CN107694556A - A kind of preparation method of high storage oxygen high heat stability type hydrogen-storing material - Google Patents
A kind of preparation method of high storage oxygen high heat stability type hydrogen-storing material Download PDFInfo
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- CN107694556A CN107694556A CN201710961673.7A CN201710961673A CN107694556A CN 107694556 A CN107694556 A CN 107694556A CN 201710961673 A CN201710961673 A CN 201710961673A CN 107694556 A CN107694556 A CN 107694556A
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- 239000000463 material Substances 0.000 title claims abstract description 61
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000001301 oxygen Substances 0.000 title claims abstract description 43
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 43
- 238000003860 storage Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229920000151 polyglycol Polymers 0.000 claims abstract description 14
- 239000010695 polyglycol Substances 0.000 claims abstract description 14
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052796 boron Inorganic materials 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 10
- 229930006000 Sucrose Natural products 0.000 claims abstract description 10
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims abstract description 10
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 35
- 238000007873 sieving Methods 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 32
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 229910002651 NO3 Inorganic materials 0.000 claims description 20
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 20
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 19
- 230000001376 precipitating effect Effects 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 16
- 239000003643 water by type Substances 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 235000012907 honey Nutrition 0.000 claims description 8
- 239000007822 coupling agent Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 150000002823 nitrates Chemical class 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical class [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims description 2
- 238000003801 milling Methods 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims 1
- 238000010168 coupling process Methods 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 abstract description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 abstract description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003837 high-temperature calcination Methods 0.000 abstract description 2
- 239000013049 sediment Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 32
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 8
- 230000032683 aging Effects 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- HWQKBOCRKYUANM-UHFFFAOYSA-N [Zr].[Tb] Chemical compound [Zr].[Tb] HWQKBOCRKYUANM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B01J35/613—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The present invention relates to hydrogen-storing material preparing technical field, and in particular to a kind of preparation method of high storage oxygen high heat stability type hydrogen-storing material.Hydrogen peroxide, white sugar and polyglycol solution are modified by the present invention to cerous nitrate, zirconium nitrate, aluminum nitrate and yttrium nitrate, in high-temperature calcination, white sugar can be with the bonding of other compositions in hydrogen-storing material, add polyglycol solution, can effectively dispersed ion, improve specific surface area and improve the oxygen storage capacity of hydrogen-storing material.The polyglycol solution surfactant of addition can be effectively protected in calcination process.Sediment is slowly converted into oxide in roasting process, improves the heat endurance and oxygen storage capacity of hydrogen-storing material.Boron mud and aluminium hydroxide are added, during the course of the reaction, modified aluminium hydroxide resolves into aluminum oxide at high temperature, further improves the heat endurance of hydrogen-storing material, is with a wide range of applications.
Description
Technical field
The present invention relates to hydrogen-storing material preparing technical field, and in particular to a kind of high storage oxygen high heat stability type hydrogen-storing material
Preparation method.
Background technology
Hydrogen-storing material is a kind of composite oxides, has the function that reversible storage and release oxygen.Be using cerium oxide as
The binary or multicomponent composite oxide that main rare earth element, alkali earth metal or transition metal forms.Typically in powder
Last shape, predominantly yellow, brown etc..It is mainly used in automobile, motorcycle exhaust processing.
With developing rapidly for economy, increasing family possesses private car, and motor-vehicle tail-gas also turns into urban atmosphere
Primary pollution source.The main harmful components included in vehicle exhaust have carbon monoxide（CO）, hydrocarbon（HC）And nitrogen oxidation
Thing（NOx）.Cerium zirconium sosoloid hydrogen-storing material is as a kind of catalyst aid of important purifying vehicle exhaust, as vehicle exhaust is arranged
Put standard progressively to add sternly, high performance auto-exhaust catalyst needs the cerium zirconium compound oxide auxiliary agent material of further high-temperature stable
Material.
