mix the back heating and melting, slowly join in the mixture of steps A gained, be mixed to and form even colloid; Under airtight condition, resulting mixture is carried out homogeneous precipitation under 70～200 ℃ of temperature, 1～10 hour reaction time, aging then, obtain the nano-aluminum hydroxide gel;
Weight with the resulting mixture of step B is benchmark; Inorganic aluminate (butt), precipitating reagent and water consumption are 60.0wt%～93.0wt%; Be preferably 75.0wt%～92.0wt%, the mol ratio of water and aluminium atom is 3～15: 1, is preferably 3～10: 1; The mol ratio of aluminium atom and precipitating reagent is 1: 0.9～5, be preferably 1: 1.2～and 3; Amount of surfactant is 0.1wt%～15.0wt%, better is 0.5wt%～12.0wt%; The consumption of hydrocarbon component is 6.9wt%～32.0wt%, better is 7.5wt%～24.5wt%; Wherein water can add with the crystallization water and/or free water form in steps A and/or step B.
The condition of the described nano-aluminum hydroxide gel drying of step (2) is following: 100～130 ℃ of baking temperatures, 1～30 hour drying time.
Among the present invention, in order to obtain purer aluminium oxide, also can be at the nano-aluminum hydroxide gel of step (2) gained through washing Zhiyin ion weight concentration less than 0.5%, and then carry out drying.Described washing generally adopts water washing just can reach requirement, with water washing to the weight concentration of Na ion and Fe ion all below 0.5%, water wherein preferably adopts distilled water or deionized water.
The said forming method of step (2) can adopt the conventional method for preparing carrier, preferred pressed disc method or extruded moulding method.Described pressed disc method process is following: with nano-aluminum hydroxide gel drying powder, putting into tablet press machine, is under 0.08～2.00MPa condition at pressure, compression molding.In the pressed disc method, can in nano-aluminum hydroxide gel drying powder, add releasing agent, releasing agent is a carbon black, and consumption is 0～5% of a nano-aluminum hydroxide gel drying powder weight, is preferably 0.1%～5.0%.
Described extrusion method process is following: nano-aluminum hydroxide gel drying powder and binding agent are mixed; Peptizing agent, water and cosolvent are mixed, be added to then in the mixture of nano-aluminum hydroxide gel drying powder and binding agent, stir, on batch mixer, mix, moulding in banded extruder then.Described batch mixer can be kneader or roller.In the described extrusion process, controlled pressure is at 10～50MPa.Described peptizing agent can be in acetic acid, formic acid, nitric acid, hydrochloric acid, phosphoric acid and the sulfuric acid one or more; Consumption is 1%～15% (mass fraction) of nano-aluminum hydroxide gel drying powder and binder mixtures weight; Described water preferably adopts deionized water; Consumption is 5%～100% (mass fraction) of nano-aluminum hydroxide gel drying powder and binder mixtures weight, preferred 20%～70%.Peptization course also need add cosolvent, and cosolvent is one or more in methyl alcohol, ethanol and the propyl alcohol, and consumption is 1%～15% (mass fraction) of nano-aluminum hydroxide gel drying powder and binder mixtures weight.
Described binding agent preferably adopts intends thin water-aluminum hydroxide; Intending thin water-aluminum hydroxide can be that macropore is intended thin water-aluminum hydroxide; Also can be that aperture is intended thin water-aluminum hydroxide, the component that its consumption is introduced binding agent finally accounts for below 65% of carrying alumina body weight, is preferably 5%～50%.
Drying condition after the said moulding is following: under 100～130 ℃ of temperature, carried out drying 1～30 hour.Described roasting can be adopted a conventional one-step baking method; Condition was following: 180～1200 ℃ of roastings 4～40 hours; Programming rate was 1～5 ℃/min, preferably divides one-step baking, and condition is following: 180～300 ℃ of roasting temperatures 1～3 hour; 500～1100 ℃ of roastings 2～10 hours, programming rate was 1～5 ℃/min.
