CN104338527A - Heavy oil hydrogenation diasphaltene catalyst, and preparation method and application thereof - Google Patents
Heavy oil hydrogenation diasphaltene catalyst, and preparation method and application thereof Download PDFInfo
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- CN104338527A CN104338527A CN201310334181.7A CN201310334181A CN104338527A CN 104338527 A CN104338527 A CN 104338527A CN 201310334181 A CN201310334181 A CN 201310334181A CN 104338527 A CN104338527 A CN 104338527A
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Abstract
The invention relates to a heavy oil hydrogenation diasphaltene catalyst, and a preparation method and an application thereof. The catalyst comprises a carrier and hydrogenation active metal components. The hydrogenation active metal components are selected from at least one VIB-family metal component and at least one VB-family metal component. The carrier is a bimodal pore alumina carrier comprising an IVB-family metal component. Characterized by mercury intrusion porosimetry, the carrier has pore volume of 0.6-1.4 ml/g, and specific surface area of 80-400 m<2>/g. The pore volume of pores with diameters of 5-20nm accounts for 30-60% of the total pore volume. The pore volume of pores with diameters of 100-300nm accounts for 15-45% of the total pore volume. Compared with prior arts, when the catalyst provided by the invention is used in residual oil hydrogenation treatment, the catalyst has better hydrogenation diasphaltene and demetalization performances.
Description
Technical field
The present invention relates to a kind of hydrogenation diasphaltene catalyst and preparation and application thereof.
Background technology
Carry out deep processing to the mink cell focus comprising residual oil to be not only conducive to improving the utilization rate of crude oil, alleviate the nervous trend of energy supply, can also environmental pollution be reduced simultaneously, reach the clean utilization of the energy.Compared with distillate, containing a large amount of macromolecular reaction things such as asphalitine, colloid in mink cell focus, and the heteroatomic compound such as sulphur, nitrogen, oxygen in mink cell focus and the heavy metal such as nickel and vanadium and condensed-nuclei aromatics major part concentrate in asphalitine, these impurity and heavy metal can pollute corresponding catalyst in follow-up process, and thus bitum hydro-conversion is a critical step in residual hydrogenation process.And in bitum conversion and subtractive process, need according to bitum characteristic, select activity high and the catalyst of the function admirable of good stability.
For the hydrogenation catalyst of diasphaltene, its pore-size distribution is of great significance catalyst performance tool.Bitum molecular size is about tens of to hundreds of nanometer, if the spacing of catalyst active center is less than asphaltene molecules, then asphaltene molecules is difficult to be contacted with the activated centre of catalyst by diffusion, and be mainly adsorbed on outer surface or the aperture of catalyst, along with the carrying out of reaction can only form coke because of thermal condensation, cause catalysqt deactivation.Macroporous catalyst is conducive to bitum removing, but the aperture of catalyst and specific surface negative correlation each other, the catalyst that namely average pore size is large, its specific area is just little.Therefore in order to take into account this character, catalyst needs rational pore size distribution.
The weak point of existing Heavy oil hydrogenation catalyst is its S, N removal efficiency, can not reaches good coupling between heavy metal removing rate and asphaltene removal, such as, often S, N removal efficiency and asphaltene removal are not high to remove the high catalyst of metal active.The reason producing problems is very complicated.First be raw material, in residual oil, the feature of each component is that molecular weight is large, and complex structure, saturation degree low (armaticity is high), S, N content are high.And beyond sulphur removal, the overwhelming majority of impurity again more to be present in asphalitine, therefore for removing this type of S, N, the conversion (comprising saturated, open loop and hydrogenolysis etc.) of appropriateness must be carried out to asphaltene molecules.Next is catalyst.In prior art, having the catalyst being suitable for carrying out this type of reaction aperture is guard catalyst and catalyst for demetalation, such as:
A kind of disclosed in CN1267537C have Hydrodemetalation catalyst of lower carbon deposition quantity and greater activity and preparation method thereof.
A kind of residuum hydrogenating and metal-eliminating catalyst disclosed in CN1796500A, the carrier that this catalyst has a double-hole by a kind of and load molybdenum on this carrier and/or tungsten and cobalt and/or nickel metal component form.The preparation method of carrier that catalyst uses comprise a kind of precursor of aluminium oxide is mixed with the nitrogen-containing compound beyond a kind of deacidification, shaping and roasting.
Catalyst for heavy oil fixed bed hydrogenating treatment and preparation method etc. disclosed in CN1233795C.
But the asphaltene removal of these catalyst is general lower.
Summary of the invention
The technical problem to be solved in the present invention be to provide a kind of newly, there is the better catalyst of hydrogenation diasphaltene performance, the preparation method of this catalyst and application.
The present invention relates to following content:
1. a heavy-oil hydrogenation diasphaltene catalyst, containing carrier and hydrogenation active metals component, described hydrogenation active metals component is selected from the metal component of at least one group vib and the metal component of at least one VB race, wherein, described carrier is a kind of Bimodal-pore alumina support containing IVB race metal component, characterize with mercury injection method, the pore volume of described carrier is 0.6-1.4 ml/g, and specific area is 80-400 rice
2/ gram, diameter is the 30-60% that the pore volume in 5-20nm hole accounts for total pore volume, and diameter is the 15-45% that the pore volume in 100-300nm hole accounts for total pore volume.
2. the catalyst according to 1, is characterized in that, the pore volume of described carrier is 0.7-1.3 ml/g, and specific area is 100-300 rice
2/ gram, diameter is the 35-50% that the pore volume in 5-20nm hole accounts for total pore volume, and diameter is the 20-40% that the pore volume in 100-300nm hole accounts for total pore volume.
3, the catalyst according to 1, is characterized in that, described IVB race metal component is selected from one or more in titanium, zirconium, hafnium, and with described carrier for benchmark and with oxide basis, in described carrier, the content of the IVth race's metal is 0.1-6 % by weight.
4, the catalyst according to 3, is characterized in that, described IVB race metal component is titanium, and with described carrier for benchmark and with oxide basis, in described carrier, the content of IVB race metal is 0.3-4 % by weight.
5, the catalyst according to 4, is characterized in that, with described carrier for benchmark and with oxide basis, in described carrier, the content of IVB race metal is 0.5-2.5 % by weight.
6. the catalyst according to 1, it is characterized in that, described hydrogenation active metals component is selected from the combination of the metal component of at least one group vib and the metal component of at least one VB race, be benchmark with oxide basis and with catalyst, the content of described group vib metal component is the content of 0.2-15 % by weight, VB race metal component is 0.2-12 % by weight.
