CN104492415A - Preparation method of cerium-zirconium based solid solution catalytic material - Google Patents
Preparation method of cerium-zirconium based solid solution catalytic material Download PDFInfo
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- CN104492415A CN104492415A CN201410723260.1A CN201410723260A CN104492415A CN 104492415 A CN104492415 A CN 104492415A CN 201410723260 A CN201410723260 A CN 201410723260A CN 104492415 A CN104492415 A CN 104492415A
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- 239000006104 solid solution Substances 0.000 title claims abstract description 61
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 230000003197 catalytic effect Effects 0.000 title abstract description 9
- 238000001556 precipitation Methods 0.000 claims abstract description 14
- 239000012670 alkaline solution Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000008139 complexing agent Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- -1 zirconium ions Chemical class 0.000 claims abstract description 8
- 238000004381 surface treatment Methods 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 50
- 229910002651 NO3 Inorganic materials 0.000 claims description 29
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 29
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 29
- 150000002910 rare earth metals Chemical class 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 26
- 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 description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 16
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 14
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 229910052684 Cerium Inorganic materials 0.000 claims description 12
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 230000032683 aging Effects 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 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 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 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 6
- 239000006185 dispersion Substances 0.000 claims description 5
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 2
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 2
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 10
- 239000002245 particle Substances 0.000 abstract description 9
- 239000000047 product Substances 0.000 abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 7
- 238000005406 washing Methods 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 238000004140 cleaning Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 4
- 238000007084 catalytic combustion reaction Methods 0.000 abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 239000000969 carrier Substances 0.000 abstract description 2
- 230000000536 complexating effect Effects 0.000 abstract description 2
- 230000008030 elimination Effects 0.000 abstract description 2
- 238000003379 elimination reaction Methods 0.000 abstract description 2
- 239000003345 natural gas Substances 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- 239000003929 acidic solution Substances 0.000 abstract 1
- 229910052726 zirconium Inorganic materials 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 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 8
- 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 8
- 229960001484 edetic acid Drugs 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 5
- 238000005352 clarification Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 2
- PZZOEXPDTYIBPI-UHFFFAOYSA-N 2-[[2-(4-hydroxyphenyl)ethylamino]methyl]-3,4-dihydro-2H-naphthalen-1-one Chemical compound C1=CC(O)=CC=C1CCNCC1C(=O)C2=CC=CC=C2CC1 PZZOEXPDTYIBPI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- FZMFJORHWIAQFU-UHFFFAOYSA-N [Y].[Zr].[Ce] Chemical compound [Y].[Zr].[Ce] FZMFJORHWIAQFU-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method of a cerium-zirconium based solid solution catalytic material. The preparation method comprises the following sequential steps: (1) preparation of an acidic solution A; (2) preparation of an alkaline solution B; (3) precipitation reaction; (4) washing; (5) surface treatment of wet cake; (6) roasting. The precipitation speed in the precipitation reaction process is controlled by virtue of complexing coordination of an organic complexing agent and zirconium ions, so that a precursor uniform and stable in particle size is obtained; the surface treatment is performed on the precipitate precursor by use of an alcohol solvent, and therefore, the agglomeration problem of particles in the roasting process is solved, and the pore diameter and the pore volume of the roasted product are increased by virtue of the roasting of organic matters, and consequently, the cerium-zirconium based solid solution catalytic material excellent in heat stability is obtained. The preparation method is suitable for the preparation of the solid solution, and in particular suitable for motor vehicle exhaust cleaning catalysts, and carriers and auxiliaries for catalysts for exhaust cleaning or catalytic combustion such as organic exhaust elimination and natural gas catalytic combustion.
Description
Technical field
The invention belongs to catalyst field, relate to a kind of preparation method of motor vehicle vent gas purification catalysis material, be specifically related to a kind of preparation method of cerium zirconium based solid solution.
