CN102451768A - Method for preparing zirconia-alumina composite oxide xerogel - Google Patents
Method for preparing zirconia-alumina composite oxide xerogel Download PDFInfo
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- CN102451768A CN102451768A CN2010105144190A CN201010514419A CN102451768A CN 102451768 A CN102451768 A CN 102451768A CN 2010105144190 A CN2010105144190 A CN 2010105144190A CN 201010514419 A CN201010514419 A CN 201010514419A CN 102451768 A CN102451768 A CN 102451768A
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Abstract
The invention discloses a method for preparing a zirconia-alumina composite oxide xerogel. An aluminum hydroxide sol and a zirconium-containing sol are prepared firstly, and then are mixed, aged, washed, filtrated and dried to obtain the composite oxide xerogel. In the method, most of zirconia is distributed on the surface of alumina, the impact on a pore structure of the alumina is weakened, the co-catalysis of the zirconia is improved, the advantages of the alumina and the zirconia are fully utilized, and the obtained composite oxide xerogel has the characteristics of large pore volume, high specific surface area, concentrated pore size distribution and controllable acidity, and is suitable for being used as a hydrogenation catalyst carrier.
Description
Technical field
The present invention relates to the preparation method of the dried glue of a kind of Zirconia-alumina composite oxide, particularly a kind of preparation method who is used to prepare the dried glue of Zirconia-alumina composite oxide of hydrofining catalyst carrier.
Background technology
The preparation technology of alumina support is simple, and specific area is high, and mechanical strength is good; The aperture is suitable; Be one of present most widely used catalyst carrier, but the co-acting force of lip-deep reactive metal of pure alumina and carrier is bigger, is prone to form the species of non-activity; Like nickel aluminate, be difficult for forming the active phase of highly active II type.Therefore the preparation and the modification of relevant alumina support, the preparation that contains aluminium composite oxide are the directions that the scientific worker studies always.At present, zirconia material is owing to have acid and basic surface center simultaneously, and oxidisability and reproducibility, and good ion-exchange performance demonstrate unique catalytic activity and selectivity as carrier or catalyst at catalytic field.Zirconia material also has premium properties such as high-melting-point, high strength; Compare with conventional carrier as the catalyst of carrier and to have shown special advantages; Good like anti-sulphur property; The metal that supports is easy to reduction etc., but zirconic specific area is less and sharply descend with the rising of sintering temperature, receives very big restriction as support applications.Zirconia is dispersed in alumina surface, can makes the composite oxide carrier of both advantages.
CN00123133.2 discloses a kind of alumina carrier containing Zr and preparation method thereof, through in the forming process of carrier, making alumina carrier containing Zr to mix the form adding zirconium-containing compound of pinching; This carrier side pressure strength is improved, and acidity maintains a comparatively stable stage, and infrared acidity is 0.25～0.32mmol/g, and pore distribution concentration is in the mesopore scope, and shortcoming is the precursor that when kneading and compacting, adds zirconium, is unfavorable for the even dispersion of zirconium, can cause ZrO
2Utilization rate reduces, and is unfavorable for the raising of catalyst serviceability.
CN200710158366.1 discloses a kind of method for preparing zirconium-containing alumina with coprecipitation; Because coprecipitation is the co-precipitations under certain conditions of two or more species; Then co-precipitation condition can not guarantee all species all in optimal conditions, and there is intrinsic defective in this method thus.But also can cause ZrO
2In coprecipitation process, get into the body phase, weaken the influence of zirconia, thereby influence the physical and chemical performance of final carrier carrier surface.
CN200710158368.0 discloses a kind of preparation method of siliceous and zirconium aluminum oxide dry glue powder; Aluminum contained compound solution becomes the glue reaction with precipitating reagent after; Under conditions such as control appropriate pH value, add zirconium-containing compound solution; Before adding zirconium-containing compound, add silicon-containing compound afterwards or simultaneously, after washing, filtration, drying, obtain the alumina dry glue of siliceous and zirconium then.Zirconia is when carrier becomes glue, to add in this method, and the pH value of aluminium oxide is acidity and contain zirconium solution in alkaline range; When mixing, both are prone to cause the zirconia rapid precipitation; Particle size differs, and original precipitation of alumina is peptization again, adds alkaline reagent again; The particle size distribution of aluminium oxide is wide, causes the pore-size distribution disperse easily.