7. the catalyst according to 3, it is characterized in that, the metal component of described group vib is selected from molybdenum and/or tungsten, VB race metal component is selected from vanadium and/or niobium, be benchmark with oxide basis and with catalyst, the content of described group vib metal component is the content of 0.5-12 % by weight, VB race metal component is 0.5-9 % by weight.
8. the preparation method of catalyst according to 1, comprise the alumina support containing the IVth B race metal component that preparation has structure of double peak holes, the preparation method of described carrier comprises and mix with a kind of modifier PC of the hydrated alumina containing boehmite by hydrated alumina PA and PB containing boehmite and to introduce containing the compound of the IVth B race metal component, shaping, drying also roasting in the mixture, wherein, the Mixing ratio by weight of described PA, PB and PC is 20-60:20-50:5-50, the κ value of PC is 0 to being less than or equal to 0.9, described κ=DI
2/ DI
1, DI
1for the sour peptization index of PC hydrated alumina before modified, DI
2for the sour peptization index of described PC.
9. the method according to 8, is characterized in that, the Mixing ratio by weight of described PA, PB and PC is 30-50:35-50:10-30.
10. the method according to 8, it is characterized in that, described IVth B race metal is selected from one in titanium, zirconium, hafnium and composition thereof, and be benchmark with oxide basis and with carrier, the described introduction volume containing the IVth B race metallic compound makes the content of the IVth B race metal in final carrier be 0.1-6 % by weight.
11. methods according to 10, it is characterized in that, described IVth B race metal is titanium, is benchmark with oxide basis and with carrier, and the described introduction volume containing the IVth B race metallic compound makes the content of the IVth B race metal in final carrier be 0.3-4 % by weight.
12. methods according to 8, is characterized in that, the k value of described PC is 0 to being less than or equal to 0.6.
13. methods according to 8 or 9, is characterized in that, the pore volume of the described hydrated alumina PA containing boehmite is 0.75-1 ml/g, and specific surface is 200-450 rice
2/ gram, can and bore dia 3-10nm; The pore volume of the described hydrated alumina PB containing boehmite is 0.9-1.4 ml/g, and specific surface is 100-350 rice
2/ gram, can and bore dia be greater than 10 to being less than or equal to 30nm.
14. methods according to 13, is characterized in that, the pore volume of the described hydrated alumina PA containing boehmite is 0.80-0.95 ml/g, and specific surface is 200-400 rice
2/ gram, can and bore dia 5-10nm; The pore volume of the described hydrated alumina PB containing boehmite is 0.95-1.3 ml/g, and specific surface is 120-300 rice
2/ gram, can and bore dia be greater than 10 to being less than or equal to 25nm.
15. methods according to 8 or 9, it is characterized in that, described PC is 80-300 object particle.
16. methods according to 15, it is characterized in that, described PC is 100-200 object particle.
17. methods according to 8, it is characterized in that, the condition of described drying comprises: temperature is 40-350 DEG C, and the time is 1-24 hour, and the condition of described roasting comprises: temperature is for being greater than 500 to being less than or equal to 1200 DEG C, and the time is 1-8 hour.
18. methods according to 17, it is characterized in that, the condition of described drying comprises: temperature is 100-200 DEG C, and the time is 2-12 hour, and the condition of described roasting comprises: temperature is for being greater than 800 to being less than or equal to 1000 DEG C, and roasting time is for being 2-6 hour.
19. methods according to 8, it is characterized in that, by shaping, dry for the described hydrated alumina containing boehmite by one of hydrated alumina method being modified as PC containing boehmite, afterwards its all or part of carrying out is ground, sieves, the condition of described drying comprises: temperature is 40-350 DEG C, and the time is 1-24 hour; Two of method is article shaped roastings method one obtained, and sintering temperature is for being greater than 350 to being less than or equal to 1400 DEG C, and roasting time is 1-8 hour, afterwards its all or part of carrying out is ground, is sieved; Three of method is dodged by the hydrated alumina containing boehmite to do, and dodge dry temperature for being greater than 150 to being less than or equal to 1400 DEG C, flash-off time is 0.05-1 hour; Four of method is mixed to get one or more in two and the modifier that obtains with three of method of one of method, method.
20. methods according to 19, it is characterized in that, the condition of the drying in described method one comprises: temperature is 100-200 DEG C, and the time is 2-12 hour; Method two in sintering temperature be 500-1200 DEG C, roasting time is 0.1-6 hour; Method three in sudden strain of a muscle to do temperature be 200-1000 DEG C, flash-off time is 0.1-0.5 hour.
21. methods according to 19, is characterized in that, described PC is 80-300 object particle in the modifier of hydrated alumina containing boehmite.
22. methods according to 21, is characterized in that, described PC is 100-200 object particle in the modifier of hydrated alumina containing boehmite.
23. methods according to 8, it is characterized in that described method is included in described supported on carriers hydrogenation active metals component, the method of the component of load hydrogenation active metals is on the carrier infusion process, comprise preparation contain the solution of the compound of hydrogenation active metals and use this solution impregnating carrier, carry out drying afterwards, roasting or not roasting, described hydrogenation active metals component is selected from metal component and at least one VB race metal component of at least one group vib, be benchmark with oxide basis and with catalyst, the concentration of described maceration extract and consumption make the content of group vib metal component described in final catalyst be 0.2-15 % by weight, the content of VB race metal component is 0.2-12 % by weight, described drying condition is: temperature 80-200 DEG C, time 1-8 hour, roasting condition is: temperature 400-600 DEG C, time 2-8 hour.
24. methods according to 23, it is characterized in that, the metal component of described group vib is selected from molybdenum and/or tungsten, VB race metal component is selected from vanadium and/or niobium, be benchmark with oxide basis and with catalyst, the concentration of described maceration extract and consumption make the content of group vib metal component described in final catalyst be 0.5-12 % by weight, the content of VB race metal component is 0.5-9 % by weight, described drying condition is: temperature 100-150 DEG C, time 2-6 hour, roasting condition is: temperature 420-500 DEG C, time 3-6 hour.
25. methods according to 24, it is characterized in that, be benchmark with oxide basis and with catalyst, it is 1-9 % by weight that the concentration of described maceration extract and consumption make the content of group vib metal component described in final catalyst be the content of 5-12 % by weight, VB race metal component.
