CN102649069B - With the Hydrogenation active protective agent that is carrier containing IVB race burning aluminium, preparation and application thereof - Google Patents
With the Hydrogenation active protective agent that is carrier containing IVB race burning aluminium, preparation and application thereof Download PDFInfo
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Abstract
A kind of with the Hydrogenation active protective agent that is carrier containing IVB race burning aluminium, preparation and application thereof; this protective agent contains containing IVB race burning alumina supporter and load hydrogenation active metals component on this carrier; it is characterized in that; described hydrogenation active metals component is at least one metal component that is selected from VIII race and the combination of at least one metal component being selected from VB race; be benchmark with oxide basis and with protective agent; the content of described VIII race's metal component is the content of 0.2-15 % by weight, VB race metal component is 0.2-15 % by weight.Compared with the hydrogenation protecting agent provided with prior art, it is active that hydrogenation protecting agent provided by the invention has better HDM.
Description
Technical field
The present invention relates to a kind of Hydrogenation active protective agent, 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.
Summary of the invention
The technical problem to be solved in the present invention be to provide a kind of newly, the Hydrogenation active protective agent with higher HDM activity, the preparation of this catalyst and application thereof.
The present invention relates to following invention:
1, to contain the Hydrogenation active protective agent that IVB race burning aluminium is carrier; containing containing IVB race burning alumina supporter and load hydrogenation active metals component on this carrier; it is characterized in that; described hydrogenation active metals component is at least one metal component that is selected from VIII race and the combination of at least one metal component being selected from VB race; be benchmark with oxide basis and with protective agent; the content of described VIII race's metal component is the content of 0.2-15 % by weight, VB race metal component is 0.2-15 % by weight.
2, the protective agent according to 1; it is characterized in that; one or more in the metal component chosen from Fe of described VIII race, cobalt, nickel; VB race metal component is selected from vanadium and/or niobium; be benchmark with oxide basis and with protective agent; the content of described VIII race's metal component is the content of 0.5-8 % by weight, VB race metal component is 0.5-10 % by weight.
3, the protective agent according to 2, is characterized in that, the metal component of described VIII race is cobalt or nickel; VB race metal component is vanadium; be benchmark with oxide basis and with protective agent, the content of described VIII race's metal component is the content of 0.5-3 % by weight, VB race metal component is 1-8 % by weight.
4, the protective agent according to 1; it is characterized in that; described containing IVB race burning aluminium be selected from containing IVB race metal have γ-, η-, θ-, δ-and χ-the aluminium oxide of single or multiphase; described IVB race metal is titanium; with oxide basis and with described carrier for benchmark, in described carrier, the content of IVB race metal is 0.1-6 % by weight.
5, the protective agent according to 4; it is characterized in that; described containing IVB race burning aluminium be selected from containing IVB race metal have γ-, η-, θ-and δ-the aluminium oxide of single or multiphase; with oxide basis and with described carrier for benchmark, in described carrier, the content of IVB race metal is 0.3-4 % by weight.
6, the protective agent according to 5, is characterized in that, with oxide basis and with described carrier for benchmark, in described carrier, the content of IVB race metal is 0.5-2 % by weight.
7, a kind of preparation method of the Hydrogenation active protective agent to be carrier containing IVB race burning aluminium; be included in containing load hydrogenation active metals component on IVB race burning alumina supporter; it is characterized in that; described hydrogenation active metals component is at least one metal component that is selected from VIII race and the combination of at least one metal component being selected from VB race; be benchmark with oxide basis and with catalyst; it is 0.2-15 % by weight that the consumption of each component makes the content of the described VIII race's metal component in described catalyst be the content of 0.2-15 % by weight, VB race metal component.
8, the method according to 7, it is characterized in that, one or more in the metal component chosen from Fe of described VIII race, cobalt, nickel, VB race metal component is selected from vanadium and/or niobium, be benchmark with oxide basis and with catalyst, it is 0.5-10 % by weight that the consumption of each component makes the content of described VIII race's metal component be the content of 0.5-8 % by weight, VB race metal component.
