CN102451766A - Preparation method of composite oxide carrier - Google Patents
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Abstract
The invention discloses a preparation method of a composite oxide carrier. A composite oxide gel adopted in the method of the invention is obtained by the steps of: first preparing an aluminum hydroxide sol and a water solution containing a group IVB metal complex, then mixing the sol and the water solution, adding dropping a hydrolysis promoter so as to obtain a mixed precipitate, which is then subjected to aging, washing, filtering and drying. The composite oxide gel obtained by the method can make most of group IVB metal oxides distributed on an alumina surface so as to weaken influence on an alumina pore structure, enhance the catalysis assisting effect of group IVB metal oxides, and improve the pore structure and surface performance of the composite oxide carrier. Therefore, the vulcanizing property of a catalyst with the carrier of the invention can be improved, and loaded active metals are easy for reduction.
Description
Technical field
The present invention relates to a kind of preparation method of composite oxide carrier, particularly a kind of preparation method who is used to prepare the composite oxide carrier of Hydrobon catalyst.
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 lip-deep reactive metal of pure alumina and carrier interactions power are bigger, are 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; IVB family metal oxide (zirconia, titanium oxide) is owing to have acid and basic surface center simultaneously; Oxidisability and reproducibility and good ion-exchange performance demonstrate unique catalytic activity and selectivity as carrier or catalyst at catalytic field.This oxide also has premium properties such as high-melting-point, high strength; Compare with conventional alumina support as the catalyst of carrier and to have shown special advantages; Good like sulfur resistance, the reactive metal that supports is easy to reduction etc., but the specific area of this oxide is less; And sharply descend with the rising of sintering temperature, receive very big restriction as support applications.The research of the composite oxides that therefore both combined has obtained the common concern of researcher.
CN 00123133.2 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; Acidity maintains a comparatively stable stage, and infrared acidity is 0.25～0.32mmol/g, and pore distribution concentration is in the mesopore scope; Shortcoming is the precursor that when kneading and compacting, adds zirconium; On the one hand the dispersion of zirconium is inhomogeneous, on the other hand the part zirconium get into carrier body mutually in, can cause ZrO
2Utilization rate reduces, and is unfavorable for the raising of catalyst serviceability.
CN 200710158366.1 discloses a kind of method for preparing zirconium-containing alumina with coprecipitation; EP0339640 discloses a kind of method for preparing titanium-contained aluminum oxide with coprecipitation; Because coprecipitation is the co-precipitations under certain conditions of two or more species; Then co-precipitation condition can not guarantee that all species all in optimal conditions, so there is intrinsic defective in this method, but also can cause zirconia or titanium oxide in coprecipitation process, to get into the body phase; Weaken the influence of zirconia or titanium oxide, thereby influence the physical and chemical performance of final carrier carrier surface.
CN 200710158368.0 discloses a kind of preparation method of siliceous and zirconium alumina dry glue; 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.CN200410050716.9 discloses a kind of preparation method of alumina support of siliceous and titanium, when aluminium oxide becomes glue, adds silicon-containing compound, become glue after, add titanium-containing compound before aging, improve the surface acid property of carrier.But zirconium in the said method or titanium are after aluminium oxide becomes glue, to add; The pH value of aluminium oxide and contains zirconium solution or titaniferous solution for acid in alkaline range, be prone to cause zirconia or titanium oxide rapid precipitation when both mix; Particle size differs; Original precipitation of alumina is peptization again, and the particle size distribution of aluminium oxide is wide, and then influences the rerum natura and the surface nature of carrier.
Summary of the invention
To the deficiency of prior art, the invention provides a kind of preparation method of composite oxide carrier.The present invention prepares the method for the dried glue of composite oxides; Can make most of IVB family metal oxide be distributed in alumina surface; Weakened the alumina pore effect on structure, improved the catalytic action of IVB family metal oxide, improved the pore structure and the surface property of composite oxide carrier.
The preparation method of composite oxide carrier of the present invention; Wherein composite oxides comprise IVB family metal oxide and aluminium oxide; The preparation process comprises: with the dried glue kneading and compacting of composite oxides; Process composite oxide carrier through dry and roasting again, the preparation method of the dried glue of wherein said composite oxides is following:
(1), aluminum contained compound solution and precipitating reagent be carried out to the glue reaction, obtains aluminum hydroxide sol;
(2), the aqueous solution of IVB family metal oxide precursor is mixed with complexing agent, make the aqueous solution that contains IVB family metal complex;
(3), the aluminum hydroxide sol of step (1) gained and the aqueous solution that contains IVB family metal complex of step (2) gained, the powerful stirring slowly splashes into hydrolytic accelerating agent, obtains mixed sediment;
(4), the mixed sediment of step (3) gained is through aging, and then through washing, filtration, drying, obtains the dried glue of composite oxides.
