CN102652921A - Hydrodemetallization catalyst using halogen-containing aluminum oxide as carrier as well as preparation and application thereof - Google Patents
Hydrodemetallization catalyst using halogen-containing aluminum oxide as carrier as well as preparation and application thereof Download PDFInfo
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Abstract
The invention discloses a hydrodemetallization catalyst using halogen-containing aluminum oxide as a carrier as well as preparation and application of the hydrodemetallization catalyst. The catalyst contains a halogen-containing aluminum oxide carrier and a hydrogenation active metal component which is loaded on the carrier, wherein the hydrogenation active metal component is combination of at least one metal component selected from VIB group and at least one metal component selected from VB group; and according to oxide and taking the catalyst as standard, the content of the VIB group metal component is 0.2-15wt.% and the content of the VB group metal component is 0.2-12wt.%. Compared with the catalysts in the prior art, the catalyst provided by the invention has the advantage that the hydrodemetallization, asphaltene desorption and carbon residue desorption activities are markedly improved.
Description
Technical field
The present invention relates to a kind of Hydrodemetalation catalyst, preparation and application thereof that is suitable for especially residual hydrocracking process of heavy oil.
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 active and stable catalyst, preparation and an application thereof of high HDM.
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 the stability of catalyst is improved through selection to the catalyst activity metal component.
The present invention relates to following invention:
1, with halogen-containing aluminium oxide is the Hydrodemetalation catalyst of carrier; Contain halogen-containing alumina support and load on the hydrogenation active metals component on this carrier; It is characterized in that described hydrogenation active metals component is at least a metal component and the combination that is selected from least a metal component of VB family that is selected from 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 halogen-containing aluminium oxide be selected from the halogen-containing γ of having-, η-, θ-, δ-and χ-single or mix the aluminium oxide of crystalline phase; Said halogen is a fluorine, is benchmark in element and with said carrier, and the content of halogen is 1-8 weight % in the said carrier.
5, according to 4 described catalyst; It is characterized in that; Said halogen-containing aluminium oxide be selected from the halogen-containing γ of having-, η-, θ-and δ-single or mix the aluminium oxide of crystalline phase, be benchmark in element and with said carrier, the content of halogen is 2-6 weight % in the said carrier.
6, according to 5 described catalyst, it is characterized in that, is benchmark in element and with said carrier, and the content of halogen is 2-4 weight % in the said carrier.
7, a kind of is the preparation method of the Hydrodemetalation catalyst of carrier with halogen-containing aluminium oxide; Be included in load hydrogenation active metals component on the halogen-containing alumina support; It is characterized in that described hydrogenation active metals component is at least a metal component and the combination that is selected from least a metal component of VB family that is selected from 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 %.
8, according to 7 described methods; It is characterized in that; The metal component of said group vib is 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 %.
9, according to 8 described methods; It is characterized in that the metal component of said group vib is that molybdenum or tungsten VB family metal component are vanadium, is benchmark in oxide and with the catalyst; The content of said group vib metal component is 5-12 weight %, and the content of VB family metal component is 1-9 weight %.
10, according to 7 described methods; It is characterized in that; Said halogen-containing aluminium oxide be selected from the halogen-containing γ of having-, η-, θ-, δ-and χ-single or mix the aluminium oxide of crystalline phase; Said halogen is a fluorine, is benchmark in element and with said carrier, and the content of halogen is 1-8 weight % in the said carrier.
11, according to 10 described methods; It is characterized in that; Said halogen-containing aluminium oxide be selected from the halogen-containing γ of having-, η-, θ-and δ-single or mix the aluminium oxide of crystalline phase, be benchmark in element and with said carrier, the content of halogen is 2-6 weight % in the said carrier.
12, according to 11 described methods, it is characterized in that, is benchmark in element and with said carrier, and the content of halogen is 2-4 weight % in the said carrier.
13, according to 7,10,11 or 12 each described methods; It is characterized in that; Said halogen-containing alumina support is the article shaped of halogen-containing aluminium oxide; Said article shaped by comprise with the precursor of aluminium oxide and/or aluminium oxide and halogen contained compound, 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 ℃, the time is 1-24 hour; Roasting condition is: temperature 350-1000 ℃, the time is 1-10 hour.