Background technology
Reduce automobile exhaust pollution, environment protection quality, realizing the sustainable development of ecological environment and society, is one of important topic of China environmental protection in the current and following long duration.
In order to decreasing pollution, must break through from improving gasoline quality, improving engine combustion state and increasing exhaust purification catalytic efficiency three aspect.Up to the present, using cleaning catalyst for tail gases of automobiles to be most effective way is exactly reduced the content of HC, CO and NOx tri-kinds of toxic gases in tail gas by three-way catalytic apparatus, and cerium zirconium based solid solution catalysis material is the important component part in three way catalytic conversion device, it plays the effect regulating atmosphere in tail gas clean-up process, when atmosphere is in lean burn condition, cerium zirconium based solid solution catalysis material will absorb unnecessary oxygen, when atmosphere is in fuel-rich state, cerium zirconium based solid solution catalysis material releases oxygen, and three kinds of gases are effectively transformed.Therefore, the quality of the Oxygen storage capacity of cerium zirconium based solid solution catalysis material directly affects the transformation efficiency of tail gas.Simultaneously cerium zirconium based solid solution catalysis material can the dispersion of effective stabilizing active component, therefore there is large specific area, larger pore volume and suitable pore-size distribution, and there is good high-temperature aging resisting performance, the cerium zirconium based oxygen storage material of excellent low-temperature catalyzed performance becomes the critical material of new three-way catalyst.
Due to simple CeO
2at high temperature easily sinter, particle growth, cause specific area to reduce, thus reduce until lose oxygen storage capacity.1987, the people such as M.Ozawa began through and add zirconia to improve CeO
2heat endurance.With pure CeO
2compare, high-performance rare-earth hydrogen-storing material technology of preparing has become core technology and the source technology of Advanced Automotive Exhaust Catalyst, does not have high-performance rare-earth hydrogen-storing material, and it is impossible for preparing the cleaning catalyst for tail gases of automobiles with the market competitiveness.
ZrO2 adds CeO to
2in, can CeO be formed
2-ZrO
2solid solution and improve CeO
2body phase behaviour, be beneficial to migration and the diffusion of body phase oxygen atom, make body phase reaction process become active, can CeO be improved
2oxygen storage capacity and high-temperature stability.Meanwhile, the rare earths such as Pr, Nd, Y, Nb, La and Ba and alkaline earth element add the high-temperature aging resisting that can strengthen cerium zirconium based solid solution catalysis material further, improve its oxygen storage capacity.
China Patent No. is that the patent of invention of ZL200510115874.2 discloses a kind of solid solution composition of cerium zirconium compound oxide with high specific surface and preparation method thereof, surfactant or amine salt or inorganic ammonium salt or ethanol is added by being added in the suspension that is settled out, and high temperature crystallization, after crystallization, product washs through ethanol, high-temperature roasting.
But above-mentioned complicated process of preparation, simultaneously by high temperature crystallization, ethanol washs, and is unfavorable for industrial production, and is common liquid-phase precipitation during precipitation, and particle is larger.
China Patent Publication No. is that the patent of invention of CN101637721B discloses a kind of porous yttrium-cerium-zirconium solid solution and preparation method thereof; by adding protective agent, norium salting liquid and active polystyrene microballoon emulsion; normal temperature precipitates; 80-100 DEG C of ageing, collecting precipitation thing, washing, drying, roasting obtain target product.
In above-mentioned preparation method, polystyrene microsphere emulsion cannot mix with metal salt solution, easily causes the stable homogeneous of product.
