CN102553567A - Hydrogenation catalyst containing VB metal components and provided with aluminum oxide serving as carrier and preparation and application thereof - Google Patents
Hydrogenation catalyst containing VB metal components and provided with aluminum oxide serving as carrier and preparation and application thereof Download PDFInfo
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Abstract
Provided are a hydrogenation catalyst containing VB metal components and provided with aluminum oxide serving as a carrier and preparation and application thereof. The catalyst contains an aluminum oxide carrier and hydrogenation active metal components loaded on the aluminum oxide carrier. The catalyst is characterized in that the hydrogenation active metal components are selected from at least one metal component of VIB groups and at least one composition selected from metal components of VB groups. With oxidate as metering standard and the catalyst as reference, the content of the VIB-group metal component is 0.2-15% by weight, and the content of the VB-group metal component is 0.2-12% by weight. Compared with the catalyst in the prior art, the hydrodemetallization, the diasphaltening and the decarburization residue activity of the hydrogenation catalyst are remarkably improved.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst, preparation and application thereof, particularly a kind ofly is suitable for HDM, the diasphaltene of processing of heavy oil and takes off carbon residue catalyst, preparation and application thereof.
Background technology
Along with the contradiction of worldwide crude oil heaviness, poor qualityization and the petrochemicals diversification of demand, lighting is becoming increasingly acute, the main task of petroleum chemical industry will concentrate in the heavy oil lighting.Residual oil is cut the heaviest in the crude oil, and big, the baroque ampholyte species of crude oil molecular weight after distilling is in residual oil, and these impurity have material impact to follow-up process and product property, thus must be earlier through hydrotreatment with these impurity removals.Compare with distillate, except having impurity such as sulphur, nitrogen, also contain the metal impurities such as Ni, V of higher proportion in the heavy oil, and asphalt content is high, carbon residue is higher.Wherein metal impurities such as Ni, V can have a negative impact to downstream catalyst if can not get effective elimination, clog downstream catalyst duct, thus cause the inactivation of downstream catalyst.Therefore, the high Hydrodemetalation catalyst of exploitation metal removal activity can effectively prolong the service life of downstream catalyst, thereby plays the effect of protection downstream catalyst and prolong operating period.Because the These characteristics of residual oil, the activity stability of residual oil hydrocatalyst is very important in commercial Application, and how tame patent merchant releases 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 characteristics are to adopt physics method and two kinds of means of chemical method 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 characteristics are in used carrier, to contain a kind of halogen; The ratio of halogen accounts for the 0.1-5 weight % of carrier; The acidity that makes its carrier is less than 0.2 mM/gram (carrier acid amount is lower), and when making the higher HDM of catalyst maintenance active, coke content is low.
CN1946831A and US7608558 disclose the hydrotreating catalyst of a kind of VB of comprising family metal; It is characterized in that metal component (calculating with oxide) constitutes at least 50 weight % of catalyst, wherein the mol ratio between the metal component meets following formula: (group vib+VB family): (VIII family)=0.5-2: 1.
US5275994 has described the hydrotreating catalyst that is applicable to the hydrocarbon charging, and it comprises VIII family metal component, group vib metal component and VB family metal component.This trimetallic catalyst must load on silica or the aluminium oxide and be characteristic in the metal component (with oxide) that comprises less than 28 weight % preferably.In Preparation of Catalyst, VB family metal component must be in water-less environment adds as alkoxide, and preferably with catalyst integral body at least 500 ℃ of roastings.
Summary of the invention
The technical problem that the present invention will solve provide a kind of new, have high HDM, diasphaltene and take off the active and stable catalyst of carbon residue, this Preparation of catalysts and application thereof.
Inventor of the present invention finds that the stability of heavy oil hydrogenation demetal reacting middle catalyst is relevant with the fuel factor in the course of reaction.The hydrodesulfurization that wherein takes place is a strong exothermal reaction, is a kind of key factor that causes this type of catalysqt deactivation.Therefore,, can make catalyst when the high HDM of maintenance is active, hydrodesulfurization activity is controlled at a proper level, and then improve the stability of this type of catalyst through selection to the catalyst activity metal component.