Summary of the invention
To the deficiency of prior art, the invention provides the preparation method of the dried glue of a kind of composite oxides.The inventive method can make most of zirconia be distributed in alumina surface, has weakened the alumina pore effect on structure, has improved zirconic promoting catalysis, has given full play to aluminium oxide and zirconic advantage.
The preparation method of the dried glue of Zirconia-alumina composite oxide of the present invention, the preparation process is following:
(1), aluminum contained compound solution and precipitating reagent be carried out to the glue reaction, obtains aluminum hydroxide sol;
(2), zirconium-containing compound solution and acidity or alkaline precipitating agent are carried out to the glue reaction, obtain containing zirconium colloidal sol;
(3), the zirconium colloidal sol that contains of the aluminum hydroxide sol of step (1) gained and step (2) gained mixes, and stirs, and is aging then; Wherein before mixing, the pH value that contains zirconium colloidal sol of the aluminum hydroxide sol of step (1) gained and step (2) gained differs 0～2, is preferably 0～1;
(4), with the washing of the material of step (3) gained, filter, through dry, obtain the dried glue of Zirconia-alumina composite oxide.
The dried glue of Zirconia-alumina composite oxide of the present invention is benchmark with the butt of composite oxides, and the weight content of aluminium oxide is 40%～95%, and zirconic weight content is 5%～60%.
In the inventive method, the dried glue of described Zirconia-alumina composite oxide can also contain silica, is benchmark with the butt of composite oxides; The weight content of silica is 0.5%～20.0%; The introducing mode can adopt usual manner, such as CN 200710158368.0, CN200410050716.9 disclosed method, preferably introduces silicon when aluminium hydroxide becomes glue in step (1); Introduce silicon before perhaps in step (3), wearing out, Ludox, silica gel or waterglass can be adopted in the silicon source.
In the inventive method step (1), described aluminum contained compound is one or more in aluminum nitrate, aluminium chloride, the aluminum sulfate; Described precipitating reagent is one or more in NaOH, potassium hydroxide, ammoniacal liquor, ammonium carbonate, carbonic hydroammonium, sodium metaaluminate, the potassium metaaluminate.It is 20～90 ℃ that step (1) is controlled to the glue temperature, and preferred 20～60 ℃, becoming glue pH value is 7.0～11.0, and gelation time is 30min～180min.
In the inventive method step (2), described zirconium-containing compound is one or more in zirconium carbonate, zirconium nitrate, zirconium chloride, the zirconium sulfate; Described alkaline precipitating agent is one or more in NaOH, potassium hydroxide, ammoniacal liquor, ammonium carbonate, the carbonic hydroammonium, and described acidic precipitation agent is one or more in oxalic acid, hydrochloric acid, sulfuric acid, carbon dioxide, the nitric acid.In the described zirconium-containing compound solution, the concentration of zirconium is counted 0.5～30g/100mL with element, is preferably 1～20g/100mL.It is 20～110 ℃ that step (2) is controlled to the glue temperature, and becoming glue pH value is 5.0～11.0, and gelation time is 30min～180min.
In the inventive method step (2); For improving the dispersiveness of colloidal sol; Can before becoming glue, add organic solvent or surfactant; Organic solvent is generally one or more of ethanol, glycerine, methyl alcohol, butanols, isobutanol, normal heptane, normal octane, and the addition of organic solvent is no more than step (2) gained and contains 10% of zirconium sol volume.Described surfactant such as cationic surfactant dodecyl sodium sulfate, softex kw etc.; Perhaps non-ionic surface active agent such as glymes, the addition of surfactant is no more than step (2) gained and contains 1% of zirconium sol volume.
The inventive method step (3) is before mixing, and the pH value that contains zirconium colloidal sol of the aluminum hydroxide sol of step (1) gained and step (2) gained differs 0～2.When the difference of the pH value that contains zirconium colloidal sol of the aluminum hydroxide sol of step (1) gained and step (2) gained is higher than 2, can adopt distilled water, diluted acid or diluted alkaline to regulate, preferably adopt the way that adds distilled water to regulate.