Among the present invention, the IVB family metal oxide is preferably one or both in titanium oxide and the zirconia.
The dried glue of composite oxides of the present invention is benchmark with the butt of composite oxides, and the weight content of aluminium oxide is 10%～95%, and the weight content of IVB family metal oxide is 5%～90%.
In the inventive method; Described composite oxides can also contain silica, are benchmark with the butt of composite oxides, and 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 when becoming glue, introduces in aluminium oxide silicon, perhaps the aging preceding silicon of introducing in step (4) in step (1); Ludox, silica gel or waterglass can be adopted in the silicon source, contain in the silica weight content in the silicon source to be not less than 1%.
In the inventive method, described aluminum contained compound is one or more in aluminum nitrate, aluminium chloride, the aluminum sulfate.The concentration of aluminum contained compound solution is 0.01～10mol/L, is preferably 0.5～5mol/L.Described precipitating reagent is one or more in NaOH, potassium hydroxide, ammoniacal liquor, ammonium carbonate, carbonic hydroammonium, sodium metaaluminate, the potassium metaaluminate.Described IVB family metal oxide predecessor comprises one or more in titania precursor thing and the zirconia predecessor.Described zirconia predecessor is one or more in zirconium carbonate, zirconium nitrate, zirconium chloride, the zirconium sulfate.Described titania precursor thing is one or more in metatitanic acid, titanium carbonate, Titanium Nitrate, titanium chloride, the titanium sulfate.In the aqueous solution of described IVB family metal oxide predecessor, contain IVB family concentration of metal and count 0.5～50g/100mL, be preferably 1～30g/100mL with element.Described complexing agent is one or more in tartrate, citrate, acetylacetone,2,4-pentanedione, ethylenediamine tetra-acetic acid (EDTA), the nitrilotriacetic acid (NTA).The addition of said complexing agent is 1.0～1.2 times of the complete complexing amount of theoretical IVB family's metal.Described hydrolytic accelerating agent is a hydrogen peroxide solution.The addition of described hydrolytic accelerating agent is 1.5～10.0 times of IVB family metal molar number.The reinforced time of said hydrolytic accelerating agent is 1min～40min, is preferably 3min～20min.
In the inventive method, 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.
The described powerful stirring of step (3) is generally rotating speed and is not less than 100 rev/mins.
The described aging condition of step (4) is following: aging temperature is 50～80 ℃, and ageing time is 1～5 hour.The mode of washing of described washing employing 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.
Prepare in the composite oxide carrier process in the present invention, the drying condition after the moulding is following: 50～200 ℃ of dryings 2～8 hours, roasting condition was following: 300～700 ℃ of roastings 2～10 hours, preferably 350～700 ℃ of roastings 2～6 hours.
Composite oxide carrier of the present invention can also add in adhesive, extrusion aid, peptizing agent, auxiliary agent, the alumina dry glue one or more as required before moulding, the concrete material that adopts can be definite by this area knowledge with addition.Such as, said extrusion aid can be the sesbania powder, its consumption is the 1.0wt%～5.0wt% of composite oxide carrier weight.Said peptizing agent can be inorganic acid and/or organic acid, and inorganic acid can be a nitric acid; Organic acid can be formic acid, acetic acid, citric acid, oxalic acid and their mixture, and its consumption is the 0.5wt%～10.0wt% of composite oxide carrier weight.Described adhesive can be the aperture aluminium oxide, and its consumption is the 5wt%～30wt% of composite oxide carrier weight.
Described alumina dry glue is for adopting the known systems preparation, like aluminium chloride-ammoniacal liquor method, carbonizatin method or the boehmite of aluminum sulfate method production and the SB aluminium oxide of Zlegler synthetic reaction accessory substance etc.Described auxiliary agent is one or more in zinc, magnesium, boron, phosphorus, the fluorine etc., and the mode of the alumina dry glue that this auxiliary agent can be through additive modification is introduced in the carrier, and the mode that also can before the carrier moulding, add is separately introduced in the carrier.The addition of alumina dry glue accounts for below 50% of composite oxide carrier in aluminium oxide.The addition of auxiliary agent generally accounts for below 15% of composite oxide carrier weight.