It is to adopt conventional immersion process for preparing that described alumina-based supports adopts infusion process supported active metal component, can adopt the method for spraying, saturated infusion process or supersaturation infusion process.Behind the dipping active metal component,, get residuum hydrogenating and metal-eliminating catalyst of the present invention through drying and roasting.Described drying condition is under 100～130 ℃ of temperature, to carry out drying 1～5 hour; Described roasting condition is 400～550 ℃ of roastings 2～10 hours.
Hydrodemetalation catalyst of the present invention is used in residue fixed-bed hydrogenation technique; Can adopt a beds; Also can adopt a plurality of beds, when wherein adopting a plurality of beds, along residual oil Flow of Goods and Materials direction; The bulk density of residuum hydrogenating and metal-eliminating catalyst increases gradually, and activity increases gradually.
The operating condition that is adopted in the residue fixed-bed hydrogenation technique of the present invention is following: 365～410 ℃ of reaction temperatures, hydrogen dividing potential drop 12.7～17.5MPa, volume space velocity 0.5～1.5h during liquid
-1, hydrogen to oil volume ratio 380～1000: 1.
Alumina-based supports of the present invention is that the gel aluminum hydroxide that adopts ultra solubilising micelle method to obtain is that raw material roasting after moulding obtains.Because ultra solubilising method is to adopt VB value less than the reversed phase micelle that 1 surfactant forms, and obtains unique ultra solubilising nanometer " reactor ", the nano particle process self assembly of reaction generation obtains the gel aluminum hydroxide of club shaped structure.Owing to contain surfactant and hydrocarbon component in the gel aluminum hydroxide; In forming process, still can keep club shaped structure; And in high-temperature calcination process; Surfactant is progressively deviate from, and surfactant still has the carrying out that self assembly property is being controlled reaction during this, makes the aluminium hydroxide of polymerization deviate from the nano alumina particles that forms behind the moisture and still has bar-shaped basic structure.Bar-shaped nano aluminium oxide is unordered being deposited in together each other, and the frame structure of formation does not have fixing outer surface, and the aperture is bigger; The duct penetrability is good; Especially concerning big molecule, can not resemble the aperture of ink bottle type, stop up because of the aperture and make catalysqt deactivation; Help increasing the deposition of impurity, prolong the service cycle of catalyst.
The cumulative volume of aluminum hydroxyl nano particle self-assembly organic moiety of the present invention is exactly the solvent hydrocarbon component sum of surfactant VB value lipophilic group part and reversed phase micelle.This part behind shaping and roasting, will form the duct part as template in carrier, make alumina support have bigger pore volume, aperture and porosity.The present invention can be adjusted pore volume, aperture, porosity and the pore size distribution of alumina support by the size of this organic moiety amount.
Conventional method is not owing to there is template, and the intensity of the catalyst carrier of being synthesized and pore volume are conflicting, and along with the adding of peptizing agent and the increase of pressure, the pore volume of porous powder and aperture will reduce.And in the inventive method because the existence of template during moulding; The factor of pressure will not have the effect that destroys duct and pore volume; Peptization acid can be deviate from the frame structure that forms after the template and just can keep very high intensity with aluminium oxide very secure bond together like this.
The hydrocarbon component that contains in the gel aluminum hydroxide of the present invention mainly contains two effects in the nanometer self assembling process: the one, and as the reversed micelle solvent of ultra solubilising micelle system, the 2nd, together play the effect of expanding the duct with surfactant.Interaction between the lipophilic group of hydrocarbon component and surfactant is the effect between the hydrophobic bond, and adhesion is less.When moulding, under the effect of pressure and/or adhesive, bonding has taken place between the aluminium hydroxide, owing to contain the hydrophilic radical of strong interaction, surfactant and aluminium hydroxide have also formed strong absorption and have interacted.When hydrocarbon component content is very high; The VB value is less in the gel aluminum hydroxide, the hydrocarbon component in the huge mixing lipophilic group under pressure, depending merely on interacts with the surfactant lipophilic group is not enough to be kept in the aluminum hydroxide particles of nanometer self assembly; This has just caused the part hydrocarbon component to leave nanometer self assembly particle; Form hydrocarbon accumulation, caused the distribution of duct wide region, the large pore volume alumina-based supports is formed from nanometer to micron-sized different frames structure pore.