The present invention relates to following invention:
1, with the aluminium oxide is the hydrogenation catalyst that contains the VB metal component of carrier; Contain alumina support and load on the hydrogenation active metals component on this carrier; It is characterized in that described hydrogenation active metals component is the combination of metal component that is selected from metal component and at least a VB of the being selected from family of at least a group vib, is benchmark in oxide and with the catalyst; The content of said group vib metal component is 0.2-15 weight %, and the content of VB family metal component is 0.2-12 weight %.
2, according to 1 described catalyst; It is characterized in that; The metal component of said group vib is selected from molybdenum and/or tungsten, and VB family metal component is selected from vanadium and/or niobium, is benchmark in oxide and with the catalyst; The content of said group vib metal component is 0.5-12 weight %, and the content of VB family metal component is 0.5-9 weight %.
According to 2 described catalyst, it is characterized in that 3, the metal component of said group vib is molybdenum or tungsten; VB family metal component is a vanadium; In oxide and with the catalyst is benchmark, and the content of said group vib metal component is 5-12 weight %, and the content of VB family metal component is 1-9 weight %.
4, according to 1 described catalyst, it is characterized in that, said aluminium oxide be selected from γ-, η-, θ-, δ-and χ-aluminium oxide in one or more.
5, a kind of is the hydrogenization catalyst preparation method that contains the VB metal component of carrier with the aluminium oxide; Comprise the preparation alumina support and load hydrogenation active metals component on this carrier; It is characterized in that; Described hydrogenation active metals component is the combination of metal component that is selected from metal component and at least a VB of the being selected from family of at least a group vib; In oxide and with the catalyst is benchmark, and it is 0.2-15 weight % that the consumption of each component makes the content of the said group vib metal component in the said catalyst, and the content of VB family metal component is 0.2-12 weight %.
6, according to 5 described methods; It is characterized in that; The metal component of said group vib is selected from molybdenum and/or tungsten, and VB family metal component is selected from vanadium and/or niobium, is benchmark in oxide and with the catalyst; It is 0.5-12 weight % that the consumption of each component makes the content of said group vib metal component, and the content of VB family metal component is 0.5-9 weight %.
7, according to 6 described methods; It is characterized in that; The metal component of said group vib is molybdenum or tungsten, and VB family metal component is a vanadium, is benchmark in oxide and with the catalyst; It is 5-12 weight % that the consumption of each component makes the content of said group vib metal component, and the content of VB family metal component is 1-9 weight %.
According to 5 described methods, it is characterized in that 8, said aluminium oxide is selected from one or more among γ, η, θ, δ and the χ.
9, according to 5 described methods; It is characterized in that said alumina support is the article shaped of aluminium oxide, said article shaped by comprise with the precursor of aluminium oxide and/or aluminium oxide and water, help forming agent to contain or do not contain that peptizing agent mixes, the method preparation of moulding, dry and roasting; Described drying condition is: temperature 40-350 ℃; Time is 1-24 hour, and roasting condition is: temperature 350-1000 ℃, the time is 1-10 hour.
According to 9 described methods, it is characterized in that 10, said forming method is an extruded moulding, described drying condition is: temperature 100-200 ℃, the time is 2-12 hour, and roasting condition is: temperature 600-950 ℃, the time is 2-6 hour.
11, according to 5 described methods, it is characterized in that, described on carrier load hydrogenation active metals component method be infusion process, comprising: a) preparation contains group vib metallic compound and/or VB family solution of metal compound; B) solution impregnation of alumina carrier of preparing with step a); C) impregnation product that dry and calcination steps b) obtains; Wherein, In oxide and with the catalyst is benchmark, and the concentration of said maceration extract and consumption make that the content of group vib metal component described in the final catalyst is 0.5-12 weight %, and the content of VB family metal component is 0.5-9 weight %; Said drying condition is: temperature 80-200 ℃; Time 1-8 hour, roasting condition was: temperature 400-600 ℃, and time 2-8 hour.
12, according to 11 described methods, it is characterized in that, is benchmark in oxide and with the catalyst; The concentration of said maceration extract and consumption make that the content of group vib metal component described in the final catalyst is 5-12 weight %; The content of VB family metal component is 1-9 weight %, and said drying condition is: temperature 100-150 ℃, and time 2-6 hour; Roasting condition is: temperature 420-500 ℃, and time 3-6 hour.
13, a kind of heavy oil hydrogenation demetal method is included under the heavy oil hydrogenation demetal reaction condition heavy raw oil is contacted with Hydrodemetalation catalyst, and said catalyst is each described catalyst of aforementioned 1-4.