After 2～6 hours, the character of gained is following through 300～700 ℃ of roastings for the dried glue of these composite oxides: specific area is 330～500m
2/ g is preferably 350～480m
2/ g, pore volume is 0.7～1.2ml/g, is preferably 0.8～1.1ml/g, average pore size is 6.0～14.0nm, NH
3-TPD total acid content 0.4～0.9mmol/g is preferably total acid content 0.5～0.7mmol/g.The dried glue butt of these composite oxides is 65%～75%.
The composite oxide carrier of the inventive method preparation can be used as catalyst carrier for hydrgenating, is used to process distillate, particularly heavier distillate.
The present invention has following advantage compared with prior art:
(1) the used composite oxide carrier of the present invention has large pore volume and high-specific surface area; And can realize acid regulation and control through the addition of regulating the IVB family metal oxide; Be more suitable for as catalyst carrier for hydrgenating, help the dispersion of metal component and the diffusion of reactant.
(2) the present invention prepares in the dried glue process of composite oxides; Slowly splash into hydrolytic accelerating agent, make to contain the slow decomplexing of IVB family metal oxide precursor, around aluminium oxide particles, generate homogeneous precipitation; The size of IVB family metal oxide particle is only relevant with hydrolytic accelerating agent; Irrelevant with the pH value of aluminum hydroxide sol, IVB family metal oxide particle size distribution is even, and is evenly distributed on the surface of aluminium oxide particles.Therefore; The composite oxide carrier of gained not only can effectively weaken the influence of IVB family metal oxide to the pore structure of aluminium oxide; And can also improve the utilization rate of IVB family metal oxide; Give full play to the catalytic performance that helps of IVB family metal, can improve, and the reactive metal of load is easy to reduction as the sulfur resistance of the catalyst of carrier.
(3) can produce the high composite oxide carrier of IVB family metal oxide content, outstanding IVB family metal oxide 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% representes mass fraction.
Analytical method of the present invention: specific surface and pore volume adopt the low temperature liquid nitrogen physisorphtion, and acid strength distributes and sour total amount is to adopt NH
3-TPD method is measured.
Embodiment 1
1000ml 2mol/L aluminum nitrate and 22ml silica gel (are contained SiO
225wt%) mix, add ammoniacal liquor, regulating the pH value is 8.5, reacts down at 60 ℃ promptly to get Sol A.Zr (NO with 10g/100ml
3)
4Solution mixes with the ammonium tartrate of theoretical complexing amount and promptly gets complex solution B.Sol A is mixed with complex solution B, and powerful the stirring, and normal temperature adds the hydrogen peroxide solution of 30wt% down, makes Zr
4+: H
2O
2=1: 3 (mol ratios), react be warming up to after 3 hours 60 ℃ aging 1 hour, suction filtration spends deionised water 3 times, pulverizes in 3 hours 120 ℃ of dryings and obtains the dried glue of composite oxides.The dried glue of these composite oxides gets composite oxides through 600 ℃ of roastings after 3 hours, wherein zirconic content is 10wt%, and the content of silica is 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, main character is listed in table 2.
Embodiment 2
1mol/L aluminum sulfate is mixed with sodium metaaluminate 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, the dried glue of the composite oxides that obtain.The dried glue of these composite oxides gets composite oxides through 600 ℃ of roastings after 3 hours, wherein zirconic content is 50wt%, 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, and its main character is listed in table 2.
Embodiment 3
1000ml 2mol/L aluminum nitrate and 22ml silica gel (are contained SiO
225wt%) mix, add ammoniacal liquor, regulating the pH value is 7.5, reacts down at 60 ℃ promptly to get Sol A, with the TiCl of 20g/100ml
4Solution mixes with the EDTA of theoretical complexing amount and promptly gets complex solution B.Sol A is mixed with complex solution B, and powerful the stirring, and normal temperature adds the hydrogen peroxide solution of 100ml 30wt% down; React be warming up to after 3 hours 60 ℃ aging 1 hour; Suction filtration spends deionised water 3 times, pulverizes in 3 hours 120 ℃ of dryings and obtains the dried glue of composite oxides.The dried glue of these composite oxides gets composite oxides through 600 ℃ of roastings after 3 hours, wherein the content of titanium oxide is 10wt%, and the content of silica is 5wt%, 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, its main character is listed in table 2.
Embodiment 4
1mol/L aluminum sulfate is mixed with sodium metaaluminate and the stream of 1mol/L, and regulating the pH value is 7.0, reacts down at 50 ℃ promptly to get Sol A.Make complexing agent into ammonium citrate, all the other are identical with embodiment 3, the dried glue of the composite oxides that obtain.The dried glue of these composite oxides gets composite oxides through 600 ℃ of roastings after 3 hours, wherein the content of titanium oxide is 60wt%, and its main character is listed in table 1.