Residue fixed-bed hydrogenation technique adopts Hydrodemetalation catalyst of the present invention, and especially grading loading can make metal deviate to homogeneously precipitate in whole beds, keeps long-term operation, also can reach very high desulfurization degree and denitrification percent simultaneously.Residuum hydrogenating and metal-eliminating catalyst of the present invention can also pass through adjustment of acidity, suppresses the generation of carbon deposit, reaches the maximum ability of deviating from impurity.
Hydrodemetalation catalyst large pore of the present invention duct proportion is high, micron order duct especially, and the metal impurities uniform deposition and forms bar-shaped precipitated metal thing in the catalyst duct, formed new active catalyst for demetalation center.Its mechanism is that the asphalitine micelle can be spread in the micron order duct, and after deviating from a large amount of precipitated metals, precipitated metal is gathered into fibrous, through constantly depositing, has formed bar-shaped vanadic sulfide and iron sulfide etc., and these metal sulfides become new reaction center again.
Description of drawings
Fig. 1 is that Comparative Examples 1 gained catalyst DHDM-1 amplifies 40000 times of ESEMs (SEM) figure.
Fig. 2 is that embodiment 1 gained catalyst HDM-1 amplifies 40000 times of SEM figure.
Fig. 3 is the section plated metal distribution curve of embodiment 1 gained catalyst runs useless agent after 3000 hours.
Fig. 4 is the section plated metal distribution curve of Comparative Examples 1 gained catalyst runs useless agent after 3000 hours.
The section duct SEM figure of Fig. 5 embodiment 1 catalyst runs useless agent after 3000 hours.
The section duct SEM figure of Fig. 6 embodiment 1 catalyst runs useless agent after 3000 hours.
The specific embodiment
Pore volume among the present invention, specific surface, average pore size, pore size distribution, porosity adopt mercury injection method to record.Crushing strength adopts intensity meter to measure.Bulk density adopts the graduated cylinder method to measure.Infrared acidity adopts infrared spectroscopic determination.
Comparative Examples 1
Adopt the method for CN1068975A embodiment 1 to obtain aluminium colloidal sol, adopt the forming method and the condition of the embodiment of the invention 1 then, i.e. moulding in banded extruder, controlled pressure is at 20MPa.Article shaped was carried out drying 10 hours under 100 ℃ of temperature, 240 ℃ of roasting temperatures 3 hours, 850 ℃ of roastings 4 hours, wherein programming rate was 5 ℃/min, obtained alumina support DM1.Exterior appearance is seen Fig. 1, is to amplify 40000 times of sem photographs.
The alumina support DM1 of gained soaks reactive metal Mo and Ni, under 110 ℃ of temperature, carries out drying 3 hours then, 480 ℃ of roastings 6 hours, obtains residuum hydrogenating and metal-eliminating catalyst DHDM-1, wherein contains 8% (mass fraction) MoO
3, 3% (mass fraction) NiO.
Under stirring condition; 375g nine water aluminum nitrates and 90g urea are mixed and heated to 100 ℃; Be added in the mixture of the 150HVI neutral oil of 5g polyisobutene maleic acid triethanolamine ester and 88g under the equal temperature condition; Form ultra solubilising micelle, 100 ℃ of reactions 3 hours, obtain the nano-aluminum hydroxide gel then.With 200ml distilled water washing three times, 120 ℃ of dryings of warp 10 hours.Nano-aluminum hydroxide gel drying powder 70g and binding agent boehmite 30g are mixed; The rare nitric acid of 1.6g (mass concentration 17%), 160g water and 10g cosolvent are mixed; Be added to then in the mixture of nano-aluminum hydroxide gel drying powder and binding agent; Moulding in banded extruder then, controlled pressure is at 20MPa.Article shaped was carried out drying 10 hours under 100 ℃ of temperature, 240 ℃ of roasting temperatures 3 hours, 850 roastings 4 hours, wherein programming rate was 5 ℃/min, obtained alumina support A1 of the present invention.