According to 13 described methods, it is characterized in that 14, 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.
15, according to 7 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 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 0.2-15 weight %, and the content of VB family metal component is 0.2-12 weight %; Said drying condition is: temperature 80-200 ℃; Time 1-8 hour, roasting condition was: temperature 400-600 ℃, and time 2-8 hour.
16, according to 15 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 0.5-12 weight %; The content of VB family metal component is 0.5-9 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.
17, according to 16 described methods; It is characterized in that; 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 5-12 weight %, and the content of VB family metal component is 1-9 weight %.
18, a kind of heavy-oil hydrogenation processing method; Be included under the heavy-oil hydrogenation processing reaction condition heavy raw oil is contacted with catalyst; It is characterized in that, comprise Hydrodemetalation catalyst in the said catalyst, said Hydrodemetalation catalyst is each described catalyst of aforementioned 1-6.
According to catalyst provided by the invention, wherein, said halogen-containing aluminium oxide can be the halogen-containing γ of having-, η-, θ-, δ-and χ-single or mix the aluminium oxide of crystalline phase, preferably have γ-, η-, θ-and δ-single or mix the aluminium oxide of crystalline phase.Said halogen is preferably fluorine, is benchmark in element and with the carrier, and the content of said halogen is preferably 2-6 weight %, further is preferably 2-4 weight %.Optionally, said halogen alumina support can be processed the article shaped of easy operating arbitrarily.Said moulding can be undertaken by conventional method, all can like methods such as compressing tablet, spin, extrusions.When moulding; Extruded moulding for example; Carry out smoothly for guaranteeing said moulding; Can in the mixture of the precursor of described aluminium oxide and/or aluminium oxide and halogen contained compound, add entry, extrusion aid and/or adhesive, contain or not contain expanding agent, 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.For example, CN1966616A (200510115349.0) discloses a kind of halogen-containing alumina support and preparation method thereof, and wherein, said halogen-containing alumina support is a benchmark in element and with said carrier, and the content of said halogen is 0.5-10 weight %.The preparation method of said carrier comprises precursor moulding and roasting with aluminium oxide, wherein; Before moulding and roasting; The precursor of aluminium oxide is mixed with halogen contained compound, and said sintering temperature is 850-1200 ℃, roasting time 1-10 hour; In element and with the carrier total amount is benchmark, and the consumption of each component makes the halogen that contains 1-7 weight % in the final alumina support.CN1626625A (200310117322.6) discloses a kind of halogen-containing alumina support and preparation method thereof, said carrier by comprise with a kind of hydrated alumina and expanding agent through mix, the method for moulding and roasting makes, said expanding agent comprises a kind of organic expanding agent and a kind of halide; Sintering temperature is 600-850 ℃, is preferably 650-800 ℃, roasting time 1-0 hour; Being preferably 2-8 hour, is benchmark with the carrier, and the consumption of each component makes final carrier contain the aluminium oxide of 95-99 weight %; Be preferably-7-99 weight %; In element, the halogen of 0-1-5 weight % is preferably 0-2-3 weight %; Preferred my fluoride, for example ammonium fluoride and/or the hydrofluoric acid of said halide.The disclosed employing dipping method of CN85104438 prepares the method for halogen-containing alumina support, and these all can be suitable for the present invention, quote as a reference in the lump here.In element and with the carrier total amount is benchmark, and the content of halogen is preferably 1-8 weight % in the carrier described in preferred embodiment, further is preferably 2-6 weight %, is more preferably 2-4 weight %.
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 V.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 1-9 weight % more.
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 alkali metal or 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 %.
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.