Get the dried glue 121g of composite oxides, SB powder 27.8g 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, its main character is listed in table 2.
Comparative example 1
1000ml 2mol/L aluminum nitrate, 2000ml 0.05mol/L zirconium nitrate and 22ml silica gel (are contained SiO
225wt%) mixing, 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,, 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, main character is listed in table 2.
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 50wt%.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, main character is listed in table 2.
Embodiment 5
Take by weighing molybdenum oxide 46.48g, basic nickel carbonate 15.8g adds deionized water 60ml and mixes; Add 85wt% phosphoric acid 6ml, be 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 3.
Embodiment 6-8
Adopt the composite oxide carrier of embodiment 2-4 gained respectively, the preparation catalyst, all the other are identical with embodiment 5.
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 5.
Embodiment 9
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 10700 μ g/g, and Cetane number is 35, and boiling range is 181～374 ℃.
The catalyst of 10ml embodiment 5-8 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 3.
The character of the dried glue of table 1 composite oxides
The character of table 2 composite oxide carrier
Table 3 activity of such catalysts evaluating data
| Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Comparative example 3 | Comparative example 4 | |
| 20 ℃ of density, g/cm 3 | 0.861 | 0.859 | 0.858 | 0.856 | 0.862 | 0.859 |
| Yield, wt% | 99.1 | 99.2 | 99.4 | 99.8 | 95.2 | 98.4 |
| Cetane number | 51.9 | 53.6 | 50.5 | 53.2 | 47.3 | 47.8 |
| Sulfur content, μ g/g | 42.3 | 38.1 | 31.9 | 25.2 | 100.2 | 82.5 |
Data by table 1, table 2 and table 3 can be found out; Compare with the comparative example method; The dried glue specific area height of composite oxides that the composite oxide carrier of the inventive method preparation is used, pore volume is big, 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.In addition, the content of IVB family metal oxide is high in the dried glue of these composite oxides, has given prominence to the advantage of IVB family metal oxide in carrier; Make the acid amount of catalyst suitable, improved the yield of liquid-phase product, improved the Cetane number of diesel oil; And reactive metal more is prone to sulfuration; Improved the sulphidity of catalyst, and then improved the utilization rate of active component, the desulphurizing activated of catalyst is improved significantly.
Claims (17)
1. the preparation method of a composite oxide carrier; Wherein composite oxides comprise IVB family metal oxide and aluminium oxide; The preparation process comprises: with the dried glue kneading and compacting of composite oxides; Process composite oxide carrier through dry and roasting again, the preparation method of the dried glue of wherein said composite oxides is following:
(1), aluminum contained compound solution and precipitating reagent be carried out to the glue reaction, obtains aluminum hydroxide sol;
(2), the aqueous solution of IVB family metal oxide predecessor is mixed with complexing agent, make the aqueous solution that contains IVB family metal complex;
(3), the aluminum hydroxide sol of step (1) gained and the aqueous solution that contains IVB family metal complex of step (2) gained, the powerful stirring slowly splashes into hydrolytic accelerating agent, obtains mixed sediment;
(4), the mixed sediment of step (3) gained is through aging, and then through washing, filtration, drying, obtains the dried glue of described composite oxides.
2. according to the described method of claim 1, it is characterized in that described IVB family metal oxide is one or both in titanium oxide and the zirconia.
3. according to the described method of claim 1, it is characterized in that the dried glue of described composite oxides, is benchmark with the weight of composite oxides butt, and the weight content of aluminium oxide is 10%～95%, and the weight content of IVB family metal oxide is 5%～90%.
4. according to the described method of claim 1, it is characterized in that, introduce silicon when aluminium oxide becomes glue, perhaps the aging preceding silicon of introducing in step (4) in step (1); One or more in Ludox, silica gel and the waterglass are adopted in the silicon source.
5. according to claim 1,2,3 or 4 described methods, it is characterized in that described composite oxides comprise silica, is benchmark with the weight of composite oxides butt, and the content of silica is 0.5%～20.0%.
6. according to the described method of claim 1, it is characterized in that 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.
7. according to the described method of claim 1, it is characterized in that described IVB family metal oxide predecessor comprises one or more in titania precursor thing and the zirconia predecessor; Described zirconia predecessor is one or more in zirconium carbonate, zirconium nitrate, zirconium chloride, the zirconium sulfate; Described titania precursor thing is one or more in metatitanic acid, titanium carbonate, Titanium Nitrate, titanium chloride, the titanium sulfate.
8. according to the described method of claim 1, it is characterized in that in the aqueous solution of described IVB family metal oxide predecessor, contain IVB family concentration of metal and count 0.5～50g/100mL with element.