The application of catalyst in 26. claim 1-7 described in any one in hydrocarbon oil hydrogenation process.
According to catalyst provided by the invention, described IVB race metal component is selected from one or more in titanium, zirconium, hafnium, be preferably titanium, with oxide basis and with described carrier for benchmark, the content of described IVB race metal is 0.1-0.6 % by weight, be preferably 0.3-4 % by weight, more preferably 0.5-2.5 % by weight.
Optionally, described carrier can make the article shaped being easy to arbitrarily operate, such as spherical, cellular, nest like, tablet or bar shaped (clover, butterfly, cylindrical etc.).Wherein, be conventional method by the method for described PA, PB and PC mixing, such as, PA, PB and PC of powder dropped in stirring-type batch mixer according to ingredient proportion and mixes.In described PA, PB and PC mixture, the method introduced containing the compound of the IVth B race metal is conventional method, such as, can be directly be mixed in aforesaid PA, PB and PC mixed process by the compound containing the IVth B race metal of aequum.
Concrete prepare in the embodiment of carrier at one, the method introduced in the mixture of described PA, PB and PC containing the compound of the IVth B race metal is mixed with the aqueous solution by containing the IVth B race metallic compound, this aqueous solution is mixed into while described PA, PB and PC mixing or again this aqueous solution is mixed into after described PA, PB and PC mixing, aftershaping, dry and roasting.The described compound containing the IVth B race metal can be one or more in the water soluble compound of arbitrary IVth B race metal.Such as, one or more in the water-soluble inorganic salt of the IVth B race metal.
In the present invention, describedly shapingly to carry out according to a conventional method, such as, a kind of method in spin, compressing tablet and extruded moulding or the combination of several method.When shaping, such as extruded moulding, for ensureing described shapingly to carry out smoothly, can add in described mixture water, extrusion aid and/or adhesive, containing or not containing expanding agent, then extrusion molding, carry out drying also roasting afterwards.The kind of described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, such as common extrusion aid can be selected from one or more in sesbania powder, methylcellulose, starch, polyvinyl alcohol, PVOH, described peptizing agent can be inorganic acid and/or organic acid, and described expanding agent can be one or more in starch, synthetic cellulose, polymeric alcohol and surfactant.Synthetic cellulose is wherein preferably one or more in CMC, methylcellulose, ethyl cellulose, hydroxyl fiber fat alcohol polyethylene ether, polymeric alcohol is preferably one or more in polyethylene glycol, poly-propyl alcohol, polyvinyl alcohol, one or more in the propenyl copolymer that surfactant is preferably fat alcohol polyethylene ether, fatty alkanol amide and derivative thereof, molecular weight is 200-10000 and maleic acid copolymer.
In the present invention, after described sour peptization index D I refers to that hydrated alumina containing boehmite and the hydrated alumina modifier containing boehmite add nitric acid by certain sour aluminum ratio, within certain reaction time by the hydrated alumina containing boehmite of peptization with Al
2o
3the percentage of meter, DI=(1-W
2/ W
1) × 100%, W
1and W
2before being respectively hydrated alumina containing boehmite and acid reaction and with acid reaction after with Al
2o
3the weight of meter.
The mensuration of DI comprises: (calcination base content refers to quantitative boehmite in 600 DEG C of roastings 4 hours calcination base (also referred to as the butt) content of hydrated alumina (1) measuring containing boehmite, its ratio burning rear weight and burn front weight, be expressed as a percentage), count a; (2) take the hydrated alumina W containing boehmite with assay balance
0gram, W
0amount meet with Al
2o
3the W of meter
1be 6 grams of (W
1/ a=W
0), take deionized water W gram, W=40.0-W
0, under stirring, the hydrated alumina containing boehmite taken and deionized water are added in beaker and mix; With 20mL pipette pipette 20mL, concentration is the dilute nitric acid solution of 0.74N, is joined by this acid solution in the beaker of step (2), stirs lower reaction 8 minutes; (4) step (3) reacted slurries are carried out centrifugation in centrifuges, inserted by sediment in the crucible of having weighed, afterwards, by it in 125 DEG C of dryings 4 hours, in Muffle furnace, 850 DEG C of roastings 3 hours, weigh and obtain calcination sample size W
2gram; (5) according to formula DI=(1-W
2/ W
1) × 100% calculates.
Under being enough to make final carrier meet the prerequisite of application claims, the present invention does not specially require described hydrated alumina PA and PB containing boehmite, it can be boehmite prepared by any prior art, also can be the mixture of boehmite and other hydrated alumina, other hydrated alumina described be selected from one or more in a Water oxidize aluminium, gibbsite and amorphous hydrated aluminium oxide.
In a detailed description of the invention, the described preferred pore volume of hydrated alumina PA containing boehmite is 0.75-1 ml/g, and specific surface is 200-450 rice
2/ gram, can and bore dia 3-10nm, preferably pore volume is 0.80-0.95 ml/g further, and specific surface is 200-400 rice
2/ gram, can and bore dia 5-10nm; The described preferred pore volume of hydrated alumina PB containing boehmite is 0.9-1.4 ml/g, and specific surface is 100-350 rice
2/ gram, can and bore dia be greater than 10 to being less than or equal to 30nm, preferably pore volume is 0.95-1.3 ml/g further, and specific surface is 120-300 rice
2/ gram, can and bore dia be greater than 10 to being less than or equal to 25nm.
In the present invention, the pore volume of the hydrated alumina containing boehmite, specific area and can and aperture, be that the described hydrated alumina containing boehmite after 4 hours in 600 DEG C of roastings, is characterized by BET N2 adsorption and obtains.
In further preferred embodiment, characterize with X diffraction, the boehmite content in described hydrated alumina PA and PB containing boehmite is not less than 50%, is more preferably not less than 60%.
The present inventor is surprised to find, hydrated alumina containing boehmite is heat-treated and obtains modifier PC, relative to the original hydrated alumina containing boehmite, the peptization index of modifier PC changes, by this modifier and PA and PB mixed-forming, dry and after roasting, the carrier obtained has obvious bimodal pore distribution.Particularly by 80-300 object particle wherein, preferred 100-200 object particle and PA and PB mixed-forming, dry and after roasting, the carrier obtained bimodal in each unimodal pore size distribution concentrated especially.Here, described 80-300 object particle, preferred 100-200 object particle refers to that described modifier is through sieve (step comprising fragmentation or grinding if desired), its screening thing (screenings) meets 80-300 object particle, the percentage (by weight) that preferred 100-200 object particle accounts for total amount is not less than 60%, is preferably not less than 70% further.Here the hydrated alumina containing boehmite can be boehmite prepared by any prior art, also can be the mixture of boehmite and other hydrated alumina, other hydrated alumina described be selected from one or more in a Water oxidize aluminium, gibbsite and amorphous hydrated aluminium oxide.In a preferred embodiment, described PC is the modifier of PA and/or PB.
