CN101590433B - Modified aluminium oxide carrier, hydrogenation catalyst prepared thereby and preparation method - Google Patents
Modified aluminium oxide carrier, hydrogenation catalyst prepared thereby and preparation method Download PDFInfo
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Abstract
The invention relates to a hydrogenation catalyst, comprising a modified aluminium oxide carrier and an active metal; wherein, the carrier is obtained by adding fluorocarbon surfactant into aluminium oxide and/or an aluminium oxide precursor for modification. The preparation method of the hydrogenation catalyst comprises the following steps: mixing the aluminium oxide and/or aluminium oxide precursor and a peptizing agent, adding water of moderate amount and kneading into a paste; adding fluorocarbon surfactant and inorganic acid into the paste, kneading and molding to obtain a molding product; baking the molding product in multiple stages to obtain the modified aluminium oxide carrier; dipping the modified aluminium oxide carrier into a stabilized solution which contains one or more of the VIII group metals and one or more of the VIB group metal compounds for once or a plurality of times; drying and baking to obtain the product. The hydrogenation catalyst prepared by the method is characterized by large pore diameter, pore distribution concentration, moderate acid amount and high dispersion degree of active metal.
Description
Technical field
The invention belongs to hydrogenation catalyst field, particularly relate to a kind of hydrogenation catalyst of making for the modified aluminium oxide supports of diesel oil fraction hydrogenating processing with by this carrier and preparation method thereof.
Background technology
In recent years, along with world oil reserves reduce, the trend order benefit that crude oil heaviness and sulfur content increase obviously, in order to make full use of limited resources, petroleum refining industry needs the more effective technology that removes sulphur, wherein hydrogen addition technology is to produce clean fuel, alleviate one of effective measures of environmental pollution, therefore exploitation have high activity and optionally hydrogenation catalyst be subject to people's extensive concern.At present, industrial normally used hydrogenation catalyst is to be that carrier and the metal active constituent that is attached on carrier form by aluminium oxide, silicon-containing alumina and modifier thereof.For improving activity and the stability of catalyst, conventionally need to carrier carry out modification obtaining pore volume, hole area is larger, the carrier of pore distribution concentration.
Chinese patent CN1103009A discloses a kind of preparation method with double-hole alumina support, this preparation method mixes two kinds of different aluminium oxide of pore-size distribution, and add carbon powder, peptizing agent, suitable quantity of water and surfactant mixed-forming by a certain percentage, make through super-dry, roasting.The main purpose that wherein adds surfactant is the effect of playing pore-forming and control pore-size distribution in aluminium oxide calcining process.But in prior art, still there is following defect:
1) surfactant using in prior art is traditional surfactant, its effect is only pore-forming and controls pore-size distribution, and can not play the effect that improves the active metal decentralization that adheres to of carrier surface, therefore in the product that the disclosure technology obtains, the active metal decentralization of load on carrier is not high, thereby affect desulfurized effect, cause desulfurized effect not good.
2) in prior art, mixture after mixed-forming is first dried to a period of time at a lower temperature, after this directly obtain product by the roasting under a higher temperature, this roasting process is taked temperature-rise period one time, easily cause alumina pore crystal structure irregularity because temperature-rise period is too fast, make the specific area often can not be very large, thereby limited the loading of the active metal adhering on carrier.
Summary of the invention
For this reason, technical problem to be solved by this invention is: overcome in prior art on carrier active metal decentralization not high, the defect of alumina support crystal structure irregularity, provides a kind of high modified aluminium oxide supports of active metal decentralization of load; The preparation method of the modified aluminium oxide supports that a kind of crystal structure is good is further provided; The present invention also provides a kind of high hydrogenation catalyst of active metal decentralization of load; And further provide the preparation method of the hydrogenation catalyst that a kind of crystal structure is good.
For solving the problems of the technologies described above, the invention provides a kind of modified aluminium oxide supports, described modified aluminium oxide supports obtains by add fc-surfactant modification in aluminium oxide and/or aluminium oxide precursor.
Described fc-surfactant comprises perfluoroalkyl ethyoxyl ether alcohol, perfluoro butyl sulfonic acid fluoride.