9, the method according to 8, it is characterized in that, the metal component of described VIII race is molybdenum or tungsten, VB race metal component is vanadium, be benchmark with oxide basis and with catalyst, it is 1-8 % by weight that the consumption of each component makes the content of described VIII race's metal component be the content of 0.5-3 % by weight, VB race metal component.
10, the method according to 7, it is characterized in that, described containing IVB race burning aluminium be selected from containing IVB race metal have γ-, η-, θ-, δ-and χ-the aluminium oxide of single or multiphase, described IVB race metal is titanium, with oxide basis and with described carrier for benchmark, in described carrier, the content of IVB race metal is 0.1-6 % by weight.
11, the method according to 10, it is characterized in that, described containing IVB race burning aluminium be selected from containing IVB race metal have γ-, η-, θ-and δ-the aluminium oxide of single or multiphase, with oxide basis and with described carrier for benchmark, in described carrier, the content of IVB race metal is 0.3-4 % by weight.
12, the method according to 11, is characterized in that, with oxide basis and with described carrier for benchmark, in described carrier, the content of IVB race metal is 0.5-2 % by weight.
13, the method according to 7,10,11 or 12 any one, it is characterized in that, described is the article shaped containing IVB race burning aluminium containing IVB race burning alumina supporter, described article shaped by comprise by the precursor of aluminium oxide and/or aluminium oxide with containing IVB race metallic compound, water, help forming agent to contain or do not carry out mixing containing peptizing agent, prepared by shaping, the dry and method of roasting, described drying condition is: temperature 40-350 DEG C, time is 1-24 hour, roasting condition is: temperature 350-1000 DEG C, and the time is 1-10 hour.
14, the method according to 13, is characterized in that, described forming method is extruded moulding, and described drying condition is: temperature 100-200 DEG C, and the time is 2-12 hour, and roasting condition is: temperature 600-950 DEG C, and the time is 2-6 hour.
15, the method according to 7, is characterized in that, described is infusion process at supported on carriers hydrogenation active metals multi-component approach, comprising: a) preparation contains the solution of VIII race's metallic compound and VB race metallic compound; B) solution impregnation of alumina carrier using step a) to prepare; C) dry and calcination steps b) impregnation product that obtains; Wherein, be benchmark with oxide basis and with catalyst, the concentration of described maceration extract and consumption make the content of VIII race's metal component described in final catalyst be 0.5-15 % by weight, the content of VB race metal component is 0.2-15 % 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.
16, the method according to 15, it is characterized in that, be benchmark with oxide basis and with catalyst, the concentration of described maceration extract and consumption make the content of VIII race's metal component described in final catalyst be 0.5-8 % by weight, the content of VB race metal component is 0.5-10 % by weight, and 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.
17, the method according to 16, it is characterized in that, be benchmark with oxide basis and with catalyst, it is 1-8 % by weight that the concentration of described maceration extract and consumption make the content of VIII race's metal component described in final catalyst be the content of 0.5-3 % by weight, VB race metal component.
18, a kind of heavy oil hydrogenation treatment method; be included in heavy raw oil and catalyst exposure under heavy-oil hydrogenation processing reaction condition; it is characterized in that, described catalyst comprises Hydrogenation active protective agent, and described Hydrogenation active protective agent is the catalyst described in aforementioned any one of 1-6.
According to catalyst provided by the invention, wherein, described containing IVB race burning aluminium can be containing IVB race metal have γ-, η-, θ-, the aluminium oxide of δ-and χ-single or multiphase, preferably have γ-, η-, the aluminium oxide of θ-and δ-single or multiphase.Described IVB race metal is preferably titanium, and with oxide basis and with described carrier for benchmark, the content of described IVB race metal is 0.1-6 % by weight, is preferably 0.3-4 % by weight, more preferably 0.5-2 % by weight.They can be that commercially available commodity also can be prepared by any one method in prior art.Optionally, the described IVB race burning alumina supporter that contains can make the article shaped being easy to arbitrarily operate.Describedly shapingly can to carry out according to a conventional method, as methods such as compressing tablet, spin, extrusions.When shaping, such as extruded moulding, for ensureing described shapingly to carry out smoothly, can to the precursor of described aluminium oxide and/or aluminium oxide with containing add in the mixture of IVB race metallic compound water, extrusion aid and/or adhesive, containing or not containing expanding agent, then extrusion molding, carries out drying and roasting afterwards.The described compound containing IVB race metal can be their compounds known arbitrarily, such as, and the oxide of IVB race metal and the salt containing IVB race metal.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.The temperature of described drying can be 40-350 DEG C, and be preferably 100-200 DEG C, the time is 1-24 hour, is preferably 2-12 hour; Sintering temperature is 350-1000 DEG C, and be preferably 600-950 DEG C, roasting time is 1-10 hour, is preferably 2-6 hour.The precursor of described aluminium oxide is selected from mixtures in hibbsite, monohydrate alumina and amorphous hydroted alumina or several.They can be that commercially available commodity also can be prepared by any one method in prior art.
Described VIII race's metal component is preferably one or more in iron, cobalt, nickel, more preferably cobalt or nickel, 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 metal component of group VIII is preferably 0.2-15 % by weight, more preferably 0.5-8 % by weight, is more preferably 0.5-3 % by weight; The content of VB race metal component is preferably 0.2-15 % by weight, more preferably 0.5-10 % by weight, is more preferably 1-8 % by weight.
According to catalyst provided by the invention, can also the invention provides containing any impact the material that catalyst performance maybe can improve the catalytic performance of catalyst provided by the invention.As contained the component such as alkali metal or phosphorus, be benchmark with oxide basis and with catalyst, the content of said components is no more than 10 % by weight, is preferably 0.5-5 % by weight.
Be enough under the prerequisite that described hydrogenation active metals component is carried on described alumina support, the present invention is not particularly limited described carrying method, preferred method is infusion process, comprise 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.
Wherein, one or more (are included in cosolvent and there is lower water-soluble compound) in their water soluble compound are selected from containing the compound of described metal.For the cobalt of VIII race, can be selected from as one or more in cobalt nitrate, cobalt acetate, basic cobaltous carbonate, cobalt chloride, preferably cobalt nitrate, basic cobaltous carbonate wherein; For nickel, can be selected from as one or more in nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride, preferably nickel nitrate, basic nickel carbonate wherein; 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.
When also containing the component such as alkali metal or phosphorus in described catalyst, the introducing method of the components such as described alkali metal or phosphorus can be arbitrary method, as can be by containing as described in the component such as alkali metal or phosphorus compound directly with as described in aluminium oxide precursor (as boehmite) and contain that group vib metallic compound mixes, shaping and roasting; Can be by the compound containing components such as described alkali metal or phosphorus be mixed with containing the compound of hydrogenation active metals component after mixed solution with described carrier contact; Can also be by after independent for the compound containing the component such as alkali metal or phosphorus obtain solution with described carrier contact and roasting.When the component such as alkali metal or phosphorus and hydrogenation active metals introduce described carrier respectively, preferably first use containing auxiliary compound solution and described carrier contact and roasting, contact with the solution of the compound containing hydrogenation active metals component more afterwards, such as by the method for dipping, described sintering temperature is 400-600 DEG C, be preferably 420-500 DEG C, roasting time is 2-6 hour, is preferably 3-6 hour.
According to heavy oil hydrogenation treatment method provided by the present invention, the reaction condition of described heavy-oil hydrogenation process 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, 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 example below.
Embodiment 1 illustrates and the invention provides catalyst macropore alumina supporter used and preparation method thereof.
Embodiment 1
(butt is 73% to take the dry glue powder that Chang Ling oil plant catalyst plant produces, wherein boehmite content is 68%, gibbsite content is 5 % by weight, surplus is amorphous alumina) 1000 grams, 36 grams of sesbania powder (Lankao, Henan sesbania gum factory product), 25g CMC mixes.Getting titanium tetrachloride 12g, is salting liquid with 1000mL deionized water dissolving; Get 20mL nitric acid, add 200mL deionized water and be configured to dilute acid soln; Above-mentioned salting liquid and dilute acid soln are mixed, joins in above-mentioned mixing boehmite powder, kneading 20 minutes.Double screw banded extruder is extruded into the butterfly bar of external diameter φ 1.1mm.Wet bar, in 120 DEG C of dryings 4 hours, after 4 hours, obtains carrier Z1 in 880 DEG C of roastings.The physico-chemical property of carrier Z1 is in table 1.
Table 1
| Bearer number | Pore volume, ml/g | Specific surface, m 2/g | TiO 2, % by weight |
| Z1 | 0.75 | 142 | 1.2 |
Embodiment 2-5 illustrates Catalysts and its preparation method provided by the invention.
Embodiment 2
Carrier Z1200 gram prepared by Example 1, with 500 milliliters containing V
2o
550 grams per liters, ammonium metavanadate and the nickel nitrate mixed solution of NiO14 grams per liter flood 1 hour, dry 4 hours after filtration in 120 DEG C, and 400 DEG C of roastings 3 hours, obtain protective agent C1.The composition of protective agent C1 is listed in table 2.
Comparative example 1
Carrier Z1200 gram prepared by Example 1, contains MoO with 500 milliliters respectively
350 grams per liters, ammonium heptamolybdate and the nickel nitrate mixed solution of NiO14 grams per liter flood 1 hour, dry 4 hours after filtration in 120 DEG C, and 400 DEG C of roastings 2 hours, obtain protective agent D1.The composition of protective agent D1 is listed in table 2.
Embodiment 3
Carrier Z1200 gram prepared by Example 1, with 500 milliliters containing V
2o
518 grams per liters, ammonium metavanadate and the nickel nitrate mixed solution of NiO 29 grams per liter flood 1 hour, dry 4 hours after filtration in 120 DEG C, and 400 DEG C of roastings 3 hours, obtain protective agent C2.The composition of protective agent C2 is listed in table 2.
Embodiment 4
Carrier Z1200 gram prepared by Example 1, with 500 milliliters containing V
2o
575 grams per liters, ammonium metavanadate and the nickel nitrate mixed solution of NiO 8 grams per liter flood 1 hour, dry 4 hours after filtration in 120 DEG C, and 400 DEG C of roastings 3 hours, obtain protective agent C3.The composition of protective agent C3 is listed in table 2.
Comparative example 2
Carrier Z1200 gram prepared by Example 1, contains MoO with 500 milliliters respectively
375 grams per liters, ammonium heptamolybdate and the nickel nitrate mixed solution of NiO8 grams per liter flood 1 hour, dry 4 hours after filtration in 120 DEG C, and 400 DEG C of roastings 2 hours, obtain protective agent D2.The composition of protective agent D2 is listed in table 2.
Embodiment 5
Carrier Z1200 gram prepared by Example 1, with 500 milliliters containing V
2o
550 grams per liters, ammonium metavanadate and the cobalt nitrate mixed solution of CoO 15 grams per liter flood 1 hour, dry 4 hours after filtration in 120 DEG C, and 400 DEG C of roastings 3 hours, obtain protective agent C4.The composition of protective agent C4 is listed in table 2.
Table 2
Embodiment 6-9
Embodiment 6-9 illustrates application and the effect thereof of hydrogenation protecting catalyst provided by the invention.
With the normal slag of Kuwait for raw material, 100 milliliters of small fixed reactors evaluate protective agent.
Catalyst C1, C2, C3, C4 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 after 200 hours and samples.
