CN103007922B - Method for preparing loaded hydrofining catalyst - Google Patents
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Abstract
The invention relates to a method for preparing a loaded hydrofining catalyst. The method comprises the following steps of: dissolving metal salts into an aqueous hydrogen peroxide solution so as to obtain impregnation liquid; carrying out impregnation on a carrier by using the impregnation liquid; and drying and roasting an impregnation product so as to obtain the loaded hydrofining catalyst. The catalyst prepared by using the method disclosed by the invention is higher in active component dispersity and poor in interaction of active components and carriers, and has better hydrodesulfurization activity and hydro-dearomatization activity in comparison with a catalyst prepared by using the conventional impregnation method.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst, particularly relate to a kind of preparation method of load hydrogenation catalyst for refining, belong to Hydrobon catalyst preparing technical field.
Background technology
World's oil product demand presents the trend of rise, and so large oil product demand can bring very important impact to society and environment, and wherein, oil quality has become the emphasis that present society is paid close attention to.Along with the increasingly stringent of environmental legislation, oil quality standard is progressively upgraded, and the production of clear gusoline becomes one gradually and significantly works.
Hydrofining Technology is the important means that clear gusoline is produced, and is current most popular Hydrobon catalyst with the loaded catalyst that W or Mo of group vib is host, VIII race's W metal or Co be auxiliary agent, aluminium oxide is carrier.The raising of the activity of Hydrobon catalyst is the emphasis of research at present, part research work is conceived to the selective of active component and carrier, in addition, the decentralization making great efforts to improve active component in catalyst is also one of effective way improving catalyst activity, and therefore preparation method and preparation condition have important impact to the decentralization of catalyst and performance.
At present, the method for carried metal active component mainly contains: the precipitation method, hydro-thermal method and infusion process.Applying more in the precipitation method is coprecipitation, and it is that active presoma and carrier ion are mixed into solution, coprecipitation, then obtains catalyst through calcination process.Hydro-thermal method sedimentation is actual be hydrothermal treatment consists and precipitation in conjunction with processing method, first surfactant and precipitating reagent jointly in the presence of, conservative control hydrothermal temperature and time obtain suspension, then by suspension filtered, washing roasting.The precipitation method compare evenly with the distribution of the active component particles of hydrothermal deposition method, but operating parameter is too many, are often difficult to control and repeat.Infusion process have preparation simple, the features such as strong can be operated, be the common method preparing loaded catalyst.The preparation process of infusion process is immersed in by carrier in the solution containing active component presoma, then obtain loaded catalyst through suitable oven dry and calcination process, mainly comprises step impregnation method and co-impregnation.But, under normal conditions, in the catalyst that infusion process obtains, there is following problem: metal active constituent is at carrier surface skewness, and active component particles is large, and decentralization is low, and this have impact on the activity of catalyst.
Reduce active component particles size by suitable mode, improve decentralization, increase activated centre quantity, will the raising of catalytic activity be promoted.Equilibrium Adsorption Method utilizes the reaction on active component presoma and carrier surface hydroxyl and makes active constituent loading on carrier, active component can be made to form less crystal grain and have good contact with carrier surface, be evenly distributed, improve decentralization ((N.Spanos et al., Journal of Catalysis, 1990,124 (2): 301; L Karakonstantis et al., Journal of Catalysis, 1990,124 (2): 315; Kordulis et al., Applied Catalysis A:General, 2001,209:85), but this method can strengthen the interaction between active component and carrier, cause active component to pile up the reduction of degree, form relatively many I class hydrogenation sites, be difficult to sulfuration.
Therefore, realized the raising of activity of hydrocatalyst component disperses degree by suitable method, weaken the accumulation degree that active component and carrier interphase interaction improve activated centre, be one of this area problem demanding prompt solution simultaneously.
Summary of the invention
For solving the problems of the technologies described above, the object of the present invention is to provide a kind of preparation method of load hydrogenation catalyst for refining, it floods carrier with hydrogen peroxide solution to prepare maceration extract and prepare the method for load hydrogenation catalyst for refining, the active component decentralization of catalyst can be improved, and the interaction that can weaken between active component and carrier, improves the accumulation degree in activated centre.
The present invention also aims to provide a kind of load hydrogenation catalyst for refining prepared by above-mentioned preparation method.