The described aluminum hydroxide sol of step (3) stirred 1～5 hour after zirconium colloidal sol mixes with containing, and described aging condition is following: aging temperature is 50～80 ℃, and ageing time is 1～5 hour.
The mode of washing of the described washing employing of step (4) routine like making beating washing or the flushing of plate basket etc., generally is to adopt deionized water to be washed till the approaching neutrality of pH value of cleaning solution.Conventional filter type is adopted in described filtration, generally adopts suction filtration.Described drying condition was following: 50～200 ℃ of dryings 2～8 hours.
After 2～6 hours, the character of gained is following through 300～700 ℃ of roastings for the dried glue of this Zirconia-alumina composite oxide: specific area is 350～500m
2/ g is preferably 400～480m
2/ g, pore volume is 0.7～1.2ml/g, is preferably 0.8～1.1ml/g, and average pore size is 6.0～14.0nm, and the shared pore volume in the hole of 6～10nm is more than 60% of total pore volume, NH
3-TPD total acid content 0.4～0.9mmol/g is preferably total acid content 0.5～0.7mmol/g, and butt is 65wt%～75wt%.
The present invention has following advantage compared with prior art:
(1) the dried glue of composite oxides has large pore volume and high-specific surface area, and can realize acid regulation and control through regulating zirconic addition, is more suitable for as catalyst carrier for hydrgenating.
(2) contain zirconium colloidal sol and mix mutually with identical or close pH value with aluminum hydroxide sol, produce deposition or peptization because of the pH value is different in the time of can avoiding both to mix like this, do not destroy the existing even skeleton of aluminium oxide, the pore-size distribution of carrier is narrow.The Zirconia particles size is evenly distributed in the surface of aluminium oxide; The skeleton structure that not only can keep aluminium oxide; And can also improve zirconic utilization rate, and giving full play to its catalytic performance that helps, can improve as the curability of the catalyst of carrier; And the reactive metal of load is easy to reduction, raising activity of such catalysts and selectivity.
(3) can produce the high composite oxides of zirconia content, outstanding zirconia is the advantage of carrier, makes metal more be prone to sulfuration, improves activity of such catalysts.
(4) production technology is simple, and the preparing carriers cost is low, and is environmentally friendly.
The specific embodiment
Further describe technical characterstic of the present invention through specific embodiment and comparative example below, but these embodiment can not limit the present invention.Among the present invention, wt% is a mass fraction, and v% is a volume fraction.
Embodiment 1
1000ml 2mol/L aluminum nitrate and 20ml silica gel (are contained SiO
225wt%) mix, adding ammoniacal liquor adjusting pH value is 7, reacts down at 80 ℃ promptly to get Sol A.ZrCl with 1mol/l
4Solution and weak aqua ammonia and drip are added in the beaker that fills ethanol and deionized water, and ethanol accounts for the 15v% of the water yield, and control pH value is 6.5, and 45 ℃ of reaction temperatures promptly get sol B.Sol B is mixed with Sol A, stir and be warming up to 50 ℃ after 2 hours, aging 2 hours; Suction filtration behind the adding ethanol 200ml spends deionised water 3 times, pulverizes in 3 hours 120 ℃ of dryings and obtains the dried glue of composite oxides; Got composite oxides in 3 hours through 600 ℃ of roastings; Wherein zirconic content is 60wt%, and the content of silica is 1.5wt%, and its main character is listed in table 1.
Get the dried glue 123g of composite oxides, SB powder 13.9g adds 3g sesbania powder, and the rare nitric acid of 5ml mixes and pinches, after the extrusion, 120 ℃ of dryings 3 hours, 600 ℃ of roastings after 3 hours composite oxide carrier.