China Patent Publication No. is that the patent of invention of CN100496745C discloses a kind of wire or rod-like polycrystal Ce
0.6zr
0.3y
0.1o
2solid solution preparation method, be US 5 by adding softex kw as surface-active U.S. Patent number, 747, the patent of invention of 401 and U.S. patents number are US 5,723, the patent of invention of 101 discloses and adopts hydrothermal decomposition method or coprecipitation altogether to obtain mixed sediment, then carries out washing or flooding with alkyl oxide solution, obtains solid solution and has high-ratio surface, uniform particle distribution and high oxygen storage power.Cerium solution used is tetravalence (can add hydrogen peroxide by electrolytic oxidation, ammonium ceric nitrate or dissolved carbon hydrochlorate to obtain), Ce
4+concentration is greater than 85%, 900 DEG C, 6 hours specific surface: 51.7m
2/ g.
Above-mentioned preparation method, by hydrothermal treatment consists, needs high-tension apparatus, is unfavorable for that industrialization is produced.
Therefore, a kind of cerium zirconium based solid solution catalysis material of special needs and preparation method thereof, to solve above-mentioned existing Problems existing.
Summary of the invention
The technical problem to be solved in the present invention, is to provide a kind of preparation method of cerium zirconium based sosoloid catalyst, and prepared cerium zirconium based solid solution has that specific area is large, high temperature ageing resistance is good, store oxygen ability high.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A preparation method for cerium zirconium based solid solution catalysis material, it carries out according to following steps order:
(1) preparation of acid solution A: by water-soluble to ammonium ceric nitrate, other rare earth soluble nitrate except cerium and zirconyl nitrate, add organic complexing agent, obtain acid solution A;
(2) preparation of alkaline solution B: by mass fraction be 25% ammoniacal liquor pure water be diluted to 10%, obtain alkaline solution B;
(3) precipitation reaction: alkaline solution B is joined and is heated in the acid solution A of 70-80 DEG C, the pH to precipitation terminal is 9-10, then dynamic ageing 2-4h under agitation, obtains solid-liquid mixing system C;
(4) wash: solid-liquid mixing system C is dewatered, rinsing, filter, obtain wet cake D;
(5) surface treatment of wet cake: by the hot water of wet cake D and 80-90 DEG C with mass ratio 1:1 reslurry, add alcohols solvent, shear dispersion, obtain mud E;
(6) roasting: by mud E roasting 4-6h at 600-800 DEG C, obtains described cerium zirconium based solid solution catalysis material.
Limit as one of the present invention, described other rare earth soluble nitrate except cerium are two or three in lanthana, yittrium oxide, praseodymium oxide and neodymia.
Limit as another kind of the present invention, the organic complexing agent in described step (1) is aminocarboxylic base class complex compound.
As the further restriction of above-mentioned restriction, described aminocarboxylic acids complex compound is the one in EDTA (ethylenediamine tetra-acetic acid), HEDTA (ethoxy three amine triacetic acid), DTPA (diethylenediaminepentaacetic acid).
As the further restriction of above-mentioned restriction, described organic complexing agent, in mass, addition is ammonium ceric nitrate, the 20-30% of other metal nitrate raw material gross masses such as rare earth soluble nitrate and zirconyl nitrate except cerium.
Limit as of the present invention the third, in described step (1), the ratio of each nitrate is:
Limit as another kind of the present invention, in described step (1), in mass, ammonium ceric nitrate, other metal nitrates such as rare earth soluble nitrate and zirconyl nitrate except cerium account for the 10%-15% of acid solution A gross mass.
As the further restriction of above-mentioned restriction, the alcohols solvent described in described step (5) is the one or more combination in propane diols, glycerine.
As the further restriction of above-mentioned restriction, described alcohols solvent, addition is cerous nitrate in mass, the 30-50% of the gross mass of other rare earth soluble nitrate except cerium and zirconium nitrate.
The present invention also has a kind of restriction, the composite oxides that obtained cerium zirconium based solid solution catalysis material is made up of cerium oxide, zirconia and other rare earth oxide except cerium zirconium form, its percentage by weight is as follows: cerium oxide: 30-60%, zirconia: 25-65%, and except cerium zirconium other rare earth oxide: 11-14%.