Cerium zirconium auxiliary agent serves as an oxygen buffer, has storage oxygen, puts oxygen function, effectively widens the air-fuel ratio of three-way catalyst
Action pane, lift the clean-up effect of catalyst.Main way is that the 3rd or even fourth element are introduced into cerium zirconium sosoloid
Multicomponent composite oxide is formed, to improve the Oxygen storage capacity of solid solution.On the one hand less metal ion substitutes larger metal
Ion produces more lattice defect, effectively improves migration velocity of the Lattice Oxygen in body phase；Another aspect substituted metal ion
The change of valence state is advantageous to produce more oxygen vacancies in body phase, so as to improve the Oxygen storage capacity of solid solution.Numerous studies show,
The ion of trivalent or divalence, such as Pr are introduced in cerium zirconium sosoloid3+、Nd3+、Y3+、La3+、Sn3+、Ba2+、Sr2+Deng rare earth or alkali
Earth elements can be effectively improved the high-temperature aging resisting performance of hydrogen-storing material.Relative to simple cerium zirconium sosoloid, multicomponent cerium zirconium
Compound hydrogen-storing material is all significantly improved in oxygen storage capacity, the texture property for storing oxygen speed and material etc..Praseodymium zirconium,
Terbium zirconium mixed oxide is also a kind of catalyst promoter material well, and there is height to store oxygen ability, be catalyzed in motor-vehicle tail-gas
There is very big application value in terms of control and industrial waste gas purifying.Although cerium zirconium sosoloid can keep good storage oxygen at high temperature
Can, but the heat endurance of texture is poor, and it is more relatively low than surface, tetragonal zirconium dioxide of easily dissociating at relatively high temperatures, make single
Cubic phase transition into multiphase coexistence.
With development of the increasingly strict and petrol engine of automobile emissions standards to lean-burn direction, it is desirable to hydrogen-storing material
Storage put oxygen performance with higher high temperature than Modificati on and Geng Gao.Therefore, the following research to hydrogen-storing material is gesture
What must be gone.
The content of the invention
The technical problems to be solved by the invention：For the heat endurance of current hydrogen-storing material is poor and Oxygen storage capacity not
A kind of the defects of high, there is provided preparation method of high storage oxygen high heat stability type hydrogen-storing material.
In order to solve the above technical problems, the present invention is using technical scheme as described below：
A kind of preparation method of high storage oxygen high heat stability type hydrogen-storing material, it is characterised in that specifically preparation process is：
（1）Weigh 6~8g cerous nitrates, 4~6g zirconium nitrates, 3~5g aluminum nitrates and the mixing of 2~4g yttrium nitrates be placed in 80~
Mixed in the beaker of 100mL deionized waters, stir added in backward beaker 6~10mL hydrogen peroxide, 4~6g white sugar and 3~
5mL polyglycol solutions, continue to mix, obtain modified self-control nitrate solution；
（2）Sal volatile, sodium hydroxide solution and ammoniacal liquor are mixed, obtain making alkaline precipitating agent by oneself；
（3）100 mesh sieves will be crossed after boron mud and aluminium hydroxide grinding, collect sieving powder, then will sieving powder, titanate coupling agent
KR-9S and honey mix, and obtain modified sieving powder colloidal sol；
（4）Count in parts by weight, it is molten to weigh modified self-control nitrate solution, self-control alkaline precipitating agent, modified sieving powder respectively
Glue, ammoniacal liquor and deionized water, modified self-control nitrate solution hybrid reaction is first added dropwise into self-control alkaline precipitating agent, it is to be precipitated to fill
After analyzing, continue heat temperature raising, after reaction, adjust pH value with ammoniacal liquor, be put into suction filtration machine and filtered after regulation, take out filter
Cake, after being washed with deionized, it is put into Muffle furnace and calcines, naturally cool to room temperature, discharges, obtain hydrogen-storing material base substrate；
（5）One layer of modified sieving powder colloidal sol is smeared to above-mentioned hydrogen-storing material billet surface, is put into baking oven and dries after smearing, discharge,
It can be prepared by high storage oxygen high heat stability type hydrogen-storing material.
Step（1）Described mixing time is 12~16min, and the concentration of hydrogen peroxide is 2mol/L, polyglycol solution
Concentration is 2mol/L, and continuation mixing time is 1~2h.
Step（2）The volume ratio of described sal volatile, sodium hydroxide solution and ammonia spirit is 1：1：1, ammonium carbonate
Liquid quality fraction is 30%, and the mass fraction of sodium hydroxide solution is 20%, and the mass fraction of ammonia spirit is 10%, mixing
Mixing time is 6~8min.
Step（3）Described boron mud and the mass ratio of aluminium hydroxide are 2：1, milling time is 6~8min, sieving powder,
The mass ratio of titanate coupling agent KR-9S and honey is 4：2：1, the mixing time is 10~12min.
