CN104368347A - Hydrogenation activity protection catalyst and preparation and use thereof - Google Patents
Hydrogenation activity protection catalyst and preparation and use thereof Download PDFInfo
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- CN104368347A CN104368347A CN201310354120.7A CN201310354120A CN104368347A CN 104368347 A CN104368347 A CN 104368347A CN 201310354120 A CN201310354120 A CN 201310354120A CN 104368347 A CN104368347 A CN 104368347A
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Abstract
The invention discloses a hydrogenation activity protection catalyst and preparation and use thereof, the hydrogenation activity protection catalyst comprises a carrier and a hydrogenation activity metal component loaded on the carrier, the hydrogenation activity metal component is selected from at least one VIIIB family metal component and at least one VB metal component, the carrier is an alkaline earth metal component-containing dual-peak pore alumina carrier which is characterized by the mercury injection method, the carrier pore volume is 0.6-1.4 ml / g, the specific surface area is 80-400 m <2> / g, the volume of the pore with the diameter of 5-20nm accounts for 30-55% of the total pore volume, and the volume of the pore with the diameter of 100-300nm accounts for 15-45% of the total pore volume. Compared with the prior art, the hydrogenation activity protection catalyst has better hydrogenation metal removal performance.
Description
Technical field
The present invention relates to a kind of hydrogenation activity guard catalyst and preparation and application thereof.
Background technology
Along with the aggravation of crude oil heaviness, in poor quality trend, crude oil difficulty of processing strengthen, light oil yield reduce, and market to the demand of high grade light-end products in continuous increase, environmental regulation is also more and more tending towards strict.At present, the processing and making full use of of heavy oil especially residual oil just becomes the staple of conversation that global Oil Refining Industry is paid close attention to, and residual hydrogenation technology is a kind of widely used processing technology in processing of heavy oil technique, is generally acknowledged economic environment-friendly type deep process technology.Containing metal impurities and solid impurities such as a large amount of Ni, V, Fe, Ca in residual oil, if this part impurity can not effectively be removed, downstream hydrogenation catalyst can be had a negative impact, be easy to make downstream catalyst inactivation.One of effective way addressed this problem is the protective agent in the filling of hydrogenation catalyst top with hydrogenation activity, and therefore developing metal removal activity protective agent that is high, that hold metal ability strong is one of key technology of heavy-oil hydrogenation process.In prior art, the disclosed example about hydrogenation activity guard catalyst and preparation method thereof comprises:
CN101890381A discloses a kind of hydrotreating guard catalyst for residual oil and application thereof.This catalyst pore volume is large, and aperture is large, and porosity is high, reasonable pore distribution, and outer surface orifice is comparatively large, and duct penetrability is good, and more than 1000nm contains more than 36% in duct.
CN00124903.7 discloses a kind of hydrogenation protecting catalyst; this catalyst contains a kind of alumina support and load molybdenum on the alumina support and/or tungsten and nickel and/or cobalt; wherein; total ammonia integral heat of adsorption of described alumina support is not more than 25 joule/gram, and the percentage that the ammonia integral heat of adsorption that ammonia differential heat of adsorption is greater than 100 kj/mol accounts for total ammonia integral heat of adsorption is not more than 10%.
Patent CN98111379.6 discloses a kind of hydrogenation protecting catalyst and preparation method thereof, and catalyst carrier is ultra-large aperture, and aperture is the bimodal hole of 0.1-30 μm, and catalyst pore volume is 0.1-0.8ml/g, specific surface 0.1-20m
2/ g, containing VI B race metallic element 6.65m%-20.0m% and/or VIII race metallic element 8.7m1% ,-26.13m%.Preparation method adopts particle to pile up legal system for alumina support, then adopts containing molybdenum solution and solution containing nickel equivalent impregnation, and the catalyst after dipping, at 100-120 DEG C of dry 2-5h, configures roast 2-5h at 500-550 DEG C.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of new hydrogenation activity guard catalyst, the preparation method of this hydrogenation activity guard catalyst and application.