The alumina support A1 of gained soaks reactive metal Mo and Ni, under 110 ℃ of temperature, carries out drying 3 hours then, 480 ℃ of roastings 6 hours, obtains residuum hydrogenating and metal-eliminating catalyst HDM-1, wherein contains 8% (mass fraction) MoO
3, 3% (mass fraction) NiO.
Embodiment 2
Residuum hydrogenating and metal-eliminating catalyst HDM-1 is used for the experiment of residual oil raw material HDM, and residual oil character: nickel contains 21.06 μ g/g, and vanadium contains 67.67 μ g/g.Experimental condition is following: 390 ℃ of reaction temperatures, hydrogen to oil volume ratio 1000, volume space velocity 1.0h during liquid
-1, hydrogen dividing potential drop 15.4MPa turned round 3000 hours continuously, and the porous of running rear catalyst is seen table 1.Precipitated metal is in the diffusivity and the Metal Distribution in catalyst duct in the investigation residual oil; Adopt JSM-7500F type awkward silence at a meeting emission scan Electronic Speculum (FESEM) to measure Metal Distribution,, survey then along the Metal Distribution of catalyst cross section long axis direction with catalyst half place's crosscut longitudinally; Specifically see Fig. 3; Wherein abscissa is the distance of sample point apart from the center, and the center is 0, and outer surface is 1.
Comparative Examples 2
Test method according to embodiment 2 adopts residuum hydrogenating and metal-eliminating catalyst DHDM-1 to test, and the result sees table 1.Survey Metal Distribution with embodiment 2 same procedure, specifically see Fig. 4.
The performance comparison of table 1 embodiment 1 and Comparative Examples 1
| | Embodiment | 1 HDM-1 | After |
Fresh dose of DHDM-1 of reference agent | After reference agent DHDM-1 used the agent roasting |
| Pore volume/cm 3.g -1 | 1.65 | 0.793 | 0.55 | 0.08 | |
| Specific surface/m 2.g -1 | 407 | 120 | 183 | 30.8 | |
| Average pore size/nm | 16.2 | 26.4 | 12 | 10.7 | |
| Pore size distribution, % | |||||
| ＜10nm | 14.0 | 3.50 | 9 | - | |
| 10-100nm | 41 | 45 | 80 | - | |
| 100-1000nm | 27 | 33.3 | 8 | - | |
| ＞1000nm | 18 | 17 | 3 | - | |
| Bulk density/g.cm -3 | 0.33 | 0.51 | 0.50 | 0.85 | |
| Plated metal content *, % (mass fraction) | |||||
| V | - | 15.5 | - | 6.49 | |
| Ni | - | 6.29 | - | 4.58 |
* plated metal content is the percentage by weight that the V that deposits in the dead catalyst or Ni account for dead catalyst, and wherein the amount of V and Ni adopts plasma emission spectrometry to measure (ICP).
The fresh dose of DHDM-1 that embodiment 1 obtains fresh dose of HDM-1 and Comparative Examples 1 obtain turned round 3000 hours under the same conditions; The deposition amount of metal exceeds more than 1 times than Comparative Examples 1 among the embodiment 1; More remaining porous used agent HDM-1 to still have bigger pore volume, and the above duct of 10nm still accounts for 95.5%; Use agent DHDM-1 pore volume very little, be merely 0.08ml/g.Comparative Examples 1 useless agent bulk density is up to 0.85g.cm
-3, and embodiment 1 useless agent bulk density is low to 0.5g.cm
-3Identical with 1 fresh dose of Comparative Examples, the residue pore volume of embodiment 1 useless agent shows very big appearance metal ability in addition up to 0.793ml/g.Behind the embodiment 1 useless agent running 3000h, held the V of 15.5g/100g.And Comparative Examples 1 gained catalyst has only held the V of 6.49g/100g.Fig. 3 is that the plated metal of the section of embodiment 1 useless agent distributes, and can find out that normalized curve is equally distributed, and the useless agent section Metal Distribution of Fig. 4 Comparative Examples 1, the curve that the outer surface tenor is high.The section duct of Fig. 5 embodiment 1 useless agent, the many bar-shaped precipitated metals of 100-300nm, Fig. 6 have an inside, 2 μ m duct that the bar-shaped precipitated metal of many intersections is arranged.