According to catalyst provided by the invention, wherein, said aluminium oxide be selected from γ-, η-, θ-, δ-and χ-aluminium oxide in one or more, preferred γ-, η-, θ-and δ-aluminium oxide in one or more.They can be commercially available commodity, also can be to adopt existing arbitrarily method preparation.
Said group vib metal component is preferably molybdenum and/or tungsten, further is preferably molybdenum or tungsten, and VB family metal component is preferably vanadium and/or niobium, further is preferably vanadium.In oxide and with the catalyst is benchmark, and the content of said group vib metal component is preferably 0.2-15 weight %, further is preferably 0.5-12 weight %, is more preferably 5-12 weight %; The content of VB family metal component is preferably 0.2-12 weight %, further is preferably 0.5-9 weight %, is more preferably 1-9 weight %.
According to catalyst provided by the invention, can also contain does not anyly influence the present invention and provides catalyst performance maybe can improve the material of the catalytic performance of catalyst provided by the invention.As can contain components such as phosphorus, and be benchmark in oxide and with the catalyst, the content of said components is no more than 10 weight %, is preferably 0.5-5 weight %.
When also containing components such as phosphorus in the said catalyst, the introducing method of components such as said phosphorus can be an arbitrary method, as can be with the compound that contains components such as said phosphorus directly mix with said boehmite, moulding and roasting; Can be with the compound that contains components such as said phosphorus with contact with said carrier after the compound that contains the hydrogenation active metals component is mixed with mixed solution; Can also be with contacting and roasting with said carrier behind the independent obtain solution of compound that contains component such as phosphorus.When components such as phosphorus and hydrogenation active metals are introduced said carrier respectively; Preferably at first auxiliary compound solution contacts with said carrier and roasting with containing, and contacts with the solution of the compound that contains the hydrogenation active metals component more afterwards, for example the method through flooding; Said sintering temperature is 400-600 ℃; Be preferably 420-500 ℃, 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 said alumina support comprises that the existing arbitrarily method of employing carries out roasting with the precursor of said aluminium oxide, make its be converted into as described γ-, η-, θ-, δ-and χ-aluminium oxide in one or more.Optionally, before or after described roasting, comprise precursor moulding,, for example, be prepared into sphere, compressing tablet and bar shaped to prepare the step that is fit to the needed article shaped of practical operation with said aluminium oxide and/or aluminium oxide.Said moulding can be undertaken by conventional method, all can like methods such as compressing tablet, spin, extrusions.When moulding, for example extruded moulding carries out for guaranteeing said moulding smoothly, can in the precursor of described aluminium oxide and/or aluminium oxide, add entry, extrusion aid and/or adhesive, contain or not contain expanding agent, and drying and roasting are carried out in extrusion molding then afterwards.The kind of said extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art; For example common extrusion aid can be selected from sesbania powder, methylcellulose, starch, polyvinyl alcohol, gather in the ethanol one or more; Said 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 the surfactant.Synthetic cellulose wherein is preferably one or more in CMC, methylcellulose, ethyl cellulose, the hydroxyl fiber fat alcohol polyethylene ether; Polymeric alcohol is preferably polyethylene glycol, gathers propyl alcohol, in the polyvinyl alcohol one or more, and it is the propenyl copolymer of 200-10000 and in the maleic acid copolymer one or more that surfactant is preferably fat alcohol polyethylene ether, fatty alkanol amide and derivative thereof, molecular weight.。The temperature of said drying can be 40-350 ℃, is preferably 100-200 ℃, and the time is 1-24 hour, is preferably 2-12 hour; Sintering temperature is 350-1000 ℃, is preferably 600-950 ℃, and roasting time is 1-10 hour, is preferably 2-6 hour.The precursor of said aluminium oxide is selected from hibbsite, monohydrate alumina and the amorphous hydroted alumina or several kinds mixture.They can be that commercially available commodity also can be by any one method preparation in the prior art.
Described hydrogenation active metals component is carried under the prerequisite on the described alumina support being enough to; The present invention is to the not special restriction of said carrying method; Preferable methods is an infusion process; Comprise that preparation contains the dipping solution of the compound of said metal, uses the described alumina support of this solution impregnation afterwards.Described dipping method is a conventional method, for example, can be excessive liquid dipping, hole saturation infusion process.
Wherein, the compound that contains said metal is selected from one or more (are included in cosolvent and have water-soluble compound down) in their water soluble compound.Molybdenum with group vib is an example, can be selected from like in molybdenum oxide, molybdate, the paramolybdate one or more preferred molybdenum oxide, ammonium molybdate, ammonium paramolybdate wherein; Tungsten with group vib is example, can be selected from like in tungstates, metatungstate, the ethyl metatungstate one or more preferred ammonium metatungstate, ethyl ammonium metatungstate wherein; Vanadium with VB family is an example, can be selected from like in vanadic anhydride, ammonium vanadate, ammonium metavanadate, vanadic sulfate, the vanadium heteropoly acid one or more preferred ammonium metavanadate, ammonium vanadate wherein.
According to heavy oil hydrogenation demetal method provided by the present invention; To the not special restriction of the reaction condition of said heavy oil hydrogenation demetal, in preferred embodiment, said HDM reaction condition is: reaction temperature 300-550 ℃; Further preferred 330-480 ℃; Hydrogen dividing potential drop 4-20 MPa, further preferred 6-18 MPa, volume space velocity 0.1-3.0 hour
-1, further preferred 0.15-2 hour
-1, hydrogen to oil volume ratio 200-2500, further preferred 300-2000.
The device of said hydrogenation reaction can be enough to make said feedstock oil under the hydrotreatment reaction condition Yu in the catalytic reactor of said catalyst, to carry out any, for example, at said fixed bed reactors, carries out in moving-burden bed reactor or the fluidized bed reactor.
According to the conventional method in this area; Said hydrotreating catalyst is before using; Usually can be in the presence of hydrogen; Under 140-370 ℃ temperature, carry out presulfurization with sulphur, hydrogen sulfide or sulfur-bearing raw material, this presulfurization can be carried out outside device also can original position sulfuration in device, and the active metal component of its load is converted into the metal sulfide component.
Catalyst provided by the invention can use separately, also can use with other catalyst combination, this catalyst be particularly suitable for heavy oil particularly poor residuum carry out HDM so that qualified feedstock oil is provided for subsequent technique (like catalytic cracking process).
Compare with the mink cell focus Hydrodemetalation catalyst that prior art provides, the HDM of Hydrodemetalation catalyst provided by the invention is active, asphaltene removal and take off the carbon residue activity and be significantly improved.
The specific embodiment
Following embodiment will further specify the present invention.
Embodiment 1-2 explanation the present invention provide used alumina support of catalyst and preparation method thereof.
Embodiment 1
(butt is 73% to take by weighing the dry glue powder that Chang Ling oil plant catalyst plant produces; Wherein boehmite content is 68%, and gibbsite content is 5 weight %, and surplus is an amorphous alumina) 1000 grams; 27 gram sesbania powder (Lankao, Henan sesbania gum factory product); The 25g CMC mixes, and adds 1200 milliliters of the aqueous solution that contain nitric acid 24g afterwards, on the plunger type banded extruder, is extruded into the butterfly bar of external diameter φ 1.1mm.Wet bar after 3 hours, obtains carrier Z1 in 930 ℃ of roastings in 120 ℃ of dryings 4 hours.The physico-chemical property of carrier Z1 is seen table 1.
Embodiment 2
(butt is 69% to take by weighing the dry glue powder that Shanxi Aluminium Plant produces; Wherein boehmite content is 71%, and gibbsite content is 6 weight %, and surplus is an amorphous alumina) 1000 grams; 27 gram sesbania powder (Lankao, Henan sesbania gum factory product); 25g polyvinyl alcohol (Chang Ling catalyst plant) mixes, and adds 1200 milliliters of the aqueous solution that contain nitric acid 24g afterwards, on the twin-screw banded extruder, is extruded into the cloverleaf pattern bar of external diameter φ 1.1mm.Wet bar after 3 hours, obtains carrier Z2 in 750 ℃ of roastings in 120 ℃ of dryings 4 hours.The physico-chemical property of carrier Z2 is seen 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 explains Catalysts and its preparation method provided by the invention.
Embodiment 3
Get carrier Z1 200 grams of embodiment 1 preparation, contain MoO with 500 milliliters
380 grams per liters, V
2O
5The ammonium heptamolybdate of 16 grams per liters and ammonium metavanadate mixed solution dipping 1 hour filters the back in 120 ℃ of oven dry 4 hours, and 400 ℃ of roastings 3 hours obtain Hydrodemetalation catalyst CZ1.The composition of Hydrodemetalation catalyst CZ1 is listed in the table 2.
