CN102553567B - Take aluminium oxide as the hydrogenation catalyst containing VB metal component of carrier, preparation and application thereof - Google Patents
Take aluminium oxide as the hydrogenation catalyst containing VB metal component of carrier, preparation and application thereof Download PDFInfo
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Abstract
A kind of with aluminium oxide be carrier containing the hydrogenation catalyst of VB race metal component, preparation and application thereof, this catalyst contains alumina support and load hydrogenation active metals component on this carrier, it is characterized in that, described hydrogenation active metals component is be selected from the combination that the metal component of at least one group vib and at least one are selected from the metal component of VB race, be benchmark with oxide basis and with catalyst, the content of described group vib metal component is the content of 0.2-15 % by weight, VB race metal component is 0.2-12 % by weight.Compared with the catalyst provided with prior art, the invention provides the HDM of catalyst, diasphaltene and de-carbon residue activity and significantly improve.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst, preparation and application thereof, particularly a kind of be suitable for processing of heavy oil HDM, diasphaltene and de-carbon residue catalyst, preparation and application thereof.
Background technology
Along with the contradiction of worldwide crude oil heaviness, in poor quality and the petrochemicals diversification of demand, lighting is becoming increasingly acute, the main task of petroleum chemical industry will concentrate in heavy oil lighting.Residual oil is cut the heaviest in crude oil, crude oil through distillation after large, the baroque ampholyte species of molecular weight in residual oil, these impurity have material impact to follow-up process and product property, thus must first by hydrotreatment by these impurity removals.Compared with distillate, in heavy oil except there is the impurity such as sulphur, nitrogen, the metal impurities such as Ni, V also containing higher proportion, and asphalt content is high, carbon residue is higher.If wherein the metal impurities such as Ni, V can not get effectively removing, can downstream catalyst be had a negative impact, clog downstream catalyst duct, thus the inactivation causing downstream catalyst.Therefore, the Hydrodemetalation catalyst that exploitation metal removal activity is high effectively can extend the service life of downstream catalyst, thus plays the effect of protection downstream catalyst and prolong operating period.Due to the These characteristics of residual oil, in commercial Application, the activity stability of residual oil hydrocatalyst is very important, and many patent business release multiple residuum hydrogenating and metal-eliminating agent both at home and abroad.
CN1054393C discloses a kind of preparation method of residuum hydrogenating and metal-eliminating catalyst, and its feature is to adopt Physical and chemical method two kinds of means to improve the pore structure of residuum hydrogenating and metal-eliminating agent.
CN1267537C discloses a kind of preparation method of residuum hydrogenating and metal-eliminating catalyst, its feature is in used carrier containing a kind of halogen, the ratio of halogen accounts for the 0.1-5 % by weight of carrier, the acidity of its carrier is less than 0.2 mM/gram (carrier acid amount is lower), while the HDM activity making catalyst keep higher, coke content is low.
CN1946831A and US7608558 discloses a kind of hydrotreating catalyst comprising VB race metal, it is characterized in that metal component (calculating with oxide) is formed at least 50 % by weight of catalyst, the mol ratio wherein between metal component meets following formula: (group vib+VB race): (VIII)=0.5-2: 1.
US5275994 describes the hydrotreating catalyst being applicable to hydrocarbon charging, and it comprises group VIII metal component, group vib metal component and VB race metal component.This trimetallic catalyst must load on silica or aluminium oxide and preferably with comprise be less than 28 % by weight metal component (with oxide basis) for feature.In catalyst preparing, VB race metal component must add as alkoxide in water-less environment, and preferably by monolith at least 500 DEG C of roastings.
Summary of the invention
The technical problem to be solved in the present invention be to provide a kind of newly, the catalyst with high HDM, diasphaltene and de-carbon residue Activity and stabill, the preparation of this catalyst and application thereof.
The present inventor finds, the stability of heavy oil hydrogenation demetal reacting middle catalyst is relevant with the fuel factor in course of reaction.The hydrodesulfurization wherein occurred is strong exothermal reaction, is a kind of key factor causing this type of catalysqt deactivation.Therefore, by the selection to catalyst activity metal component, can make catalyst while the HDM activity that maintenance is high, hydrodesulfurization activity be controlled a suitable level, and then improve the stability of this type of catalyst.