Embodiment 3
85g second line of distillation dewaxed oil and 54g SP-60 are mixed, and 90 ℃ of heating for dissolving mix; The 820g ANN aluminium nitrate nonahydrate is heated to 90 ℃ of fusions, slowly adds in the said mixture, mix forming evenly ultra solubilising colloid in 20 minutes.Drip 20 ℃ of saturated ammoniacal liquor 220g, aging 3 hours, obtain the nano-aluminum hydroxide gel.With 200ml distilled water washing three times, 120 ℃ of dryings of warp 10 hours.Nano-aluminum hydroxide gel drying powder 80g and binding agent boehmite 20g are mixed; The rare nitric acid of 3.2g (mass concentration 17%), 15g water and 3g cosolvent ethanol are mixed, moulding in banded extruder then, controlled pressure is at 23MPa.Article shaped was carried out drying 10 hours under 100 ℃ of temperature, 240 ℃ of roasting temperatures 3 hours, 850 ℃ of roastings 4 hours, wherein programming rate was 5 ℃/min, obtained alumina support A2 of the present invention.
The alumina support A2 of gained soaks reactive metal Mo and Ni, under 120 ℃ of temperature, carries out drying 3 hours then, 520 ℃ of roastings 5 hours, obtains residuum hydrogenating and metal-eliminating catalyst HDM-2, wherein contains 4% (mass fraction) MoO
3, 0.5% (mass fraction) NiO.
Embodiment 4
17g is subtracted four lines oil, 44g first vacuum side stream, 13.5g second line of distillation slack wax, 11gSP-80 mixing, and 100 ℃ of heating for dissolving mix; The 750g ANN aluminium nitrate nonahydrate is heated to 100 ℃ of fusions, slowly adds in the said mixture, mix forming evenly ultra solubilising colloid in 30 minutes, drip 150g sodium metasilicate (silica weight content is 30%) then, mix.In closed reactor, in ultra solubilising colloid, add 50 ℃ of 110g liquefied ammonia, 180 ℃ of reactions 2 hours, wash to Na less than below 0.05, through 100 ℃ of dryings 10 hours, obtain nanometer silicon hydroxide-gel aluminum hydroxide.Step By Condition obtains siliceous alumina support A3 with embodiment 3 afterwards.
The siliceous alumina support A3 of gained soaks reactive metal Mo and Co, under 120 ℃ of temperature, carries out drying 3 hours then, 500 ℃ of roastings 5 hours, obtains residuum hydrogenating and metal-eliminating catalyst HDM-3, wherein contains 7% (mass fraction) MoO
3, 1% (mass fraction) NiO.
The siliceous alumina powder jointed of gained obtained carrier A 4 at 0.9MP pressure lower sheeting; Soak reactive metal Mo and Ni, under 120 ℃ of temperature, carried out drying 3 hours then, 500 ℃ of roastings 5 hours; Obtain residual hydrogenation protective agent HDM-4, wherein contain 10% (mass fraction) MoO
3, 2% (mass fraction) NiO.
Embodiment 6
Be loaded into Hydrodemetalation catalyst DHDM-1, HDM-2, HDM-3 and HDM-4 in the fixed bed hydrogenation reactor respectively; Handled raw material is identical with experimental condition; Running is 3000 hours continuously; Take off contaminant characteristics and see table 3, catalyst system therefor holds the amount of metal result and sees table 4, and the used percentage of table 3 and table 4 is mass fraction.Handled residual oil raw material character is following: the sulphur weight content is 3.03%, and nitrogen content is 2108 μ g/g, and nickel contains 21.06 μ g/g, and vanadium contains 67.67 μ g/g.Experimental condition is following: 390 ℃ of reaction temperatures, hydrogen to oil volume ratio 1000, volume space velocity 1.0h during liquid
-1, hydrogen dividing potential drop 15.4MPa.