Step（4）Described meter in parts by weight, weigh respectively 12~20 parts of modified self-control nitrate solutions, 10~12 parts
Make alkaline precipitating agent, 6~8 parts of modified sieving powder colloidal sol, 3~5 parts of ammoniacal liquor and 8~10 parts of deionized waters, reaction time 1 by oneself
~2h, it is 0.5mL/min to control rate of addition, and heat temperature raising temperature is 60~80 DEG C, and the reaction time is 2~4h, adjusts pH value
For 8~10, calcining heat is 800~1200 DEG C, and calcination time is 4~6h.
Step（5）Described smearing thickness is 0.5~0.7mm, and drying temperature is 45~65 DEG C, and drying time is 1~2h.
Compared with other method, advantageous effects are the present invention：
（1）The present invention is first by hydrogen peroxide, white sugar and polyglycol solution to cerous nitrate, zirconium nitrate, aluminum nitrate and yttrium nitrate
It is modified, in high-temperature calcination, wherein having sticking white sugar fusing, it is possible to increase the bonding of hydrogen-storing material and other compositions
Property, then the addition by polyglycol solution, promote high polymer to form colloidal sol, effectively dispersed ion, then calcine height
Many duct holes and surface defect position are formed after polymers, in hydrogen-storing material, its specific surface area is improved, improves hydrogen-storing material
Oxygen storage capacity, but because polyglycol solution and surfactant are added in preparation process can be effectively reduced sediment
Inside surface tension and duct because of high temperature and caused by contraction, make its preparation in high heat stability hydrogen-storing material, drying and calcination
During the pore passage structure of sample be effectively protected, and ammoniacal liquor-sodium hydroxide solution-carbon is employed in precipitation process
Acid ammonium solution mixed precipitant causes Ce4+、Zr4+、Y3+And Al3+Ion is settled out in the form of hydroxide and carbonate simultaneously
Come, because the decomposition temperature of carbonate is far above hydroxide so that it is deposited in roasting process and is slowly converted into oxide, from
And the pore passage structure of sample is effectively protected, so as to improve the heat endurance of hydrogen-storing material and oxygen storage capacity；
（2）The present invention is by adding boron mud and aluminium hydroxide, wherein having strongly using the sodium oxide molybdena in boron mud and boron oxide
Vitrifying is inclined to, and during the course of the reaction, molten product solidification temperature range can be made substantially to reduce, be improved the thermostabilization of hydrogen-storing material
Property, and modified aluminium hydroxide resolves into aluminum oxide at high temperature, aluminum oxide can improve the chemistry of hydrogen-storing material in glass
Stability, and the tendency towards devitrification of glass can be reduced and reduce the thermal coefficient of expansion of glass, the heat for further improving hydrogen-storing material is steady
It is qualitative, it is with a wide range of applications.
Embodiment
Weigh 6~8g cerous nitrates, 4~6g zirconium nitrates, 3~5g aluminum nitrates and the mixing of 2~4g yttrium nitrates be placed in 80~
12~16min is mixed in the beaker of 100mL deionized waters, it is 2mol/L to stir and 6~10mL concentration is added in backward beaker
Hydrogen peroxide, 4~6g white sugar and 3~5mL concentration be 2mol/L polyglycol solution, continue 1~2h of mixing, changed
Property self-control nitrate solution, be by volume 1：1：Sal volatile that mass fraction is 30%, mass fraction are 20% by 1
Sodium hydroxide solution and the ammoniacal liquor that mass fraction is 10% mix 6~8min, obtain making alkaline precipitating agent by oneself, in mass ratio
For 2：1 will cross 100 mesh sieves after 6~8min of boron mud and aluminium hydroxide grinding, collects sieving powder, is in mass ratio 4：2：1 incited somebody to action
Sieve powder, titanate coupling agent KR-9S and honey and mix 10~12min, obtain modified sieving powder colloidal sol, by weight
Number meter, 12~20 parts of modified self-control nitrate solutions, 10~12 parts of self-control alkaline precipitating agents, 6~8 parts of modified sievings are weighed respectively
Powder colloidal sol, 3~5 parts of ammoniacal liquor and 8~10 parts of deionized waters, it is molten that modified self-control nitrate is first added dropwise into self-control alkaline precipitating agent
Liquid 1~2h of hybrid reaction, it is 0.5mL/min to control rate of addition, after fully precipitation to be precipitated, continues to be heated to 60~80
DEG C, after reacting 2~4h, pH value is adjusted to 8~10 with ammoniacal liquor, is put into suction filtration machine and is filtered after regulation, take out filter cake, spend
After ion water washing, it is put into the Muffle furnace that temperature is 800~1200 DEG C and calcines 4~6h, naturally cool to room temperature, discharge, obtain
To hydrogen-storing material base substrate, the modified sieving powder colloidal sol that a layer thickness is 0.5~0.7mm is smeared to hydrogen-storing material billet surface,
It is put into after smearing in baking oven, 1~2h, discharging is dried at 45~65 DEG C, you can high storage oxygen high heat stability type hydrogen-storing material is made.