For achieving the above object, the present invention provide firstly a kind of preparation method of load hydrogenation catalyst for refining, and it comprises the following steps:
The salt of metal is dissolved in hydrogen peroxide solution and obtains maceration extract;
Above-mentioned maceration extract is utilized to flood carrier;
Drying, roasting are carried out to impregnation product, obtains load hydrogenation catalyst for refining.
Above-mentioned preparation method provided by the invention goes for the preparation of Hydrobon catalyst, and the metal (i.e. active component) of load on a catalyst can be group vib metal etc., and preferably, above-mentioned group vib metal is tungsten or molybdenum etc.
Above-mentioned preparation method provided by the invention substitutes traditional water as solvent to prepare maceration extract (or claiming precursor solution) using hydrogen peroxide, obtain the solution containing active component species, realize the high dispersive of catalyst metals active component on carrier and high stacking, the hydrodesulfurization of catalyst and the activity of hydrogenation dearomatization are significantly improved, preferably, the concentration of the hydrogen peroxide solution adopted is 10-45wt%, is more preferably 30wt%.
According to concrete technical scheme of the present invention, above-mentioned preparation method can also comprise the step adding dispersant, and this dispersant preferably joins in the maceration extract of hydrogen peroxide preparation.By adding dispersant in maceration extract, except can playing the effect of divided active component, can also with the presoma species coordination of active component, affect further the interaction between carrier and active component presoma species.Dispersant of the present invention can be one or more in the binary organic carboxyl acid containing 2-12 carbon or ternary organic carboxyl acid etc.; Preferably, above-mentioned dispersant is one or more in citric acid, tartaric acid and oxalic acid etc.According to the concrete technical scheme of the present invention, preferably, the addition of dispersant may be controlled to the 0.1-2% of maceration extract gross weight.
In above-mentioned preparation method provided by the invention, preferably, maceration extract is being adopted to control as 10-60 DEG C the temperature that carrier floods.
In above-mentioned preparation method provided by the invention, the carrier adopted can be conventional hydro refining catalytic agent carrier, preferably, the carrier adopted is porous oxide carrier, more preferably, above-mentioned carrier is the aluminium oxide etc. of the molecular sieve modified aluminium oxide of aluminium oxide, beta or Y molecular sieve modification.Wherein, when adopting the aluminium oxide of Y molecular sieve modification, in the compound of the two, the mass ratio of aluminium oxide and Y molecular sieve can be 8-4: 1; When the aluminium oxide adopting beta molecular sieve modified, in the compound of the two, the mass ratio of aluminium oxide and beta molecular sieve can be 8-4: 1.
The preparation method of load hydrogenation catalyst for refining provided by the present invention is a kind of hydrogen peroxide infusion process, it is in hydrogen peroxide system, using as the metal (such as vib metal) of active component and hydrogen peroxide solution mixing, utilize the peculiar property of hydrogen peroxide solution, change the state of metal precursor, form peroxometalate presoma.The change of metal precursor can change the interphase interaction of metal and carrier, and prepare pattern and the controlled oxide of granularity, this preparation method's technique is simple, cheaper starting materials, environmental friendliness.
With W/Al
2o
3catalyst is example, in the preparation process in accordance with the present invention, and WO
3load be in hydrogen peroxide system, add after ammonium metatungstate stirs in hydrogen peroxide solution, solution becomes yellow transparent solution, forms peroxide tungsten species.The formation of peroxide tungsten species, shows that the tungsten atom center Coordination Space in solution is occupied by peroxy-radical, so just can weaken the interaction between peroxide tungsten species and carrier.According to preferred version of the present invention, by adding dispersant in maceration extract, except dispersion WO can be played
3effect, can also with the coordination of peroxide tungsten species, affect carrier and tungsten Species interaction further.According to all right preparation example of preparation method provided by the invention as Mo/Al
2o
3catalyst etc., the choice and operation wherein for the salt (active presoma) of active metal all can realize according to the known technology of this area.
Present invention also offers a kind of load hydrogenation catalyst for refining, it is prepared by the preparation method of above-mentioned load hydrogenation catalyst for refining.
The preparation method of load hydrogenation catalyst for refining provided by the present invention has the following advantages: by the improvement to traditional infusion process, has effectively improved active component (the such as WO in prepared catalyst
3) decentralization, reduce the interaction between active component and carrier, therefore, the catalyst of the active identical active metallic content all prepared higher than traditional infusion process of the hydrodesulfurization of catalyst prepared by method provided by the present invention and Tuo Fang.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the embodiment of the present invention and comparative example hydrogenation catalyst;
Fig. 2 is the hydrogen temperature programmed reduction figure of the embodiment of the present invention and comparative example hydrogenation catalyst.
