CN108339541A - The preparation method for the alumina support that spinelle is modified - Google Patents
The preparation method for the alumina support that spinelle is modified Download PDFInfo
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- CN108339541A CN108339541A CN201810121465.0A CN201810121465A CN108339541A CN 108339541 A CN108339541 A CN 108339541A CN 201810121465 A CN201810121465 A CN 201810121465A CN 108339541 A CN108339541 A CN 108339541A
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- spinelle
- alumina support
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- preparation
- pickling
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000465 moulding Methods 0.000 claims abstract description 20
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 238000007598 dipping method Methods 0.000 claims description 38
- 238000005554 pickling Methods 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 26
- 238000001354 calcination Methods 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000008246 gaseous mixture Substances 0.000 claims description 16
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 16
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- 159000000007 calcium salts Chemical class 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 150000001299 aldehydes Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 23
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 238000012986 modification Methods 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 229910052593 corundum Inorganic materials 0.000 abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 37
- -1 mantoquita Chemical class 0.000 description 33
- 229910002651 NO3 Inorganic materials 0.000 description 24
- 239000011777 magnesium Substances 0.000 description 18
- 239000011701 zinc Substances 0.000 description 18
- 229910052596 spinel Inorganic materials 0.000 description 15
- 239000011029 spinel Substances 0.000 description 15
- 229910052749 magnesium Inorganic materials 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 229910052725 zinc Inorganic materials 0.000 description 12
- 238000002803 maceration Methods 0.000 description 11
- 238000010792 warming Methods 0.000 description 11
- 238000005299 abrasion Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- CRHLEZORXKQUEI-UHFFFAOYSA-N dialuminum;cobalt(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Al+3].[Co+2].[Co+2] CRHLEZORXKQUEI-UHFFFAOYSA-N 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002002 slurry Substances 0.000 description 4
- 230000001476 alcoholic effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052833 almandine Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052566 spinel group Inorganic materials 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B01J35/60—
Abstract
The invention discloses a kind of preparation methods for the alumina support that spinelle is modified, and this method is to molding γ Al2O3Surface is pre-processed, using modifying element to γ Al2O3Surface is modified, and spinelle is generated in roasting process, to obtain the alumina support of spinelle modification.This method solves the problems, such as that spinelle modified aluminium oxide supports high-specific surface area and high resistance against wear intensity mutually restrict, the alumina catalyst carrier being modified using spinelle prepared by this technique not only has lower spinelle content, higher specific surface area and suitable pore structure, and there is higher wear resistance, make it that there is good application value as carrier.Modified aluminium oxide supports prepared by this method are suitable for all kinds of catalysis reaction paste state bed reactor and fluidized-bed reactor.
Description
Technical field
The present invention relates to the preparation method of modified aluminium oxide supports, the alumina support being modified in particular to a kind of spinelle
Preparation method.
Background technology
It, can be by play when the heterogeneous reaction as this kind of such as F- T synthesis that catalyst carries out in slurry bed system and fluidized-bed reactor
Strong collision and friction, over time, catalyst can occur significantly to wear.Abrasion causes catalyst amount to increase, and improves behaviour
Make cost, and wear the fine powder generated and easily block filter, involuntary stoppage can be caused when situation is serious.Therefore, in order to improve
Catalyst life and reduction operating cost, carrier must have higher wear resistance.
Aluminium oxide is cheap because of excellent specific surface area, suitable pore structure, abundant acid centre and basic center
The advantages that, it is to be widely used in one of catalyst carrier of chemical field.But in order to match slurry bed system and fluidized-bed reaction
The reaction operating mode of sharp impacts and friction, the abrasion resistance of aluminium oxide need to be improved in device.