Example 1
6g cerous nitrates, 4g zirconium nitrates, 3g aluminum nitrates and the mixing of 2g yttrium nitrates is weighed to be placed in the beaker with 80mL deionized waters
12min is mixed, stirring addition 6mL concentration is 2mol/L in backward beaker hydrogen peroxide, 4g white sugar and 3mL concentration is
2mol/L polyglycol solution, continue to mix 1h, obtain modified self-control nitrate solution, be by volume 1：1：1 will
The ammoniacal liquor that the sodium hydroxide solution and mass fraction that sal volatile that mass fraction is 30%, mass fraction are 20% are 10%
6min is mixed, obtains making alkaline precipitating agent by oneself, is in mass ratio 2：1 will cross 100 after boron mud and aluminium hydroxide grinding 6min
Mesh sieve, sieving powder is collected, is in mass ratio 4：2：1 mixes sieving powder, titanate coupling agent KR-9S and honey
10min, obtain modified sieving powder colloidal sol, count in parts by weight, weigh respectively 12 parts of modified self-control nitrate solutions, 10 parts from
Alkaline precipitating agent, 6 parts of modification sieving powder colloidal sols, 3 parts of ammoniacal liquor and 8 parts of deionized waters processed, first drip into self-control alkaline precipitating agent
Add modified self-control nitrate solution hybrid reaction 1h, it is 0.5mL/min to control rate of addition, after fully precipitation to be precipitated, is continued
60 DEG C are heated to, after reacting 2h, pH value is adjusted to 8 with ammoniacal liquor, is put into suction filtration machine and is filtered after regulation, take out filter
Cake, after being washed with deionized, it is put into the Muffle furnace that temperature is 800 DEG C and calcines 4h, naturally cool to room temperature, discharge, obtain
Hydrogen-storing material base substrate, the modified sieving powder colloidal sol that a layer thickness is 0.5mm is smeared to hydrogen-storing material billet surface, is put after smearing
Enter in baking oven, 1h is dried at 45 DEG C, discharge, you can high storage oxygen high heat stability type hydrogen-storing material is made.
Example 2
7g cerous nitrates, 5g zirconium nitrates, 4g aluminum nitrates and the mixing of 3g yttrium nitrates is weighed to be placed in the beaker with 90mL deionized waters
14min is mixed, stirring addition 8mL concentration is 2mol/L in backward beaker hydrogen peroxide, 5g white sugar and 4mL concentration is
2mol/L polyglycol solution, continue to mix 1.5h, obtain modified self-control nitrate solution, be by volume 1：1：1
By the sodium hydroxide solution that sal volatile that mass fraction is 30%, mass fraction are 20% and the ammonia that mass fraction is 10%
Water mixes 7min, obtains making alkaline precipitating agent by oneself, is in mass ratio 2：1 by boron mud and aluminium hydroxide grinding 7min after mistake
100 mesh sieves, sieving powder is collected, is in mass ratio 4：2：1 stirs sieving powder, titanate coupling agent KR-9S and honey mixing
Mix 11min, obtain modified sieving powder colloidal sol, count in parts by weight, weigh respectively 16 parts of modified self-control nitrate solutions, 11 parts
Alkaline precipitating agent, 7 parts of modified sieving powder colloidal sol, 4 parts of ammoniacal liquor and 9 parts of deionized waters are made by oneself, first into self-control alkaline precipitating agent
Modified self-control nitrate solution hybrid reaction 1.5h is added dropwise, it is 0.5mL/min to control rate of addition, after fully precipitation to be precipitated,
Continue to be heated to 70 DEG C, after reacting 3h, adjust pH value to 9 with ammoniacal liquor, be put into suction filtration machine and filtered after regulation, taken out
Filter cake, after being washed with deionized, it is put into the Muffle furnace that temperature is 1000 DEG C and calcines 5h, naturally cool to room temperature, discharge, obtain
To hydrogen-storing material base substrate, the modified sieving powder colloidal sol that a layer thickness is 0.6mm is smeared to hydrogen-storing material billet surface, after smearing
It is put into baking oven, 1.5h is dried at 55 DEG C, discharge, you can high storage oxygen high heat stability type hydrogen-storing material is made.