Because the preparation method of existing cerium zirconium based solid solution has a variety of, mainly liquid phase method, comprises coprecipitation, sol-gal process, masterplate method, microemulsion method etc.And coprecipitation is as conventional preparation method, that precipitating reagent is joined in the salting liquid of metal, the component of solubility is converted into slightly solubility component, after filtration, the step such as washing, drying, roasting obtains target compound, but at high temperature roasting can cause the decline of specific area, the agglomeration of particle, the choose reasonable etc. of aperture pore volume can be related in addition in the processes such as precipitation, drying, roasting.Therefore the technical parameter in involved in the present invention preparation method has significant impact for the index of the product cerium zirconium based solid solution of final preparation.In addition, in preparation process, the temperature of feed concentration, chemical reaction, the concentration of precipitating reagent, the screening of various additive and the control of addition etc. are all key factors prepared by material, this relates to sedimentary granularity, uniformity, dispersiveness, settleability etc., also relates to the aggregation of target product, pattern, solid solubility, aperture pore volume etc.
Owing to have employed above-mentioned technical scheme, compared with prior art, acquired technological progress is in the present invention:
(1) the present invention contains organic complexing agent by metal-nitrate solutions, by the complex coordination of organic complexing agent and rare earth and zirconium ion, controls the settling velocity in precipitation reaction process, obtains uniform particle diameter, stable presoma.
(2) raw material containing cerium selected by the present invention are selected from ammonium ceric nitrate, because the valence state of cerium is+4 valencys in ammonium ceric nitrate, on the one hand, as the rare earth ion of hard acid class, charge number is larger, and electrostatic attraction is large, and coordination ability is strong, add the complexing power of rare earth ion and complex, improve the stability of complex compound; On the other hand, facilitate rare earth ion and zirconium ion solid solution ability, ensure that the solid solution phase that target product has had, even if still there is no phase-splitting under the high temperature ageing of 1000 DEG C.
(3) carry out surface treatment by alcohols solvent at sediment presoma, on the one hand, solve the agglomeration traits of particle in roasting process; On the other hand, by organic roasting, improve the aperture of product of roasting, pore volume, obtain the cerium zirconium based solid solution catalysis material of good thermal stability.
(4) to be selected by hybrid metal feed liquid and concentration, the selection of precipitating reagent and concentration, the screening of additive and the control of addition, the suitable selection of the condition, roasting condition etc. of association reaction and control, obtain that to have particle little, specific area be large, the cerium zirconium based solid solution catalysis material of high temperature ageing resistance and active advantages of higher.
The present invention is applicable to the preparation of cerium zirconium based solid solution, is particularly useful for carriers for catalysts and the auxiliary agent of the waste gas purifications such as Vehicle Exhaust Gas Cleaning Catalysts, organic exhaust gas elimination and natural gas catalytic combustion or catalytic combustion.
The present invention is described in further detail below in conjunction with Figure of description and specific embodiment.
Accompanying drawing explanation
Fig. 1 is the XRD schematic diagram that embodiments of the invention 1 prepare cerium zirconium based solid solution catalysis material.
Fig. 2 is the XRD schematic diagram that embodiments of the invention 1 prepare cerium zirconium based solid solution catalysis material 1000 DEG C of roasting 4h.
Fig. 3 is the XRD schematic diagram that comparative example 1 of the present invention prepares cerium zirconium based solid solution catalysis material 1000 DEG C of roasting 4h.
Detailed description of the invention
The preparation method of embodiment 1 one kinds of cerium zirconium based solid solution catalysis materials
Preparation 100kg quality group become 30% cerium oxide, 5% lanthana, 6% yittrium oxide, 59% zirconic cerium zirconium based solid solution catalysis material, according to calculating, (total amount of rare earth REO is 31%, cerium-oxide contents CeO to need 96.77kg ammonium ceric nitrate
2/ REO>=99.9%), (total amount of rare earth REO is 38% to 13.16kg lanthanum nitrate, lanthana content La
2o
3/ REO>=99.9%), (total amount of rare earth REO is 37% to 16.22kg yttrium nitrate, yttria levels Y
2o
3/ REO>=99.9%), 197kg zirconyl nitrate (ZrO
2content 30%).