Studies have shown that in alumina support spinelle presence, have the function of improve catalyst wear strength.But point
The condition that spar generates is harsh, could be formed in the high-temperature roasting higher than 650 DEG C, and the abrasion resistance of spinelle at this time
Also poor.To improve the wear resistance of spinelle, two kinds of approach are generally used：A kind of approach is to improve calcination temperature, the way
Diameter points out that the gama-alumina containing spinelle roasts at a temperature of more than 1100 DEG C, and abrasion resistance is significantly improved, but high temperature
Crystal transfer has occurred in gama-alumina after calcining, and the specific surface area of carrier is caused drastically to drop to more than ten m2/ g, spinelle are modified
There is the problem of mutual restriction in the high-specific surface area and high resistance against wear intensity of alumina support.Another way is to increase carrier
The content of middle spinelle, it is excellent, but spinelle that the load capacity of bivalent compound, which is more than 10wt% (in terms of metal), under normal circumstances
It is a large amount of generation can occupy duct or block aperture, cause the specific surface of alumina support to reduce, this will make catalyst activity
At detrimental effect, while the metallic compound for adding a large amount of expensive formation Spinels substantially increases cost, limits
Its as carrier catalytic field application.
To solve the above problems, the prior art discloses a kind of side of catalyst of the low cost preparation with high wear resistance
Method.This method by gama-alumina, can be formed Spinel metallic compound and trivalent aluminium soluble compound mixing shape
At slurry, through 950 DEG C~1050 DEG C high-temperature roastings after spray drying, part changing containing metal aluminate spinelle is finally obtained
Property alumina support.Although above-mentioned method of modifying can obtain with the modified metal of lower content wear-resistant at relatively low temperatures
Spinel composition, but its calcination temperature is still up to 1000 DEG C, forms the content of the metallic compound of spinelle 5%~10%
Between, content is still higher.Compared with former gama-alumina, although attrition value by 6.8 it is minimum be down to 0.9, finally contain Spinel
Alumina support specific surface area and hole hold respectively by 170m2/g、0.73cm340m drastically drops in/g2/g、0.22cm3/ g, limitation
Its as carrier catalytic field application.
Above-mentioned preparation process, although improving carrier wear resistance to a certain extent, but still unresolved spinelle is modified
The problem of high-specific surface area and high resistance against wear intensity of alumina support mutually restrict, while the metal of spinelle is formed in carrier
The content of compound is still higher.Therefore, selection provides a kind of preparation method for the alumina support that spinelle is modified, and makes oxidation
Alumina supporter realizes that high-specific surface area and high resistance against wear intensity have great importance simultaneously in relatively low spinelle content.
Invention content
It is an object of the present invention to provide a kind of preparation methods for the alumina support that spinelle is modified, and this method is to molding
γ-Al2O3Surface is pre-processed, using modifying element to γ-Al2O3Surface is modified, and it is brilliant to generate point in roasting process
Stone, to obtain the alumina support of spinelle modification.This method efficiently solves spinelle modified aluminium oxide supports Gao Bibiao
The problem of area and high resistance against wear intensity mutually restrict, the alumina catalyst carrier being modified using spinelle prepared by this technique
Not only there is lower spinelle content, higher specific surface area and suitable pore structure, but also there is higher abrasion resistance
Can, make it that there is good application value as carrier.Modified aluminium oxide supports prepared by this method are suitable for anti-in slurry bed system
All kinds of catalysis in device and fluidized-bed reactor are answered to react.
To achieve the above object, the preparation method for the alumina support that a kind of spinelle provided by the invention is modified, including
Following steps：
1) pickling
At room temperature, by molding γ-Al2O3It is washed in nitric acid, then filters, is 50~150 DEG C of conditions in temperature
1~6h of lower drying obtains the γ-Al of pickling2O3；
2) dipping solution is prepared
Soluble metallic salt is dissolved in organic solvent, dipping solution is made；Wherein, soluble metallic salt be cobalt salt,
Any one in zinc salt, mantoquita, magnesium salts, calcium salt, manganese salt, nickel salt and molysite；
3) it impregnates
By the γ-Al of pickling2O3It is placed in dipping solution and carries out incipient impregnation or excessive dipping；Obtain dipping mixing
Object；Wherein, the amount of dipping solution is 1~3 times of pore volume of carrier in excessive dipping；
4) dry
Dip compound carries out rotating pressure-decreasing drying under the conditions of temperature is 30~120 DEG C, until collecting less than condensate liquid
Body；Obtain dried object；
5) it calcines
Dried object is put into calcining furnace, into calcining furnace is passed through NO's and Ar with rate for 30mL/min~120mL/min
Gaseous mixture, and 5~12h is calcined to get the alumina support being modified to spinelle under the conditions of temperature is 650~1300 DEG C；Its
In, the quality of almandine spinel accounts for γ-Al in carrier2O31~15wt% of quality.