In addition, the present invention also provides a kind of preparation method of above-mentioned modified aluminium oxide supports, comprises the steps:
A) aluminium oxide and/or aluminium oxide precursor are mixed with peptizing agent, and add after appropriate water, be kneaded into paste;
B) in described paste, add fc-surfactant and inorganic acid, after kneading, forming process, obtain article shaped;
C) described article shaped, after multistage roasting, obtains modified aluminium oxide supports.
Described fc-surfactant comprises perfluoroalkyl ethyoxyl ether alcohol, perfluoro butyl sulfonic acid fluoride.
Described fc-surfactant addition is the 0.2-3% of described modified aluminium oxide supports weight.
In step c, described article shaped, after two-stage roasting, obtains modified aluminium oxide supports.
In described two-stage roasting process, described article shaped is at 161-400 DEG C of constant temperature 1-2 hour, and at 600-800 DEG C of constant temperature 0.5-4 hour, the heating rate before each thermostatic process is 3-6 DEG C/min.
In step a, in described aluminium oxide and/or aluminium oxide precursor, further add extrusion aid.
In step a, further add phosphoric acid and/or nitric acid.
In step c, further comprise the step by article shaped described in organic solvent washing, then carry out multistage roasting.
Described organic solvent is ether and/or ethylenediamine.
The present invention further provides a kind of hydrogenation catalyst that adopts above-mentioned modified aluminium oxide supports to prepare, comprise modified aluminium oxide supports and be carried on the oxide of the active metal on described modified aluminium oxide supports, described active metal comprises one or more VIII family metals, and one or more group vib metals.
The oxide of described VIII family metal accounts for the 2-13% of described hydrogenation catalyst weight, and the oxide of described group vib metal accounts for the 12-26% of described hydrogenation catalyst weight.
Described VIII family metal is nickel and/or cobalt, described group vib tungsten and/or molybdenum.
The present invention also provides a kind of preparation method of above-mentioned hydrogenation catalyst, comprises the steps:
A) aluminium oxide and/or aluminium oxide precursor are mixed with peptizing agent, and add after appropriate water, be kneaded into paste;
B) in described paste, add fc-surfactant and inorganic acid, after kneading, forming process, obtain article shaped;
C) described article shaped, after multistage roasting, obtains modified aluminium oxide supports;
D) described modified aluminium oxide supports one or many is soaked in and contains in one or more VIII family metals and one or more group vib metallic compound stabilizing solutions;
E) through super-dry, roasting, obtain hydrogenation catalyst.
Stabilizing solution described in steps d is Mo-Ni-P or Mo-Ni-W-P acid total immersion.
Tool of the present invention has the following advantages:
1) the present invention is in alumina support modifying process, add fluorine-containing surfactant, make it have better surface nature and heat endurance, and make supported metal active constituent on catalyst surface, there is higher decentralization and good dispersity, thereby greatly improved desulfuration efficiency.
2) the present invention adopts the method for multistage roasting to carry out modification to alumina support, can effectively control and improve alpha-alumina crystals structure, can improve load capacity and the decentralization of active metal, thereby further improve desulfuration efficiency.
Detailed description of the invention
By following examples, the present invention is further elaborated.But it should be noted that these embodiment are only for method of the present invention is described, and scope of the present invention can not be confined to this.
The prepared hydrogenation catalyst of the present invention is to be made up of modified aluminium oxide supports and load active metal thereon, and wherein, the physical property of this modified aluminium oxide supports is: specific surface 260-500m
2/ g, pore volume is 0.5-0.8ml/g, aperture 10-20nm accounts for the 74-86% of pore volume; With hydrogenation catalyst as a whole, it consists of: the oxide of group VIII gold belongs to the 2-13% that accounts for hydrogenation catalyst gross weight, the oxide of described group vib metal accounts for the 12-26% of hydrogenation catalyst gross weight, the auxiliary agent such as peptizing agent, extrusion aid always accounts for the 1-5% of hydrogenation catalyst gross weight, and all the other are aluminium oxide.The wherein preferred tungsten of group vib metal and/or molybdenum; The preferred nickel of VIII family metal and/or cobalt.Next respectively the preparation process of modified aluminium oxide supports and hydrogenation catalyst is described and described.
the preparation process of modified aluminium oxide supports
In specific embodiments of the invention, alumina support has added fc-surfactant in modifying process, to introduce fluorine element at carrier surface, its concrete preparation process is as follows:
A) after aluminium oxide and/or aluminium oxide precursor, peptizing agent, extrusion aid are mixed, and add after appropriate water, be kneaded into paste.