9. according to the described method of claim 1, it is characterized in that in the aqueous solution of described IVB family metal oxide precursor, contain IVB family concentration of metal and count 1～30g/100mL with element.
10. according to the described method of claim 1, it is characterized in that described complexing agent is one or more in tartrate, citrate, acetylacetone,2,4-pentanedione, ethylenediamine tetra-acetic acid, the nitrilotriacetic acid; The addition of said complexing agent is 1.0～1.2 times of the complete complexing amount of theoretical IVB family's metal.
11., it is characterized in that described hydrolytic accelerating agent is a hydrogen peroxide solution according to the described method of claim 1; The addition of described hydrolytic accelerating agent is 1.5～10.0 times of IVB family metal molar number, and the reinforced time of said hydrolytic accelerating agent is 1min～40min.
12. according to claim 1 or 9 described methods, 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, gelation time is 30min～180min.
13. according to claim 1 or 9 described methods, it is characterized in that the described aging condition of step (4) is following: aging temperature is 50～80 ℃, and ageing time is 1～5 hour; Described drying condition was following: 50～200 ℃ of dryings 2～8 hours.
14. according to the described preparation method of claim 1, it is characterized in that the drying condition after the moulding is following in preparation composite oxide carrier process: 50～200 ℃ of dryings 2～8 hours, roasting condition was following: 300～700 ℃ of roastings 2～10 hours.
15. according to the described preparation method of claim 1, it is characterized in that, before the composite oxide carrier moulding, in the dried glue of composite oxides, add in adhesive, extrusion aid, peptizing agent, auxiliary agent, the alumina dry glue one or more.
16. according to the described preparation method of claim 15, it is characterized in that said extrusion aid is the sesbania powder, its consumption accounts for the 1.0wt%～5.0wt% of composite oxide carrier weight; Said peptizing agent is inorganic acid and/or organic acid, and its consumption accounts for the 0.5wt%～10.0wt% of composite oxide carrier weight, and wherein inorganic acid is a nitric acid, and organic acid is one or more in formic acid, acetic acid, citric acid, the oxalic acid; Described adhesive is little porous aluminum oxide, and its consumption accounts for the 5wt%～30wt% of composite oxide carrier weight.
17. according to the described preparation method of claim 15; It is characterized in that described auxiliary agent is one or more in zinc, magnesium, boron, phosphorus, the fluorine, auxiliary agent accounts for 15% the following stated of composite oxide carrier weight in oxide the addition of alumina dry glue accounts for below 50% of composite oxide carrier weight in aluminium oxide.
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| CN110015674A (en) * | 2019-02-03 | 2019-07-16 | 中海油天津化工研究设计院有限公司 | A kind of preparation method of pure Beta-type aluminum hydroxide |
| WO2020209742A1 (en) * | 2019-04-08 | 2020-10-15 | Public Joint Stock Company "Sibur Holding" | Support, catalyst for the dehydrogenation, method for preparing |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101491775A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Catalyst carrier and preparation method thereof |
| CN101491768A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst containing silicon and zirconium |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106232526A (en) * | 2014-04-24 | 2016-12-14 | 第稀元素化学工业株式会社 | The manufacture method of garnet type compound and garnet type compound, and all solid lithium secondary battery containing this garnet type compound |
| CN106232526B (en) * | 2014-04-24 | 2019-07-30 | 第一稀元素化学工业株式会社 | The manufacturing method of garnet type compound |
| CN105944725A (en) * | 2016-05-25 | 2016-09-21 | 安徽中恩化工有限公司 | Preparation method of catalyst for high-grade oxidizing |
| CN105944725B (en) * | 2016-05-25 | 2019-05-24 | 安徽中恩化工有限公司 | A kind of preparation method of the catalyst for advanced oxidation |
| CN110015674A (en) * | 2019-02-03 | 2019-07-16 | 中海油天津化工研究设计院有限公司 | A kind of preparation method of pure Beta-type aluminum hydroxide |
| CN110015674B (en) * | 2019-02-03 | 2021-05-28 | 中海油天津化工研究设计院有限公司 | Preparation method of pure beta-type aluminum hydroxide |
| WO2020209742A1 (en) * | 2019-04-08 | 2020-10-15 | Public Joint Stock Company "Sibur Holding" | Support, catalyst for the dehydrogenation, method for preparing |
| RU2801222C2 (en) * | 2019-04-08 | 2023-08-03 | Публичное акционерное общество "СИБУР Холдинг" | Carrier, dehydrogenation catalyst, production method |
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| CN102451766B (en) | 2013-08-28 |
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