Further, in the step 1), molding γ-Al2O3For spherical or graininess, specific surface area is 30~
400m2/ g, aperture are 5~50nm, and pore volume is 0.2~2cm3/ g, grain size are 50~400 μm.
Still further, in the step 1), the concentration of nitric acid is 0.01~0.1mol/L, preferably 0.01~
0.05mol/L.50~150 DEG C of drying temperature, it is preferable that drying temperature is 80~120 DEG C, and drying time is 3~6h.
Still further, in the step 2), soluble metallic salt is in magnesium nitrate, nickel nitrate, zinc nitrate and cobalt nitrate
Any one or more, the organic solvent is any one or more in methanol, ethyl alcohol and acetone.
Still further, in the step 3), in excessive dipping the amount of dipping solution be the pore volume of carrier 1.5~
2.5 again.
Still further, in the step 4), drying temperature is 50~80 DEG C.
Still further, in the step 5), the volume fraction of NO is the mixed of 5%, NO and Ar in the gaseous mixture of NO and Ar
The rate for closing gas is 50mL/min~100mL/min, and calcination temperature is 650~900 DEG C, and calcination time is 6~10h.
Still further, in the step 5), the quality of spinelle accounts for γ-Al in carrier2O31~5wt% of quality.
In the preparation method for the gamma-aluminium oxide carrier that the spinelle of the present invention is modified, the reaction principle of each step and preparation
Process parameter control principle is as follows：
By molding γ-Al in step 1)2O3Pickling is carried out using nitric acid, effectively removes surface impurity, while generating more
Active sites.
Using organic solvent as maceration extract in step 2), intergranular aggregation can be effectively reduced, is conducive to point of spinelle
It dissipates, improves dispersion degree, while the agglomeration of spinel particles can be inhibited in roasting process, so that particle is maintained smaller
Size.
Step 3) 4) uses the excessive method that impregnates and be dried under reduced pressure the metal salt that forms spinelle are supported on γ-oxygen
Change on aluminium, spinel components dispersion can be made relatively uniform.
Step 5) calcines the carrier after drying in the gaseous mixture of NO and Ar, promotes being uniformly distributed for spinel particle.
The beneficial effects of the present invention are：
1) alumina support of spinelle modification, the alumina support of the modification has been made in the present invention at a lower temperature
Not only there is higher specific surface area and suitable pore structure, but also have higher wear resistance, efficiently solve spinelle
The problem of high-specific surface area and high resistance against wear intensity of modified aluminium oxide supports mutually restrict makes it have as carrier good
Application value；
2) present invention carries out pre-activate with pickling to alumina support, using organic solvent as dipping solution, using excessive leaching
Stain and the method calcined under the atmosphere of NO and Ar gaseous mixtures, it is suppressed that the spinel particle size of the reunion of particle, generation is smaller, point
Divergence is high, and the spinelle for effectively preventing generating occupies duct or blocks aperture to drop so as to cause the specific surface of alumina support
It is low；
3) present invention is with molding γ-Al2O3For carrier, modified technique is simple, the abrasion resistance of the alumina support of preparation
Can be high, while the content of spinelle is less than 5% in carrier, greatly reduces modified cost；
4) pass through modifying element γ-Al2O3Surface carries out surface modification, in γ-Al2O3Surface forms one layer of spinel
Object is closed, can not only improve the wear resistance of carrier, but also can inhibit between the active metal of catalyst surface and carrier
Reaction, improves the surface texture of carrier, and the catalyst for making the aluminium oxide being modified using spinelle as carrier and preparing is in long-time
Higher activity and stability can be kept in operation.
Description of the drawings
Fig. 1 is the evaluation expression activitiy schematic diagram of catalyst
Specific implementation mode
In order to preferably explain the present invention, below in conjunction with the specific embodiment main contents that the present invention is furture elucidated, but
Present disclosure is not limited solely to following embodiment.
Molding γ-Al used in the present embodiment2O3For the γ-Al of market purchase2O3, specific surface area 132.2m2/ g,
Aperture is 13.56nm, Kong Rongwei 0.45cm2/g。
Embodiment 1
1) at room temperature, by the molding γ-Al of 10g2O3It is washed, is then filtered, at 100 DEG C in 0.03mol/L nitric acid
Lower dry 4h obtains the γ-Al of pickling2O3；
2) by 0.72g magnesium nitrate Mg (NO3)2·6H2O is dissolved in 8.7mL methanol solutions and is configured to dipping solution；
3) by the γ-Al of pickling2O3It is placed in the round-bottomed flask being connect with Rotary Evaporators, it will in rotary course
Dipping solution is slowly added into the γ-Al of pickling2O3In, after impregnating 2h, obtain dip compound；
4) dip compound, which rotates to be dried under reduced pressure at 60 DEG C, removes extra maceration extract, obtains dried object；
5) dried object is put into tube calciner, gaseous mixture (the wherein NO of NO and Ar is passed through with the rate of 80mL/min
Volume fraction be 5%), with the rate of 1 DEG C/min be warming up to 800 DEG C calcining 8h, be naturally cooling to room temperature, obtain magnesium aluminate point
The alumina support that spar is modified, wherein the quality of magnesium aluminate accounts for γ-Al2O3The 4wt% of quality.
Embodiment 2
1) at room temperature, by the molding γ-Al of 10g2O3It is washed, is then filtered, at 110 DEG C in 0.02mol/L nitric acid
Lower dry 3h obtains the γ-Al of pickling2O3；
2) by 0.33g nickel nitrate Ni (NO3)2·6H2O is dissolved in 8.88mL ethanol solutions and is configured to dipping solution；
3) by the γ-Al of pickling2O3It is placed in the round-bottomed flask being connect with Rotary Evaporators, it will in rotary course
Dipping solution is slowly added into the γ-Al of pickling2O3In, after impregnating 2h, obtain dip compound；
4) dip compound, which rotates to be dried under reduced pressure at 75 DEG C, removes extra maceration extract, obtains dried object；
5) dried object is put into tube calciner, gaseous mixture (the wherein NO of NO and Ar is passed through with the rate of 60mL/min
Volume fraction be 5%), with the rate of 1 DEG C/min be warming up to 700 DEG C calcining 9h, be naturally cooling to room temperature, obtain nickel aluminate point
The alumina support that spar is modified；Wherein, the quality of nickel aluminate accounts for γ-Al2O3The 2wt% of quality.
Embodiment 3
1) at room temperature, by the molding γ-Al of 10g2O3It is washed, is then filtered, at 100 DEG C in 0.05mol/L nitric acid
Lower dry 4h obtains the γ-Al of pickling2O3；
2) by 0.49g zinc nitrate Zn (NO3)2·6H2O is dissolved in 6.57mL ethanol solutions and is configured to dipping solution；
3) by the γ-Al of pickling2O3It is placed in the round-bottomed flask being connect with Rotary Evaporators, it will in rotary course
Dipping solution is slowly added into the γ-Al of pickling2O3In, after impregnating 2h, obtain dip compound；
4) dip compound, which rotates to be dried under reduced pressure at 70 DEG C, removes extra maceration extract, obtains dried object；
5) dried object is put into tube calciner, gaseous mixture (the wherein NO of NO and Ar is passed through with the rate of 70mL/min
Volume fraction be 5%), with the rate of 1 DEG C/min be warming up to 750 DEG C calcining 9h, be naturally cooling to room temperature, obtain zinc aluminate point
The alumina support that spar is modified, wherein the quality of zinc aluminate accounts for γ-Al2O3The 3wt% of quality.
Embodiment 4
1) at room temperature, by the molding γ-Al of 10g2O3It is washed, is then filtered, at 80 DEG C in 0.04mol/L nitric acid
Lower dry 6h obtains the γ-Al of pickling2O3；
2) by 0.16g cobalt nitrate Co (NO3)2·6H2O is dissolved in 6.69mL acetone solns and is configured to dipping solution,
3) by the γ-Al of pickling2O3It is placed in the round-bottomed flask being connect with Rotary Evaporators, it will in rotary course
Dipping solution is slowly added into the γ-Al of pickling2O3In, after impregnating 2h, obtain dip compound；
4) dip compound, which rotates to be dried under reduced pressure at 50 DEG C, removes extra maceration extract, obtains dried object；
5) carrier after drying is put into tube calciner, the gaseous mixture of NO and Ar is passed through with the rate of 50mL/min
(wherein the volume fraction of NO is 5%) is warming up to 650 DEG C of calcining 10h with the rate of 1 DEG C/min, is naturally cooling to room temperature, obtains
The alumina support that cobalt aluminate spinel is modified, wherein the quality of cobalt aluminate accounts for γ-Al2O3The 1wt% of quality.
Embodiment 5
1) at room temperature, by the molding γ-Al of 10g2O3It is washed, is then filtered, at 90 DEG C in 0.05mol/L nitric acid
Lower dry 5h obtains the γ-Al of pickling2O3；
2) by 0.36g magnesium nitrate Mg (NO3)2·6H2O and 0.33g nickel nitrate Ni (NO3)26H2O is dissolved in 8.73mL second
Dipping solution is configured in alcoholic solution,
3) by the γ-Al of pickling2O3It is placed in the round-bottomed flask being connect with Rotary Evaporators, it will in rotary course
Dipping solution is slowly added into the γ-Al of pickling2O3In, after impregnating 2h, obtain dip compound；
4) dip compound, which rotates to be dried under reduced pressure at 75 DEG C, removes extra maceration extract, obtains dried object；
5) dried object is put into tube calciner, gaseous mixture (the wherein NO of NO and Ar is passed through with the rate of 75mL/min
Volume fraction be 5%), with the rate of 1 DEG C/min be warming up to 800 DEG C calcining 8h, be naturally cooling to room temperature, obtain magnesium aluminate and
The alumina support that nickel aluminate spinelle is modified, wherein magnesium aluminate and nickel aluminate quality account for γ-Al respectively2O3The 2wt% of quality
And 2wt%.
Embodiment 6
1) at room temperature, by the molding γ-Al of 10g2O3It is washed, is then filtered, at 120 DEG C in 0.01mol/L nitric acid
Lower dry 3h obtains the γ-Al of pickling2O3；
2) by 0.18g magnesium nitrate Mg (NO3)2·6H2O and 0.16g zinc nitrate Zn (NO3)2·6H2O is dissolved in 8.81mL second
Dipping solution is configured in alcoholic solution；
3) by the γ-Al of pickling2O3It is placed in the round-bottomed flask being connect with Rotary Evaporators, it will in rotary course
Dipping solution is slowly added into the γ-Al of pickling2O3In, after impregnating 2h, obtain dip compound；
4) dip compound, which rotates to be dried under reduced pressure at 75 DEG C, removes extra maceration extract, obtains dried object；
5) dried object is put into tube calciner, gaseous mixture (the wherein NO of NO and Ar is passed through with the rate of 80mL/min
Volume fraction be 5%), with the rate of 1 DEG C/min be warming up to 750 DEG C calcining 9h, be naturally cooling to room temperature, obtain magnesium aluminate and
The alumina support that zinc aluminate spinel is modified, wherein the quality of magnesium aluminate and zinc aluminate accounts for γ-Al respectively2O3Quality
1wt% and 2wt%.
Embodiment 7
1) at room temperature, by the molding γ-Al of 10g2O3It is washed, is then filtered, at 110 DEG C in 0.03mol/L nitric acid
Lower dry 3h obtains the γ-Al of pickling2O3；
2) by 0.16g cobalt nitrate Co (NO3)2·6H2O and 0.16g zinc nitrate Zn (NO3)2·6H2O is dissolved in 6.63mL second
Dipping solution is configured in alcoholic solution；
3) by the γ-Al of pickling2O3It is placed in the round-bottomed flask being connect with Rotary Evaporators, it will in rotary course
Dipping solution is slowly added into the γ-Al of pickling2O3In, after impregnating 2h, obtain dip compound；
4) dip compound, which rotates to be dried under reduced pressure at 70 DEG C, removes extra maceration extract, obtains dried object；
5) dried object is put into tube calciner, gaseous mixture (the wherein NO of NO and Ar is passed through with the rate of 65mL/min
Volume fraction be 5%), with the rate of 1 DEG C/min be warming up to 700 DEG C calcining 9h, be naturally cooling to room temperature, obtain cobalt aluminate and
The alumina support that zinc aluminate spinel is modified, wherein the quality of cobalt aluminate and zinc aluminate accounts for γ-Al respectively2O3Quality
1wt% and 1wt%.
Embodiment 8
1) at room temperature, by the molding γ-Al of 10g2O3It is washed, is then filtered, at 100 DEG C in 0.02mol/L nitric acid
Lower dry 4h obtains the γ-Al of pickling2O3；
2) by 0.18g magnesium nitrate Mg (NO3)2·6H2O, 0.16g nickel nitrates Ni (NO3)2·6H2O and 0.33g zinc nitrates Zn
(NO3)2·6H2O is dissolved in 8.74mL ethanol solutions and is configured to dipping solution；
3) by the γ-Al of pickling2O3It is placed in the round-bottomed flask being connect with Rotary Evaporators, it will in rotary course
Dipping solution is slowly added into the γ-Al of pickling2O3In, after impregnating 2h, obtain dip compound；
4) dip compound, which rotates to be dried under reduced pressure at 75 DEG C, removes extra maceration extract, obtains dried object；
5) dried object is put into tube calciner, gaseous mixture (the wherein NO of NO and Ar is passed through with the rate of 85mL/min
Volume fraction be 5%), with the rate of 1 DEG C/min be warming up to 800 DEG C calcining 8h, be naturally cooling to room temperature, obtain magnesium aluminate,
The alumina support that nickel aluminate and zinc aluminate spinel are modified, wherein the quality of magnesium aluminate, nickel aluminate and zinc aluminate accounts for respectively
γ-Al2O31wt%, 1wt% and 2wt% of quality.
Embodiment 9
1) at room temperature, by the molding γ-Al of 10g2O3It is washed, is then filtered, at 90 DEG C in 0.04mol/L nitric acid
Lower dry 3h obtains the γ-Al of pickling2O3；
2) by 0.36g magnesium nitrate Mg (NO3)2·6H2O, 0.16g zinc nitrates Zn (NO3)2·6H2O and 0.33g cobalt nitrates Co
(NO3)2·6H2O is dissolved in 10.92mL ethanol solutions and is configured to dipping solution,
3) by the γ-Al of pickling2O3It is placed in the round-bottomed flask being connect with Rotary Evaporators, it will in rotary course
Dipping solution is slowly added into the γ-Al of pickling2O3In, after impregnating 2h, obtain dip compound；
4) dip compound, which rotates to be dried under reduced pressure at 80 DEG C, removes extra maceration extract, obtains dried object；
5) dried object is put into tube calciner, gaseous mixture (the wherein NO of NO and Ar is passed through with the rate of 100mL/min
Volume fraction be 5%), with the rate of 1 DEG C/min be warming up to 900 DEG C calcining 6h, be naturally cooling to room temperature, obtain magnesium aluminate,
The alumina support that zinc aluminate and cobalt aluminate spinel are modified, wherein the quality of magnesium aluminate, zinc aluminate and cobalt aluminate accounts for respectively
γ-Al2O32wt%, 1wt% and 2wt% of quality.