Embodiment 2
100ml 2mol/L aluminum nitrate and 20ml silica gel (are contained SiO
225wt%) mix, adding ammoniacal liquor adjusting pH value is 7.0, reacts down at 60 ℃ promptly to get Sol A.Under stirring condition, oxalic acid (0.1mol/l) slowly splashes in the 0.1mol/l zirconium nitrate, makes pH value=5.5, continues to stir after 10 minutes, puts it into and is heated to 95 ℃ in the there-necked flask, and constant temperature refluxes and promptly got sol B in 2 hours.Sol B is mixed with Sol A after with the distilled water diluting twice, stir and be warming up to 50 ℃ after 2 hours, aging 2 hours; Suction filtration behind the adding ethanol 200ml spends deionised water 3 times, pulverizes in 3 hours 120 ℃ of dryings and obtains the dried glue of composite oxides; Got composite oxides in 3 hours through 600 ℃ of roastings; Wherein zirconic content is 30wt%, and the content of silica is 2wt%, and its main character is listed in table 1.
Get the dried glue 114g of composite oxides, SB powder 27.8g adds 3g sesbania powder, and the rare nitric acid of 3ml and 2ml acetic acid mix and pinches, and after the extrusion, 120 ℃ of dryings 3 hours, 600 ℃ of roastings must composite oxide carrier after 3 hours.
Embodiment 3
1mol/L aluminum sulfate is mixed with sodium aluminate and the stream of 1mol/L, and regulating the pH value is 7.0, reacts down at 50 ℃ promptly to get Sol A.All the other are identical with embodiment 1.Wherein zirconic content is 10wt% in the composite oxides, and its main character is listed in table 1.
Get the dried glue 132g of composite oxides, SB powder 13.9g adds 3g sesbania powder, and the rare nitric acid of 5ml mixes and pinches, after the extrusion, 120 ℃ of dryings 3 hours, 600 ℃ of roastings after 3 hours composite oxide carrier.
Comparative example 1
1000ml 2mol/L aluminum nitrate is mixed with 2000ml 0.05mol/L zirconium nitrate, and adding ammoniacal liquor adjusting pH value is 8.0, reacts down and wears out 1 hour at 60 ℃ at 80 ℃; Suction filtration spent deionised water 3 times, 120 ℃ of dryings 3 hours; Obtain the dried glue of composite oxides; Through 600 ℃ of roastings 3 hours, get composite oxides, wherein zirconic content is 10wt%.Its main character is listed in table 1.
Get the dried glue 123g of composite oxides, SB powder 13.9g adds 3g sesbania powder, and the rare nitric acid of 5ml mixes and pinches, after the extrusion, 120 ℃ of dryings 3 hours, 600 ℃ of roastings after 3 hours composite oxide carrier.
Comparative example 2
Sodium metaaluminate and the stream of 1mol/L aluminum sulfate and 1mol/L are mixed, and regulating pH value is 7.0, reacts down and wears out 1 hour at 60 ℃ at 60 ℃; Slowly drip the zirconium nitrate of 0.05mol/L, during add less ammonia and make pH value remain on 7.0, add the silica gel continued and wore out 2 hours; Suction filtration spent deionised water 3 times, 120 ℃ of dryings 3 hours; Obtain the dried glue of composite oxides,, get composite oxides through 600 ℃ of roastings 3 hours; Wherein zirconic content is 10wt%, and the content of silica is 5wt%.Its main character is listed in table 1.
Get the dried glue 123g of composite oxides, SB powder 13.9g adds 3g sesbania powder, and the rare nitric acid of 5ml mixes and pinches, after the extrusion, 120 ℃ of dryings 3 hours, 600 ℃ of roastings after 3 hours composite oxide carrier.
Embodiment 4
Take by weighing molybdenum oxide 46.48g, basic nickel carbonate 15.8g adds deionized water 60ml and mixes; Adding concentration is 85wt% phosphoric acid 6ml, is heated to 75 ℃, constant temperature 1 hour; Obtain bottle green clear solution, spray the composite oxide carrier of embodiment 1 gained, 120 ℃ of dryings 3 hours with this solution; 500 ℃ of roastings obtained catalyst after 3 hours, and this activity of such catalysts evaluation result is seen table 2.
Embodiment 5-6
Adopt the composite oxide carrier of embodiment 2-3 gained respectively, the preparation catalyst, all the other are identical with embodiment 4.
Comparative example 3-4
Adopt the composite oxide carrier of comparative example 1,2 gained respectively, the preparation catalyst, all the other are identical with embodiment 4.
