CN102451766B - Preparation method of composite oxide carrier - Google Patents
Preparation method of composite oxide carrier Download PDFInfo
- Publication number
- CN102451766B CN102451766B CN 201010514182 CN201010514182A CN102451766B CN 102451766 B CN102451766 B CN 102451766B CN 201010514182 CN201010514182 CN 201010514182 CN 201010514182 A CN201010514182 A CN 201010514182A CN 102451766 B CN102451766 B CN 102451766B
- Authority
- CN
- China
- Prior art keywords
- ivb family
- oxide
- composite oxide
- glue
- composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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 of the composite oxide carrier for the preparation of Hydrobon catalyst.
Background technology
The preparation technology of alumina support is simple, the specific area height, mechanical strength is good, the aperture is suitable, be one of present most widely used catalyst carrier, but the lip-deep reactive metal of pure alumina and carrier interactions power are bigger, easily form the species of non-activity, as nickel aluminate, be difficult for forming the active phase of highly active II type.Therefore 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 selective 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 as 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, be very restricted as support applications.Therefore the research of the composite oxides of both combinations has been obtained the common concern of researcher.
CN 00123133.2 discloses a kind of alumina carrier containing Zr and preparation method thereof, by make alumina carrier containing Zr to mix the form adding zirconium-containing compound of pinching in the forming process of carrier; This carrier side pressure strength is improved, acidity maintains a comparatively stable stage, infrared acidity is 0.25～0.32mmol/g, pore distribution concentration is in the mesopore scope, shortcoming is the precursor that adds zirconium when kneading and compacting, on the one hand the dispersion of zirconium is inhomogeneous, on the other hand the part zirconium enter 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 are all in optimal conditions, so there is intrinsic defective in this method, but also can cause zirconia or titanium oxide in coprecipitation process, to enter the body phase, weaken zirconia or titanium oxide to the influence of carrier surface, thereby influence the physical and chemical performance of final carrier.
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, adds silicon-containing compound when aluminium oxide becomes glue, become glue after, add titanium-containing compound before aging, improve the surface acid property of carrier.But the zirconium in the said method or titanium are to add after aluminium oxide becomes glue, the pH value of aluminium oxide is in alkaline range, and contain zirconium solution or titaniferous solution for acid, when mixing, both easily cause zirconia or titanium oxide rapid precipitation, particle size differs, original precipitation of alumina is peptization again, and the particle size distribution of aluminium oxide is wide, and then influences rerum natura and the surface nature of carrier.
Summary of the invention
At the deficiencies in the 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, weaken the influence to the alumina pore structure, improved the catalytic action of IVB family metal oxide, improved 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, preparation process comprises: with the dried glue kneading and compacting of composite oxides, composite oxide carrier is made in drying and roasting again, and the preparation method of the dried glue of wherein said composite oxides is as follows:
(1), aluminum contained compound solution becomes glue reaction with precipitating reagent, obtain 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, butt with composite oxides is benchmark, 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 in step (1), introduce silicon before perhaps in step (4), wearing out, 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 with element, be preferably 1～30g/100mL.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 described complexing agent is 1.0～1.2 times of the complete complexing amount of theoretical IVB family's metal.Described hydrolytic accelerating agent is hydrogen peroxide.The addition of described hydrolytic accelerating agent is 1.5～10.0 times of IVB family metal molar number.The reinforced time of described 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 as follows: aging temperature is 50～80 ℃, and ageing time is 1～5 hour.Conventional mode of washing is adopted in described washing, as making beating washing or the flushing of plate basket etc., generally is that the pH value that adopts deionized water to be washed till cleaning solution approaches neutral.Conventional filter type is adopted in described filtration, generally adopts suction filtration.Described drying condition was as follows: 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 as follows: 50～200 ℃ of dryings 2～8 hours, roasting condition was as follows: 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 and addition can be determined by this area knowledge.Such as, described extrusion aid can be the sesbania powder, its consumption is the 1.0wt%～5.0wt% of composite oxide carrier weight.Described peptizing agent can be inorganic acid and/or organic acid, and inorganic acid can be 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, as 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 by additive modification is introduced in the carrier, and also the mode that can add separately before the carrier moulding is 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 as follows 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 for the processing 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 by the addition of regulating the IVB family metal oxide, be more suitable for as catalyst carrier for hydrgenating, be conducive to 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 and 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 IVB family metal oxide to the influence of 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 as the sulfur resistance of the catalyst of carrier, and the reactive metal of load is easy to reduction.