Embodiment 10
1) at room temperature, by the molding γ-Al of 10g2O3It is washed, is then filtered, at 80 DEG C in 0.05mol/L nitric acid
Lower dry 6h obtains the γ-Al of pickling2O3；
2) by 0.18g magnesium nitrate Mg (NO3)2·6H2O, 0.16g nickel nitrates Ni (NO3)2·6H2O, 0.33g zinc nitrates Zn
(NO3)2·6H2O and 0.16g cobalt nitrate Co (NO3)2·6H2O is dissolved in 10.93mL ethanol solutions and is configured to dipping solution；
3) by the γ-Al of pickling2O3It is placed in the round-bottomed flask being connect with Rotary Evaporators, it will in rotary course
Dipping solution is slowly added into the γ-Al of pickling2O3In, after impregnating 2h, obtain dip compound；
4) dip compound, which rotates to be dried under reduced pressure at 80 DEG C, removes extra maceration extract, obtains dried object；
5) dried object is put into tube calciner, gaseous mixture (the wherein NO of NO and Ar is passed through with the rate of 90mL/min
Volume fraction be 5%), with the rate of 1 DEG C/min be warming up to 850 DEG C calcining 7h, be naturally cooling to room temperature, obtain magnesium aluminate,
The alumina support that nickel aluminate, zinc aluminate and cobalt aluminate spinel are modified, wherein magnesium aluminate, nickel aluminate, zinc aluminate and cobalt aluminate
Quality account for γ-Al respectively2O31wt%, 1wt%, 2wt% and 1wt% of quality.
Comparative example 1
By molding γ-Al2O3Carrier is put into tube calciner, and 750 DEG C of calcining 9h are warming up to the rate of 1 DEG C/min.
Polishing machine is tested
With reference to ASTM D5757, using high speed injection experiment method, alumina support is put into the test of MS-C type abrasion of particles
In instrument, it is in fluidized state under the jet-action of air stream to make sample, and 5h, the examination of 1h blowouts are purged under constant gas velocity
Sample, which discards, to be disregarded, the sample that 4h is blown out after collection, by the alumina support in the sample of blowout and abrasion index determinator device
Recycling, is analyzed after mixing with laser particle size analyzer, is obtained grain size and is less than 10 μm of percentage by volume, using the value as resisting
The index of abrasiveness, value is lower, and wear resistence is better.
The physicochemical properties for the alumina support that 1 spinelle of table is modified
As can be seen from Table 1, the present invention successfully prepares the oxygen of spinelle modification at lower temperature (650 DEG C -900 DEG C)
Change alumina supporter, compared with comparative example 1, abrasion loss rate by 17.41 it is minimum be down to 2.97, illustrate that the method for modifying of the present invention can be big
The big wear resistance for improving alumina support, while as can be seen from Table 1, the carrying alumina physical efficiency that spinelle is modified keeps high
Surface area and suitable aperture.To sum up, method of modifying provided by the invention can successfully prepare spinelle and change at a lower temperature
Property alumina support, effectively solve what spinelle modified aluminium oxide supports high-specific surface area and high resistance against wear intensity mutually restricted
Problem makes it have a good application prospect as carrier.
Embodiment 11
Weigh 12.22g Co (NO3)2·6H2O and 0.01g Pt (NH4)4(NO3)2It is dissolved in 11ml deionized waters, uses
Solution is impregnated on carrier prepared by 10g embodiments 9 by infusion process, is placed 120 DEG C of dry 12h after 12h at room temperature, is subsequently placed at
300 DEG C of roasting 3h in Muffle furnace.
Comparative example 2
Weigh 12.22g Co (NO3)2·6H2O and 0.01g Pt (NH4)4(NO3)2It is dissolved in 11ml deionized waters, uses
Solution is impregnated on carrier prepared by 10g comparative examples 1 by infusion process, is placed 120 DEG C of dry 12h after 12h at room temperature, is subsequently placed at
300 DEG C of roasting 3h in Muffle furnace.
The performance evaluation of catalyst
It is carried out on paste state bed reactor.First catalyst is activated before reaction, 5g catalyst is packed into pipe reaction
In device, N at room temperature2Purging, then with H2(purity>99.999%) it is reducibility gas, 1.5Mpa, is risen to 1 DEG C/min
350 DEG C, 10h is kept in the temperature.5g catalyst after activation is put into 0.5L paste state bed reactors, reaction condition is：H2/CO
=2, T=220 DEG C, P=3.0Mpa, GHSV=8000h-1.The CO conversion ratio performances that Fig. 1 gives catalyst compare.