Wherein, aluminium oxide precursor refers to the mixture that can generate the hydrous oxide of aluminium oxide after one or more roastings, can be one or more of boehmite, boehmite, SB powder.Peptizing agent and extrusion aid can adopt any commercially available conventional products, in the present invention, be preferably easy to get and cheap Ludox as peptizing agent, sesbania powder is as extrusion aid, and suitable peptizing agent, extrusion aid can improve thermally-stabilised activity, the mechanical strength of modified aluminium oxide supports as modifier.In this step, appropriate water can be replaced with to inorganic aqueous acid, can improve the physical property of alumina support, make it to be more applicable to catalyst of the present invention.The inorganic acid that the present invention selects is nitric acid and/or phosphoric acid solution, wherein adds phosphoric acid and can introduce P element, and it can be used as co-catalyst and improves metal active; If add nitric acid, because it can decompose at roasting process, therefore can play the effect that improves carrier hole structure.
B) in described paste, add fc-surfactant and inorganic acid, after kneading, forming process, obtain article shaped.
Wherein, the 0.2-3% that fc-surfactant addition is vehicle weight.The main purpose that adds fc-surfactant is to make the alignment characteristics of alpha-alumina crystals particle change and form larger offspring, change pore structure parameter, favourable and formation gross porosity simultaneously, and in improving the pore passage structure of aluminium oxide, introduce fluorine element, roasting process fluorine can with aluminium oxide effect, can effectively improve the acidity of carrier, therefore, in the time of supported active metal, can play and improve active metal decentralization and metal.In the present invention, preferred fc-surfactant is the organic carbon fluorine surfactant of perfluoroalkyl ethyoxyl ether alcohol, the contour fluorinated volume of perfluoro butyl sulfonic acid fluoride, on the one hand can introducing fluorine element as much as possible, organic surface active agent can be removed completely in roasting process on the other hand, can residual impurity, thus avoid affecting the desulfurized effect of hydrogenation catalyst.
In this step, forming process can adopt extrusion modling, drip ball forming, compression molding, preferably extrusion modling; Support shapes can be sheet, spherical, strip, preferably strip.Carrier diameter can be 1.0-2.0mm.In forming process, can also add appropriate adhesive and/or extrusion aid, because this process is known by those skilled in the art, therefore do not repeat.
The preferred nitric acid of inorganic acid, phosphoric acid, the hydrochloric acid that use.Inorganic acid concentration is generally unsuitable too high, selects inorganic acid that concentration is lower easily, owing to being well known to those skilled in the art, therefore do not repeat herein.
C) described article shaped, after multistage roasting, obtains modified aluminium oxide supports.
Wherein, in a specific embodiment, adopt two-stage roasting method, the method specifically: by described article shaped, at 161-400 DEG C of constant temperature 1-2 hour, at 600-800 DEG C of constant temperature 0.5-4 hour, the heating rate before each thermostatic process is 3-6 DEG C/min.This two-stage roasting process can obtain larger specific surface by controlling suitable programming rate, improves the loading of metal active constituent; Adopt the process of multistage roasting can make organic additive be burnt to remove organic residue completely, and form better alpha-alumina crystals structure.Certainly, the present invention can also adopt the roasting process such as three sections, four sections, correspondingly the programming rate before constant temperature is adjusted, thereby is reached best modified effect.
In addition, in step c, article shaped is carried out before roasting, further comprise a process by organic solvent washing article shaped, the object of this process is: on the one hand in order to the part compatible solutes of acid solution, the surfactant etc. of article shaped surface attachment is removed; On the other hand, the infiltration by organic solvent in article shaped, absorption, then the quilt process in place to go completely in roasting process, makes article shaped form good surface nature, thereby improves the decentralization of active metal component.The organic solvent using in the present invention can be ether, ethylenediamine.
the preparation process of hydrogenation catalyst
First, according to above-mentioned
the preparation process of modified aluminium oxide supportsprepare modified aluminium oxide supports.