The present invention relates to following content:
1. a hydrogenation activity guard catalyst; containing carrier and load hydrogenation active metals component on this carrier; described hydrogenation active metals component is selected from the metal component that the metal component of at least one VIII race and at least one are selected from VB race; described carrier is a kind of Bimodal-pore alumina support of alkaline including earth 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 30-55% 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 alkaline earth metal component is selected from one or more in beryllium, magnesium, calcium, strontium and barium, is benchmark with oxide basis and with carrier, and the content of described alkaline earth metal component is 0.1-6 % by weight.
4. the catalyst according to 3, is characterized in that, described alkaline earth metal component is magnesium or calcium, is benchmark with oxide basis and with carrier, and the content of described alkaline earth metal component is 0.3-4 % by weight.
5. the catalyst according to 4, is characterized in that, is benchmark in element and with carrier, and the content of described alkaline-earth metal is 0.5-2.5 % by weight.
6. the hydrogenation activity guard catalyst according to 1; it is characterized in that; described metal component of group VIII is selected from cobalt and/or nickel; the metal component of VB race is selected from vanadium and/or niobium; be benchmark with oxide basis and with catalyst; the content of described VIII race's metal component is greater than 0 to being less than or equal to 0.8 % by weight, and the content of the Vth B race metal component is greater than 0 to being less than or equal to 4 % by weight.
7. the hydrogenation activity guard catalyst according to 6, is characterized in that, is benchmark with oxide basis and with catalyst, and the content of described VIII race's metal component is 0.1-0.6 % by weight, and the content of the Vth B race metal component is 1.5-3.5 % by weight.
8. the preparation method of the hydrogenation activity guard catalyst according to 1; comprise the alumina support that preparation has the alkaline including earth metal component of structure of double peak holes; the preparation method of described carrier comprises hydrated alumina PA and PB containing boehmite is mixed the compound also introducing alkaline including earth metal in the mixture, shaping, dry also roasting with a kind of modifier PC of the hydrated alumina containing boehmite; 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 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; The k value of described PC is 0 to being less than or equal to 0.6; 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, most probable 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, most probable bore dia is greater than 10 to being less than or equal to 30nm; With oxide basis and with described carrier for benchmark, the introduction volume of the compound of described alkaline including earth metal makes the content of alkaline earth metal component in final carrier be 0.1-6 % by weight.
10. the method according to 9, 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, most probable 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, most probable bore dia is greater than 10 to being less than or equal to 25nm; With oxide basis and with described carrier for benchmark, the introduction volume of the compound of described alkaline including earth metal makes the content of alkaline earth metal component in final carrier be 0.3-4 % by weight.
11. methods according to 10, it is characterized in that, with oxide basis and with described carrier for benchmark, the introduction volume of the compound of described alkaline including earth metal makes the content of alkaline earth metal component in final carrier be 0.5-2.5 % by weight.
12. methods according to 8 or 9, it is characterized in that, described PC is 80-300 object particle.
13. methods according to 12, it is characterized in that, described PC is 100-200 object particle.
14. 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.
15. methods according to 14, 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.
16. 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.
17. methods according to 16, 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.
18. methods according to 8 or 16, is characterized in that, described PC is 80-300 object particle in the modifier of hydrated alumina containing boehmite.
19. methods according to 18, is characterized in that, described PC is 100-200 object particle in the modifier of hydrated alumina containing boehmite.
20. methods according to 8, it is characterized in that, be included in described supported on carriers hydrogenation active metals component, the described method in supported on carriers hydrogenation active metals component is 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 the metal component of at least one the VIIIth race and the metal component of at least one VB race, be benchmark with oxide basis and with catalyst, the described compound containing hydrogenation active metals makes the content of the metal component of the VIIIth race in final catalyst for being greater than 0 to being less than or equal to 0.8 % by weight in the concentration of described solution and the consumption of described solution, the content of the metal component of described VB race is for being greater than 0 to being less than or equal to 4 % by weight, described drying condition comprises: temperature is 100-250 DEG C, and the time is 1-10 hour, described roasting condition comprises: temperature is 360-500 DEG C, and the time is 1-10 hour.