Example 3
8g cerous nitrates, 6g zirconium nitrates, 5g aluminum nitrates and the mixing of 4g yttrium nitrates is weighed to be placed in the beaker with 100mL deionized waters
16min is mixed, stirring addition 10mL concentration is 2mol/L in backward beaker hydrogen peroxide, 6g white sugar and 5mL concentration is
2mol/L polyglycol solution, continue to mix 2h, obtain modified self-control nitrate solution, be by volume 1：1：1 will
The ammoniacal liquor that the sodium hydroxide solution and mass fraction that sal volatile that mass fraction is 30%, mass fraction are 20% are 10%
8min is mixed, obtains making alkaline precipitating agent by oneself, is in mass ratio 2：1 will cross 100 after boron mud and aluminium hydroxide grinding 8min
Mesh sieve, sieving powder is collected, is in mass ratio 4：2：1 mixes sieving powder, titanate coupling agent KR-9S and honey
12min, obtain modified sieving powder colloidal sol, count in parts by weight, weigh respectively 20 parts of modified self-control nitrate solutions, 12 parts from
Alkaline precipitating agent, 8 parts of modification sieving powder colloidal sols, 5 parts of ammoniacal liquor and 10 parts of deionized waters processed, first drip into self-control alkaline precipitating agent
Add modified self-control nitrate solution hybrid reaction 2h, it is 0.5mL/min to control rate of addition, after fully precipitation to be precipitated, is continued
80 DEG C are heated to, after reacting 4h, pH value is adjusted to 10 with ammoniacal liquor, is put into suction filtration machine and is filtered after regulation, take out filter
Cake, after being washed with deionized, it is put into the Muffle furnace that temperature is 1200 DEG C and calcines 6h, naturally cool to room temperature, discharge, obtain
Hydrogen-storing material base substrate, the modified sieving powder colloidal sol that a layer thickness is 0.7mm is smeared to hydrogen-storing material billet surface, is put after smearing
Enter in baking oven, 2h is dried at 65 DEG C, discharge, you can high storage oxygen high heat stability type hydrogen-storing material is made.
The hydrogen-storing material that comparative example is produced with Nanjing company is high to high storage oxygen produced by the present invention as a comparison case
Hydrogen-storing material in thermostable type hydrogen-storing material and comparative example is detected, and testing result is as shown in table 1：1st, method of testing
Oxygen storage capacity test condition：Example 1~3 and comparative example product are placed in the U-shaped crystal reaction tube of chemical adsorption instrument, in H2In
550 DEG C are warming up to, reduction uses N after 45 minutes2Purging, is cooled to 200 DEG C, constant temperature afterpulse O2, oxygen storage capacity OSC is determined, calculates O2
Adsorption volume produces the OSC of sample.
Ageing management condition：By hydrogen-storing material in high temperature process furnances at 1000 DEG C after aging 4 hours, using surface area hole
Footpath tester and the method for oxygen storage capacity test carry out the test of specific surface area and oxygen storage capacity.
Hydrogen-storing material specific surface area is bigger, bigger with the contact area of vehicle exhaust, and the disposal ability of vehicle exhaust is got over
By force.
Table 1
| Test event | Example 1 | Example 2 | Example 3 | Comparative example |
| Specific surface area when being not used（m2/g） | 170 | 172 | 178 | 145 |
| Specific surface area after aging（m2/g） | 65 | 68 | 72 | 35 |
| 200 DEG C of oxygen storage capacities（OSC） | 372 | 376 | 382 | 331 |
It can be seen from data in table 1, high storage oxygen high heat stability type hydrogen-storing material specific surface area produced by the present invention is big, to car tail
The disposal ability of gas is strong, and in high temperature environments, oxygen storage capacity effect is good and ageing-resistant ability is stronger.Therefore,
With wide prospect of the application.