Detailed description of the invention
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, referring now to Figure of description, following detailed description is carried out to technical scheme of the present invention, but can not be interpreted as to of the present invention can the restriction of practical range.
Embodiment 1
Get the H that 12.5mL concentration is 30wt%
2o
2solution, is added drop-wise to 9.92g (containing WO
3for 90.0wt%) in ammonium metatungstate, after stirring, obtain maceration extract;
Be added drop-wise to by maceration extract on the alumina support of 24.2g, at room temperature flood 6 hours, then 110 DEG C of dryings 2 hours, 480 DEG C of roastings 4 hours, obtain W/Al
2o
3catalyst C1, adopts x-ray fluorescence spectrometry tungsten oxide content to be 26.8wt%.
Embodiment 2
Get the H that 12.5mL concentration is 30wt%
2o
2solution, is added drop-wise to 9.92g (containing WO
3for 90.0wt%) in ammonium metatungstate, after stirring, obtain maceration extract, then add 0.6g citric acid and mix;
Be added drop-wise to by maceration extract on the alumina support of 24.2g, at room temperature flood 6 hours, then 110 DEG C of dryings 2 hours, 480 DEG C of roastings 4 hours, obtain W/Al
2o
3catalyst C2, adopts x-ray fluorescence spectrometry tungsten oxide content to be 26.8wt%.
Embodiment 3
Get the H that 12.5mL concentration is 30wt%
2o
2solution, is added drop-wise to 9.92g (containing WO
3for 90.0wt%) in ammonium metatungstate, after stirring, obtain maceration extract, then add 0.5g tartaric acid and mix;
Be added drop-wise to by maceration extract on the alumina support of 24.2g, at room temperature flood 6 hours, then 110 DEG C of dryings 2 hours, 480 DEG C of roastings 4 hours, obtain W/Al
2o
3catalyst C3, adopts x-ray fluorescence spectrometry tungsten oxide content to be 26.8wt%.
Embodiment 4
Get the H that 12.5mL concentration is 30wt%
2o
2solution, is added drop-wise to 9.92g (containing WO
3for 90.0wt%) in ammonium metatungstate, after stirring, obtain maceration extract;
Be added drop-wise to by maceration extract on the alumina support of 24.2g, flood 5 hours under 50 DEG C of temperature, then 110 DEG C of dryings 2 hours, 500 DEG C of roastings 4 hours, obtain W/Al
2o
3catalyst C4, adopts x-ray fluorescence spectrometry tungsten oxide content to be 26.8wt%.
Embodiment 5
Get the H that 12.5mL concentration is 27.5wt%
2o
2solution, is added drop-wise to 9.92g (containing WO
3for 90.0wt%) in ammonium metatungstate, after stirring, obtain maceration extract;
Be added drop-wise to by maceration extract on the alumina support of 24.2g, at room temperature flood 6 hours, then 110 DEG C of dryings 2 hours, 480 DEG C of roastings 4 hours, obtain W/Al
2o
3catalyst C5, adopts x-ray fluorescence spectrometry tungsten oxide content to be 26.8wt%.
Embodiment 6
Get the H that 12.5mL concentration is 35wt%
2o
2solution, is added drop-wise to 9.92g (containing WO
3for 90.0wt%) in ammonium metatungstate, after stirring, obtain maceration extract;
Be added drop-wise to by maceration extract on the alumina support of 24.2g, at room temperature flood 6 hours, then 110 DEG C of dryings 2 hours, 480 DEG C of roastings 4 hours, obtain W/Al
2o
3catalyst C6, adopts x-ray fluorescence spectrometry tungsten oxide content to be 26.8wt%.
Embodiment 7
Get the H that 20.8mL concentration is 30wt%
2o
2solution, is added drop-wise to 9.92g (containing WO
3for 90.0wt%) in ammonium metatungstate, after stirring, obtain maceration extract;
Be added drop-wise to by maceration extract on the alumina support of 40.8g, at room temperature flood 6 hours, then 110 DEG C of dryings 2 hours, 480 DEG C of roastings 4 hours, obtain W/Al
2o
3catalyst C7, adopts x-ray fluorescence spectrometry tungsten oxide content to be 17.9wt%.