21. methods according to 20, it is characterized in that, the metal component of described VIIIth race is selected from nickel and/or cobalt, the metal component of VB race is selected from vanadium and/or niobium, be benchmark with oxide basis and with catalyst, the described compound containing hydrogenation active metals makes the content of the metal component of group VIII in final catalyst be 0.2-0.6 % by weight in the concentration of described solution and the consumption of described solution, and the content of the metal component of VB race is 1.5-3.5 % by weight; Described drying condition comprises: temperature is 100-140 DEG C.
The application of hydrogenation activity guard catalyst in hydrocarbon oil hydrogenation process in 22. claim 1-7 described in any one.
According to catalyst provided by the invention, require that carrier wherein can be made into the various article shaped being easy to operate depending on different, 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.The method introducing the compound of alkaline including earth metal in described PA, PB and PC mixture is conventional method, such as, can be directly be mixed in aforesaid PA, PB and PC mixed process by the compound of the alkaline including earth metal of aequum.
Concrete prepare in the embodiment of carrier at one, the method introducing the compound of alkaline including earth metal in the mixture of described PA, PB and PC is that the compound of alkaline including earth metal is mixed with the aqueous solution, 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 compound of described alkaline including earth metal can be one or more in the water soluble compound of arbitrary alkaline including earth metal.Such as, one or more in the water-soluble inorganic salt of alkaline-earth metal.
In the present invention, describedly shapingly can 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.
After sour peptization index D I in the preparation of described carrier refers to that the hydrated alumina containing boehmite adds 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
2be respectively intend thin water aluminium and acid reaction front 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, most probable bore dia 3-10nm, preferably pore volume is 0.80-0.95 ml/g further, and specific surface is 200-400 rice
2/ gram, most probable 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, most probable bore dia is greater than 10 to being less than or equal to 30nm, and preferably pore volume is 0.95-1.3 ml/g further, and specific surface is 120-300 rice
2/ gram, most probable bore dia is 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 most probable pore size are that the described hydrated alumina containing boehmite after 4 hours in 600 DEG C of roastings, is characterized by BET N2 adsorption and obtained.
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 hydrogenation protecting catalyst provided by the invention; wherein; the preferred metal component of group VIII of described hydrogenation active metals component is cobalt and/or nickel; the metal component of VB race is vanadium and/or niobium; be benchmark with oxide basis and with catalyst; the content of described metal component of group VIII is for being greater than 0 to being less than or equal to 0.8 % by weight; preferred 0.1-0.7 % by weight; more preferably 0.2-0.6 % by weight; the content of described VB race metal component is for being greater than 0 to being less than or equal to 4 % by weight; preferred 1-4 % by weight, more preferably 1.5-3.5 % 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 V B race in them, such as, 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.Described containing the compound being selected from VIII race's metal component be selected from their soluble compound one or more, as one or more in the soluble complexes of cobalt nitrate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and cobalt, be preferably cobalt nitrate, basic cobaltous carbonate; One or more in the soluble complexes of nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and nickel, are preferably nickel nitrate, basic nickel carbonate.
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 the Hydrogenation active protective agent provided with prior art, it is active that Hydrogenation active protective agent provided by the invention has good HDM while having GPF (General Protection False agent function.
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, most probable 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, most probable 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, most probable 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, most probable 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 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 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 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 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 1-5 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 obtained with embodiment 2 mix, add containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product), the aqueous solution 1300 milliliters containing 12.91g magnesium nitrate, 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 obtained with embodiment 6 mix, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1300 milliliters containing 12.91g magnesium nitrate, 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 obtained with embodiment 8 mix, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1300 milliliters containing 10.25g calcium nitrate, 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 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 mixing containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1300 milliliters containing 12.91g magnesium nitrate, 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 obtained with embodiment 9 mix, add containing 10 milliliters, nitric acid (Tianjin chemical reagent three factory product), the aqueous solution 1300 milliliters containing 26.19g magnesium nitrate, 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 Z4.The character of carrier Z4 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 obtained with embodiment 10 mix, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters containing 26.19g magnesium nitrate, 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 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 obtained with embodiment 5 mix, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters containing 26.19g magnesium nitrate, 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.