The character of table 2 catalyst
| Sample | HDM-2 | HDM-3 | HDM-4 |
| Pore volume/cm 3.g -1 | 1.4 | 1.8 | 2.1 |
| Specific surface/m 2.g -1 | 280 | 200 | 189 |
| Average pore diameter/ |
20 | 36 | 55 |
| Infrared acidity/mmol/g | 0.40 | 0.55 | 0.65 |
| Pore size distribution, % | |||
| ＜10nm | 18 | 16 | 13 |
| 10-100nm | 52 | 38 | 43 |
| 100- |
20 | 28 | 30 |
| ＞ |
10 | 18 | 14 |
| Bulk density/g.cm -3 | 0.45 | 0.38 | 0.30 |
| Porosity/% | 80 | 89 | 93 |
| Intensity, N/mm | 16 | 14 | 12 |
Table 3 feedstock oil takes off the dirl butter result
| Catalyst | HDM-2 | HDM-3 | HDM-4 | DHDM-1 |
| Desulfurization degree, % | 34 | 39 | 31 | 33 |
| Denitrification percent, % | 11 | 16 | 14 | 18 |
| Take off V+Ni and lead, % | 58.9 | 60.2 | 61.4 | 52.0 |
Table 4 catalyst metals deposition test result
| Catalyst | HDM-2 | HDM-3 | HDM-4 | DHDM-1 |
| Plated metal content * | ||||
| ?V，％ | 4.8 | 7.6 | 10.0 | 3.5 |
| ?Ni，％ | 0.5 | 1.8 | 2.7 | 0.3 |
Claims (14)
1. a Hydrodemetalation catalyst comprises alumina-based supports and active metal component, and the character of said catalyst is following: pore volume is 1.3～2.6ml/g, and specific surface is 180～450m
2/ g, average pore size is 20～55nm, porosity is 80%～93%; Pore size distribution is following: bore dia is below 20% of total pore volume less than the shared pore volume in the hole of 10nm; Bore dia is that the shared pore volume in the hole of 10-100nm is 35%～55% of total pore volume; Bore dia is that the shared pore volume in the hole of 100nm-1000nm is 20%～35% of total pore volume, and bore dia is that the above shared pore volume in hole of 1000nm is 16%～35% of total pore volume; The rod-like nano oxide that contains in the described alumina-based supports, this rod-like nano oxide are aluminium oxide or the aluminium oxide that contains auxiliary agent, and the diameter of this rod-like nano oxide is 50nm～500nm, and length is 2～10 times of diameter; The weight content of described rod-like nano oxide in alumina-based supports is 30%～100%.
2. according to the described catalyst of claim 1, it is characterized in that the character of said catalyst is following: pore volume is 1.6～2.3ml/g, and specific surface is 200～350m
2/ g, average pore size is 30～45nm, porosity is 85%～93%.
3. according to the described catalyst of claim 1; The pore size distribution that it is characterized in that said catalyst is following: bore dia is below 15% of total pore volume less than the shared pore volume in the hole of 10nm; Bore dia is that the shared pore volume in the hole of 10-100nm is 35%～55% of total pore volume; Bore dia is that the shared pore volume in the hole of 100-1000nm is 20%～35% of total pore volume, and the above shared pore volume in hole of 1000nm is 18%～30% of total pore volume.
4. according to the described catalyst of claim 1, the diameter that it is characterized in that described rod-like nano oxide is 80nm～300nm, and length is 2～10 times of diameter; The weight content of described rod-like nano oxide in alumina-based supports is 60%～90%.
5. according to claim 1 or 4 described catalyst, it is characterized in that the weight content of described alumina-based supports in Hydrodemetalation catalyst is 86%～96%; Alumina weight content is more than 90% in the described alumina-based supports.
6. according to the described catalyst of claim 1, it is characterized in that containing in the described alumina-based supports in auxiliary agent silica, titanium oxide, the phosphorous oxide one or more, the weight of auxiliary agent accounts for 2%～10% of alumina-based supports.