Embodiment 8
Get the H that 20.8mL concentration is 30wt%
2o
2solution, is added drop-wise to 9.92g (containing WO
3for 90.0wt%) in ammonium metatungstate, after stirring, obtain maceration extract, then add 0.1g oxalic acid and mix;
Be added drop-wise to by maceration extract on the alumina support of 40.8g, at room temperature flood 6 hours, then 110 DEG C of dryings 2 hours, 480 DEG C of roastings 4 hours, obtain W/Al
2o
3catalyst C8, adopts x-ray fluorescence spectrometry tungsten oxide content to be 17.9wt%.
Embodiment 9
Get the H that 20.8mL concentration is 30wt%
2o
2solution, is added drop-wise to 9.92g (containing WO
3for 90.0wt%) in ammonium metatungstate, after stirring, obtain maceration extract, then add 0.2g terephthalic acid (TPA) and mix;
Be added drop-wise to by maceration extract on the alumina support of 40.8g, at room temperature flood 6 hours, then 110 DEG C of dryings 2 hours, 480 DEG C of roastings 4 hours, obtain W/Al
2o
3catalyst C9, adopts x-ray fluorescence spectrometry tungsten oxide content to be 17.9wt%.
Embodiment 10
Get the H that 20.8mL concentration is 30wt%
2o
2solution, is added drop-wise to 9.92g (containing WO
3for 90.0wt%) in ammonium metatungstate, after stirring, obtain maceration extract;
Be added drop-wise to by maceration extract on the aluminium oxide of 40.8g and the complex carrier (mass ratio of the two is 5: 1) of Y molecular sieve, at room temperature flood 6 hours, then 110 DEG C of dryings 2 hours, 480 DEG C of roastings 4 hours, obtain W/Al
2o
3+ Y catalyst C10, adopts x-ray fluorescence spectrometry tungsten oxide content to be 17.9wt%.
Embodiment 11
Get the H that 20.8mL concentration is 30wt%
2o
2solution, is added drop-wise to 9.92g (containing WO
3for 90.0wt%) in ammonium metatungstate, after stirring, obtain maceration extract;
Be added drop-wise to by maceration extract on the aluminium oxide of 40.8g and the complex carrier of beta molecular sieve (mass ratio of the two is 5: 1), at room temperature flood 6 hours, then 110 DEG C of dryings 2 hours, 480 DEG C of roastings 4 hours, obtain W/Al
2o
3+ beta catalyst C11, adopts x-ray fluorescence spectrometry tungsten oxide content to be 17.9wt%.
Comparative example 1
Traditional saturated infusion process of pore volume is adopted to prepare W/Al
2o
3catalyst, specifically carries out according to following steps:
Take 9.92g (containing WO
3for 90.0wt%) ammonium metatungstate, be mixed with 12.5mL aqueous impregnation liquid;
Be added drop-wise to by maceration extract on the alumina support of 24.2g, at room temperature flood 6 hours, then 110 DEG C of dryings 2 hours, 480 DEG C of roastings 4 hours, obtain W/Al
2o
3catalyst F1, adopts x-ray fluorescence spectrometry tungsten oxide content to be 26.8wt%.
Comparative example 2
Traditional saturated infusion process of pore volume is adopted to prepare W/Al
2o
3catalyst, specifically carries out according to following steps:
Take 9.92g (containing WO
3for 90.0wt%) ammonium metatungstate, be mixed with 12.5mL aqueous impregnation liquid, then add 0.6g citric acid and mix;
Be added drop-wise to by maceration extract on the alumina support of 24.2g, at room temperature flood 6 hours, then 110 DEG C of dryings 2 hours, 480 DEG C of roastings 4 hours, obtain W/Al
2o
3catalyst F2, adopts x-ray fluorescence spectrometry tungsten oxide content to be 26.8wt%.
Comparative example 3
Traditional saturated infusion process of pore volume is adopted to prepare W/Al
2o
3catalyst, specifically carries out according to following steps:
Take 9.92g (containing WO
3for 90.0wt%) ammonium metatungstate, be mixed with 20.8mL aqueous impregnation liquid;
Be added drop-wise to by maceration extract on the alumina support of 40.8g, at room temperature flood 6 hours, then 110 DEG C of dryings 2 hours, 480 DEG C of roastings 4 hours, obtain W/Al
2o
3catalyst F3, adopts x-ray fluorescence spectrometry tungsten oxide content to be 17.9wt%.
Comparative example 4
Traditional saturated infusion process of pore volume is adopted to prepare W/Al
2o
3+ Y catalyst, specifically carries out according to following steps:
Take 9.92g (containing WO
3for 90.0wt%) ammonium metatungstate, be mixed with 20.8mL aqueous impregnation liquid;
Maceration extract to be added drop-wise on the aluminium oxide of 40.8g and the complex carrier of Y molecular sieve (complex carrier and embodiment 10 with), at room temperature to flood 6 hours, then 110 DEG C of dryings 2 hours, 480 DEG C of roastings 4 hours, obtain W/Al
2o
3+ Y catalyst F4, adopts x-ray fluorescence spectrometry tungsten oxide content to be 17.9wt%.
Comparative example 5
Traditional saturated infusion process of pore volume is adopted to prepare W/Al
2o
3+ beta catalyst, specifically carries out according to following steps:
Take 9.92g (containing WO
3for 90.0wt%) ammonium metatungstate, be mixed with 20.8mL aqueous impregnation liquid;
This solution to be added drop-wise on the aluminium oxide of 40.8g and the complex carrier of beta molecular sieve (complex carrier and embodiment 11 with), at room temperature to flood 6 hours, then 110 DEG C of dryings 2 hours, 480 DEG C of roastings 4 hours, obtain W/Al
2o
3+ beta catalyst F5, adopts x-ray fluorescence spectrometry tungsten oxide content to be 17.9wt%.
Test example 1
Evaluate in accordance with the following methods the hydrodesulfurization activity of catalyst prepared by embodiment 1-11 and comparative example 1-5 and Tuo Fang activity in this test example, its result is respectively in table 1 and table 2.
Hydrodesulfurization activity evaluation method: the sulphur model compound being dissolved in n-decane preparation in dibenzothiophenes is that micro-anti-feedstock oil is (with sulphur 1000 μ gg
-1) investigate the hydrodesulfurization activity of catalyst; After sulfuration completes, then enter feedstock oil, at reaction pressure 4.0MPa, volume velocity 7.53mLh
-1, hydrogen to oil volume ratio 500: 1 condition under, investigate the hydrodesulfurization activity under reaction temperature 573K condition; After question response is stable, carry out on-line analysis sulfur content, the hydrodesulfurization reaction conversion ratio [HDS Conversion (%)] of catalyst adopts following formula to represent:
HDS Conversion(％)＝[(S
feed-S
product)/S
feed]×100
Wherein, S
feedrepresent sulfur content in feedstock oil, S
produdsulfur content in oil is generated after representing hydrogenation.
Hydrogenation dearomatization activity rating method: the aromatic hydrocarbons model compound being dissolved in n-decane preparation with naphthane (10wt.%) is that micro-anti-feedstock oil is to investigate the arene saturating activity of catalyst; After sulfuration completes, then enter feedstock oil, at reaction pressure 4.0MPa, volume velocity 3.62mLh
-1, hydrogen to oil volume ratio 500: 1 condition under, investigate the conversion ratio of naphthane during reaction temperature 613K.When after reacting balance, collect condensed fluid sample to analyze, in sample, the content of naphthane adopts the HP4890 type chromatograph being furnished with DM-5 capillary chromatograph (30.0m × 0.25mm × 0.32 μm) and hydrogen flame ionization detector to measure, and in different catalysts, naphthane conversion ratio [Conversion of tetralin (%)] adopts following formula to represent:
Conversion of tetralin(％)＝(T
feed-T
product)/T
feed×100
Wherein, T
feedrepresent naphthane content in feedstock oil, T
productnaphthane content in oil is generated after representing hydrogenation.
The hydrodesulfurization activity evaluation result of table 1 catalyst
| Embodiment | Catalyst | Hds conversion (%) |
| Embodiment 1 | C1 | 65.2 |
| Embodiment 2 | C2 | 69.1 |
| Embodiment 3 | C3 | 68.6 |
| Embodiment 4 | C4 | 65.3 |
| Embodiment 5 | C5 | 64.8 |
| Embodiment 6 | C6 | 66.7 |
| Comparative example 1 | F1 | 59.6 |
| Comparative example 2 | F2 | 59.8 |
| Embodiment 7 | C7 | 53.2 |
| Embodiment 8 | C8 | 55.0 |
| Embodiment 9 | C9 | 54.8 |
| Comparative example 3 | F3 | 48.6 |
| Embodiment 10 | C10 | 72.3 |
| Comparative example 4 | F4 | 67.0 |
| Embodiment 11 | C11 | 71.9 |
| Comparative example 5 | F5 | 66.8 |
The hydrogenation dearomatization Activity evaluation of table 2 catalyst
| Embodiment | Catalyst | Hydrogenation dearomatization conversion ratio (%) |
| Embodiment 1 | C1 | 48.3 |
| Embodiment 2 | C2 | 49.2 |
| Embodiment 3 | C3 | 49.0 |
| Embodiment 4 | C4 | 48.6 |
| Embodiment 5 | C5 | 47.8 |
| Embodiment 6 | C6 | 48.7 |
| Comparative example 1 | F1 | 44.3 |
| Comparative example 2 | F2 | 44.5 |
| Embodiment 7 | C7 | 40.2 |
| Embodiment 8 | C8 | 41.8 |
| Embodiment 9 | C9 | 41.6 |
| Comparative example 3 | F3 | 38.6 |
| Embodiment 10 | C10 | 69.2 |
| Comparative example 4 | F4 | 66.8 |
| Embodiment 11 | C11 | 70.0 |
| Comparative example 5 | F5 | 66.0 |
Can be illustrated by the result of table 1 and table 2, load hydrogenation catalyst for refining prepared by hydrogen peroxide infusion process provided by the invention, the Hydrobon catalyst prepared than the conventional infusion process of same metal active component content has higher hydrodesulfurization activity and hydrogenation dearomatization activity.
Test example 2
This test example is the characterization result of XRD and TPR of the catalyst C2 of embodiment 2 preparation and the comparative catalyst F2 of comparative example 2 preparation.
Fig. 1 is the X-ray diffractogram (XRD) of catalyst C2 and comparative catalyst F2.During high content of metal, the XRD spectra of catalyst can characterize catalyst activity metal dispersity.As seen in Figure 1: in the spectral line of comparative catalyst F2, occurred obvious body phase WO
3diffraction maximum (2 θ=23.5 °), illustrates that metallic particles is larger, can be detected by XRD; And in the spectral line of catalyst C2, there is not obvious body phase WO
3diffraction maximum, illustrate that metallic particles is smaller, decentralization is high.
Fig. 2 is the hydrogen temperature programmed reduction figure (TPR) of catalyst C2 and comparative catalyst F2.The interaction that TPR can characterize in loaded catalyst between active component and carrier is strong and weak.As can be seen from Figure 2: the reduction peak of comparative catalyst F2 does not also occur completely 1000 DEG C time, and the reduction peak of catalyst C2 appears at about 948 DEG C.In both comparative illustration catalyst C2, metal weakens than catalyst F2 to some extent with the Interaction Force comparison of carrier.
Can be found out by above-mentioned contrast, compared with the catalyst adopting conventional infusion process to prepare, by the catalyst adopting hydrogen peroxide infusion process provided by the invention to prepare, there is higher active component decentralization and the interaction of more weak active component and carrier, thus, catalyst provided by the present invention can have the better hydrodesulfurization activity of the catalyst prepared than conventional infusion process and hydrogenation dearomatization activity.
Claims (6)
1. a preparation method for load hydrogenation catalyst for refining, it comprises the following steps:
The salt of VI B race metal is dissolved in hydrogen peroxide solution and obtains maceration extract, add dispersant, the addition of described dispersant is the 0.1-2% of maceration extract gross weight, described dispersant is one or more in binary organic carboxyl acid containing 2-12 carbon or ternary organic carboxyl acid, and described VI B race metal is tungsten or molybdenum;
Utilize described maceration extract to flood carrier, wherein, described carrier is the aluminium oxide of the molecular sieve modified aluminium oxide of aluminium oxide, beta or Y molecular sieve modification;
Drying, roasting are carried out to impregnation product, obtains described load hydrogenation catalyst for refining.
2. preparation method according to claim 1, wherein, the concentration of described hydrogen peroxide solution is 10-45wt%.
3. preparation method according to claim 2, wherein, the concentration of described hydrogen peroxide solution is 30wt%.
4. preparation method according to claim 1, wherein, described dispersant is one or more in citric acid, tartaric acid and oxalic acid.
5. preparation method according to claim 1, wherein, the temperature of described dipping controls as 10-60 DEG C.
6. preparation method according to claim 1, wherein, described carrier is porous oxide carrier.
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| 水热沉积法制备高分散W/Al2O3加氢脱硫催化剂;王豪等;《催化学报》;20070430;第28卷(第4期);364-370 * |
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