Fig. 1 the result shows that, after being evaluated by 800h, the CO conversion ratios of catalyst prepared by comparative example 2 reduce 33%,
And the CO conversion ratios of the catalyst prepared by embodiment 11 reduce 16%, catalyst CO conversion ratios reduce amplitude and substantially reduce,
Illustrate that the method for the present invention effectively increases the abrasion resistance properties of catalyst, makes catalyst that can keep higher in long-play
Activity and stability, extend catalyst life.
Other unspecified parts are the prior art.Although above-described embodiment is made that the present invention and retouches in detail
State, but it is only a part of the embodiment of the present invention, rather than whole embodiments, people can also according to the present embodiment without
Other embodiment is obtained under the premise of creativeness, these embodiments belong to the scope of the present invention.
Claims (9)
1. a kind of preparation method for the alumina support that spinelle is modified, it is characterised in that：Include the following steps：
1) pickling
At room temperature, by molding γ-Al2O3It is washed in nitric acid, then filters, is dry under the conditions of temperature is 50~150 DEG C
Dry 1~6h obtains the γ-Al of pickling2O3；
2) dipping solution is prepared
Soluble metallic salt is dissolved in organic solvent, dipping solution is made；Wherein, soluble metallic salt be cobalt salt, zinc salt,
Any one in mantoquita, magnesium salts, calcium salt, manganese salt, nickel salt and molysite；
3) it impregnates
By the γ-Al of pickling2O3It is placed in dipping solution and carries out incipient impregnation or excessive dipping；Obtain dip compound；Its
In, the amount of dipping solution is 1~3 times of the pore volume of carrier in excessive dipping；
4) dry
Dip compound carries out rotating pressure-decreasing drying under the conditions of temperature is 30~120 DEG C, until collecting less than condensed fluid, obtains
To dried object；
5) it calcines
Dried object is put into calcining furnace, is passed through the mixing of NO and Ar into calcining furnace for 30mL/min~120mL/min with rate
Gas, and 5~12h is calcined to get the alumina support being modified to spinelle under the conditions of temperature is 650~1300 DEG C；Wherein, it carries
The quality of spinelle accounts for γ-Al in body2O31~15wt% of quality.
2. the preparation method for the alumina support that spinelle is modified according to claim 1, it is characterised in that：The step 1)
In, molding γ-Al2O3For spherical or graininess, specific surface area is 30~400m2/ g, aperture are 5~50nm, and pore volume is
0.2~2cm3/ g, grain size are 50~400 μm.
3. the preparation method for the alumina support that spinelle is modified according to claim 1, it is characterised in that：The step 1)
In, the concentration of nitric acid is 0.01~0.1mol/L；Drying temperature is 80~120 DEG C, and drying time is 3~6h.
4. the preparation method for the alumina support that spinelle is modified according to claim 1, it is characterised in that：The step 2)
In, soluble metallic salt is any one or more in magnesium nitrate, nickel nitrate, zinc nitrate and cobalt nitrate, and the organic solvent is
Any one or more in alcohol, ether, aldehyde, ketone.
5. the preparation method for the alumina support that spinelle is modified according to claim 4, it is characterised in that：It is described organic molten
Agent is any one or more in methanol, ethyl alcohol and acetone.
6. the preparation method for the alumina support that spinelle is modified according to claim 1, it is characterised in that：The step 3)
In, the amount of dipping solution is 1.5~2.5 times of the pore volume of carrier in excessive dipping.
7. the preparation method for the alumina support that spinelle is modified according to claim 1, it is characterised in that：The step 4)
In, drying temperature is 50~80 DEG C.
8. the preparation method for the alumina support that spinelle is modified according to claim 1, it is characterised in that：The step 5)
In, it is 50~100mL/min that the volume fraction of NO, which is the rate of the gaseous mixture of 5%, NO and Ar, in the gaseous mixture of NO and Ar, calcining
Temperature is 650~900 DEG C, and calcination time is 6~10h.
9. the preparation method for the alumina support that spinelle is modified according to claim 1, it is characterised in that：The step 5)
In, the quality of spinelle accounts for γ-Al in carrier2O31~5wt% of quality.
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Application publication date: 20180731 |