Comparative example 2
Take 400 grams of PA-1,600 grams of PB-1, add after mixing containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1300 milliliters containing 26.19g magnesium nitrate, 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 DZ2.The character of carrier DZ2 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 obtained with embodiment 4 mix, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution aqueous solution 1440 milliliters containing 52.93 magnesium nitrates, 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 Z7 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 obtained with embodiment 2 mix, add containing nitric acid Tianjin chemical reagent three factory product) 10 milliliters, the aqueous solution 1440 milliliters containing 42.02 calcium nitrate, 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 DZ3.The character of carrier DZ3 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 42.02 calcium oxide, 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, that is prepared by the method for the invention provides has obvious structure of double peak holes containing magnesium or calcium alumina support.
Embodiment 19-24 illustrates Catalysts and its preparation method provided by the invention.
Embodiment 19
Get 200 grams of carrier Z1, with 220 milliliters containing V
2o
528.6 grams per liters, ammonium metavanadate and the nickel nitrate mixed solution of NiO5 grams per liter flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst C1.The composition of C1 is listed in table 3.
Embodiment 20
Get 200 grams of carrier Z2, with 220 milliliters containing V
2o
528.6 grams per liters, ammonium metavanadate and the cobalt nitrate mixed solution of CoO5 grams per liter flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst C2.The composition of C2 is listed in table 3.
Embodiment 21
Get 200 carrier Z3, with 220 milliliters containing V
2o
525 grams per liters, ammonium metavanadate and the nickel nitrate mixed solution of NiO3 grams per liter flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst C3.The composition of C3 is listed in table 3.
Embodiment 22
Get 200 grams of carrier Z4, with 220 milliliters containing V
2o
525 grams per liters, ammonium metavanadate and the cobalt nitrate mixed solution of CoO3 grams per liter flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst C4.The composition of C4 is listed in table 3.
Embodiment 23
Get 200 grams of carrier Z5, with 220 milliliters containing V
2o
519.0 grams per liters, ammonium metavanadate and the nickel nitrate mixed solution of NiO2 grams per liter flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst C5.The composition of C5 is listed in table 3.
Embodiment 24
Get 200 grams of carrier Z8, with 220 milliliters containing V
2o
519.0 grams per liters, ammonium metavanadate and the nickel nitrate mixed solution of NiO2 grams per liter flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst C6.The composition of C6 is listed in table 3.
Contrast row 6
Get 200 grams of carrier DZ1, with 220 milliliters containing V
2o
528.6 grams per liters, ammonium metavanadate and the nickel nitrate mixed solution of NiO5 grams per liter flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst DC1.The composition of DC1 is listed in table 3.
Contrast row 7
Get 200 grams of carrier DZ2, with 220 milliliters containing WO
328.6 grams per liters, ammonium metatungstate and the nickel nitrate mixed solution of NiO5 grams per liter flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst DC2.The composition of DC2 is listed in table 3.
Comparative example 8
Get 200 grams of carrier DZ3, with 220 milliliters containing V
2o
525 grams per liters, ammonium metavanadate and the nickel nitrate mixed solution of NiO3 grams per liter flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst DC3.The composition of DC3 is listed in table 3.
Comparative example 9
Get 200 grams of carrier DZ4, with 220 milliliters containing MoO
325 grams per liters, ammonium molybdate and the cobalt nitrate mixed solution of CoO3 grams per liter flood 1 hour, and dry 4 hours for 120 DEG C, 400 DEG C of roastings 3 hours, obtain hydrogenation activity guard catalyst DC4.The composition of DC4 is listed in table 3.
Table 3
In catalyst, the content of each metal component is calculated value.