Secondly, described modified aluminium oxide supports one or many is soaked in and is contained in one or more VIII family metals and one or more group vib metallic compound stabilizing solutions.Wherein, the preferred nickel of compound of VIII family metal and group vib metal and/or the water-soluble good compound of cobalt and molybdenum and/or tungsten, as nickel nitrate, cobalt nitrate, ammonium molybdate, ammonium metatungstate, metatungstic acid nickel etc.By repeatedly testing, the preferred Mo-Ni-P of stabilizing solution or Mo-Ni-W-P acid total immersion in the present invention, can obtain the hydrogenation catalyst of desulfurized effect the best.Carrier soaks number of times to be determined according to the concrete condition of catalyst, can once soak, and also can repeatedly soak.
Finally, through super-dry, roasting, obtain hydrogenation catalyst.Wherein, baking temperature: 40-160 DEG C, is preferably 100-150 DEG C; Drying time 10-48 hour.Sintering temperature 300-600 DEG C; Roasting time 3-6 hour.
Identical with common hydrogenation catalyst, need through presulfurization before using hydrogenation catalyst of the present invention, the mode of hydrogen sulfide or other sulfide of can injecting in hydrogen stream is carried out.
The hydrogenation catalyst obtaining in the present invention can be applied in hydrogenation process: at temperature 320-400 DEG C, and pressure 5.0-8.0MPa, liquid air speed 1.0-3.0h
-1, under the condition that hydrogen to oil volume ratio is 400-1000V/V, carry out.
The hydrogenation catalyst preparing by said method has that aperture is large, pore distribution concentration, there is suitable acid amount, active metal has the feature compared with high degree of dispersion.Be applicable to all kinds of distillate hydrogenation processing, be particularly useful for the hydrotreatment of poor ignition quality fuel.
Above to modified aluminas and adopt composition and the preparation process of hydrogenation catalyst prepared by described modified aluminas to be illustrated and to describe, below in conjunction with embodiment, modified aluminium oxide supports of the present invention and hydrogenation catalyst are further described and are described, in addition provide embodiment in comparative example and the present invention to compare, can more have a clear understanding of the advantage of the embodiment of the present invention.But it should be noted that these embodiment are only for method and apparatus of the present invention is described, and scope of the present invention can not be confined to this.
Embodiment 1 Kaolinite Preparation of Catalyst carrier Z1
Take 100g boehmite (butt 72w%) and add 60ml to contain 2% aqueous solution of nitric acid, 20g Ludox, the mixing of 5g sesbania powder, be kneaded into paste.By 2.6g perfluoroalkyl ethyoxyl ether alcohol [RFH
2cH
2(OC
2h
4)
8oH] add 30ml to contain in 2% phosphorus aqueous acid, after stirring and dissolving, by this solution in above-mentioned paste kneading, extruded moulding.Article shaped is immersed in 30ml ethylenediamine to 2 hours, then takes out article shaped and be placed at 161 DEG C roasting 2 hours, 600 DEG C 3 hours, before each constant temperature, heating rate is 4 DEG C/min.Obtain carrier Z1.Its physico-chemical property is in table 1.
Embodiment 2 Kaolinite Preparation of Catalyst carrier Z2
Take 100g boehmite (butt 72w%) and add 60ml to contain 2% aqueous solution of nitric acid, 20g Ludox, the mixing of 5g sesbania powder, be kneaded into paste.By 0.18g perfluoro butyl sulfonic acid fluoride (C
4f
9sO
2f) add 20ml to contain in 3% phosphorus aqueous acid, after stirring and dissolving, by this solution in above-mentioned paste kneading, extruded moulding.Article shaped is immersed in 30ml ethylenediamine to 2 hours, then takes out article shaped and be placed at 360 DEG C roasting 1.5 hours, 700 DEG C of roastings 2 hours, before each constant temperature, heating rate was 6 DEG C/min.Obtain carrier Z2.Its physico-chemical property is in table 1.
Embodiment 3 Kaolinite Preparation of Catalyst carrier Z3
The present embodiment is substantially the same manner as Example 2, and difference is that the addition of (1) perfluoro butyl sulfonic acid fluoride is 1.2g; (2) roasting condition is roasting 1 hour at 400 DEG C, and then 800 DEG C of roastings 0.5 hour, before each constant temperature, heating rate is 3 DEG C/min.Obtain carrier Z3.Its physico-chemical property is in table 1.