(1) preparation of acid solution A: by 96.77kg ammonium ceric nitrate, 13.16kg lanthanum nitrate, 16.22kg yttrium nitrate, 197kg zirconyl nitrate, join in the pure water of 2907kg, dissolve clarification, after obtaining the solution of clear, add 64.6kg EDTA (ethylenediamine tetra-acetic acid), after to be dissolved, be heated to 70 DEG C and obtain acid solution A;
(2) preparation of alkaline solution B: by mass fraction be 25% ammoniacal liquor pure water be diluted to 10%, obtain alkaline solution B;
(3) precipitation reaction: alkaline solution B is joined and is heated in the acid solution A of 70 DEG C, the pH to precipitation terminal is 9, then dynamic ageing 2h under agitation, obtains solid-liquid mixing system C;
(4) wash: solid-liquid mixing system C is dewatered, rinsing, filter, obtain wet cake D;
(5) surface treatment of wet cake: by the hot water of wet cake D and 90 DEG C with mass ratio 1:1 reslurry, add 97kg glycerine, shear dispersion, obtain mud E;
(6) roasting: by mud E roasting 6h at 600 DEG C, obtains described cerium zirconium based solid solution catalysis material.
The specific area of the cerium zirconium based solid solution catalysis material obtained is 90.5m
2/ g, through XRD analysis, is shown in Fig. 1; The specific area of this catalysis material after 1000 DEG C of roasting 4h is 58.2m
2/ g, through XRD analysis, see Fig. 2; Specific area after 1050 DEG C of roasting 12h is 38.5m
2/ g.
The preparation method of embodiment 2-6 cerium zirconium based solid solution catalysis material
Embodiment 2-6 is respectively a kind of preparation method of cerium zirconium based solid solution catalysis material, and its method is similar to Example 1, and difference is only that wherein involved technical parameter is different, shown in table specific as follows:
Comparative example 1
The present embodiment prepare 100kg quality group become 30% cerium oxide, 5% lanthana, 6% yittrium oxide, 59% zirconic cerium zirconium based solid solution catalysis material, according to calculating, (total amount of rare earth REO is 39%, cerium-oxide contents CeO to need 76.9kg cerous nitrate
2/ REO>=99.9%), (total amount of rare earth REO is 38% to 13.16kg lanthanum nitrate, lanthana content La
2o
3/ REO>=99.9%), (total amount of rare earth REO is 37% to 16.22kg yttrium nitrate, yttria levels Y
2o
3/ REO>=99.9%), 197kg zirconyl nitrate (ZrO
2content 30%).
By 76.9kg ammonium ceric nitrate, 13.16kg lanthanum nitrate, 16.22kg yttrium nitrate, 197kg zirconyl nitrate, join in the pure water of 2907kg, dissolve clarification, after obtaining the solution of clear, be heated to the solution A that 70 DEG C obtain clear; Under agitation, slowly adding the ammoniacal liquor of 10% in solution A, is 9.0 to pH.Then under agitation, after insulation 2h, by the solid-liquid mixing system that obtains through suction filtration, washing, cerium zirconium based solid solution catalysis material presoma filter cake is obtained.Filter cake is proceeded to saggar, at 600 DEG C of roasting 6h, obtains described cerium zirconium based solid solution catalysis material.
The specific area of the cerium zirconium based solid solution catalysis material obtained is 80.5m
2/ g, the specific area of this catalysis material after 1000 DEG C of roasting 4h is 18.2m
2/ g, through XRD analysis, is shown in Fig. 3; Specific area after 1050 DEG C of roasting 12h is 10.5m
2/ g.Its specific area before and after high-temperature catalytic all comparatively embodiment 1-6 all have obvious decline.
Comparative example 2
The present embodiment prepare 100kg quality group become 30% cerium oxide, 5% lanthana, 6% yittrium oxide, 59% zirconic cerium zirconium based solid solution catalysis material, according to calculating, (total amount of rare earth REO is 31%, cerium-oxide contents CeO to need 96.77kg ammonium ceric nitrate
2/ REO>=99.9%), (total amount of rare earth REO is 38% to 13.16kg lanthanum nitrate, lanthana content La
2o
3/ REO>=99.9%), (total amount of rare earth REO is 37% to 16.22kg yttrium nitrate, yttria levels Y
2o
3/ REO>=99.9%), 197kg zirconyl nitrate (ZrO
2content 30%).
By 96.77kg ammonium ceric nitrate, 13.16kg lanthanum nitrate, 16.22kg yttrium nitrate, 197kg zirconyl nitrate, join in the pure water of 2907kg, dissolve clarification, after obtaining the solution of clear, add 64.6kg EDTA (ethylenediamine tetra-acetic acid), after to be dissolved, be heated to the solution A that 70 DEG C obtain clear; Under agitation, slowly adding the ammoniacal liquor of 10% in solution A, is 9.0 to pH.Then under agitation, after insulation 2h, by the solid-liquid mixing system that obtains through suction filtration, washing, cerium zirconium based solid solution catalysis material presoma filter cake is obtained.Filter cake is proceeded to saggar, at 600 DEG C of roasting 6h, obtains described cerium zirconium based solid solution catalysis material.
The specific area of the cerium zirconium based solid solution catalysis material obtained is 90.5m
2/ g, the specific area of this catalysis material after 1000 DEG C of roasting 4h is 23.2m
2/ g, the specific area after 1050 DEG C of roasting 12h is 14.5m
2/ g.Its specific area after high-temperature catalytic all comparatively embodiment 1-6 all have obvious decline.
Comparative example 3
The present embodiment prepare 100kg quality group become 30% cerium oxide, 5% lanthana, 6% yittrium oxide, 59% zirconic cerium zirconium based solid solution catalysis material, according to calculating, (total amount of rare earth REO is 31%, cerium-oxide contents CeO to need 96.77kg ammonium ceric nitrate
2/ REO>=99.9%), (total amount of rare earth REO is 38% to 13.16kg lanthanum nitrate, lanthana content La
2o
3/ REO>=99.9%), (total amount of rare earth REO is 37% to 16.22kg yttrium nitrate, yttria levels Y
2o
3/ REO>=99.9%), 197kg zirconyl nitrate (ZrO
2content 30%).
By 96.77kg ammonium ceric nitrate, 13.16kg lanthanum nitrate, 16.22kg yttrium nitrate, 197kg zirconyl nitrate, join in the pure water of 2907kg, dissolve clarification, after obtaining the solution of clear, be heated to the solution A that 70 DEG C obtain clear; Under agitation, slowly adding the ammoniacal liquor of 10% in solution A, is 9.0 to pH.Then under agitation, after insulation 2h, by the solid-liquid mixing system that obtains through suction filtration, washing, cerium zirconium based solid solution catalysis material presoma filter cake is obtained.The hot pure water of filter cake and 90 DEG C is pulled an oar according to mass ratio 1:1, adds 60kg glycerine, after shearing dispersion 1h, proceed to saggar, at 600 DEG C of roasting 6h, obtain described cerium zirconium based solid solution catalysis material.
The specific area of the cerium zirconium based solid solution catalysis material obtained is 90.5m
2/ g, the specific area of this catalysis material after 1000 DEG C of roasting 4h is 28.2m
2/ g, the specific area after 1050 DEG C of roasting 12h is 18.5m
2/ g.Its specific area after high-temperature catalytic all comparatively embodiment 1-6 all have obvious decline.