In the present invention, the Mixing ratio by weight of described PA, PB and PC refers to the ratio of the shared parts by weight of PA, PB and PC difference in the mixture of every hundred parts of described PA, PB and PC.Wherein, PA:PB:PC is preferably 20-60:20-50:5-50, more preferably 30-50:35-50:10-30.
In the present invention, described PC conveniently can be obtained by following method:
Below, the method for PC is obtained with described PA and PB for initiation material illustrates.
(1) obtain PC based on drying, comprise and prepare in regular oxidation alumina supporter process by hydrated alumina PA and/or PB containing boehmite is shaping according to a conventional method, the tailing of drying by-product, such as: in extruded moulding, bar shaped article shaped is at tailing (being called dry waste material traditionally) that is dry, integer process by-product, this tailing is milled, sieves and obtain PC.
(2) obtain based on roasting, comprise and prepare in regular oxidation alumina supporter process by hydrated alumina PA and/or PB containing boehmite is shaping according to a conventional method, through the tailing (being called roasting waste material traditionally) of roasting by-product, such as, in roller forming, the tailing of spheric granules by-product in roasting process, mills this tailing, sieves and obtain PC; Or directly PA and/or PB is dodged dry obtaining, when directly dodging dry by PA and/or PB, flash-off time is preferably 0.05-1 hour, more preferably 0.1-0.5 hour.
(3) two or more be mixed to get in the modifier PC obtained based on preceding method.When adopting mixed method to obtain C, the mixed proportion of the modifier PC that aforementioned several method obtains respectively is not limited.
According to catalyst provided by the invention, wherein, described group vib metal component is preferably molybdenum and/or tungsten, more preferably molybdenum or tungsten, and VB race metal component is preferably vanadium and/or niobium, more preferably vanadium.Be benchmark with oxide basis and with catalyst, the content of described group vib metal component is preferably 0.2-15 % by weight, more preferably 0.5-12 % by weight, is more preferably 5-12 % by weight; The content of VB race metal component is preferably 0.2-12 % by weight, more preferably 0.5-9 % by weight, is more preferably 1-9 % by weight.
Be enough under the prerequisite that described hydrogenation active metals component is carried on described carrier, the present invention is not particularly limited described carrying method, preferred method is infusion process, comprises the dipping solution of preparation containing the compound of described metal, afterwards with the carrier described in this solution impregnation.Described dipping method is conventional method, such as, can be excessive immersion stain, hole saturation infusion process.One or more in the described soluble compound be selected from containing the metal component compound being selected from VI B race in them, as one or more in molybdenum oxide, molybdate, paramolybdate, preferably molybdenum oxide, ammonium molybdate, ammonium paramolybdate wherein; One or more in tungstates, metatungstate, ethyl metatungstate, preferably ammonium metatungstate, ethyl ammonium metatungstate wherein.Described containing the compound being selected from VB race metal component be selected from their soluble compound one or more, for the vanadium of VB race, can be selected from as one or more in vanadic anhydride, ammonium vanadate, ammonium metavanadate, vanadic sulfate, vanadium heteropoly acid, preferably ammonium metavanadate, ammonium vanadate wherein.
According to catalyst provided by the invention, can also the invention provides containing any impact the addO-on therapy that catalyst performance maybe can improve the catalytic performance of catalyst provided by the invention.As contained the addO-on therapy such as phosphorus, be benchmark with oxide basis and with catalyst, the content of described addO-on therapy is no more than 10 % by weight, is preferably 0.1-4 % by weight.
When in described catalyst also containing the addO-on therapy such as phosphorus time, the introducing method of described addO-on therapy can be arbitrary method, as can be by containing as described in the component such as phosphorus compound directly with as described in boehmite mix, shaping and roasting; Can be flood described carrier after the compound containing components such as described phosphorus and the compound containing hydrogenation active metals component are mixed with mixed solution; Can also be flood described carrier and roasting by after independent for the compound containing components such as phosphorus obtain solution.When the addO-on therapy such as phosphorus and hydrogenation active metals introduce described carrier respectively, preferably first use carrier described in the solution impregnation containing described addO-on therapy compound and roasting, afterwards again by the solution impregnation containing hydrogenation active metals component composition.Wherein, described sintering temperature is 400-600 DEG C, and be preferably 420-500 DEG C, roasting time is 2-6 hour, is preferably 3-6 hour.
According to hydrocarbon ils provided by the present invention (comprising residual oil) hydrotreating method, the reaction condition of the hydrotreatment of described hydrocarbon ils is not particularly limited, in a preferred embodiment, described hydrotreatment reaction condition is: reaction temperature 300-550 DEG C, preferred 330-480 DEG C further, hydrogen dividing potential drop 4-20 MPa, further preferred 6-18 MPa, volume space velocity 0.1-3.0 hour
-1, preferred 0.15-2 hour further
-1, hydrogen to oil volume ratio 200-2500, further preferred 300-2000.
The device of described hydrogenation reaction can carry out in the reactor that described feedstock oil is reacted with described catalyst exposure at hydrotreating reaction conditions in any being enough to, and such as, at described fixed bed reactors, carries out in moving-burden bed reactor or fluidized bed reactor.
According to the conventional method in this area, described hydrotreating catalyst before the use, usually can be in presence of hydrogen, presulfurization is carried out with sulphur, hydrogen sulfide or sulfur-bearing raw material at the temperature of 140-370 DEG C, this presulfurization can be carried out outside device also can be In-situ sulphiding in device, and the active metal component of its load is converted into metal sulfide component.
Catalyst provided by the invention can be used alone, and also can use with other catalyst combination, this catalyst be particularly suitable for heavy oil particularly poor residuum carry out hydrotreatment, to provide qualified feedstock oil for subsequent technique (as catalytic cracking process).Compared with prior art, catalyst provided by the invention is for having better hydrogenation diasphaltene and demetalization performance during residual hydrocracking.