Embodiment 4 Kaolinite Preparation of Catalyst C1
Take 16.2g ammonium tetramolybdate (containing molybdenum oxide 85.0%) and add in 100ml deionized water, after dissolving, add and 21.5g ammonium metatungstate (containing tungsten oxide 80.6%), stirring and dissolving; In 20ml deionized water, add 10g nickel nitrate (Ni (NO
3)
26H
2and 10ml phosphoric acid O), after stirring and dissolving, mix two kinds of solution, filter, add appropriate amount of deionized water, obtain stable Mo-Ni-W-P acid total immersion 100ml.Get at room temperature saturated dipping of the above-mentioned co-impregnated solution of carrier Z1 described in 100g embodiment 1, hold over night; Prepare same Mo-Ni-W-P acid total immersion 100ml, carrier Z1 after soaking is soaked for the second time, then at 130 DEG C dry 10 hours, at 450 DEG C, be dried 5 hours, in the catalyst obtaining, molybdenum oxide weight content is 12%, and tungsten oxide weight content is 14%, and nickel oxide weight content is 2%.Make catalyst C1.
Embodiment 5 Kaolinite Preparation of Catalyst C2
Take 5.2g ammonium tetramolybdate (containing molybdenum oxide 85.0%) and add in 100ml deionized water, after dissolving, add and 14.2g ammonium metatungstate (containing tungsten oxide 80.6%), stirring and dissolving; In 20ml deionized water, add 56g nickel nitrate (Ni (NO
3)
26H
2and 10ml phosphoric acid O), after stirring and dissolving, mix two kinds of solution, filter, add appropriate amount of deionized water, obtain stable Mo-Ni-W-P acid total immersion 100ml.Get at room temperature saturated dipping of the above-mentioned co-impregnated solution of carrier Z2 described in 100g embodiment 2, hold over night, then at 130 DEG C dry 10 hours, at 450 DEG C, be dried 5 hours, in the catalyst obtaining, molybdenum oxide weight content is 4%, tungsten oxide weight content is 8%, and nickel oxide weight content is 13%.Make catalyst C2.
Embodiment 6 Kaolinite Preparation of Catalyst C3
Take 12.1g ammonium tetramolybdate (containing molybdenum oxide 85.0%) and add in 100ml deionized water, after dissolving, add and 15.8g ammonium metatungstate (containing tungsten oxide 80.6%), stirring and dissolving; In 20ml deionized water, add 21g nickel nitrate (Ni (NO
3)
26H
2and 10ml phosphoric acid O), after stirring and dissolving, mix two kinds of solution, filter, add appropriate amount of deionized water, obtain stable Mo-Ni-W-P acid total immersion 100ml.Get at room temperature saturated dipping of the above-mentioned co-impregnated solution of carrier Z3 described in 100g embodiment 3, hold over night, then at 130 DEG C dry 10 hours, at 450 DEG C, be dried 5 hours, in the catalyst obtaining, molybdenum oxide weight content is 8.1%, and molybdenum oxide weight content is 11.8%, and nickel oxide weight content is 4.8%.Make catalyst C3.
Comparative example 1 Kaolinite Preparation of Catalyst carrier S Z1 and catalyst S C1
Take 100g boehmite (butt 72w%) and add 60ml to contain 2% aqueous solution of nitric acid, 20g Ludox, the mixing of 5g sesbania powder, be kneaded into paste, extruded moulding.Article shaped is immersed in 30ml ethylenediamine to 2 hours, then takes out article shaped and be placed at 150 DEG C dry 2 hours; Then 650 DEG C of roastings 3 hours.Obtain carrier S Z1.Its physico-chemical property is in table 1.
Get the at room temperature saturated dipping of stable co-impregnated solution described in embodiment 4 for the above-mentioned carrier S Z1 of 100g, hold over night, then at 130 DEG C dry 10 hours, at 450 DEG C dry 5 hours.Make catalyst S C1.
Catalyst hydrogenation activity is evaluated: the diesel oil hydrogenation activity rating of above each routine catalyst the results are shown in Table 2.