Embodiment 4
Get carrier Z2 200 grams of embodiment 2 preparations, contain MoO with 500 milliliters
380 grams per liters, V
2O
5The ammonium heptamolybdate of 16 grams per liters and ammonium metavanadate mixed solution dipping 1 hour filters the back in 120 ℃ of oven dry 4 hours, and 400 ℃ of roastings 3 hours obtain Hydrodemetalation catalyst CZ2.The composition of Hydrodemetalation catalyst CZ2 is listed in the table 2.
Comparative Examples 1-2
Get carrier Z1, each 200 gram of Z2 of embodiment 1,2 preparations, contain MoO with 500 milliliters respectively
380 grams per liters, the ammonium heptamolybdate of NiO16 grams per liter and nickel nitrate mixed solution dipping 1 hour filters the back in 120 ℃ of oven dry 4 hours, and 400 ℃ of roastings 2 hours obtain Hydrodemetalation catalyst DZ1, DZ2.The composition of Hydrodemetalation catalyst DZ1, DZ2 is listed in the table 2.
Comparative Examples 3
Get carrier Z1 200 grams of embodiment 1 preparation, contain 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 dipping 1 hour filters the back in 120 ℃ of oven dry 4 hours, and 400 ℃ of roastings 2 hours obtain Hydrodemetalation catalyst D3.The composition of Hydrodemetalation catalyst D3 is listed in the table 2.
Embodiment 5
Get carrier Z1 200 grams of embodiment 1 preparation, contain MoO with 500 milliliters
3120 grams per liters, V
2O
5The ammonium heptamolybdate of 50 grams per liters and ammonium metavanadate mixed solution dipping 1 hour filters the back in 120 ℃ of oven dry 4 hours, and 400 ℃ of roastings 3 hours obtain Hydrodemetalation catalyst C2.The composition of Hydrodemetalation catalyst C2 is listed in the table 2.
Embodiment 6
Get carrier Z1 200 grams of embodiment 1 preparation, contain MoO with 500 milliliters
370 grams per liters, V
2O
5The ammonium heptamolybdate of 90 grams per liters and ammonium metavanadate mixed solution dipping 1 hour filters the back in 120 ℃ of oven dry 4 hours, and 400 ℃ of roastings 3 hours obtain Hydrodemetalation catalyst C3.The composition of Hydrodemetalation catalyst C3 is listed in the table 2.
Embodiment 7
Get carrier Z1 200 grams of embodiment 1 preparation, contain WO with 500 milliliters
380 grams per liters, V
2O
5The ammonium tungstate of 16 grams per liters and ammonium metavanadate mixed solution dipping 1 hour filters the back in 120 ℃ of oven dry 4 hours, and 400 ℃ of roastings 3 hours obtain Hydrodemetalation catalyst C4.The composition of Hydrodemetalation catalyst C4 is listed in the table 2.
Table 2
Embodiment 8-12
Embodiment 8-12 explain Hydrodemetalation catalyst provided by the invention demetallization per, diasphaltene rate, take off carbon yield and desulfurization degree.
With the normal slag of Kuwait is raw material, on 100 milliliters of small stationary bed bioreactors, estimates protective agent.
Catalyst CZ1, CZ2, C2, C3, C4 are broken into the particle of diameter 2-3 millimeter, and the catalyst loading amount is 100 milliliters.Reaction condition is: 380 ℃ of reaction temperatures, hydrogen dividing potential drop 14 MPas, liquid hourly space velocity (LHSV) are 0.7 hour
-1, hydrogen to oil volume ratio is 1000, reacts sampling after 200 hours.
Demetallization per, diasphaltene rate, the concrete computational methods of taking off carbon yield and desulfurization degree are following:
Feedstock oil character is listed in table 3, and evaluation result is listed in the table 4.
Comparative Examples 4-6
According to demetallization per, the diasphaltene rate of the method evaluate catalysts DZ1 of embodiment 8, DZ2, D3, take off carbon yield and desulfurization degree, the result sees table 4.