Embodiment 7
On miniature hydrogenation reaction device, carry out the diesel oil hydrogenation activity rating of catalyst, the useful load of catalyst is 10ml, estimates and uses the mixture of sulfurized oil for boat coal and carbon disulfide, and its density is 0.798g/cm
3, sulfur content is 20000 μ g/g, and nitrogen content is 1.0 μ g/g, and boiling range is 161～276 ℃.Estimate and use crude oil to be catalytic cracking diesel oil, its density is 0.87g/cm
3, sulfur content is 6834 μ g/g, and Cetane number is 35, and boiling range is 181～374 ℃.
The catalyst of 10ml embodiment 4-6 and comparative example 3-4 preparation is packed in the hydrogenation reactor, connect hydrogen, keep-uping pressure is 3.5MPa; Hydrogen flowing quantity 200ml/min rises to 150 ℃, constant temperature 1 hour with the programming rate of 5 ℃/h; Begin into sulfurized oil, oil inlet quantity is 30ml/min, and the programming rate with 5 ℃/h rises to 350 ℃ again; Constant temperature is swap-in feedstock oil after 3 hours, and constant temperature is sample analysis after 2 hours.Evaluation result is seen table 2.
The character of table 1 composite oxides
Table 2 activity of such catalysts evaluating data
| Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example 3 | Comparative example 4 | |
| 20 ℃ of density, g/cm 3 | 0.866 | 0.853 | 0.849 | 0.862 | 0.859 |
| Yield, wt% | 99.2 | 99.4 | 99.1 | 95.2 | 98.4 |
| Cetane number | 53.6 | 53.1 | 51.7 | 47.3 | 47.8 |
| Sulfur content, μ g/g | 48.1 | 35.6 | 40.4 | 100.2 | 82.5 |
Data by table 1 and table 2 can be found out, compare with the comparative example method, and the specific area of the composite oxides of the inventive method preparation is high; Pore volume is big; Pore-size distribution concentrates on 6-10nm, during infusion process supported active metal, helps the dispersion of reactive metal; When especially maceration extract was high concentration, full-bodied liquid (like molybdenum nickel phosphorus solution), advantage was more obvious.And, the catalyst that adopts composite oxides of the present invention to prepare, the yield of liquid-phase product is high, and the Cetane number of diesel oil is high, and desulphurizing activated height obviously is superior to the catalyst that the comparative example method prepares.
Claims (14)
1. the preparation method of the dried glue of Zirconia-alumina composite oxide, the preparation process is following:
(1), aluminum contained compound solution and precipitating reagent be carried out to the glue reaction, obtains aluminum hydroxide sol;
(2), zirconium-containing compound solution and acidity or alkaline precipitating agent are carried out to the glue reaction, obtain containing zirconium colloidal sol;
(3), the zirconium colloidal sol that contains of the aluminum hydroxide sol of step (1) gained and step (2) gained mixes, and stirs, and is aging then; Wherein before mixing, the pH value that contains zirconium colloidal sol of the aluminum hydroxide sol of step (1) gained and step (2) gained differs 0～2;
(4), with the washing of the material of step (3) gained, filter, through dry, obtain the dried glue of Zirconia-alumina composite oxide.
2. according to the described method of claim 1, it is characterized in that the dried glue of described Zirconia-alumina composite oxide, is benchmark with the butt of composite oxides, and the weight content of aluminium oxide is 40%～95%, and zirconic weight content is 5%～60%.
3. according to the described method of claim 1, it is characterized in that the dried glue of described Zirconia-alumina composite oxide contains silica, is benchmark with the butt of composite oxides, and the weight content of silica is 0.5%～20.0%.
4. according to the described method of claim 3; It is characterized in that; Silicon is introduced the mode of the dried glue of Zirconia-alumina composite oxide for to introduce when aluminium hydroxide becomes glue in step (1), perhaps aging preceding introducing the, wherein silicon source employing Ludox, silica gel or waterglass in step (3).