Detailed description of the invention
The present invention will be further described for the following examples, but therefore should not be interpreted as limitation of the invention.
Agents useful for same in example, except as expressly described, is chemically pure reagent.
The boehmite used below in an example comprises:
PA-1: (pore volume is 0.9 ml/g to the dry glue powder that Chang Ling catalyst branch company produces, and specific surface is 280 meters
2/ gram, can and bore dia 8.5nm.Butt is 73%, and wherein boehmite content is 68%, and gibbsite content is 5 % by weight, and surplus is amorphous alumina, DI value 34.6).
PA-2: (pore volume is 0.9 ml/g to the dry glue powder of the limited production of the neat cyclopentadienyl catalyst in Zibo, and specific surface is 290 meters
2/ gram, can and bore dia 8.3nm.Butt is 73%, and wherein boehmite content is 68%, and gibbsite content is 5 % by weight, and surplus is amorphous alumina, DI value 33.2).
PB-1: (pore volume is 1.2 mls/g to the dry glue powder that Chang Ling catalyst branch company produces, and specific surface is 280 meters
2/ gram, can and bore dia 15.8nm.Butt is 73%, and wherein boehmite content is 68%, and gibbsite content is 5 % by weight, and surplus is amorphous alumina, DI value 15.8).
PB-2: (pore volume is 1.1 mls/g to the dry glue powder that Yantai Heng Hui Chemical Co., Ltd. produces, and specific surface is 260 meters
2/ gram, can and bore dia 12nm.Butt is 71%, and wherein boehmite content is 67%, and gibbsite content is 5 % by weight, and surplus is amorphous alumina, DI value 17.2).
Embodiment 1-10 illustrates PC of the present invention and preparation method thereof.
Embodiment 1
Take 1000 grams of PA-1, add the aqueous solution 1000 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product) afterwards, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar was in 120 DEG C of dryings 4 hours, and obtain dried strip, by dried strip shaping, sieve, the dried strip material (being commonly referred to as industrially drying bar waste material) length being less than 2mm is milled, and sieves, gets wherein 100 ~ 200 mesh sieves and divide, obtain the modifier PC-A1 of PA-1.The k value of PC-A1 is in table 1.
Embodiment 2
Take 1000 grams of PA-1, add the aqueous solution 1000 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product) afterwards, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar was in 120 DEG C of dryings 4 hours, and 800 DEG C of roastings 4 hours, obtain carrier, by carrier strip shaping, sieve, the carrier strip material (being commonly referred to as industrial carrier waste material) length being less than 2mm is milled, sieve, get wherein 100 ~ 200 mesh sieves and divide, obtain the modifier PC-A2 of PA-1.The k value of PC-A2 is in table 1.
Embodiment 3
Take 1000 grams of PA-2, dodge dry 6 minutes in 400 DEG C, obtain the modifier PC-A3 of PA-2.The k value of PC-A3 is in table 1.
Embodiment 4
The each 200 grams of Homogeneous phase mixing of the PC-A3 that the PC-A1 obtain embodiment 1 and embodiment 3 obtain, obtain the modifier PC-A4 of PA-1 and PA-2.The k value of PC-A4 is in table 1.
Embodiment 5
Take 1000 grams of PB-1, add the aqueous solution 1440 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product) afterwards, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar was in 120 DEG C of dryings 4 hours, and 1200 DEG C of roastings 4 hours, obtain carrier, by carrier strip shaping, sieve, the carrier strip material (being commonly referred to as industrial carrier waste material) length being less than 2mm is milled, sieve, get wherein 100 ~ 200 mesh sieves and divide, obtain the modifier PC-B1 of PB-1.The k value of PC-B1 is in table 1.
Embodiment 6
Take 1000 grams of PB-2, dodge dry 10 minutes in 650 DEG C, obtain the modifier PC-B2 of PB-2.The k value of PC-B2 is in table 1.
Embodiment 7
Take 1000 grams of PB-2, add the aqueous solution 1440 milliliters containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product) afterwards, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar was in 120 DEG C of dryings 4 hours, and obtain dried strip, by dried strip shaping, sieve, the dried strip material (being commonly referred to as industrially drying bar waste material) length being less than 2mm is milled, and sieves, gets wherein 100 ~ 200 mesh sieves and divide, obtain the modifier PC-B3 of PB-2.The k value of PC-B3 is in table 1.
Embodiment 8
The each 200 grams of Homogeneous phase mixing of the PC-B2 that the PC-B1 obtain embodiment 5 and embodiment 6 obtain, obtain the modifier PC-B4 of PB-1 and PB-2.The k value of PC-B4 is in table 1.
Embodiment 9
150 grams of PC-B3 Homogeneous phase mixing that 100 grams of PC-A1 embodiment 1 obtained and embodiment 7 obtain, obtain the modifier PC-B5 of PA-1 and PB-2.The k value of PC-B5 is in table 1.
Embodiment 10
The each 150 grams of Homogeneous phase mixing of the PC-B1 that the PC-A3 obtain embodiment 3 and embodiment 5 obtain, obtain the modifier PC-B6 of PA-2 and PB-1.The k value of PC-B6 is in table 1.
Table 1
| Embodiment | Raw material | DI | k |
| 1 | PC-A1 | 10.0 | 0.29 |
| 2 | PC-A2 | 0.9 | 0.02 |
| 3 | PC-A3 | 3.6 | 0.11 |
| 4 | PC-A4 | 6.7 | 0.20 |
| 5 | PC-B1 | 0 | 0 |
| 6 | PC-B2 | 2.1 | 0.12 |
| 7 | PC-B3 | 5.3 | 0.31 |
| 8 | PC-B4 | 1.0 | 0.06 |
| 9 | PC-B5 | 7.0 | 0.29 |
| 10 | PC-B6 | 1.6 | 0.07 |
Embodiment 11-18 illustrates bimodal hole provided by the invention carrier and preparation method thereof.Comparative example 1-4 illustrates conventional catalyst carrier and preparation method thereof.
Embodiment 11
Take each 400 grams of PA-1 and PB-1, after 200 grams of raw material PC-A2 Homogeneous phase mixing that embodiment 2 is obtained, add containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product), the aqueous solution 1300 milliliters containing titanium tetrachloride 16.6g, plunger type bar extruder is extruded into external diameter 2.5mm, the Raschig ring shape bar of internal diameter 1.0mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 900 DEG C of roastings 3 hours, obtains carrier Z1.The character of carrier Z1 lists in table 2.
Embodiment 12
Take 300 grams of PA-2,200 grams of PB-2, after 500 grams of raw material PC-B2 Homogeneous phase mixing that embodiment 6 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1300 milliliters containing titanium tetrachloride 16.6g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 900 DEG C of roastings 3 hours, obtains carrier Z2.The character of carrier Z2 lists in table 2.
Embodiment 13
Take 500 grams of PA-2,300 grams of PB-2, after 200 grams of raw material PC-B4 Homogeneous phase mixing that embodiment 8 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1300 milliliters containing titanium tetrachloride 16.6g, plunger type bar extruder is extruded into external diameter 2.5mm, the Raschig ring shape bar of internal diameter 1.0mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 950 DEG C of roastings 3 hours, obtains carrier Z3.The character of carrier Z3 lists in table 2.
Comparative example 1
Take 500 grams of PA-2,500 grams of PB-2, add after Homogeneous phase mixing containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1300 milliliters containing titanium tetrachloride 16.6g, plunger type bar extruder is extruded into external diameter 2.5mm, the Raschig ring shape bar of internal diameter 1.0mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 900 DEG C of roastings 3 hours, obtains carrier DZ1.The character of carrier DZ1 lists in table 2.
Embodiment 14
Take 250 grams of PA-1,500 grams of PB-1, after 250 grams of raw material PC-B5 Homogeneous phase mixing that embodiment 9 is obtained, add containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product), the aqueous solution 1300 milliliters containing titanium tetrachloride 29.9g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 1000 DEG C of roastings 3 hours, obtains carrier Z4.The character of carrier Z4 lists in table 2.
Comparative example 2
Take 400 grams of PA-1,600 grams of PB-1, add after Homogeneous phase mixing containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1300 milliliters containing titanium tetrachloride 29.9g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 950 DEG C of roastings 3 hours, obtains carrier DZ2.The character of carrier DZ2 lists in table 2.
Embodiment 15
Take 350 grams of PA-2,350 grams of PB-2, after 300 grams of raw material PC-B6 Homogeneous phase mixing that embodiment 10 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters containing titanium tetrachloride 29.9g, double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.4mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 1000 DEG C of roastings 3 hours, obtains carrier Z5.The character of carrier Z5 lists in table 2.
Embodiment 16
Take 200 grams of PA-1,600 grams of PB-1, after 200 grams of raw material PC-B1 Homogeneous phase mixing that embodiment 5 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters containing titanium tetrachloride 29.9g, plunger type bar extruder is extruded into external diameter 2.5mm, the Raschig ring shape bar of internal diameter 1.0mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 850 DEG C of roastings 3 hours, obtains carrier Z6.The character of carrier Z6 lists in table 2.
Embodiment 17
Take 200 grams of PA-1,600 grams of PB-1, after 200 grams of raw material PC-A4 Homogeneous phase mixing that embodiment 4 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters containing titanium tetrachloride 41.6g, plunger type bar extruder is extruded into external diameter 2.5mm, the Raschig ring shape bar of internal diameter 1.0mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 850 DEG C of roastings 3 hours, obtains carrier Z7.The character of carrier Z76 lists in table 2.
Embodiment 18
Take 200 grams of PA-1,600 grams of PB-1, after 200 grams of raw material PC-A2 Homogeneous phase mixing that embodiment 2 is obtained, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters containing titanium tetrachloride 41.6g, plunger type bar extruder is extruded into external diameter 2.5mm, the Raschig ring shape bar of internal diameter 1.0mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 850 DEG C of roastings 3 hours, obtains carrier Z8.The character of carrier Z8 lists in table 2.
Comparative example 3
According to the method that patent CN1782031A embodiment 7 provides, plunger type bar extruder is extruded into external diameter 2.5mm, the Raschig ring shape bar of internal diameter 1.0mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 900 DEG C of roastings 3 hours, obtains carrier DZ3.The character of carrier DZ3 lists in table 2.
Comparative example 4
According to the method that patent CN1120971A embodiment 1 provides, plunger type bar extruder is extruded into external diameter 2.5mm, the Raschig ring shape bar of internal diameter 1.0mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 1000 DEG C of roastings 3 hours, obtains carrier DZ4.The character of carrier DZ4 lists in table 2.
Comparative example 5
Take 200 grams of PA-1,800 grams of PB-2, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1300 milliliters containing titanium tetrachloride 41.6g, plunger type bar extruder is extruded into external diameter 2.5mm, the Raschig ring shape bar of internal diameter 1.0mm.Wet bar, in 120 DEG C of dryings 4 hours, obtains article shaped, by this article shaped 1000 DEG C of roastings 3 hours, obtains carrier DZ5.The character of carrier DZ5 lists in table 2.
Table 2
Can be seen by the result of table 2, compared with conventional method, the alumina support prepared by the method for the invention provides has obvious structure of double peak holes.
Embodiment 19-23 illustrates Catalysts and its preparation method provided by the invention.
Wherein, in catalyst, the content of active metal component adopts Xray fluorescence spectrometer to measure (all appts is Rigaku electric machine industry Co., Ltd. 3271 type Xray fluorescence spectrometer, and concrete grammar is shown in Petrochemical Engineering Analysis method RIPP133-90).
Embodiment 19
Get 200 grams of carrier Z1, with 220 milliliters containing MoO
380 grams per liters, V
2o
5ammonium heptamolybdate and the ammonium metavanadate mixed solution of 16 grams per liters flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C1, the composition of C1 is listed in table 3.
Comparative example 6
Get 200 grams of DZ1, with 220 milliliters containing MoO
380 grams per liters, ammonium heptamolybdate and the nickel nitrate mixed solution of NiO16 grams per liter flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 2 hours, obtain Hydrodemetalation catalyst DC1, the composition of DC1 is listed in table 3.
Embodiment 20
Get 200 grams of carrier Z2, with 220 milliliters containing MoO
380 grams per liters, V
2o
5ammonium heptamolybdate and the ammonium metavanadate mixed solution of 16 grams per liters flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C2, the composition of C2 is listed in table 3.
Comparative example 7
Get 200 grams of carrier DZ3, with 220 milliliters containing WO
380 grams per liters, V
2o
5ammonium heptamolybdate and the ammonium metavanadate mixed solution of 16 grams per liters flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst DC2, the composition of DC2 is listed in table 3.
Embodiment 21
Get 200 grams of carrier Z3, with 220 milliliters containing MoO
380 grams per liters, V
2o
5ammonium heptamolybdate and the ammonium metavanadate mixed solution of 16 grams per liters flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C3, the composition of C3 is listed in table 3.
Comparative example 8
Get 200 grams of carrier DZ4, with 220 milliliters containing WO
360 grams per liters, V
2o
5ammonium heptamolybdate and the ammonium metavanadate mixed solution of 60 grams per liters flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst DC3, the composition of DC3 is listed in table 3.
Embodiment 22
Get 200 grams of Z6, with 220 milliliters containing MoO
390 grams per liters, V
2o
5ammonium heptamolybdate and the ammonium metavanadate mixed solution of 20 grams per liters flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C6.The composition of Hydrodemetalation catalyst C6 is listed in table 2.
Embodiment 23
Get 200 grams of Z8, with 220 milliliters containing WO
360 grams per liters, V
2o
5ammonium tungstate and the ammonium metavanadate mixed solution of 60 grams per liters flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C8.The composition of Hydrodemetalation catalyst C8 is listed in table 2.
Comparative example 9
Get 200 grams of carrier DZ5, with 500 milliliters containing MoO
390 grams per liters, V
2o
5ammonium heptamolybdate and the ammonium metavanadate mixed solution of 20 grams per liters flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst DC4, the composition of DC4 is listed in table 3.
Table 3
Embodiment 24-28
Embodiment 24-28 illustrates the residuum hydrogenating and metal-eliminating performance of catalyst provided by the invention.
The particle respectively catalyst C1, C2, C3, C4 and C5 being broken into diameter 2-3 millimeter loads reactor.Reaction condition is: reaction temperature 380 DEG C, hydrogen dividing potential drop 14 MPa, inductive coupling plasma emission spectrograph (ICP-AES) is adopted to measure the content (instrument is U.S. PE company PE-5300 type plasma quantometer, and concrete grammar is shown in Petrochemical Engineering Analysis method RIPP124-90) of nickel and vanadium in oil before and after hydrotreatment.Asphalt compound mensuration method is adopted to analyze oily studies on asphaltene mass fraction (concrete grammar is see SH/T0509-92) before and after hydrotreatment.Calculate asphalitine and metal removal rate according to the following formula:
The normal slag of Kuwait that feedstock oil is nickel content is 29.3ppm, content of vanadium is 83ppm, sulfur content is 4.7%, nitrogen content is 0.3%, carbon residue is 15.1%.
The activity data of each catalyst is in table 4.
Comparative example 10-13
According to demetallization per and the diasphaltene rate of method evaluation catalyst DC1, DC2, DC3 and DC4 of embodiment 24-28, the results are shown in Table 4.
Table 4
| Embodiment | Catalyst is numbered | Diasphaltene rate/% | Demetallization per/% |
| 24 | C1 | 89 | 75 |
| Comparative example 10 | DC1 | 65 | 69 |
| 25 | C2 | 91 | 67 |
| Comparative example 11 | DC2 | 62 | 65 |
| 26 | C3 | 88 | 76 |
| Comparative example 12 | DC3 | 68 | 73 |
| 27 | C4 | 89 | 75 |
| 28 | C5 | 89 | 80 |
| Comparative example 13 | DC4 | 76 | 71 |
Can be seen by table 4 result, in poor residuum hydroprocessing processes, will obviously be better than existing catalyst by the diasphaltene and metal removal activity that the invention provides catalyst, illustrate that this technological invention catalyst is more suitable for the processing process of poor residuum.
Claims (26)
1. a heavy-oil hydrogenation diasphaltene catalyst, containing carrier and hydrogenation active metals component, described hydrogenation active metals component is selected from the metal component of at least one group vib and the metal component of at least one VB race, wherein, described carrier is a kind of Bimodal-pore alumina support containing IVB race metal component, characterize with mercury injection method, the pore volume of described carrier is 0.6-1.4 ml/g, and specific area is 80-400 rice
2/ gram, diameter is the 30-60% that the pore volume in 5-20nm hole accounts for total pore volume, and diameter is the 15-45% that the pore volume in 100-300nm hole accounts for total pore volume.
2. the catalyst according to 1, is characterized in that, the pore volume of described carrier is 0.7-1.3 ml/g, and specific area is 100-300 rice
2/ gram, diameter is the 35-50% that the pore volume in 5-20nm hole accounts for total pore volume, and diameter is the 20-40% that the pore volume in 100-300nm hole accounts for total pore volume.
3. the catalyst according to 1, is characterized in that, described IVB race metal component is selected from one or more in titanium, zirconium, hafnium, and with described carrier for benchmark and with oxide basis, in described carrier, the content of the IVth race's metal is 0.1-6 % by weight.
4. the catalyst according to 3, is characterized in that, described IVB race metal component is titanium, and with described carrier for benchmark and with oxide basis, in described carrier, the content of IVB race metal is 0.3-4 % by weight.
5. the catalyst according to 4, is characterized in that, with described carrier for benchmark and with oxide basis, in described carrier, the content of IVB race metal is 0.5-2.5 % by weight.
6. the catalyst according to 1, it is characterized in that, described hydrogenation active metals component is selected from the metal component of at least one group vib and the metal component of at least one VB race, be benchmark with oxide basis and with catalyst, the content of described group vib metal component is the content of 0.2-15 % by weight, VB race metal component is 0.2-12 % by weight.
7. the catalyst according to 3, it is characterized in that, the metal component of described group vib is selected from molybdenum and/or tungsten, VB race metal component is selected from vanadium and/or niobium, be benchmark with oxide basis and with catalyst, the content of described group vib metal component is the content of 0.5-12 % by weight, VB race metal component is 0.5-9 % by weight.
8. the preparation method of catalyst according to 1, comprise the alumina support containing the IVth B race metal component that preparation has structure of double peak holes, the preparation method of described carrier comprises and mix with a kind of modifier PC of the hydrated alumina containing boehmite by hydrated alumina PA and PB containing boehmite and to introduce containing the compound of the IVth B race metal component, shaping, drying also roasting in the mixture, wherein, the Mixing ratio by weight of described PA, PB and PC is 20-60:20-50:5-50, the κ value of PC is 0 to being less than or equal to 0.9, described κ=DI
2/ DI
1, DI
1for the sour peptization index of PC hydrated alumina before modified, DI
2for the sour peptization index of described PC.
9. the method according to 8, is characterized in that, the Mixing ratio by weight of described PA, PB and PC is 30-50:35-50:10-30.
10. the method according to 8, it is characterized in that, described IVth B race metal is selected from one in titanium, zirconium, hafnium and composition thereof, and be benchmark with oxide basis and with carrier, the described introduction volume containing the IVth B race metallic compound makes the content of the IVth B race metal in final carrier be 0.1-6 % by weight.
11. methods according to 10, it is characterized in that, described IVth B race metal is titanium, is benchmark with oxide basis and with carrier, and the described introduction volume containing the IVth B race metallic compound makes the content of the IVth B race metal in final carrier be 0.3-4 % by weight.
12. methods according to 8, is characterized in that, the k value of described PC is 0 to being less than or equal to 0.6.
13. methods according to 8 or 9, is characterized in that, the pore volume of the described hydrated alumina PA containing boehmite is 0.75-1 ml/g, and specific surface is 200-450 rice
2/ gram, can and bore dia 3-10nm; The pore volume of the described hydrated alumina PB containing boehmite is 0.9-1.4 ml/g, and specific surface is 100-350 rice
2/ gram, can and bore dia be greater than 10 to being less than or equal to 30nm.
14. methods according to 13, is characterized in that, the pore volume of the described hydrated alumina PA containing boehmite is 0.80-0.95 ml/g, and specific surface is 200-400 rice
2/ gram, can and bore dia 5-10nm; The pore volume of the described hydrated alumina PB containing boehmite is 0.95-1.3 ml/g, and specific surface is 120-300 rice
2/ gram, can and bore dia be greater than 10 to being less than or equal to 25nm.
15. methods according to 8 or 9, it is characterized in that, described PC is 80-300 object particle.
16. methods according to 15, it is characterized in that, described PC is 100-200 object particle.
17. methods according to 8, it is characterized in that, the condition of described drying comprises: temperature is 40-350 DEG C, and the time is 1-24 hour, and the condition of described roasting comprises: temperature is for being greater than 500 to being less than or equal to 1200 DEG C, and the time is 1-8 hour.
18. methods according to 17, it is characterized in that, the condition of described drying comprises: temperature is 100-200 DEG C, and the time is 2-12 hour, and the condition of described roasting comprises: temperature is for being greater than 800 to being less than or equal to 1000 DEG C, and roasting time is for being 2-6 hour.
19. methods according to 8, it is characterized in that, by shaping, dry for the described hydrated alumina containing boehmite by one of hydrated alumina method being modified as PC containing boehmite, afterwards its all or part of carrying out is ground, sieves, the condition of described drying comprises: temperature is 40-350 DEG C, and the time is 1-24 hour; Two of method is article shaped roastings method one obtained, and sintering temperature is for being greater than 350 to being less than or equal to 1400 DEG C, and roasting time is 1-8 hour, afterwards its all or part of carrying out is ground, is sieved; Three of method is dodged by the hydrated alumina containing boehmite to do, and dodge dry temperature for being greater than 150 to being less than or equal to 1400 DEG C, flash-off time is 0.05-1 hour; Four of method is mixed to get one or more in two and the modifier that obtains with three of method of one of method, method.
20. methods according to 19, it is characterized in that, the condition of the drying in described method one comprises: temperature is 100-200 DEG C, and the time is 2-12 hour; Method two in sintering temperature be 500-1200 DEG C, roasting time is 0.1-6 hour; Method three in sudden strain of a muscle to do temperature be 200-1000 DEG C, flash-off time is 0.1-0.5 hour.
21. methods according to 19, is characterized in that, described PC is 80-300 object particle in the modifier of hydrated alumina containing boehmite.
22. methods according to 21, is characterized in that, described PC is 100-200 object particle in the modifier of hydrated alumina containing boehmite.
23. methods according to 8, it is characterized in that, described method is included in described supported on carriers hydrogenation active metals component, the method of the component of load hydrogenation active metals is on the carrier infusion process, comprise preparation contain the solution of the compound of hydrogenation active metals and use this solution impregnating carrier, carry out drying afterwards, roasting or not roasting, described hydrogenation active metals component is selected from metal component and at least one VB race metal component of at least one group vib, be benchmark with oxide basis and with catalyst, the concentration of described maceration extract and consumption make the content of group vib metal component described in final catalyst be 0.2-15 % by weight, the content of VB race metal component is 0.2-12 % by weight, described drying condition is: temperature 80-200 DEG C, time 1-8 hour, roasting condition is: temperature 400-600 DEG C, time 2-8 hour.
24. methods according to 23, it is characterized in that, the metal component of described group vib is selected from molybdenum and/or tungsten, VB race metal component is selected from vanadium and/or niobium, be benchmark with oxide basis and with catalyst, the concentration of described maceration extract and consumption make the content of group vib metal component described in final catalyst be 0.5-12 % by weight, the content of VB race metal component is 0.5-9 % by weight, described drying condition is: temperature 100-150 DEG C, time 2-6 hour, roasting condition is: temperature 420-500 DEG C, time 3-6 hour.
25. methods according to 24, it is characterized in that, be benchmark with oxide basis and with catalyst, it is 1-9 % by weight that the concentration of described maceration extract and consumption make the content of group vib metal component described in final catalyst be the content of 5-12 % by weight, VB race metal component.
The application of catalyst in 26. claim 1-7 described in any one in hydrocarbon oil hydrogenation process.
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| CN109569575A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Catalyst with hydrogenation catalyst effect and its preparation method and application and heavy-oil hydrogenation depitching matter method |
| CN114308090A (en) * | 2022-01-14 | 2022-04-12 | 中化泉州石化有限公司 | Hierarchical pore hydrotreating catalyst and preparation method thereof |
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| CN106944099B (en) * | 2016-01-07 | 2019-06-11 | 中国石油化工股份有限公司 | A kind of preparation method of hydrotreating catalyst |
| CN109569575A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Catalyst with hydrogenation catalyst effect and its preparation method and application and heavy-oil hydrogenation depitching matter method |
| CN109569575B (en) * | 2017-09-29 | 2021-12-17 | 中国石油化工股份有限公司 | Catalyst with hydrogenation catalysis effect, preparation method and application thereof, and heavy oil hydrogenation asphaltene removal method |
| CN114308090A (en) * | 2022-01-14 | 2022-04-12 | 中化泉州石化有限公司 | Hierarchical pore hydrotreating catalyst and preparation method thereof |
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