(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 the easier sulfuration of metal, 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 below by specific embodiment and comparative example, but these embodiment can not limit the present invention.Among the present invention, wt% represents 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, namely gets Sol A 60 ℃ of following reactions.Zr (NO with 10g/100ml
3)
4Solution mixes with the ammonium tartrate of theoretical complexing amount and namely gets complex solution B.Sol A is mixed with complex solution B, and powerful the stirring, adds the hydrogen peroxide of 30wt% under the normal temperature, 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, namely gets Sol A 50 ℃ of following reactions.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, 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 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, namely gets Sol A 60 ℃ of following reactions, with the TiCl of 20g/100ml
4Solution mixes with the EDTA of theoretical complexing amount and namely gets complex solution B.Sol A is mixed with complex solution B, and powerful the stirring, adds the hydrogen peroxide of 100ml 30wt% under the normal temperature, 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, namely gets Sol A 50 ℃ of following reactions.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%) mix, adding ammoniacal liquor adjusting pH value is 8.0, react down and wore out 1 hour at 60 ℃ at 80 ℃, suction filtration spends 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%, 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
1mol/L aluminum sulfate is mixed with sodium metaaluminate and the stream of 1mol/L, regulating the pH value is 7.0, react down and wore out 1 hour at 60 ℃ at 60 ℃, slowly drip the zirconium nitrate of 0.05mol/L, adding less ammonia during this time makes the pH value remain on 7.0, continued aging 2 hours after adding silica gel, suction filtration, spend 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%, 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, and adds 85wt% phosphoric acid 6ml, be heated to 75 ℃, constant temperature 1 hour obtains bottle green clear solution, sprays the composite oxide carrier of embodiment 1 gained with this solution, 120 ℃ of dryings 3 hours, 500 ℃ of roastings obtained catalyst after 3 hours, and this activity of such catalysts evaluation result sees 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
Carry out the diesel oil hydrogenation activity rating of catalyst at miniature hydrogenation reaction device, the useful load of catalyst is 10ml, and estimating with sulfurized oil is the mixture of coal and carbon disulfide of navigating, 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 ℃.Estimating with crude oil is catalytic cracking diesel oil, and 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, and hydrogen flowing quantity 200ml/min rises to 150 ℃ with the programming rate of 5 ℃/h, constant temperature 1 hour, 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 sees 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 |
By the data of table 1, table 2 and table 3 as can be seen, compare with the comparative example method, the used dried glue specific area of the composite oxides height of composite oxide carrier of the inventive method preparation, pore volume is big, be conducive to the dispersion of reactive metal, when especially maceration extract was high concentration, full-bodied liquid (as molybdenum nickel phosphorus solution), advantage was more obvious.In addition, the content height of IVB family metal oxide in the dried glue of these composite oxides, 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 the easier sulfuration of reactive metal, improved the sulphidity of catalyst, and then improved the utilization rate of active component, the desulphurizing activated of catalyst is improved significantly.
Claims (14)
1. the preparation method of a composite oxide carrier, wherein composite oxides comprise IVB family metal oxide and aluminium oxide, preparation process comprises: with the dried glue kneading and compacting of composite oxides, composite oxide carrier is made in drying and roasting again, and the preparation method of the dried glue of wherein said composite oxides is as follows:
(1), aluminum contained compound solution becomes glue reaction with precipitating reagent, obtain 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; 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 Nitrate, titanium chloride, the titanium sulfate; Described complexing agent is one or more in tartrate, citrate, acetylacetone,2,4-pentanedione, ethylenediamine tetra-acetic acid, the nitrilotriacetic acid; The addition of described complexing agent is 1.0～1.2 times of the complete complexing amount of theoretical IVB family's metal;
(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; Described hydrolytic accelerating agent is hydrogen peroxide; The addition of described hydrolytic accelerating agent is 1.5～10.0 times of IVB family metal molar number, and the reinforced time of described hydrolytic accelerating agent is 1min～40min;
(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. in accordance with the method for claim 1, it is characterized in that described IVB family metal oxide is one or both in titanium oxide and the zirconia.
3. in accordance with the method for 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. in accordance with the method for claim 1, it is characterized in that, introduce silicon when aluminium oxide becomes glue in step (1), perhaps the aging preceding silicon of introducing in step (4); 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. in accordance with the method for 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. in accordance with the method for 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.
8. in accordance with the method for 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.
9. in accordance with the method for 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.