When also containing components such as alkali metal or phosphorus in the said catalyst; The introducing method of components such as said alkali metal or phosphorus can be an arbitrary method, as can being directly with the precursor (like boehmite) of said aluminium oxide with halogen contained compound mixes, moulding and roasting with the compound that contains components such as said alkali metal or phosphorus; Can be with the compound that contains components such as said alkali metal or 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 components such as alkali metal or phosphorus.When components such as alkali metal or 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 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 with in the catalytic reaction dress of the said catalyst device, 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, Hydrodemetalation catalyst provided by the invention is when having high metal removal activity, high diasphaltene rate and taking off the carbon residue performance, and its stability obviously improves.
The specific embodiment
Following embodiment will further specify the present invention.
Embodiment 1-2 explanation the present invention and Comparative Examples are with alumina support 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%; Gibbsite content is 5 weight %, and surplus is an amorphous alumina) 1200 grams, 36 gram sesbania powder (Lankao, Henan sesbania gum factory product) mix; 1440 milliliters of the aqueous solution that add fluorinated ammonium (Tianjin chemical reagent three factory's products) 48g afterwards are extruded into the butterfly bar of external diameter φ 1.1mm on the twin-screw banded extruder.Wet bar after 2 hours, obtains carrier Z1 in 700 ℃ of roastings in 120 ℃ of dryings 4 hours.The physico-chemical property of carrier Z1 is seen table 1.
Embodiment 2
(butt is 73% to take by weighing the dry glue powder that Chang Ling oil plant catalyst plant produces; Wherein boehmite content is 68%; Gibbsite content is 5 weight %, and surplus is an amorphous alumina) 1200 grams, 36 gram sesbania powder (Lankao, Henan sesbania gum factory product) mix; 1440 milliliters of the aqueous solution that add fluorinated ammonium (Tianjin chemical reagent three factory's products) 65g afterwards are extruded into the butterfly bar of external diameter φ 1.1mm on the twin-screw banded extruder.Wet bar after 2 hours, obtains Z2 in 700 ℃ 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 | F, weight % | The acid amount, mmol/g |
| Z1 | 0.77 | 176 | 2 | 0.11 |
| Z2 | 0.85 | 183 | 3.8 | 0.18 |
Embodiment 3-6 explains Catalysts and its preparation method provided by the invention.
Embodiment 3
Get the carrier Z1200 gram 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.
Comparative Examples 1-2
Get carrier Z1, each 200 gram of Z2 of embodiment 1 and embodiment 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.
Embodiment 4
Get carrier Z1 200 grams of embodiment 1 preparation, contain MoO3 120 grams per liters, V with 500 milliliters
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 5
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 6
Get the carrier Z1200 gram 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 7-10
Embodiment 7-10 explains Application of Catalyst provided by the invention and effect thereof.
With the normal slag of Kuwait is raw material, on 100 milliliters of small stationary bed bioreactors, estimates protective agent.
Catalyst CZ1, 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, and hydrogen to oil volume ratio is 1000, react sampling after 200 hours.
Demetallization per, diasphaltene rate, the concrete computational methods of taking off carbon yield and desulfurization degree are following:
Catalyst after estimating is cleaned twice with toluene, use toluene extracting 12 hours in cable-styled extraction device again, adopt RIPP 106-90 method to measure the carbon content in the catalyst afterwards, the result lists in table 4.
Feedstock oil character is listed in table 3, and evaluation result is listed in the table 4.
Comparative Examples 3-4
According to demetallization per, the diasphaltene rate of the method evaluate catalysts DZ1 of embodiment 7, DD1, take off carbon yield and desulfurization degree, the result sees table 4.
Table 3
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 (18)
1. with halogen-containing aluminium oxide the Hydrodemetalation catalyst of carrier; Contain halogen-containing alumina support and load on the hydrogenation active metals component on this carrier; It is characterized in that described hydrogenation active metals component is at least a metal component and the combination that is selected from least a metal component of VB family that is selected from 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 halogen-containing aluminium oxide be selected from the halogen-containing γ of having-, η-, θ-, δ-and χ-single or mix the aluminium oxide of crystalline phase; Said halogen is a fluorine, is benchmark in element and with said carrier, and the content of halogen is 1-8 weight % in the said carrier.