7. according to claim 1 or 6 described catalyst, the infrared acidity that it is characterized in that described Hydrodemetalation catalyst is 0.40～0.65mmol/g.
8. according to the described catalyst of claim 1, the bulk density that it is characterized in that described Hydrodemetalation catalyst is 0.32～0.50g/cm
3, crushing strength is 6～80N/mm.
9. according to the described catalyst of claim 1, it is characterized in that described active metal component is group vib metal and/or group VIII metal, is benchmark with the weight of catalyst, and the content of reactive metal oxides is 4.0%～14.0%.
10. according to the described catalyst of claim 9; It is characterized in that described group vib metal is selected from least a among Mo and the W; The group VIII metal is selected from least a among Co and the Ni; Weight with catalyst is benchmark, and the content of described group vib metal oxide is 3.5%～12.0%, and the content of group VIII metal oxide is 0.5%～4.0%.
11., it is characterized in that in the described alumina-based supports that contain the component of being introduced by adhesive, its content accounts for below 50% of carrying alumina body weight according to the described catalyst of claim 1.
12. a residue fixed-bed hydrogenation technique is characterized in that adopting the arbitrary described catalyst of claim 1～11.
13. according to the described technology of claim 12; It is characterized in that described Hydrodemetalation catalyst adopts a beds or adopts a plurality of beds; When wherein adopting a plurality of beds; Along the residual oil raw material flow direction, the bulk density of Hydrodemetalation catalyst increases gradually, and activity increases gradually.
14. according to the described technology of claim 12, it is characterized in that the operating condition that is adopted in the described residue fixed-bed hydrogenation technique is following: 365～410 ℃ of reaction temperatures, hydrogen dividing potential drop 12.7～17.5MPa, volume space velocity 0.5～1.5h during liquid
-1, hydrogen to oil volume ratio 380～1000: 1.
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| CN102909026B (en) * | 2011-08-04 | 2016-04-27 | 中国石油化工股份有限公司 | Take titanium dioxide-aluminum oxide as Hydrogenation active protective agent and the Synthesis and applications thereof of carrier |
| CN103121900B (en) * | 2011-11-18 | 2015-01-07 | 中国石油化工股份有限公司 | Method for preparing ethylene by dehydrating ethanol |
| TWI611836B (en) | 2012-02-17 | 2018-01-21 | Advanced Refining Technologies Llc. | Catalyst support and preparation method thereof |
| TWI579043B (en) | 2012-02-17 | 2017-04-21 | 先進精鍊科技有限公司 | Spheroidal catalyst support and preparation method thereof |
| TWI632235B (en) | 2012-06-20 | 2018-08-11 | 美商先進精鍊科技有限公司 | Catalyst for hydrodesulfurization of residuum hydrocarbon feedstocks and preparaton method thereof |
| CN104263407A (en) * | 2014-07-26 | 2015-01-07 | 何巨堂 | Hydrocarbon hydrogenation method with up-flow bed layer and fixed bed operated in series |
| CN104232157A (en) * | 2014-07-28 | 2014-12-24 | 何巨堂 | Hydrocarbon hydrogenation method with particulate matter settling region and reactor adopting hydrocarbon hydrogenation method |
| CN104194829A (en) * | 2014-07-29 | 2014-12-10 | 何巨堂 | Inferior hydrocarbon hydrogenation method using self-produced ferric sulfide as pre-hydrorefining catalyst |
| CN104250566A (en) * | 2014-07-29 | 2014-12-31 | 何巨堂 | Hydrogenation method of inferior hydrocarbons containing easy-to-hydrogenolyze metallic compounds |
| CN106268969A (en) * | 2015-06-12 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of catalyst carrier and preparation method thereof and Hydrodemetalation catalyst |
| CN110935466B (en) * | 2018-09-25 | 2022-07-12 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN110935462B (en) * | 2018-09-25 | 2022-07-12 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| WO2021083270A1 (en) | 2019-10-31 | 2021-05-06 | 中国石油化工股份有限公司 | Supported catalyst, preparation method therefor and application thereof |
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