The circular of demetallization per and desulfurization degree is as follows:
Feedstock oil character lists in table 3, and evaluation result is listed in table 4.
Comparative example 3-4
According to demetallization per and the desulfurization degree of method evaluation catalyst D1, D2 of embodiment 6, the results are shown in Table 4.
Table 3
Table 4
Can be seen by the result of table 4, when tenor is suitable, the HDM performance of hydrogenation protecting agent provided by the invention is obviously better than reference agent.
Claims (16)
1. be the Hydrogenation active protective agent of carrier with titanium-contained aluminum oxide, containing titanium-contained aluminum oxide carrier and load hydrogenation active metals component on this carrier, it is characterized in that, described titanium-contained aluminum oxide be selected from titaniferous have γ-, η-, θ-, δ-and χ-the aluminium oxide of single or multiphase, with oxide basis and with described carrier for benchmark, consisting of of described carrier: the content of titanium is 0.1-6 % by weight, surplus is aluminium oxide, described hydrogenation active metals component is the vanadium being selected from the cobalt of VIII or nickel and being selected from VB race, be benchmark with oxide basis and with Hydrogenation active protective agent, consisting of of described Hydrogenation active protective agent: the content of cobalt or nickel is 0.2-15 % by weight, the content of vanadium is 0.2-15 % by weight, surplus is carrier.
2. protective agent according to claim 1, is characterized in that, is benchmark with oxide basis and with Hydrogenation active protective agent, and the content of described cobalt or nickel is 0.5-8 % by weight, and the content of vanadium is 0.5-10 % by weight, and surplus is carrier.
3. protective agent according to claim 2, is characterized in that, is benchmark with oxide basis and with Hydrogenation active protective agent, and the content of described cobalt or nickel is 0.5-3 % by weight, and the content of vanadium is 1-8 % by weight, and surplus is carrier.
4. protective agent according to claim 1; it is characterized in that; described titanium-contained aluminum oxide be selected from titaniferous have γ-, η-, θ-and δ-the aluminium oxide of single or multiphase; with oxide basis and with described carrier for benchmark; in described carrier, the content of titanium is 0.3-4 % by weight, and surplus is aluminium oxide.
5. protective agent according to claim 4, is characterized in that, with oxide basis and with described carrier for benchmark, in described carrier, the content of titanium is 0.5-2 % by weight, and surplus is aluminium oxide.
6. one kind take titanium-contained aluminum oxide as the preparation method of the Hydrogenation active protective agent of carrier, be included in load hydrogenation active metals component on titanium-contained aluminum oxide carrier, it is characterized in that, described titanium-contained aluminum oxide be selected from titaniferous have γ-, η-, θ-, δ-and χ-the aluminium oxide of single or multiphase, with oxide basis and with described carrier for benchmark, consisting of of described carrier: the content of titanium is 0.1-6 % by weight, surplus is aluminium oxide, described hydrogenation active metals component is the vanadium being selected from the cobalt of VIII or nickel and being selected from VB race, be benchmark with oxide basis and with Hydrogenation active protective agent, the consumption of each component makes consisting of of described Hydrogenation active protective agent: the content of described cobalt or nickel is 0.2-15 % by weight, the content of vanadium is 0.2-15 % by weight, surplus is carrier.
7. method according to claim 6, is characterized in that, is benchmark with oxide basis and with Hydrogenation active protective agent, and the consumption of each component makes the content of described cobalt or nickel be 0.5-8 % by weight, and the content of vanadium is 0.5-10 % by weight, and surplus is carrier.
8. method according to claim 7, is characterized in that, is benchmark with oxide basis and with Hydrogenation active protective agent, and the consumption of each component makes the content of described cobalt or nickel be 0.5-3 % by weight, and the content of vanadium is 1-8 % by weight, and surplus is carrier.
9. method according to claim 6, it is characterized in that, described titanium-contained aluminum oxide be selected from titaniferous have γ-, η-, θ-and δ-the aluminium oxide of single or multiphase, with oxide basis and with described carrier for benchmark, in described carrier, the content of titanium is 0.3-4 % by weight, and surplus is aluminium oxide.