The present invention relates to following invention:
1, with aluminium oxide be carrier containing the hydrogenation catalyst of VB metal component, containing alumina support and load hydrogenation active metals component on this carrier, it is characterized in that, described hydrogenation active metals component is be selected from the combination that the metal component of at least one group vib and at least one are selected from the metal component of VB race, be benchmark with oxide basis and with catalyst, the content of described group vib metal component is the content of 0.2-15 % by weight, VB race metal component is 0.2-12 % by weight.
2, the catalyst according to 1, it is characterized in that, the metal component of described group vib is selected from molybdenum and/or tungsten, VB race metal component is selected from vanadium and/or niobium, be benchmark with oxide basis and with catalyst, the content of described group vib metal component is the content of 0.5-12 % by weight, VB race metal component is 0.5-9 % by weight.
3, the catalyst according to 2, is characterized in that, the metal component of described group vib is molybdenum or tungsten, VB race metal component is vanadium, be benchmark with oxide basis and with catalyst, the content of described group vib metal component is the content of 5-12 % by weight, VB race metal component is 1-9 % by weight.
4, the catalyst according to 1, is characterized in that, described aluminium oxide be selected from γ-, η-, θ-, one or more in δ-and χ-aluminium oxide.
5, a kind of take aluminium oxide as the preparation method of hydrogenation catalyst containing VB metal component of carrier, comprise and prepare alumina support and the component of load hydrogenation active metals on this carrier, it is characterized in that, described hydrogenation active metals component is be selected from the combination that the metal component of at least one group vib and at least one are selected from the metal component of VB race, be benchmark with oxide basis and with catalyst, it is 0.2-12 % by weight that the consumption of each component makes the content of the described group vib metal component in described catalyst be the content of 0.2-15 % by weight, VB race metal component.
6, the method according to 5, it is characterized in that, the metal component of described group vib is selected from molybdenum and/or tungsten, VB race metal component is selected from vanadium and/or niobium, be benchmark with oxide basis and with catalyst, it is 0.5-9 % by weight that the consumption of each component makes the content of described group vib metal component be the content of 0.5-12 % by weight, VB race metal component.
7, the method according to 6, it is characterized in that, the metal component of described group vib is molybdenum or tungsten, VB race metal component is vanadium, be benchmark with oxide basis and with catalyst, it is 1-9 % by weight that the consumption of each component makes the content of described group vib metal component be the content of 5-12 % by weight, VB race metal component.
8, the method according to 5, is characterized in that, described aluminium oxide is selected from one or more in γ, η, θ, δ and χ.
9, the method according to 5, it is characterized in that, described alumina support is the article shaped of aluminium oxide, described article shaped by comprise by the precursor of aluminium oxide and/or aluminium oxide and 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, and roasting condition is: temperature 350-1000 DEG C, and the time is 1-10 hour.
10, the method according to 9, 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.
11, the method according to 5, 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 group vib metallic compound and/or 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 group vib metal component described in final catalyst be 0.5-12 % by weight, the content of VB race metal component is 0.5-9 % by weight, described drying condition is: temperature 80-200 DEG C, time 1-8 hour, roasting condition is: temperature 400-600 DEG C, time 2-8 hour.
12, the method according to 11, 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 group vib metal component described in final catalyst be 5-12 % by weight, the content of VB race metal component is 1-9 % 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.
13, a heavy oil hydrogenation demetal method, contacts heavy raw oil with Hydrodemetalation catalyst under being included in heavy oil hydrogenation demetal reaction condition, and described catalyst is the catalyst described in aforementioned any one of 1-4.
According to catalyst provided by the invention, wherein, described aluminium oxide be selected from γ-, η-, θ-, one or more in δ-and χ-aluminium oxide, preferred γ-, η-, one or more in θ-and δ-aluminium oxide.They can be commercially available commodity, also can be to adopt arbitrary existing method preparation.