Table 3
The normal slag of feedstock oil title Kuwait
Density (20 ℃), kg/m
30.998
Mean molecule quantity 804
Carbon residue, % (m) 15.9
Four components, % (m)
Saturated branch 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 carries out the result after 200 hours for evaluation response, relatively can find out, with respect to reference catalyst, the HDM of Hydrodemetalation catalyst provided by the invention is active, diasphaltene and take off the carbon residue activity apparently higher than the reference agent.
Claims (13)
1. with the aluminium oxide hydrogenation catalyst that contains VB family metal component of carrier; Contain alumina support and load on the hydrogenation active metals component on this carrier; It is characterized in that described hydrogenation active metals component is the combination of metal component that is selected from metal component and at least a VB of the being selected from family of at least a group vib, is benchmark in oxide and with the catalyst; The content of said group vib metal component is 0.2-15 weight %, and the content of VB family metal component is 0.2-12 weight %.
2. according to 1 described catalyst; It is characterized in that; The metal component of said group vib is selected from molybdenum and/or tungsten, and VB family metal component is selected from vanadium and/or niobium, is benchmark in oxide and with the catalyst; The content of said group vib metal component is 0.5-12 weight %, and the content of VB family metal component is 0.5-9 weight %.
3. according to 2 described catalyst, it is characterized in that the metal component of said group vib is molybdenum or tungsten; VB family metal component is a vanadium; In oxide and with the catalyst is benchmark, and the content of said group vib metal component is 5-12 weight %, and the content of VB family metal component is 1-9 weight %.
4. according to 1 described catalyst, it is characterized in that, said aluminium oxide be selected from γ-, η-, θ-, δ-and χ-aluminium oxide in one or more.
5. one kind is the hydrogenization catalyst preparation method that contains VB family metal component of carrier with the aluminium oxide; Comprise the preparation alumina support and load hydrogenation active metals component on this carrier; It is characterized in that; Described hydrogenation active metals component is the combination of metal component that is selected from metal component and at least a VB of the being selected from family of at least a group vib; In oxide and with the catalyst is benchmark, and it is 0.2-15 weight % that the consumption of each component makes the content of the said group vib metal component in the said catalyst, and the content of VB family metal component is 0.2-12 weight %.
6. according to 5 described methods; It is characterized in that; The metal component of said group vib is selected from molybdenum and/or tungsten, and VB family metal component is selected from vanadium and/or niobium, is benchmark in oxide and with the catalyst; It is 0.5-12 weight % that the consumption of each component makes the content of said group vib metal component, and the content of VB family metal component is 0.5-9 weight %.
7. according to 6 described methods; It is characterized in that; The metal component of said group vib is molybdenum or tungsten, and VB family metal component is a vanadium, is benchmark in oxide and with the catalyst; It is 5-12 weight % that the consumption of each component makes the content of said group vib metal component, and the content of VB family metal component is 1-9 weight %.
8. according to 5 described methods, it is characterized in that said aluminium oxide is selected from one or more among γ, η, θ, δ and the χ.
9. according to 5 described methods; It is characterized in that said alumina support is the article shaped of aluminium oxide, said article shaped by comprise with the precursor of aluminium oxide and/or aluminium oxide and water, help forming agent to contain or do not contain that peptizing agent mixes, the method preparation of moulding, dry and roasting; Described drying condition is: temperature 40-350 ℃; Time is 1-24 hour, and roasting condition is: temperature 350-1000 ℃, the time is 1-10 hour.
10. according to 9 described methods, it is characterized in that said forming method is an extruded moulding, described drying condition is: temperature 100-200 ℃, the time is 2-12 hour, and roasting condition is: temperature 600-950 ℃, the time is 2-6 hour.
11. according to 5 described methods, it is characterized in that, described on carrier load hydrogenation active metals component method be infusion process, comprising: a) preparation contains group vib metallic compound and/or VB family solution of metal compound; B) solution impregnation of alumina carrier of preparing with step a); C) impregnation product that dry and calcination steps b) obtains; Wherein, In oxide and with the catalyst is benchmark, and the concentration of said maceration extract and consumption make that the content of group vib metal component described in the final catalyst is 0.5-12 weight %, and the content of VB family metal component is 0.5-9 weight %; Said drying condition is: temperature 80-200 ℃; Time 1-8 hour, roasting condition was: temperature 400-600 ℃, and time 2-8 hour.