Claims (6)
1. a kind of preparation method of high storage oxygen high heat stability type hydrogen-storing material, it is characterised in that specifically preparation process is：
（1）Weigh 6~8g cerous nitrates, 4~6g zirconium nitrates, 3~5g aluminum nitrates and the mixing of 2~4g yttrium nitrates be placed in 80~
Mixed in the beaker of 100mL deionized waters, stir added in backward beaker 6~10mL hydrogen peroxide, 4~6g white sugar and 3~
5mL polyglycol solutions, continue to mix, obtain modified self-control nitrate solution；
（2）Sal volatile, sodium hydroxide solution and ammoniacal liquor are mixed, obtain making alkaline precipitating agent by oneself；
（3）100 mesh sieves will be crossed after boron mud and aluminium hydroxide grinding, collect sieving powder, then will sieving powder, titanate coupling agent
KR-9S and honey mix, and obtain modified sieving powder colloidal sol；
（4）Count in parts by weight, it is molten to weigh modified self-control nitrate solution, self-control alkaline precipitating agent, modified sieving powder respectively
Glue, ammoniacal liquor and deionized water, modified self-control nitrate solution hybrid reaction is first added dropwise into self-control alkaline precipitating agent, it is to be precipitated to fill
After analyzing, continue heat temperature raising, after reaction, adjust pH value with ammoniacal liquor, be put into suction filtration machine and filtered after regulation, take out filter
Cake, after being washed with deionized, it is put into Muffle furnace and calcines, naturally cool to room temperature, discharges, obtain hydrogen-storing material base substrate；
（5）One layer of modified sieving powder colloidal sol is smeared to above-mentioned hydrogen-storing material billet surface, is put into baking oven and dries after smearing, discharge,
It can be prepared by high storage oxygen high heat stability type hydrogen-storing material.
A kind of 2. preparation method of high storage oxygen high heat stability type hydrogen-storing material according to claim 1, it is characterised in that：Step
Suddenly（1）Described mixing time is 12~16min, and the concentration of hydrogen peroxide is 2mol/L, and the concentration of polyglycol solution is 2mol/
L, continuation mixing time are 1~2h.
A kind of 3. preparation method of high storage oxygen high heat stability type hydrogen-storing material according to claim 1, it is characterised in that：Step
Suddenly（2）The volume ratio of described sal volatile, sodium hydroxide solution and ammonia spirit is 1：1：1, sal volatile quality point
Number is 30%, and the mass fraction of sodium hydroxide solution is 20%, and the mass fraction of ammonia spirit is 10%, mixes the time and is
6~8min.
A kind of 4. preparation method of high storage oxygen high heat stability type hydrogen-storing material according to claim 1, it is characterised in that：Step
Suddenly（3）Described boron mud and the mass ratio of aluminium hydroxide are 2：1, milling time is 6~8min, sieving powder, titanate esters coupling
The mass ratio of agent KR-9S and honey is 4：2：1, the mixing time is 10~12min.
A kind of 5. preparation method of high storage oxygen high heat stability type hydrogen-storing material according to claim 1, it is characterised in that：Step
Suddenly（4）Described meter in parts by weight, it is heavy that 12~20 parts of modified self-control nitrate solutions, 10~12 parts of self-control alkalescence are weighed respectively
Shallow lake agent, 6~8 parts of modified sieving powder colloidal sols, 3~5 parts of ammoniacal liquor and 8~10 parts of deionized waters, reaction time are 1~2h, control
Rate of addition is 0.5mL/min, and heat temperature raising temperature is 60~80 DEG C, and the reaction time is 2~4h, and regulation pH value is 8~10, is forged
It is 800~1200 DEG C to burn temperature, and calcination time is 4~6h.
A kind of 6. preparation method of high storage oxygen high heat stability type hydrogen-storing material according to claim 1, it is characterised in that：Step
Suddenly（5）Described smearing thickness is 0.5~0.7mm, and drying temperature is 45~65 DEG C, and drying time is 1~2h.
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| CN110026178A (en) * | 2019-04-30 | 2019-07-19 | 山东国瓷功能材料股份有限公司 | A kind of cerium zirconium compound oxide and its preparation method and application |
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| CN102716733A (en) * | 2012-05-08 | 2012-10-10 | 赣州博晶科技有限公司 | Preparation method of high performance cerium zirconium aluminum oxygen-storage material |
| CN104525180A (en) * | 2014-12-30 | 2015-04-22 | 长沙矿冶研究院有限责任公司 | Preparation method for cerium-zirconium-aluminum-lanthanum-based oxygen storage material of mesoporous structure |
| CN105148926A (en) * | 2015-08-12 | 2015-12-16 | 北京石油化工学院 | Oxygen storage material and preparation method thereof |
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| JPH08157877A (en) * | 1994-12-02 | 1996-06-18 | Lion Corp | Bleaching detergent composition |
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