5. according to the described method of claim 1, it is characterized in that in the step (1), described aluminum contained compound is one or more in aluminum nitrate, aluminium chloride, the aluminum sulfate; Described precipitating reagent is one or more in NaOH, potassium hydroxide, ammoniacal liquor, ammonium carbonate, carbonic hydroammonium, sodium metaaluminate, the potassium metaaluminate.
6. according to the described method of claim 1, it is characterized in that it is 20～90 ℃ that step (1) is controlled to the glue temperature, becoming glue pH value is 7.0～11.0, and gelation time is 30min～180min.
7. according to the described method of claim 1; It is characterized in that in the step (2); Described zirconium-containing compound is one or more in zirconium carbonate, zirconium nitrate, zirconium chloride, the zirconium sulfate, and in the described zirconium-containing compound solution, the concentration of zirconium is counted 0.5～30g/100mL with element; Described alkaline precipitating agent is one or more in NaOH, potassium hydroxide, ammoniacal liquor, ammonium carbonate, the carbonic hydroammonium, and described acidic precipitation agent is one or more in oxalic acid, hydrochloric acid, sulfuric acid, carbon dioxide, the nitric acid.
8. according to the described method of claim 1, it is characterized in that it is 20～110 ℃ that step (2) is controlled to the glue temperature, becoming glue pH value is 5.0～11.0, and gelation time is 30min～180min.
9. according to the described method of claim 1, it is characterized in that before step (2) becomes glue, adding organic solvent or surfactant.
10. according to the described method of claim 1; It is characterized in that described organic solvent is one or more of ethanol, glycerine, methyl alcohol, butanols, isobutanol, normal heptane, normal octane, the addition of organic solvent is that step (2) gained contains below 10% of zirconium sol volume.
11. according to the described method of claim 1; It is characterized in that described surfactant is one or more in dodecyl sodium sulfate, softex kw, the glymes, the addition of surfactant is no more than step (2) gained and contains 1% of zirconium sol volume.
12., it is characterized in that step (3) is before mixing according to the described method of claim 1, the pH value that contains zirconium colloidal sol of the aluminum hydroxide sol of step (1) gained and step (2) gained differs 0～1.
13. according to the described method of claim 1, it is characterized in that the said aging condition of step (3) is following: aging temperature is 50～80 ℃, and ageing time is 1～5 hour.
14., it is characterized in that the described drying condition of step (4) is following: 50～200 ℃ of dryings 2～8 hours according to the described method of claim 1.
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| CN108067210A (en) * | 2016-11-17 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of zirconium-containing alumina dry glue powder and its preparation method and application |
| CN108295826A (en) * | 2017-01-12 | 2018-07-20 | 中国石油化工股份有限公司 | A kind of modified aluminas dry glue powder and its preparation method and application |
| CN108855037A (en) * | 2018-07-19 | 2018-11-23 | 刘青 | A kind of preparation method of alumina-silica zinc composite catalyzing material |
| CN110876926A (en) * | 2018-09-05 | 2020-03-13 | 中国石油化工股份有限公司 | Zirconium-aluminum composite sol, preparation method and application thereof, and preparation method of catalytic cracking catalyst |
| CN116102358A (en) * | 2022-12-22 | 2023-05-12 | 中触媒新材料股份有限公司 | Processing method of aluminum oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108067210A (en) * | 2016-11-17 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of zirconium-containing alumina dry glue powder and its preparation method and application |
| CN108295826A (en) * | 2017-01-12 | 2018-07-20 | 中国石油化工股份有限公司 | A kind of modified aluminas dry glue powder and its preparation method and application |
| CN108295826B (en) * | 2017-01-12 | 2020-02-14 | 中国石油化工股份有限公司 | Modified alumina dry glue powder and preparation method and application thereof |
| CN108855037A (en) * | 2018-07-19 | 2018-11-23 | 刘青 | A kind of preparation method of alumina-silica zinc composite catalyzing material |
| CN110876926A (en) * | 2018-09-05 | 2020-03-13 | 中国石油化工股份有限公司 | Zirconium-aluminum composite sol, preparation method and application thereof, and preparation method of catalytic cracking catalyst |
| CN116102358A (en) * | 2022-12-22 | 2023-05-12 | 中触媒新材料股份有限公司 | Processing method of aluminum oxide |
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Application publication date: 20120516 |