5. according to 4 described catalyst; It is characterized in that; Said halogen-containing aluminium oxide be selected from the halogen-containing γ of having-, η-, θ-and δ-single or mix the aluminium oxide of crystalline phase, be benchmark in element and with said carrier, the content of halogen is 2-6 weight % in the said carrier.
6. according to 5 described catalyst, it is characterized in that, is benchmark in element and with said carrier, and the content of halogen is 2-4 weight % in the said carrier.
7. one kind is the preparation method of the Hydrodemetalation catalyst of carrier with halogen-containing aluminium oxide; Be included in load hydrogenation active metals component on the halogen-containing alumina support; It is characterized in that described hydrogenation active metals component is at least a metal component and the combination that is selected from least a metal component of VB family that is selected from 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 %.
8. according to 7 described methods; It is characterized in that; The metal component of said group vib is 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 %.
9. according to 8 described methods; It is characterized in that the metal component of said group vib is that molybdenum or tungsten VB family metal component are vanadium, is benchmark in oxide and with the catalyst; The content of said group vib metal component is 5-12 weight %, and the content of VB family metal component is 1-9 weight %.
10. according to 7 described methods; It is characterized in that; Said halogen-containing aluminium oxide be selected from the halogen-containing γ of having-, η-, θ-, δ-and χ-single or mix the aluminium oxide of crystalline phase; Said halogen is a fluorine, is benchmark in element and with said carrier, and the content of halogen is 1-8 weight % in the said carrier.
11. according to 10 described catalyst; It is characterized in that; Said halogen-containing aluminium oxide be selected from the halogen-containing γ of having-, η-, θ-and δ-single or mix the aluminium oxide of crystalline phase, be benchmark in element and with said carrier, the content of halogen is 2-6 weight % in the said carrier.
12., it is characterized in that according to 11 described catalyst, be benchmark in element and with said carrier, the content of halogen is 2-4 weight % in the said carrier.
13. according to 7,10,11 or 12 each described methods; It is characterized in that; Said halogen-containing alumina support is the article shaped of halogen-containing aluminium oxide; Said article shaped by comprise with the precursor of aluminium oxide and/or aluminium oxide and halogen contained compound, 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 ℃, the time is 1-24 hour; Roasting condition is: temperature 350-1000 ℃, the time is 1-10 hour.
14., it is characterized in that said forming method is an extruded moulding according to 13 described methods, 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.
15. according to 7 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 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 0.2-15 weight %, and the content of VB family metal component is 0.2-12 weight %; Said drying condition is: temperature 80-200 ℃; Time 1-8 hour, roasting condition was: temperature 400-600 ℃, and time 2-8 hour.
16., it is characterized in that, be benchmark in oxide and with the catalyst according to 15 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 0.5-12 weight %; The content of VB family metal component is 0.5-9 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.
17. according to 16 described methods; It is characterized in that; 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 5-12 weight %, and the content of VB family metal component is 1-9 weight %.
18. heavy-oil hydrogenation processing method; Be included under the heavy-oil hydrogenation processing reaction condition heavy raw oil is contacted with catalyst; It is characterized in that, comprise Hydrodemetalation catalyst in the said catalyst, said Hydrodemetalation catalyst is each described catalyst of aforementioned 1-6.
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| CN104226342A (en) * | 2013-06-13 | 2014-12-24 | 中国石油化工股份有限公司 | Heavy oil hydrotreating catalyst and preparation and application |
| CN104368332A (en) * | 2013-08-14 | 2015-02-25 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation and applications thereof |
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| CN104226342A (en) * | 2013-06-13 | 2014-12-24 | 中国石油化工股份有限公司 | Heavy oil hydrotreating catalyst and preparation and application |
| CN104226342B (en) * | 2013-06-13 | 2017-02-08 | 中国石油化工股份有限公司 | Heavy oil hydrotreating catalyst and preparation and application |
| CN104368332A (en) * | 2013-08-14 | 2015-02-25 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation and applications thereof |
| CN104368332B (en) * | 2013-08-14 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of hydrotreating catalyst and preparation and application thereof |
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