Embodiment 25-30
Embodiment 25-30 illustrates demetallization per and the desulfurization degree of hydrogenation protecting catalyst provided by the invention.
With the normal slag of Yi Chong for raw material (feedstock oil character is in table 4), 100 milliliters of small fixed reactors evaluate protective agent.
Catalyst C1, C2, C3, C4, C5 and C6 are broken into the particle of diameter 2-3 millimeter, catalyst loading amount is 100 milliliters.Reaction condition is: reaction temperature 380 DEG C, hydrogen dividing potential drop 14 MPa, liquid hourly space velocity (LHSV) are 0.7 hour
-1, hydrogen to oil volume ratio is 1000, reacts sample analysis after 200 hours.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 metal in oil before and after hydrotreatment.Calculate metal removal rate according to the following formula:
Feedstock oil character lists in table 4, and evaluation result is listed in table 5.
Comparative example 10-13
According to the demetallization per of method evaluation catalyst DC1, DC2, DC3 and DC4 of embodiment 25-30, the results are shown in Table 5.
Table 4
| Feedstock oil title | The normal slag of Yi Chong |
| Density (20 DEG C), kg/m 3 | 0.966 |
| Mean molecule quantity | 452 |
| Ni，μg/g | 47.7 |
| V，μg/g | 133 |
| Fe，μg/g | 8.4 |
| Ca，μg/g | 29.5 |
Table 5 protective agent evaluation result
Can find out compared with existing catalyst by the data of table 5, hydrogenation protecting agent provided by the invention has higher demetallization per.
Claims (22)
1. a hydrogenation activity guard catalyst; containing carrier and load hydrogenation active metals component on this carrier; described hydrogenation active metals component is selected from the metal component that the metal component of at least one VIII race and at least one are selected from VB race; described carrier is a kind of Bimodal-pore alumina support of alkaline including earth 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 30-55% 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 alkaline earth metal component is selected from one or more in beryllium, magnesium, calcium, strontium and barium, is benchmark with oxide basis and with carrier, and the content of described alkaline earth metal component is 0.1-6 % by weight.
4. the catalyst according to 3, is characterized in that, described alkaline earth metal component is magnesium or calcium, is benchmark with oxide basis and with carrier, and the content of described alkaline earth metal component is 0.3-4 % by weight.
5. the catalyst according to 4, is characterized in that, is benchmark in element and with carrier, and the content of described alkaline-earth metal is 0.5-2.5 % by weight.
6. the hydrogenation activity guard catalyst according to 1; it is characterized in that; described metal component of group VIII is selected from cobalt and/or nickel; the metal component of VB race is selected from vanadium and/or niobium; be benchmark with oxide basis and with catalyst; the content of described VIII race's metal component is greater than 0 to being less than or equal to 0.8 % by weight, and the content of the Vth B race metal component is greater than 0 to being less than or equal to 4 % by weight.
7. the hydrogenation activity guard catalyst according to 6, is characterized in that, is benchmark with oxide basis and with catalyst, and the content of described VIII race's metal component is 0.1-0.6 % by weight, and the content of the Vth B race metal component is 1.5-3.5 % by weight.
8. the preparation method of the hydrogenation activity guard catalyst according to 1; comprise the alumina support that preparation has the alkaline including earth metal component of structure of double peak holes; the preparation method of described carrier comprises hydrated alumina PA and PB containing boehmite is mixed the compound also introducing alkaline including earth metal in the mixture, shaping, dry also roasting with a kind of modifier PC of the hydrated alumina containing boehmite; 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 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; The k value of described PC is 0 to being less than or equal to 0.6; 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, most probable 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, most probable bore dia is greater than 10 to being less than or equal to 30nm; With oxide basis and with described carrier for benchmark, the introduction volume of the compound of described alkaline including earth metal makes the content of alkaline earth metal component in final carrier be 0.1-6 % by weight.
10. the method according to 9, 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, most probable 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, most probable bore dia is greater than 10 to being less than or equal to 25nm; With oxide basis and with described carrier for benchmark, the introduction volume of the compound of described alkaline including earth metal makes the content of alkaline earth metal component in final carrier be 0.3-4 % by weight.
11. methods according to 10, it is characterized in that, with oxide basis and with described carrier for benchmark, the introduction volume of the compound of described alkaline including earth metal makes the content of alkaline earth metal component in final carrier be 0.5-2.5 % by weight.
12. methods according to 8 or 9, it is characterized in that, described PC is 80-300 object particle.
13. methods according to 12, it is characterized in that, described PC is 100-200 object particle.
14. 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.
15. methods according to 14, 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.
16. 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.
17. methods according to 16, 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.
18. methods according to 8 or 16, is characterized in that, described PC is 80-300 object particle in the modifier of hydrated alumina containing boehmite.
19. methods according to 18, is characterized in that, described PC is 100-200 object particle in the modifier of hydrated alumina containing boehmite.
20. methods according to 8, it is characterized in that, be included in described supported on carriers hydrogenation active metals component, the described method in supported on carriers hydrogenation active metals component is 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 the metal component of at least one the VIIIth race and the metal component of at least one VB race, be benchmark with oxide basis and with catalyst, the described compound containing hydrogenation active metals makes the content of the metal component of the VIIIth race in final catalyst for being greater than 0 to being less than or equal to 0.8 % by weight in the concentration of described solution and the consumption of described solution, the content of the metal component of described VB race is for being greater than 0 to being less than or equal to 4 % by weight, described drying condition comprises: temperature is 100-250 DEG C, and the time is 1-10 hour, described roasting condition comprises: temperature is 360-500 DEG C, and the time is 1-10 hour.
21. methods according to 20, it is characterized in that, the metal component of described VIIIth race is selected from nickel and/or cobalt, the metal component of VB race is selected from vanadium and/or niobium, be benchmark with oxide basis and with catalyst, the described compound containing hydrogenation active metals makes the content of the metal component of group VIII in final catalyst be 0.2-0.6 % by weight in the concentration of described solution and the consumption of described solution, and the content of the metal component of VB race is 1.5-3.5 % by weight; Described drying condition comprises: temperature is 100-140 DEG C.
The application of hydrogenation activity guard catalyst in hydrocarbon oil hydrogenation process in 22. claim 1-7 described in any one.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0098764A1 (en) * | 1982-06-17 | 1984-01-18 | Société Française des Produits pour Catalyse "PRO-CATALYSE" | Supported catalyst with resistance against metal poisoning, and its use in the hydrotreatment of petroleum fractions containing metal |
| CN1289825A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Carrier of hydrogenating catalyst for heavy oil and its preparing process |
| CN1690172A (en) * | 2004-04-29 | 2005-11-02 | 中国石油化工股份有限公司 | Hydrodemetalization catalyst for residual oil and process for preparing same |
| CN102649070A (en) * | 2011-02-24 | 2012-08-29 | 中国石油化工股份有限公司 | Hydrogenated active protective agent taking alumina containing alkali earth metals as carrier, as well as preparation and application of hydrogenated active protective agent |
-
2013
- 2013-08-14 CN CN201310354120.7A patent/CN104368347B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0098764A1 (en) * | 1982-06-17 | 1984-01-18 | Société Française des Produits pour Catalyse "PRO-CATALYSE" | Supported catalyst with resistance against metal poisoning, and its use in the hydrotreatment of petroleum fractions containing metal |
| CN1289825A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Carrier of hydrogenating catalyst for heavy oil and its preparing process |
| CN1690172A (en) * | 2004-04-29 | 2005-11-02 | 中国石油化工股份有限公司 | Hydrodemetalization catalyst for residual oil and process for preparing same |
| CN102649070A (en) * | 2011-02-24 | 2012-08-29 | 中国石油化工股份有限公司 | Hydrogenated active protective agent taking alumina containing alkali earth metals as carrier, as well as preparation and application of hydrogenated active protective agent |
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