The above is only preferred embodiment of the present invention, is not restriction the present invention being made to other form, and any those skilled in the art may utilize above-mentioned technology contents to be changed or be modified as the Equivalent embodiments of equivalent variations as enlightenment.But everyly do not depart from technical solution of the present invention content, according to technical spirit of the present invention to the simple modification done by above embodiment, equivalent variations and remodeling, still belong to the protection domain of the claims in the present invention.
Claims (9)
1. a preparation method for cerium zirconium based solid solution catalysis material, is characterized in that it carries out according to following steps order:
(1) preparation of acid solution A: by water-soluble to ammonium ceric nitrate, other rare earth soluble nitrate except cerium and zirconyl nitrate, add organic complexing agent, obtain acid solution A;
(2) preparation of alkaline solution B: by mass fraction be 25% ammoniacal liquor pure water be diluted to 10%, obtain alkaline solution B;
(3) precipitation reaction: alkaline solution B is joined and is heated in the acid solution A of 70-80 DEG C, the pH to precipitation terminal is 9-10, then dynamic ageing 2-4h under agitation, obtains solid-liquid mixing system C;
(4) wash: solid-liquid mixing system C is dewatered, rinsing, filter, obtain wet cake D;
(5) surface treatment of wet cake: by the hot water of wet cake D and 80-90 DEG C with mass ratio 1:1 reslurry, add alcohols solvent, shear dispersion, obtain mud E;
(6) roasting: by mud E roasting 4-6h at 600-800 DEG C, obtains described cerium zirconium based solid solution catalysis material.
2. the preparation method of cerium zirconium based solid solution catalysis material according to claim 1, is characterized in that: described other rare earth soluble nitrate except cerium are two or three in lanthana, yittrium oxide, praseodymium oxide and neodymia.
3. the preparation method of cerium zirconium based solid solution catalysis material according to claim 1, is characterized in that: the organic complexing agent in described step (1) is aminocarboxylic base class complex compound.
4. the preparation method of cerium zirconium based solid solution catalysis material according to claim 3, is characterized in that: described aminocarboxylic acids complex compound is EDTA, HEDTA or DTPA one wherein.
5. the preparation method of cerium zirconium based solid solution catalysis material according to claim 4, it is characterized in that: described organic complexing agent, in mass, addition be ammonium ceric nitrate, the 20-30% of other metal nitrate raw material gross masses such as rare earth soluble nitrate and zirconyl nitrate except cerium.
6. the preparation method of cerium zirconium based solid solution catalysis material according to claim 1, is characterized in that: the ratio of each nitrate in rapid (1) be:
Cerous nitrate 20-50%
Zirconium nitrate 40-76%
Other rare earth soluble nitrate 3-12% except cerium.
The percentage sum of component is 100%;
In mass, ammonium ceric nitrate, other metal nitrates such as rare earth soluble nitrate and zirconyl nitrate except cerium account for the 10%-15% of acid solution A gross mass.
7. the preparation method of cerium zirconium based solid solution catalysis material according to claim 6, is characterized in that: the alcohols solvent described in described step (5), is one or both combinations in propane diols, glycerine.
8. the preparation method of cerium zirconium based solid solution catalysis material according to claim 7, it is characterized in that: described alcohols solvent, addition be cerous nitrate in mass, the 30-50% of the gross mass of other rare earth soluble nitrate except cerium and zirconium nitrate.
9. the preparation method of the cerium zirconium based solid solution catalysis material according to any one of claim 1-8, it is characterized in that: the composite oxides that obtained cerium zirconium based solid solution catalysis material is made up of cerium oxide, zirconia and other rare earth oxide except cerium zirconium form, its percentage by weight is as follows: cerium oxide: 30-60%, zirconia: 25-65%, and except cerium zirconium other rare earth oxide: 11-14%.
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