Described group vib metal component is preferably molybdenum and/or tungsten, more preferably molybdenum or tungsten, and VB race metal component is preferably vanadium and/or niobium, more preferably vanadium.Be benchmark with oxide basis and with catalyst, the content of described group vib metal component is preferably 0.2-15 % by weight, more preferably 0.5-12 % by weight, is more preferably 5-12 % by weight; The content of VB race metal component is preferably 0.2-12 % by weight, more preferably 0.5-9 % by weight, is more preferably 1-9 % by weight.
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 components such as 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.
When in described catalyst also containing the component such as phosphorus time, the introducing method of the components such as described phosphorus 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 by the compound containing components such as described 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 components such as phosphorus obtain solution with described carrier contact and roasting.When the components such as 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 method for preparing catalyst provided by the invention, wherein, the preparation of described alumina support comprises and adopts arbitrary existing method that the precursor of described aluminium oxide is carried out roasting, make its be converted into as described in γ-, η-, θ-, one or more in δ-and χ-aluminium oxide.Optionally, comprised shaping for the precursor of described aluminium oxide and/or aluminium oxide before or after described roasting, to prepare the step of the article shaped required for applicable practical operation, such as, be prepared into spherical, compressing tablet and bar shaped.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 add in the precursor of described aluminium oxide and/or aluminium oxide 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.。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.
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 alumina support 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 molybdenum of group vib, can be selected from as one or more in molybdenum oxide, molybdate, paramolybdate, preferably molybdenum oxide, ammonium molybdate, ammonium paramolybdate wherein; For the tungsten of group vib, can be selected from as one or more in tungstates, metatungstate, ethyl metatungstate, preferably ammonium metatungstate, ethyl ammonium metatungstate 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.
According to heavy oil hydrogenation demetal method provided by the present invention, the reaction condition of described heavy oil hydrogenation demetal is not particularly limited, in a preferred embodiment, described HDM 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 HDM, to provide qualified feedstock oil for subsequent technique (as catalytic cracking process).
Compared with the mink cell focus Hydrodemetalation catalyst provided with prior art, the HDM of Hydrodemetalation catalyst provided by the invention is active, asphaltene removal and de-carbon residue activity are significantly improved.
Detailed description of the invention
The present invention will be further described for the following examples.
Embodiment 1-2 illustrates and the invention provides catalyst alumina support 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, 27 grams of sesbania powder (Lankao, Henan sesbania gum factory product), 25g CMC mixes, and adds the aqueous solution 1200 milliliters containing nitric acid 24g afterwards, plunger type bar extruder is extruded into the butterfly bar of external diameter φ 1.1mm.Wet bar, in 120 DEG C of dryings 4 hours, after 3 hours, obtains carrier Z1 in 930 DEG C of roastings.The physico-chemical property of carrier Z1 is in table 1.
Embodiment 2
Take Shanxi Aluminium Plant produce dry glue powder (butt is 69%, wherein boehmite content is 71%, gibbsite content is 6 % by weight, surplus is amorphous alumina) 1000 grams, 27 grams of sesbania powder (Lankao, Henan sesbania gum factory product), 25g polyvinyl alcohol (Chang Ling catalyst plant) mixes, and adds the aqueous solution 1200 milliliters containing nitric acid 24g afterwards, double screw banded extruder is extruded into the cloverleaf pattern bar of external diameter φ 1.1mm.Wet bar, in 120 DEG C of dryings 4 hours, after 3 hours, obtains carrier Z2 in 750 DEG C of roastings.The physico-chemical property of carrier Z2 is in table 1.
Table 1
| Bearer number | Pore volume, ml/g | Specific surface, m 2/g |
| Z1 | 0.67 | 140 |
| Z2 | 0.71 | 175 |
Embodiment 3-7 illustrates Catalysts and its preparation method provided by the invention.
Embodiment 3
Carrier Z1 200 grams prepared by Example 1, with 500 milliliters containing MoO
380 grams per liters, V
2o
5ammonium heptamolybdate and the ammonium metavanadate mixed solution of 16 grams per liters flood 1 hour, dry 4 hours after filtration in 120 DEG C, and 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst CZ1.The composition of Hydrodemetalation catalyst CZ1 is listed in table 2.
Embodiment 4
Carrier Z2 200 grams prepared by Example 2, with 500 milliliters containing MoO
380 grams per liters, V
2o
5ammonium heptamolybdate and the ammonium metavanadate mixed solution of 16 grams per liters flood 1 hour, dry 4 hours after filtration in 120 DEG C, and 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst CZ2.The composition of Hydrodemetalation catalyst CZ2 is listed in table 2.
Comparative example 1-2
Each 200 grams of carrier Z1, Z2 prepared by Example 1,2, contains MoO with 500 milliliters respectively
380 grams per liters, ammonium heptamolybdate and the nickel nitrate mixed solution of NiO16 grams per liter flood 1 hour, dry 4 hours after filtration in 120 DEG C, and 400 DEG C of roastings 2 hours, obtain Hydrodemetalation catalyst DZ1, DZ2.The composition of Hydrodemetalation catalyst DZ1, DZ2 is listed in table 2.
Comparative example 3
Carrier Z1 200 grams prepared by Example 1, contains MoO with 500 milliliters respectively
390 grams per liters, NiO18 grams per liter, V
2o
5the mixed solution of the ammonium heptamolybdate of 26 grams per liters, nickel nitrate and ammonium metavanadate floods 1 hour, dries 4 hours after filtration in 120 DEG C, and 400 DEG C of roastings 2 hours, obtain Hydrodemetalation catalyst D3.The composition of Hydrodemetalation catalyst D3 is listed in table 2.
Embodiment 5
Carrier Z1 200 grams prepared by Example 1, with 500 milliliters containing MoO
3120 grams per liters, V
2o
5ammonium heptamolybdate and the ammonium metavanadate mixed solution of 50 grams per liters flood 1 hour, dry 4 hours after filtration in 120 DEG C, and 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C2.The composition of Hydrodemetalation catalyst C2 is listed in table 2.
Embodiment 6
Carrier Z1 200 grams prepared by Example 1, with 500 milliliters containing MoO
370 grams per liters, V
2o
5ammonium heptamolybdate and the ammonium metavanadate mixed solution of 90 grams per liters flood 1 hour, dry 4 hours after filtration in 120 DEG C, and 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C3.The composition of Hydrodemetalation catalyst C3 is listed in table 2.
Embodiment 7
Carrier Z1 200 grams prepared by Example 1, with 500 milliliters containing WO
380 grams per liters, V
2o
5ammonium tungstate and the ammonium metavanadate mixed solution of 16 grams per liters flood 1 hour, dry 4 hours after filtration in 120 DEG C, and 400 DEG C of roastings 3 hours, obtain Hydrodemetalation catalyst C4.The composition of Hydrodemetalation catalyst C4 is listed in table 2.
Table 2
Embodiment 8-12
Embodiment 8-12 illustrates the demetallization per of Hydrodemetalation catalyst provided by the invention, diasphaltene rate, de-carbon yield and desulfurization degree.
With the normal slag of Kuwait for raw material, 100 milliliters of small fixed reactors evaluate protective agent.
Catalyst CZ1, CZ2, 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, diasphaltene rate, de-carbon yield and desulfurization degree is as follows:
Feedstock oil character lists in table 3, and evaluation result is listed in table 4.
Comparative example 4-6
According to the demetallization per of method evaluation catalyst DZ1, DZ2, D3 of embodiment 8, diasphaltene rate, de-carbon yield and desulfurization degree, the results are shown in Table 4.
Table 3
The normal slag of feedstock oil title Kuwait
Density (20 DEG C), kg/m
30.998
Mean molecule quantity 804
Carbon residue, % (m) 15.9
Four composition, % (m)
Saturated point 20
Fragrance divides 49.3
Colloid 23
Asphalitine 7.7
S，m％ 5.0
N，m％ 0.21
Ni，ppm 26.5
V，ppm 80
Table 4
The result that table 4 provides is the result that evaluation response carries out after 200 hours, relatively can find out, relative to reference catalyst, the HDM of Hydrodemetalation catalyst provided by the invention is active, diasphaltene and de-carbon residue active in reference agent.
Claims (8)
1. a heavy oil hydrogenation demetal method, under being included in heavy oil hydrogenation demetal reaction condition, heavy raw oil is contacted with Hydrodemetalation catalyst, it is characterized in that, described Hydrodemetalation catalyst is made up of alumina support and load hydrogenation active metals component on this carrier, described hydrogenation active metals component is be selected from the metal component of at least one group vib and the combination of vanadium metal component, be benchmark with oxide basis and with catalyst, the content of described group vib metal component is 0.2-11.2 % by weight, and the content of vanadium is 0.2-12 % by weight.
2. method according to claim 1, it is characterized in that, the metal component of described group vib is selected from molybdenum and/or tungsten, is benchmark with oxide basis and with catalyst, the content of described group vib metal component is 0.5-11.2 % by weight, and the content of vanadium is 0.5-9 % by weight.
3. method according to claim 2, is characterized in that, the metal component of described group vib is molybdenum or tungsten, is benchmark with oxide basis and with catalyst, and the content of described group vib metal component is 5-11.2 % by weight, and the content of vanadium is 1-9 % by weight.
4. method according to claim 1, is characterized in that, described aluminium oxide be selected from γ-, η-, θ-, one or more in δ-and χ-aluminium oxide.
5. method according to claim 1, the preparation method of described Hydrodemetalation catalyst comprises and prepares alumina support and the component of load hydrogenation active metals on this carrier, be infusion process at supported on carriers hydrogenation active metals multi-component approach, comprise: a) preparation is containing the solution of group vib metallic compound and vanadium metal 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 maceration extract and consumption make the content of group vib metal component described in final catalyst be 0.5-11.2 % by weight, the content of vanadium is 0.5-9 % 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.
6. method according to claim 5, it is characterized in that, described alumina support by comprise by the precursor of aluminium oxide and/or aluminium oxide and water, help forming agent to contain or do not carry out mixing containing peptizing agent, prepared by shaping, the dry and method of roasting, the drying condition of described alumina support 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.
7. method according to claim 6, is characterized in that, described forming method is extruded moulding, and the drying condition of described alumina support 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.
8. method according to claim 5, it is characterized in that, be benchmark with oxide basis and with catalyst, the concentration of maceration extract and consumption make the content of group vib metal component described in final catalyst be 5-11.2 % by weight, the content of vanadium is 1-9 % 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.
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| CN103566943B (en) * | 2012-07-30 | 2016-08-24 | 中国石油化工股份有限公司 | A kind of hydrogenation protecting catalyst and preparation thereof and application |
| CN103865568B (en) * | 2012-12-12 | 2017-03-22 | 中国石油化工股份有限公司 | VB metal component-containing hydrogenation catalyst, preparation and application thereof |
| CN104293379B (en) * | 2013-07-18 | 2016-01-20 | 中国石油化工股份有限公司 | A kind of hydroprocessing process of heavy raw oil |
| CN104293383B (en) * | 2013-07-18 | 2016-03-23 | 中国石油化工股份有限公司 | A kind of hydroprocessing process optimizing catalytically cracked material character |
| CN104338525B (en) * | 2013-08-02 | 2017-03-22 | 中国石油化工股份有限公司 | A hydrogenation demetalization catalyst for heavy oil, and preparation and applications thereof |
| CN109569575B (en) * | 2017-09-29 | 2021-12-17 | 中国石油化工股份有限公司 | Catalyst with hydrogenation catalysis effect, preparation method and application thereof, and heavy oil hydrogenation asphaltene removal method |
| CN112547034A (en) * | 2020-12-25 | 2021-03-26 | 中化泉州石化有限公司 | Residual oil hydrotreating catalyst and preparation method thereof |
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| CN1091135C (en) * | 1999-09-29 | 2002-09-18 | 中国石油化工集团公司 | Hydrogenating catalyst for heavy oil and its preparing process |
| CA2563937C (en) * | 2004-04-22 | 2011-06-21 | Albemarle Netherlands B.V. | Hydrotreating catalyst containing a group v metal |
| CN101601995B (en) * | 2008-06-12 | 2013-04-03 | 中国石油化工股份有限公司 | Aluminum oxide catalyst used for preparing dimethyl ether by gas-phase dehydration of methanol and preparation method thereof |
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