12., it is characterized in that, be benchmark in oxide and with the catalyst according to 11 described methods; The concentration of said maceration extract and consumption make that the content of group vib metal component described in the final catalyst is 5-12 weight %; The content of VB family metal component is 1-9 weight %, and said drying condition is: temperature 100-150 ℃, and time 2-6 hour; Roasting condition is: temperature 420-500 ℃, and time 3-6 hour.
13. a heavy oil hydrogenation demetal method is included under the heavy oil hydrogenation demetal reaction condition heavy raw oil is contacted with Hydrodemetalation catalyst, said catalyst is each described catalyst of aforementioned 1-4.
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| CN103865568A (en) * | 2012-12-12 | 2014-06-18 | 中国石油化工股份有限公司 | VB metal component-containing hydrogenation catalyst, preparation and application thereof |
| CN104293383A (en) * | 2013-07-18 | 2015-01-21 | 中国石油化工股份有限公司 | Hydrotreatment method for optimization of properties of catalytic cracking feedstock |
| CN104293379A (en) * | 2013-07-18 | 2015-01-21 | 中国石油化工股份有限公司 | Hydrotreating method for heavy raw oil |
| CN104338525A (en) * | 2013-08-02 | 2015-02-11 | 中国石油化工股份有限公司 | A hydrogenation demetalization catalyst for heavy oil, and preparation and applications thereof |
| CN109569575A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Catalyst with hydrogenation catalyst effect and its preparation method and application and heavy-oil hydrogenation depitching matter method |
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5275994A (en) * | 1991-06-17 | 1994-01-04 | Texaco Inc. | Process for preparing a catalyst for removal of hydroprocessing impurities |
| CN1289822A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Hydrogenating catalyst for heavy oil and its preparing process |
| CN1946831A (en) * | 2004-04-22 | 2007-04-11 | 阿尔伯麦尔荷兰有限公司 | Hydrotreating catalyst containing a group V metal |
| CN101601995A (en) * | 2008-06-12 | 2009-12-16 | 中国石油化工股份有限公司 | Be used for aluminium oxide catalyst of methanol gas phase dewatering preparing dimethy ether and preparation method thereof |
-
2010
- 2010-12-31 CN CN201010615985.0A patent/CN102553567B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5275994A (en) * | 1991-06-17 | 1994-01-04 | Texaco Inc. | Process for preparing a catalyst for removal of hydroprocessing impurities |
| CN1289822A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Hydrogenating catalyst for heavy oil and its preparing process |
| CN1946831A (en) * | 2004-04-22 | 2007-04-11 | 阿尔伯麦尔荷兰有限公司 | Hydrotreating catalyst containing a group V metal |
| CN101601995A (en) * | 2008-06-12 | 2009-12-16 | 中国石油化工股份有限公司 | Be used for aluminium oxide catalyst of methanol gas phase dewatering preparing dimethy ether and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| DEANA SOOGUND ET AL: "New Mo-V based oxidic precursor for the hydrotreatment of residues", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| HONGXING DAI ET AL: "Effects of molybdena on the catalytic properties of vanadia domains supported on alumina for oxidative dehydrogenation of propane", 《JOURNAL OF CATALYSIS》 * |
| SHUWU YANG ET AL: "Oxidative Dehydrogenation of Propane over V2O5/MoO3/Al2O3 and V2O5/Cr2O3/Al2O3: Structural Characterization and Catalytic Function", 《J. PHYS. CHEM. B》 * |
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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 |
| CN103566943A (en) * | 2012-07-30 | 2014-02-12 | 中国石油化工股份有限公司 | Hydrogenation protecting catalyst and preparation and application thereof |
| CN103865568A (en) * | 2012-12-12 | 2014-06-18 | 中国石油化工股份有限公司 | VB metal component-containing hydrogenation catalyst, preparation and application thereof |
| 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 |
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| CN104338525A (en) * | 2013-08-02 | 2015-02-11 | 中国石油化工股份有限公司 | A hydrogenation demetalization catalyst for heavy oil, and preparation and applications thereof |
| 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 |
| CN109569575A (en) * | 2017-09-29 | 2019-04-05 | 中国石油化工股份有限公司 | Catalyst with hydrogenation catalyst effect and its preparation method and application and heavy-oil hydrogenation depitching matter method |
| CN109569575B (en) * | 2017-09-29 | 2021-12-17 | 中国石油化工股份有限公司 | Catalyst with hydrogenation catalysis effect, preparation method and application thereof, and heavy oil hydrogenation asphaltene removal method |
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