It is cracked diesel oil that this example is evaluated raw materials used, it is characterized by: density (d
4 20) be 0.893g/cm
3, sulfur content is: 6154 μ g/g, and nitrogen content is: 1035 μ g/g, aniline point is 49.0 DEG C, and Cetane number is 35.8, and boiling range is 171-362 DEG C.
In this example, above each routine catalyst sulfidation is before use: 100g catalyst is packed in hydrogenation reactor, pass into hydrogen, adjustment System pressure is 6.0MPa, amounts of hydrogen is 800ml/min, reactor is warming up to 120 DEG C by heating rate with 35 DEG C/h, and constant temperature makes catalyst dehydration for 2 hours.Dehydration finishes the rear presulfurization oil that starts to pump into: presulfurization oil is for having added the aviation kerosine of 3% carbon disulfide, and charging rate is 100ml/h.Then with the programming rate of 40 DEG C/h, the temperature of reactor is risen to 200 DEG C, 240 DEG C, 280 DEG C, 320 DEG C, and each temperature spot constant temperature 1 hour; Finally be warming up to 340 DEG C, keep 12 hours, start to pump into above-mentioned cracked diesel oil feedstock oil after completing presulfurization.
This routine adopting process condition: 350 DEG C of temperature, pressure 6.0MPa, liquid air speed 1.0h
-1, hydrogen to oil volume ratio is 480V/V.
The main physico-chemical property of table 1 carrier
| Catalyst | F content % | Pore volume (ml/g) | Specific surface (m 2/g) | Bulk density (g/ml) |
| Z1 | 2.1 | 0.78 | 352 | 0.78 |
| Z2 | 2.1 | 0.76 | 345 | 0.82 |
| Z3 | 2.6 | 0.70 | 341 | 0.80 |
| SZ1 | - | 0.52 | 284 | 0.82 |
Table 2 catalyst diesel oil hydrogenation activity rating table
| Project | Raw material | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 |
| Catalyst | C1 | C2 | C3 | SC1 | |
| Density, 20 DEG C, g/cm 3 | 0.893 | 0.853 | 0.843 | 0.822 | 0.863 |
| Aniline point, DEG C | 49.0 | 56.1 | 57.2 | 56.4 | 61.0 |
| Sulfur content, μ g/g | 6154 | 110 | 113 | 120 | 175 |
| Nitrogen content, μ g/g | 1035 | 51 | 52 | 57 | 98 |
Carrier by the visible the inventive method of table 1 institute controlling catalyst has good physico-chemical property, and roasting condition has a certain impact to physico-chemical property.And can find out by table 2: the poor ignition quality fuel of the made catalyst treatment of the present invention, its sulphur nitrogen content obviously reduces, diesel oil character be improved significantly.This catalyst is a kind of hydrogenation catalyst of excellence.
Obviously, above-described embodiment is only for example is clearly described, and the not restriction to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here without also giving exhaustive to all embodiments.And the apparent variation of being extended out thus or variation are still among the protection domain in the invention.
Claims (13)
1. a modified aluminium oxide supports, is characterized in that: described modified aluminium oxide supports obtains by add fc-surfactant modification in aluminium oxide and/or aluminium oxide precursor; Described fc-surfactant addition is the 0.2-3% of described modified aluminium oxide supports weight;
The preparation method of described modified aluminium oxide supports, comprises the steps:
A) aluminium oxide and/or aluminium oxide precursor are mixed with peptizing agent, and add after appropriate water, be kneaded into paste;
B) in described paste, add fc-surfactant and inorganic acid, after kneading, forming process, obtain article shaped;
C) described article shaped, after multistage roasting, obtains modified aluminium oxide supports.
2. modified aluminium oxide supports according to claim 1, is characterized in that: described fc-surfactant comprises perfluoroalkyl ethyoxyl ether alcohol or perfluoro butyl sulfonic acid fluoride.
3. modified aluminium oxide supports according to claim 1 and 2, is characterized in that: in step c, described article shaped, after two-stage roasting, obtains modified aluminium oxide supports.
4. modified aluminium oxide supports according to claim 3, it is characterized in that: in described two-stage roasting process, described article shaped is at 161-400 DEG C of constant temperature 1-2 hour, and at 600-800 DEG C of constant temperature 0.5-4 hour, the heating rate before each thermostatic process is 3-6 DEG C/min.
5. modified aluminium oxide supports according to claim 1 and 2, is characterized in that: in step a, in described aluminium oxide and/or aluminium oxide precursor, further add extrusion aid.
6. modified aluminium oxide supports according to claim 1 and 2, is characterized in that: in step a, further add phosphoric acid and/or nitric acid.
7. modified aluminium oxide supports according to claim 1 and 2, is characterized in that: in step c, further comprise the step by article shaped described in organic solvent washing, then carry out multistage roasting.
8. modified aluminium oxide supports according to claim 7, is characterized in that: described organic solvent is ether and/or ethylenediamine.
9. a hydrogenation catalyst of preparing according to modified aluminium oxide supports described in any one in claim 1 to 8, comprise modified aluminium oxide supports and be carried on the oxide of the active metal on described modified aluminium oxide supports, it is characterized in that: described active metal comprises one or more VIII family metals, and one or more group vib metals.
10. hydrogenation catalyst according to claim 9, is characterized in that: the oxide of described VIII family gold belongs to the 2-13% that accounts for described hydrogenation catalyst gross weight, and the oxide of described group vib metal accounts for the 12-26% of described hydrogenation catalyst gross weight.
11. hydrogenation catalysts according to claim 10, is characterized in that: described VIII family metal is nickel and/or cobalt, described group vib tungsten and/or molybdenum.
Prepare according to the method for the hydrogenation catalyst described in any one in claim 9 to 11, comprise the steps: for 12. 1 kinds
A) aluminium oxide and/or aluminium oxide precursor are mixed with peptizing agent, and add after appropriate water, be kneaded into paste;
B) in described paste, add fc-surfactant and inorganic acid, after kneading, forming process, obtain article shaped;
C) described article shaped, after multistage roasting, obtains modified aluminium oxide supports;
D) described modified aluminium oxide supports one or many is soaked in and contains in one or more VIII family metals and one or more group vib metallic compound stabilizing solutions;
E) through super-dry, roasting, obtain hydrogenation catalyst.
The preparation method of 13. hydrogenation catalysts according to claim 12, is characterized in that: stabilizing solution described in steps d is Mo-Ni-P or Mo-Ni-W-P acid total immersion.
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| CN1249328A (en) * | 1998-09-28 | 2000-04-05 | 中国石油化工集团公司 | Hydroprocessing catalyst and its preparing process |
| CN1302848A (en) * | 2000-01-04 | 2001-07-11 | 中国石油化工集团公司 | Hydrogenating catalyst and its preparing process |
| CN1597515A (en) * | 2004-09-03 | 2005-03-23 | 吉林大学 | Method of synthesizing mecropore and mesopore material using semifluorine surface active agent |
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2008
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1249328A (en) * | 1998-09-28 | 2000-04-05 | 中国石油化工集团公司 | Hydroprocessing catalyst and its preparing process |
| CN1302848A (en) * | 2000-01-04 | 2001-07-11 | 中国石油化工集团公司 | Hydrogenating catalyst and its preparing process |
| CN1597515A (en) * | 2004-09-03 | 2005-03-23 | 吉林大学 | Method of synthesizing mecropore and mesopore material using semifluorine surface active agent |
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| Zhaorong Zhang等.Mesostructured γ-Al2O3 with a Lathlike Framework Morphology.《Journal of the American Chemical Society》.ACS Publications,2002,第124卷(第41期),12294-12301. * |
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| CN101590433A (en) | 2009-12-02 |
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Address after: 100080 9th floor, Dahang Jiye building, No.1 building, 33 Renmin North Road, Haidian District, Beijing Patentee after: Beijing Haixin Energy Technology Co.,Ltd. Patentee after: DALIAN INSTITUTE OF CHEMICAL PHYSICS, CHINESE ACADEMY OF SCIENCES Address before: 100080, Beijing, Haidian District people's Congress Road 33, the big line foundation building 9 floor Patentee before: BEIJING SANJU ENVIRONMENTAL PROTECTION & NEW MATERIALS Co.,Ltd. Patentee before: DALIAN INSTITUTE OF CHEMICAL PHYSICS, CHINESE ACADEMY OF SCIENCES |