10. in accordance with the method for claim 1, it is characterized in that the described aging condition of step (4) is as follows: aging temperature is 50～80 ℃, and ageing time is 1～5 hour; Described drying condition was as follows: 50～200 ℃ of dryings 2～8 hours.
11. according to the described preparation method of claim 1, it is characterized in that the drying condition after the moulding is as follows in preparation composite oxide carrier process: 50～200 ℃ of dryings 2～8 hours, roasting condition was as follows: 300～700 ℃ of roastings 2～10 hours.
12. according to the described preparation method of claim 1, it is characterized in that, before the composite oxide carrier moulding, add in adhesive, extrusion aid, peptizing agent, auxiliary agent, the alumina dry glue one or more in the dried glue of composite oxides; Described auxiliary agent is one or more in zinc, magnesium, boron, phosphorus, the fluorine.
13. according to the described preparation method of claim 12, it is characterized in that described extrusion aid is the sesbania powder, its consumption accounts for the 1.0wt%～5.0wt% of composite oxide carrier weight; Described 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 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.
14. according to the described preparation method of claim 12, it is characterized in that in described auxiliary agent zinc, magnesium, boron, phosphorus, the fluorine one or more account for below 15% of composite oxide carrier weight in oxide; The addition of described alumina dry glue accounts for below 50% of composite oxide carrier weight in aluminium oxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010514182 CN102451766B (en) | 2010-10-15 | 2010-10-15 | Preparation method of composite oxide carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010514182 CN102451766B (en) | 2010-10-15 | 2010-10-15 | Preparation method of composite oxide carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102451766A CN102451766A (en) | 2012-05-16 |
| CN102451766B true CN102451766B (en) | 2013-08-28 |
Family
ID=46035693
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010514182 Active CN102451766B (en) | 2010-10-15 | 2010-10-15 | Preparation method of composite oxide carrier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102451766B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101731240B1 (en) * | 2014-04-24 | 2017-04-28 | 다이치 키겐소 카가쿠 코교 컴퍼니 리미티드 | Method for producing garnet-type compound, garnet-type compound, and all-solid lithium secondary cell containing said garnet-type compound |
| 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 |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2010
- 2010-10-15 CN CN 201010514182 patent/CN102451766B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102451766A (en) | 2012-05-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102451765B (en) | Preparation method for composite oxide carrier | |
| CN102451766B (en) | Preparation method of composite oxide carrier | |
| CN101491775B (en) | Catalyst carrier and preparation method thereof | |
| CN102451764B (en) | Method for preparing zirconia-alumina composite oxide carrier | |
| CN1853785A (en) | Silicon and boron contained alumina carrier and production thereof | |
| CN102728374B (en) | Preparation method of hydrotreatment catalyst | |
| CN107285334A (en) | The method and catalyst of a kind of synthesis in solid state AEI type molecular sieves | |
| CN106179381B (en) | The preparation method of Hydrobon catalyst | |
| CN108187676B (en) | A kind of ester through hydrogenation synthesis of dibasic alcohol copper-based catalysts and its preparation method and application | |
| CN101927177A (en) | Preparation method of nitrogen-doped attapulgite load nano TiO2 visible light photocatalyst | |
| CN102728373A (en) | Preparation method of hydrotreating catalyst | |
| CN102451769B (en) | Preparation method of composite oxide adhesive | |
| CN107042121B (en) | The preparation method and applications of three-dimensional ordered macroporous carrier loaded Heterocompound catalyst | |
| CN101979136A (en) | Mesoporous composite oxide type solid super acidic catalyst and preparation method thereof | |
| CN104043477A (en) | ZSM-5/MCM-48 composite molecular sieve, preparation method and application thereof | |
| CN103316691A (en) | Magnetic solid acid and preparation method thereof | |
| CN111804347B (en) | Preparation method of Janus particles and application of Janus particles in cyclohexene hydration process | |
| CN109046379A (en) | A kind of perovskite composite oxides load platinum catalyst and its preparation and application | |
| CN102051208B (en) | Olefin hydroisomerization and thiophene sulfur removal method | |
| CN107008223B (en) | The adsorbent and preparation method thereof of low-load amount high dispersive type benzene refining desulfurization | |
| CN102451768A (en) | Method for preparing zirconia-alumina composite oxide xerogel | |
| CN104888797A (en) | Iron-based catalyst and preparation method thereof | |
| CN107519883A (en) | A kind of hydrophobicity copper-based catalysts and preparation method and application | |
| CN103100402B (en) | Preparation method of hydrocracking catalyst | |
| CN102451770B (en) | Preparation method of a composite oxide dry gel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |