CN100563821C - Hydrogen-storing material with low-cerium and preparation method thereof - Google Patents
Hydrogen-storing material with low-cerium and preparation method thereof Download PDFInfo
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- CN100563821C CN100563821C CNB2006100201114A CN200610020111A CN100563821C CN 100563821 C CN100563821 C CN 100563821C CN B2006100201114 A CNB2006100201114 A CN B2006100201114A CN 200610020111 A CN200610020111 A CN 200610020111A CN 100563821 C CN100563821 C CN 100563821C
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- 239000000463 material Substances 0.000 title claims abstract description 103
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 52
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 39
- 239000001301 oxygen Substances 0.000 claims abstract description 39
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 32
- 238000003860 storage Methods 0.000 claims abstract description 32
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 31
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 19
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 18
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000000975 co-precipitation Methods 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims description 25
- 239000004094 surface-active agent Substances 0.000 claims description 23
- 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
- 230000032683 aging Effects 0.000 claims description 19
- 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 description 18
- 239000003153 chemical reaction reagent Substances 0.000 claims description 17
- 230000001376 precipitating effect Effects 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000003483 aging Methods 0.000 claims description 15
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 15
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 239000007790 solid phase Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 10
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 9
- 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 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 239000002002 slurry Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000006104 solid solution Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000012071 phase Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 3
- 229960003511 macrogol Drugs 0.000 claims 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000007789 gas Substances 0.000 abstract description 8
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract description 7
- 238000004140 cleaning Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 4
- 150000002910 rare earth metals Chemical class 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 description 14
- 238000007792 addition Methods 0.000 description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 6
- 239000001099 ammonium carbonate Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229940068984 polyvinyl alcohol Drugs 0.000 description 6
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 6
- 238000005245 sintering Methods 0.000 description 6
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 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 description 4
- 239000011232 storage material Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000247 postprecipitation Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910002086 ceria-stabilized zirconia Inorganic materials 0.000 description 1
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910001952 rubidium oxide Inorganic materials 0.000 description 1
- CWBWCLMMHLCMAM-UHFFFAOYSA-M rubidium(1+);hydroxide Chemical compound [OH-].[Rb+].[Rb+] CWBWCLMMHLCMAM-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a kind of high-performance, the low cerium type rare earth hydrogen-storing material of multipurpose and preparation method thereof.Hydrogen-storing material is composite oxides.It is mainly formed component and comprises cerium oxide, zirconia and auxiliary agent, and described auxiliary agent is to be selected from least a in lanthana, strontium oxide strontia and the yittrium oxide.The component mole constitutes (in the composite oxides total amount) and is cerium oxide 15mol%～40mol%, zirconia 50mol%～85mol%, auxiliary agent 5mol%～15mol%.Hydrogen-storing material adopts the coprecipitation preparation, and through 500～600 ℃ of calcinings, its specific area can reach 120m
2More than/the g, oxygen storage capacity is not less than 370 μ mol/g at 200 ℃.Through 1000 ℃ of calcining burin-in process, still have greater than 60m
2The specific area of/g is not less than 200 μ mol/g oxygen storage capacities at 200 ℃, can be used as the carrier and the auxiliary agent of cleaning catalyst for tail gases of automobiles.
Description
One, technical field
The present invention relates to the hydrogen-storing material technical field, more particularly, relate to a kind of hydrogen-storing material technical field that is used for the carrier and the auxiliary agent of catalyst for purifying internal combustion engine tail gas.
Two, background technology
Vehicle exhaust is the primary pollution source that causes atmosphere pollution, and pollutant mainly contains hydrocarbon (HC), carbon monoxide (CO), nitrogen oxide (NO
x), in addition, also have harmful substances such as sulfur dioxide.These harmful substances are directly endangering people's physical and mental health, and environment has been caused severe contamination.Great amount of manpower and material resources is all dropped in countries in the world, financial resources are administered automobile exhaust pollution, and most countries has all been formulated automobile exhaust emission standard and strict day by day, requires all vehicular emission tail gas all must reach the required standards.
The rare earth hydrogen-storing material successfully is applied to three-effect catalyst for purifying tail gas of car as catalysis material, is the critical material in the cleaning catalyst for tail gases of automobiles.The effect of rare earth hydrogen-storing material in cleaning catalyst for tail gases of automobiles mainly contains: 1. regulate the oxygen content in the tail gas, alleviate air-fuel ratio to a certain extent and change the catalyst reaction Effect on Performance; 2. the rare earth hydrogen-storing material mainly is made up of cerium oxide, can interact between cerium oxide and the noble metal, makes noble metal that good dispersiveness at high temperature be arranged, and keeps its catalytic Contact area.
The research and development of cerium-based oxygen storage material can be divided into three phases.First generation cerium-based oxygen storage material consist of CeO
2, its main feature is that storage oxygen performance depends on specific area, poor heat stability is higher than 850 ℃ of aging back specific areas and descends rapidly, thereby loses storage oxygen performance.Second generation cerium-based oxygen storage material consist of CeO
2-ZrO
2, storage oxygen when being characterized in that the surface of hydrogen-storing material is identical with body, therefore storing up the oxygen performance not only depends on material specific area, better heat stability.At present the third generation cerium-based oxygen storage material of using is by at CeO
2-ZrO
2In add other oxide, to be hydrogen-storing material still can keep higher specific surface and oxygen storage capacity through 950～1000 ℃ after aging to its main feature.
European patent EP 0337809B1 discloses a kind of hydrogen-storing material of cerium zirconium compound oxide, adopts immersion process for preparing, promptly is dipped in the cerium solution by zirconia particles cerium is immersed on the zirconia particles, with the ceria stabilized zirconia.Dipping is after drying and calcining to X-ray diffraction no longer presents the crystal peak of cerium oxide.The weight of cerium oxide in these composite oxides is 10～50wt.%.These composite oxides after 10 hours, only show the zirconia peak of cubic crystalline phase according to its X-ray diffractogram through 900 ℃ of calcinings in air, as can be known, the cerium oxide in these composite oxides exists with zirconic cubic crystalline phase solid solution form.
Chinese patent 98108256.4 discloses a kind of high thermal stability hydrogen-storing material, and it contains the cerium oxide of 5～60wt.%, and one or more in the praseodymium oxide of 0.1～10wt.%, lanthana, yittrium oxide and the rubidium oxide are as stabilizing agent.By pore volume impregnation method and sluggish precipitation it is coated with and is loaded on the high surface area activated alumina.This material in air through 900 ℃ the calcining 10 hours after, its specific area is generally 20m
2/ g, largest specific surface area also has only 30m
2/ g, the specific area of material is little, and hydrogen-storing material as carrier or auxiliary agent in catalyst, the performance of its storage oxygen performance depends primarily on the specific area of hydrogen-storing material, so the storage oxygen performance of this hydrogen-storing material and texture property are all not ideal enough.
Because cleaning catalyst for tail gases of automobiles is worked under high-speed and high temperature (reaching sometimes more than 1000 ℃) condition, this just needs hydrogen-storing material at high temperature still to keep the stability of high-specific surface area and oxygen storage capacity.And existing hydrogen-storing material technology can not finely satisfy above-mentioned requirements.
Three, summary of the invention
Hydrogen-storing material deficiency at prior art, it is big that purpose of the present invention aims to provide a kind of specific area, storage oxygen performance is good, and at high temperature has the hydrogen-storing material and preparation method thereof of the ability of excellent maintenance high-specific surface area and oxygen storage capacity stability, and the preparation method is simple.
The present inventor just has been accomplished the present invention through arduous research under state natural sciences fund key project (20333030) and project of national nature science fund project (20273043) subsidy, realized the above-mentioned purpose that the present invention proposes.The concrete technical scheme of this realization invention above-mentioned purpose is as follows:
Hydrogen-storing material is a kind of hydrogen-storing material with low-cerium, is a kind of composite oxides, mainly forms component and comprises cerium oxide, zirconia and auxiliary agent, and its expression is Ce
aZr
bA
cO
xA is at least a in lanthana, strontium oxide strontia and the yittrium oxide, and footnote is this component shared molar ratio in composite oxides, and a is 0.15～0.4, b is 0.5～0.75, C is 0.05～0.15, and x depends on the value (surplus is a value) of a, b, C, and promptly the component mole of hydrogen-storing material with low-cerium constitutes, in the composite oxides total amount, cerium oxide 15mol%～40mol%, zirconia 50mol%～75mol%, auxiliary agent 5mol%～15mol%.The material crystals structure is zirconium dioxide (ZrO
2) cube phase solid solution structure, wherein zirconia exists with cerium oxide with as the oxide form of auxiliary agent.
Hydrogen-storing material provided by the invention is a kind of composite oxides, and its preparation method mainly comprises following processing step:
(1), converses the consumption of oxide precursor cerous nitrate, zirconium nitrate and auxiliary agent nitrate according to the content of the determined cerium oxide of material composition component, zirconia and auxiliary agent oxide, preparation is the nitrate mixed solution of solute with these oxide precursors, and preparation is as the alkaline solution of precipitating reagent;
(2), nitrate mixed solution and precipitant solution with and the stream mode add container and carry out coprecipitation reaction, and when two solution and stream add container, stir while adding, precipitation reaction liquid pH value remains on 8～13, the intact back of precipitation reaction ageing processing at least 2 hours;
(3), the reaction feed liquid after the ageing carries out Separation of Solid and Liquid, the solid phase of separating is washed earlier, and then is scattered in the solution that is mixed with by surfactant and water and forms slurries, the slurries ageing is handled and is no less than 1 hour;
(4), the slurries handled through ageing by evaporation drying carry out solid midnight from, the solid phase after the separation 400～1000 ℃ temperature lower calcination 2～10 hours, promptly make hydrogen-storing material with low-cerium.
The inventor finds in the research that utilizes the method for preparing hydrogen-storing material with low-cerium, and cerium oxide and zirconic content have tangible influence to the performance of hydrogen-storing material, and the content of cerium oxide is high more, and the storage oxygen performance of hydrogen-storing material is good more; Zirconic content is high more, and the high-temperature aging resisting of hydrogen-storing material is good more.Determine that cerium oxide and zirconic ratio should consider the purposes of hydrogen-storing material, as the carrier model material, cerium oxide content can be selected lower content, and zirconia content can be selected higher content, as cerium oxide content is 15mol%～20mol%, and zirconia content is 70mol%～75mol%; As auxiliary agent section bar material, cerium oxide content can be selected higher content, and zirconia content can be selected lower content, is 25mol%～40mol as cerium oxide content, and zirconia content is 50mol%～65mol%.
In lanthana, strontium oxide strontia and yittrium oxide as the hydrogen-storing material adjuvant component, preferential selective oxidation yttrium is as auxiliary agent.
In the above-mentioned method for preparing hydrogen-storing material with low-cerium, the concentration range of nitrate mixed solution oxide applicatory is very wide, we can say unrestrictedly, and for the ease of operation, the concentration of oxide should not be lower than 5%.
Said precipitating reagent is an alkaline solution, and alkaline solution is meant that the pH value is higher than any solution of 8.Alkaline solution is a kind of aqueous solution that contains alkali.Usually used precipitating reagent is the mixed solution that ammoniacal liquor, sal volatile or ammoniacal liquor and ammonium carbonate are mixed with.Wherein the ammonia concentration of ammoniacal liquor is 10wt%～25wt%, and the ammonium carbonate concentration of sal volatile is 30wt%～50wt%.What preferentially select for use is the mixed solution of ammoniacal liquor and sal volatile preparation, and in mixed solution, ammonia concentration is that the ammoniacal liquor of 10wt%～25wt% accounts for 1wt%～15wt%, and ammonium carbonate concentration is that the sal volatile of 30wt%～50wt% accounts for 5wt%～20wt%.As precipitating reagent, in the process of preparation hydrogen-storing material, improved the heat endurance of material with the mixed solution of ammoniacal liquor～ammonium carbonate significantly.
The mode of nitrate mixed solution and precipitating reagent employing and stream joins reaction vessel and carries out coprecipitation reaction.The ratio of nitrate mixed solution and precipitating reagent addition, because the alkalescence of the acidity of nitrate mixed solution and precipitating reagent is different, the ratio of addition changes, therefore should not directly control the ratio of their additions by the addition of control nitrate mixed solution and precipitating reagent, the mode of being convenient to operate is to control the ratio of their additions by the pH value of control precipitation reaction liquid.The pH value of precipitation reaction liquid should not be less than 10, and the preferential scope of selecting is 10～12.Desired pH value reaches by the flow velocity of regulating nitrate mixed solution and precipitating reagent.Nitrate mixed solution and precipitating reagent preferably under stirring condition is arranged and drip go in reaction vessel to carry out coprecipitation reaction.
In the above-mentioned method for preparing hydrogen-storing material with low-cerium, said surfactant is to be selected from least a in polyvinyl alcohol and the polyethylene glycol, preferentially selects for use with polyvinyl alcohol and polyethylene glycol jointly as surfactant.Sediment is handled, realized through ageing again by sediment and surfactant and water are equipped to slurries.In slurries, sedimentary weight concentration is 5wt%～40wt%, and the weight concentration of surfactant is the 5wt%～30wt% of sedimentary weight concentration.For with polyvinyl alcohol and polyethylene glycol jointly as the situation of surfactant, in the surfactant mixed solution, the weight concentration of polyvinyl alcohol be polyethylene glycol weight concentration 1-3 doubly.What specify is the surface tension that the adding of surfactant effectively reduces the surface of solids, has avoided in the high-temperature calcination process shrinking the specific surface that causes and the loss of pore volume because of the surface.
The slurries that sediment and surfactant and water are mixed with carry out Separation of Solid and Liquid by the mode of evaporation drying after the ageing that is no less than 5 hours is handled.
In the above-mentioned method for preparing hydrogen-storing material with low-cerium, sintering temperature influences the specific area and the oxygen storage capacity of hydrogen-storing material, and sintering temperature is high more, and the performance of hydrogen-storing material specific area and oxygen storage capacity decreases.Determine that sintering temperature should consider the purposes of hydrogen-storing material, as auxiliary agent section bar material, sintering temperature can be selected lower temperature, and as 400～700 ℃, as the carrier model material, sintering temperature can be selected higher temperature, as 800～1000 ℃.
Above-mentioned said hydrogen-storing material with low-cerium can be used for also can be used for as the catalyst carrier of handling vehicle exhaust as the catalyst promoter of handling vehicle exhaust.
Hydrogen-storing material with low-cerium is the composite oxides that adopt coprecipitation synthetic, as the consumption of oxide precursor cerous nitrate, zirconium nitrate and the auxiliary agent nitrate of raw material, be that molar content according to the metallic element of the zirconia in the hydrogen-storing material with low-cerium, cerium oxide and auxiliary agent oxide converts and obtains.
The inventor tests with X-ray diffraction hydrogen-storing material with low-cerium disclosed by the invention, test result X-ray diffraction figure only shows formed cube of zirconia and the auxiliary agent oxide diffraction maximum of solid solution mutually, do not detect the diffraction maximum of cerium oxide, this explanation is in hydrogen-storing material disclosed by the invention, and the metallic element of the cerium oxide that it is contained has entered zirconia and auxiliary agent oxide formed cube solid solution lattice mutually.
The inventor tests the performance of hydrogen-storing material with low-cerium provided by the invention, and at 600 ℃ of hydrogen-storing material with low-cerium through roasting in 8 hours preparation, its oxygen storage capacity is not less than 300 μ mol/g at 200 ℃, and specific surface is not less than 100m
2/ g can be used as auxiliary agent type hydrogen-storing material; At 1000 ℃ of hydrogen-storing material with low-cerium, still have greater than 60m through roasting in 10 hours preparation
2/ g specific area and be not less than 200 μ mol/g oxygen storage capacities at 200 ℃, and have very high heat endurance, can be used as the carrier model hydrogen-storing material.
Hydrogen-storing material with low-cerium disclosed by the invention is compared with the hydrogen-storing material of prior art, and the one, its storage oxygen performance, specific area and pore volume have all obtained increasing substantially.The 2nd, the heat endurance of its storage oxygen performance and texture property (particularly specific area) is very good, and this point can be confirmed from following embodiment.
These premium properties that hydrogen-storing material of the present invention had are by the peculiar ZrO of hydrogen-storing material with low-cerium of the present invention
2Cube phase solid solution structure institute extremely.This is because highly homogeneous solid solution has very high thing phase stability, and good thing has high thermal stability mutually.
Specification is specifically implemented part and is described having in of the present invention more specifically, can understand other characteristics of the present invention, details and advantage by this part of reading specification more full and accurately.
Four, description of drawings
The X-ray diffractogram of Fig. 1 Powdered hydrogen-storing material sample that to be the present invention prepare after 8 hours 800 ℃ of roastings.
The sample X-ray diffractogram that Fig. 2 is the Powdered hydrogen-storing material for preparing of the present invention after 10 hours burin-in process of 1000 ℃ of roastings.
In accompanying drawing 1 and accompanying drawing 2, abscissa is the angle of diffraction, and ordinate is a diffraction peak intensity.
Five, the specific embodiment
Provide the specific embodiment of the present invention below by embodiment.Except as otherwise noted, ratio that provides among each embodiment below and percentage are meant part by weight and percetage by weight.
Embodiment 1
Preparation is the hydrogen-storing material of auxiliary agent with the yittrium oxide, according to the metal element content in composition component cerium oxide, zirconia and the yittrium oxide of given material, calculates the weight of each oxide precursor cerous nitrate, zirconium nitrate and yttrium nitrate Y.The cerous nitrate, zirconium nitrate and the yttrium nitrate that take by weighing the amount of determining in proportion are mixed with the mixed solution of nitrate.And then under stirring condition, go in the reaction vessel with ammoniacal liquor and drip, the addition of precipitating reagent makes the pH value of reaction medium keep about 13.Reactant is fully separated out post precipitation, stops to stir also ageing and carries out Separation of Solid and Liquid by the suction filtration mode after about 10 hours, and the first water of isolated solid phase washs, and the surfactant that adds solid phase total amount about 10% is afterwards handled.Surfactant is that concentration is 20% poly-vinyl alcohol solution.After under 150 ℃ of conditions dry 24 hours, roasting 8 hours under 500 ℃ of conditions again makes the product hydrogen-storing material with low-cerium through the surfactant post-treatment solid phase.
Table 1
| Sample number into spectrum | Form | Oxygen storage capacity (μ mol/g) | BET specific surface (m 2/g) | Pore volume |
| A-Zr75 | Ce 0.15Zr 0.76Y 0.1O x | 379.7 | 108.7 | 0.25 |
| A-Zr70 | Ce 0.2Zr 0.7Y 0.1O x | 482.6 | 105.4 | 0.25 |
| A-Zr65 | Ce 0.25Zr 0.65Y 0.1O x | 534.2 | 102.2 | 0.25 |
| A-Zr60 | Ce 0.3Zr 0.6Y 0.1O x | 550.4 | 104.5 | 0.25 |
| A-Zr55 | Ce 0.35Zr 0.55Y 0.1O x | 568.4 | 105.7 | 0.25 |
The hydrogen-storing material 200mg that takes by weighing preparation places U type quartz tube reactor, uses H under 500 ℃ condition
2With per minute 25cm
3The flow reduction was stored up the test of oxygen performance after 4 hours.
Adopt the BET method to measure the specific area and the pore volume of each embodiment hydrogen-storing material sample with ZSM-5 type adsorption/desorption instrument, be listed in the table 1 with the measurement result of oxygen storage capacity.
Embodiment 2
Preparation is the hydrogen-storing material of auxiliary agent with the yittrium oxide, the concrete side of preparation is basic identical with the method for this part embodiment 1, different places be, the one, be that precipitating reagent and nitrate mixed solution and drip are gone into reaction vessel with the sal volatile, the pH value of precipitation reaction liquid remains on 8; The 2nd, sintering temperature is 600 ℃.The measurement result of oxygen storage capacity, specific area and pore volume such as following table 2 are listed.
Table 2
| Sample | Form | Oxygen storage capacity (μ mol/g) | BET specific surface (m 2/g) | Pore volume |
| A-Zr75 | Ce 0.15Zr 0.75Y 0.1O x | 310.1 | 169.5 | 0.30 |
| A-Zr70 | Ce 0.2Zr 0.7Y 0.1O x | 320.3 | 153.1 | 0.29 |
| A-Zr65 | Ce 0.25Zr 0.65Y 0.1O x | 350.5 | 172.5 | 0.32 |
| A-Zr60 | Ce 0.3Zr 0.6Y 0.1O x | 361.6 | 159.3 | 0.30 |
| A-Zr55 | Ce 0.35Zr 0.55Y 0.1O x | 377.4 | 163.4 | 0.31 |
Embodiment 3
Preparation is the hydrogen-storing material of auxiliary agent with the yittrium oxide, the concrete side of preparation is basic identical with the method for this part embodiment 1, different places be, the one, precipitating reagent is the mixed solution that ammoniacal liquor and sal volatile are mixed with, join in the reaction vessel with nitrate mixed solution and stream, the pH value of precipitation reaction liquid remains on 9; The 2nd, made hydrogen-storing material with low-cerium at 800 ℃ in 8 hours through roasting, then sample segment was worn out 10 hours at 1000 ℃.The measurement result of oxygen storage capacity, specific area and pore volume such as following table 3 are listed.
Table 3
| Sample | Form | Oxygen storage capacity (μ mol/g) | BET specific surface (m 2/g) | Pore volume |
| B-Zr75800 | Ce 0.15Zr 0.75Y 0.1O x | 222.9 | 107.3 | 0.28 |
| B-Zr751000 | Ce 0.15Zr 0.75Y 0.1O x | 204.3 | 62.9 | 0.20 |
Fig. 1 and Fig. 2 test the X-ray diffractogram that obtains with the sample of present embodiment preparation.
Two diffraction patterns clearly illustrate that structures of samples.This is Y
0.15Zr
0.85O
1.93Cubic crystal structure, show that cerium oxide in the sample is with Y
0.15Zr
0.85O
1.93The solid solution form exists.The crystal face parameter of all diffraction maximums is marked on the figure.All do not change in the position of 1000 ℃ of each diffraction maximums of aging front and back as seen from the figure, also do not have new diffraction maximum to occur, just the width of diffraction maximum has reduced, and this shows that sample crystal structure of sample behind high temperature ageing does not change, do not occur being separated, just Y yet
0.15Zr
0.85O
1.93Grain growth.
Therefore, this method can make cerium oxide evenly spread in the lattice of zirconia and yittrium oxide composite oxides.Crystal structure through 1000 ℃ of high temperature ageings this solid solution after 10 hours is still stable.The structure thermal stability of hydrogen-storing material of the present invention causes the high-temperature stability of specific area and oxygen storage capacity.
Embodiment 4
Preparation is the hydrogen-storing material of auxiliary agent with the lanthana, according to the metal element content in given material definite cerium oxide, zirconia and the lanthana, calculates the weight of each oxide precursor cerous nitrate, zirconium nitrate and lanthanum nitrate.The cerous nitrate, zirconium nitrate and the lanthanum nitrate that take by weighing the amount of determining in proportion are mixed with the mixed solution that zirconium ion concentration is 0.6mol/L nitrate.And then the mixed precipitant that is mixed with ammoniacal liquor and ammonium carbonate under stirring condition and drip go in the reaction vessel, and the addition of precipitating reagent makes the pH value of reaction medium keep about 12.Reactant is fully separated out post precipitation, stops to stir also ageing and carries out Separation of Solid and Liquid by the suction filtration mode after about 10 hours, and isolated solid phase is washed earlier, and the surfactant that adds solid phase total amount about 10% is afterwards handled.Surfactant is that concentration is 20% polyglycol solution.After under 150 ℃ of conditions dry 24 hours, roasting made the product hydrogen-storing material with low-cerium in 8 hours under 800 ℃ of conditions through the surfactant post-treatment solid phase, then sample segment was worn out 10 hours at 1000 ℃.The measurement result such as the table 4 of oxygen storage capacity, specific area and pore volume are listed.
Table 4
| Sample number into spectrum | Form | Oxygen storage capacity (μ mol/g) | BET specific surface (m 2/g) | Pore volume |
| La-Zr55800 | Ce 0.35Zr 0.55La 0.1O x | 452.6 | 77.6 | 0.24 |
| La-Zr1K | Ce 0.35Zr 0.55La 0.1O x | 447.6 | 61.3 | 0.22 |
| Sr-Zr55800 | Ce 0.15Zr 0.75Sr 0.1O x | 497.5 | 83.5 | 0.22 |
| Sr-Zr1K | Ce 0.15Zr 0.75Sr 0.1O x | 400.8 | 62.5 | 0.20 |
Embodiment 5
Preparation is the hydrogen-storing material of auxiliary agent with the strontium oxide strontia, and the method for concrete prepare side and this part embodiment 4 is basic identical, different places only be to use strontium nitrate replacement lanthanum nitrate.The measurement result such as the table 4 of oxygen storage capacity, specific area and pore volume rate are listed.
Embodiment 6
Preparation is the hydrogen-storing material of auxiliary agent with lanthana, strontium oxide strontia and yittrium oxide, according to the metal element content in hydrogen-storing material component formation cerium oxide, zirconia, lanthana, strontium oxide strontia and the yittrium oxide, calculate the weight of each oxide precursor cerous nitrate, zirconium nitrate, lanthanum nitrate, strontium nitrate and yttrium nitrate.The cerous nitrate, zirconium nitrate, lanthanum nitrate, strontium nitrate and the yttrium nitrate that take by weighing the amount of determining in proportion are mixed with the mixed solution that zirconium ion concentration is 0.8mol/L nitrate.And then the mixed precipitant that is mixed with ammoniacal liquor and ammonium carbonate under stirring condition and drip go in the reaction vessel, and the addition of precipitating reagent makes the pH value of reaction medium keep about 12.Reactant is fully separated out post precipitation, stops to stir also ageing and carries out Separation of Solid and Liquid by the suction filtration mode after about 10 hours, and isolated solid phase is washed earlier, and the surfactant that adds solid phase total amount about 10% is afterwards handled.Surfactant is the polyethylene glycol mixed solution of 8wt% polyvinyl alcohol and 20wt%.After under 150 ℃ of conditions dry 24 hours, roasting made the product hydrogen-storing material with low-cerium in 8 hours under 800 ℃ of conditions through the surfactant post-treatment solid phase, then sample segment was worn out 10 hours at 1000 ℃.The measurement result such as the table 5 of oxygen storage capacity, specific area and pore volume are listed.
Table 5
| Sample | Form | Oxygen storage capacity (μ mol/g) | BET specific surface (m 2/g) | Pore volume |
| LSY-Zr74800 | Ce 0.15Zr 0.76La 0.3Sr 0.3Y 0.3O x | 314.2 | 112.7 | 0.26 |
| LSY-Zr741000 | Ce 0.15Zr 0.76La 0.3Sr 0.3Y 0.3O x | 265.4 | 65.6 | 0.22 |
Claims (10)
1, hydrogen-storing material with low-cerium, it is a kind of combined oxidation compound, it is characterized in that by cerium oxide, zirconia and auxiliary agent are combined into, forming the component mole constitutes, in the composite oxides total amount, cerium oxide 15mol%～40mol%, zirconia 50mol%～75mol%, auxiliary agent 5mol%～15mol%, its crystalline phase is cube phase solid solution of zirconium dioxide, and described auxiliary agent is for being selected from lanthana, at least a in strontium oxide strontia and the yittrium oxide, described material is at 600 ℃ of hydrogen-storing material with low-cerium through roasting in 8 hours preparation, its oxygen storage capacity is not less than 300 μ mol/g at 200 ℃, and specific surface is not less than 100m
2/ g can be used as auxiliary agent type hydrogen-storing material; Or described material is at 1000 ℃ of hydrogen-storing material with low-cerium through roasting in 10 hours preparation, and its oxygen storage capacity is not less than 200 μ mol/g at 200 ℃, and specific surface is not less than 60m
2/ g can be used as the carrier model hydrogen-storing material.
2, hydrogen-storing material with low-cerium according to claim 1 is characterized in that said cerium oxide molar content is 15mol%～20mol%, and said zirconia molar content is 70mol%～75mol%.
3, hydrogen-storing material with low-cerium according to claim 1 is characterized in that said cerium oxide molar content is 25mol%～40mol%, and said zirconia molar content is 50mol%～65mol%.
4,, it is characterized in that said auxiliary agent is a yittrium oxide according to claim 1 or 2 or 3 described hydrogen-storing material with low-cerium.
5, the method for the described hydrogen-storing material with low-cerium of each claim in the preparation claim 1 to 4 is characterized in that comprising following processing step:
(1) precursor cerous nitrate, zirconium nitrate and the auxiliary agent nitrate for preparing with material institute oxidation-containing cerium, zirconia and auxiliary agent oxide by given material composition component is the nitrate mixed solution of solute, and preparation is as the alkaline solution of precipitating reagent;
(2) nitrate mixed solution and precipitant solution with and the stream mode add container and carry out coprecipitation reaction, and two solution limits and stream adds the limit and stirs, precipitation reaction liquid pH value remains on 8～13, the ageing processing was at least 2 hours after precipitation reaction was finished;
(3) the reaction feed liquid after the ageing is carried out Separation of Solid and Liquid, the solid phase of separating is washed earlier, and then is scattered in the solution that is mixed with by surfactant and water and forms slurries, and ageing is handled and is no less than 1 hour;
(4) slurries of handling through ageing carry out Separation of Solid and Liquid by evaporation drying, and the solid phase after the separation promptly makes hydrogen-storing material with low-cerium 400～1000 ℃ temperature lower calcination 2～10 hours.
6, the method for preparing hydrogen-storing material with low-cerium according to claim 5, the oxide weight concentration that it is characterized in that said nitrate mixed solution is not less than 5%, said precipitating reagent alkaline solution is ammoniacal liquor or sal volatile, or the mixed solution of ammoniacal liquor and sal volatile.
7, the method for preparing hydrogen-storing material with low-cerium according to claim 6 is characterized in that its ammonia concentration of said ammoniacal liquor is 10wt%～25wt%, and sal volatile concentration is 30wt%～50wt%.
8, the method for preparing hydrogen-storing material with low-cerium according to claim 5 is characterized in that described surfactant is to be selected from least a in polyvinyl alcohol and the macrogol.
9, the method for preparing hydrogen-storing material with low-cerium according to claim 5, it is characterized in that in the slurries that form by sediment, surfactant and water, sedimentary weight concentration is 5wt%～40wt%, and the weight concentration of surfactant is the 5wt%～30wt% of sedimentary weight concentration.
10, the method for preparing hydrogen-storing material with low-cerium according to claim 8 is characterized in that making surfactant jointly with polyvinyl alcohol and macrogol, and wherein the polyvinyl alcohol weight concentration is 1～3 times of weight concentration of macrogol.
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| CN110026174B (en) * | 2018-12-12 | 2020-09-08 | 四川大学 | High thermal stability CeO2-ZrO2Oxygen-storing material and its preparation |
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