10. method according to claim 9, is characterized in that, with oxide basis and with described carrier for benchmark, in described carrier, the content of titanium is 0.5-2 % by weight, and surplus is aluminium oxide.
11. methods according to any one of claim 6,9 or 10, it is characterized in that, described titanium-contained aluminum oxide carrier is the article shaped of titanium-contained aluminum oxide, described article shaped by comprise by the precursor of aluminium oxide and/or aluminium oxide and titanium-containing compound, water, help forming agent, containing or do not carry out mixing containing peptizing agent, prepared by shaping, the dry and method of roasting, described drying condition is: temperature 40-350 DEG C, time is 1-24 hour, roasting condition is: temperature 350-1000 DEG C, and the time is 1-10 hour.
12. methods according to claim 11, is characterized in that, described forming method is extruded moulding, and described drying condition is: temperature 100-200 DEG C, and the time is 2-12 hour, and roasting condition is: temperature 600-950 DEG C, and the time is 2-6 hour.
13. methods according to claim 6, is characterized in that, be infusion process, comprise at supported on carriers hydrogenation active metals multi-component approach: a) preparation contains the solution of cobalt or nickel compound and vfanadium compound; B) solution impregnation of alumina carrier using step a) to prepare; C) dry and calcination steps b) impregnation product that obtains; Wherein, be benchmark with oxide basis and with Hydrogenation active protective agent; the concentration of maceration extract and consumption make the content of cobalt or nickel described in final Hydrogenation active protective agent be 0.5-15 % by weight; the content of vanadium is 0.2-15 % 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.
14. methods according to claim 13; it is characterized in that; be benchmark with oxide basis and with Hydrogenation active protective agent; the concentration of described maceration extract and consumption make the content of cobalt or nickel described in final Hydrogenation active protective agent be 0.5-8 % by weight; the content of vanadium is 0.5-10 % by weight, and 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.
15. methods according to claim 14; it is characterized in that; be benchmark with oxide basis and with Hydrogenation active protective agent, the concentration of described maceration extract and consumption make the content of cobalt or nickel described in final Hydrogenation active protective agent be 0.5-3 % by weight, and the content of vanadium is 1-8 % by weight.
16. 1 kinds of heavy oil hydrogenation treatment methods; be included in heavy raw oil and catalyst exposure under heavy-oil hydrogenation processing reaction condition; it is characterized in that; described catalyst comprises Hydrogenation active protective agent, and described Hydrogenation active protective agent is the Hydrogenation active protective agent described in aforementioned any one of claim 1-5.
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| CN104162437B (en) * | 2013-05-20 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of hydrogenation activity guard catalyst and preparation and application thereof |
| CN104162439B (en) * | 2013-05-20 | 2017-02-08 | 中国石油化工股份有限公司 | Hydrogenation activity protective catalyst, preparation and applications thereof |
| CN104293382B (en) * | 2013-07-18 | 2016-06-22 | 中国石油化工股份有限公司 | A kind of catalytic cracking material pretreatment method |
| CN104324724B (en) * | 2013-07-22 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of hydrogenation protecting catalyst and preparation method and application |
| CN104338537B (en) * | 2013-08-02 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of hydrogenation activity guard catalyst and preparation and application thereof |
| CN104338540B (en) * | 2013-08-02 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of hydrogenation activity guard catalyst and its preparation and application |
| CN104492502B (en) * | 2014-12-25 | 2016-09-14 | 江西科帕克环保化工有限责任公司 | hydrogenation protecting agent and preparation method thereof |
| CN105983418B (en) * | 2015-02-05 | 2019-08-02 | 中国石油天然气股份有限公司 | Containing TiO2Macropore residuum hydrogenating and metal-eliminating catalyst preparation method |
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| CN102649069A (en) | 2012-08-29 |
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