CN1454707A - High thermal stability aluminium oxide and preparing method thereof - Google Patents
High thermal stability aluminium oxide and preparing method thereof Download PDFInfo
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Abstract
The invention discloses a high heat-stability alumina and the manufacturing method. The alumina comprises alumina and additive, the additive is the combination of two or above two of rare earth oxide, alkali earth oxide, transition metal oxide; each additive weight is 1-15% of alumina weight. The method includes following steps: fibrin micro-crystal powder is marinated in rare earth alkali earth, transition metal salt and aluminium salt solvent, through aging, drying, baking, there gets the product. The alumina has high heat stability. The method is simple and easy to be industrialized.
Description
Technical field
The present invention relates to a kind of aluminum oxide, relate in particular to aluminum oxide of a kind of process chemically modified and preparation method thereof.
Technical background
Activated alumina is a kind of aluminum oxide that has than the ad hoc structure of bigger serface, and it is widely used as the carrier of catalyzer.The easy sintering of the pore structure of activated alumina under the high temperature obviously reduces its specific surface area, and the active ingredient of load is assembled and catalytic activity decline.Along with catalyticcombustion and environment protection catalysis technology rapid development such as (as the catalytic purification and the catalytic purifications poisonous, harmful exhaust of vehicle exhaust); carrier to catalyzer is had higher requirement, and needs carrier not only to have good thermostability but also have bigger specific surface area.Therefore, press for the novel alumina material of research and development to the bigger serface of high-temperature stable.
The thermostability of improving aluminum oxide mainly contains two kinds of methods.The one, change the preparation method of aluminum oxide, comprise pH value, temperature, pressure and the calcination atmosphere of modulation process; The 2nd, add chemical assistant, as transition metal, alkali earth metal and rare earth element etc., form composite oxides and Solid solution by chemical assistant and the aluminum oxide that adds, energy delays the phase transformation of Jie and stable state aluminum oxide and prevents the sintering of alumina particle, can also regulate catalyst activity component (as noble metal component) and Al simultaneously
2O
3Effect between the interface, the performance of raising catalyzer.The rare earth element that can be used as chemical additive has La (the 21st the 5th phase of volume of catalysis journal, M.Ferrandon, B.Ferrand, E.Bj rnbom et al, J.Catal.2001,202:345 etc.) and Ce (M.Shelef, R.W.McCabe, Catal.Today, 2000,62:35), alkali earth metal has Mg, Ca and Ba (J.S.Church, N.W.Cant, Appl.Catal.:A, 1994,107:267), transition metal has Zr, Ti (J.Kaspar, P.Fomasiero, M.Graziani, Catal.Today1999,50:258; H.W.Jen, G.W.Graham, W.Chun, et al.Catal Today, 1999,50:309 etc.), or the like.These elements also can be used as solid support material, for example Ce-base, Zr-base, Ti-base carrier sometimes in three-way catalyst; Sometimes can be used as main additive, for example Ba-Al-O, Mg-Al-O.Zr is a kind of element with special performance, use as structural auxiliary agent usually, but zirconic existence helps to improve the activation performance of catalyzer to the hydro carbons c h bond, simultaneously the ZrO of tetragonal structure
2Has very strong high-temperature stability.BaO and MgO are considered to refractory materials, also have goodish thermostability.The interpolation of above various element is the high high-temp stability that improves aluminum oxide with the different mechanism of action.The rare report of comprehensive and cooperation to the aluminum oxide performance is added in the combination of these elements.
Cerium oxide plays important effect in three-way catalyst: the storage surface excess oxygen, quicken the transmission of surperficial oxygen and gas phase oxygen, improve the precious metal dispersity, promote NO+CO reaction etc., cerium oxide has become one of indispensable important composition in the three-way catalyst.
The method of adding cerium oxide has two kinds usually, (a) adds the Ce element in aluminum oxide, and (b) Ce and precious metals pt, Pd, Rh are immersed on the aluminum oxide simultaneously.Studies show that of bibliographical information, CeO
2Existence for Al
2O
3High high-temp stability adverse influence is arranged, at high temperature, CeO
2Easily and Al
2O
3Form CeAl
2O
4CeO
2Itself is easy-sintering also; Agglomerating CeO
2May make Al
2O
3Micropore stops up, and surface-area is descended.The thermostability that how to improve Ce in the Al-Ce-O composition has caused widely to be paid close attention to.
Hydrothermal stability is another importance of alumina stable.United States Patent (USP) (US6,303,531) is thought, when the clay of inflatable type and aluminum oxide coexistence, can improve its hydrothermal stability.Above-mentioned some additive of mentioning to improve the stability of aluminum oxide in thermal and hydric environment have suitable effect (Appl.Catal.:A, 1993,101:105).Because the existence of water has increased the amount of alumina surface hydroxyl, thus the sintering of promote the oxidation aluminium, and therefore aqueous environment more worsens than exsiccant atmosphere for aluminum oxide.In addition, more remarkable when the quick variation of surface-area occurs in temperature more than 1000 ℃ concerning aluminum oxide, therefore improving aluminum oxide hydrothermal stability at high temperature has more practicality and challenging meaning.
Summary of the invention
The technical issues that need to address of the present invention are aluminum oxide that disclose a kind of high thermal stability and preparation method thereof, to overcome the defective that prior art exists, satisfy the needs of practical application.
High thermal stability aluminum oxide of the present invention is the mixture of a complexity, comprises aluminum oxide and additive, it is characterized in that, said additive is two or more the combination in rare earth oxide, alkaline earth metal oxide, the transition metal oxide; Various additives count 1%～15% with alumina weight.Addition very little, and is not enough to the stabilization of aluminum oxide; Addition is too big, and additive self is assembled, and influence the character of aluminum oxide, and cost is high again.
Preferred rare earth oxide is cerium oxide, lanthanum trioxide, Praseodymium trioxide, Yangization Nd;
Preferred alkaline earth metal oxide is magnesium oxide, barium oxide;
Preferred transition metal oxide is zirconium white, titanium oxide, cobalt oxide, chromic oxide;
Preferred additives is lanthanum trioxide, barium oxide, cerium oxide, zirconium white, magnesian combination, and preferred additives is combined as: barium oxide, lanthanum trioxide, magnesium oxide.
Rare earth: alkaline-earth metal: transition metal oxide: aluminum oxide=0.1～1: 0.1～1: 0.1～1: 0.1～1.
The preparation method of the aluminum oxide of high thermal stability of the present invention comprises the steps:
The cellulose crystallite powder is flooded in the salts solution of rare earth, alkaline-earth metal, transition metal salt and aluminium, after aging, drying, roasting, can obtain the aluminum oxide of high thermal stability of the present invention.
The present invention is a template with the cellulose crystallite powder, is the precursor of aluminum oxide additive with the salt compounds of rare earth, alkaline-earth metal, transition metal, and the aluminium salt compounds is the precursor of aluminum oxide.Behind the cellulose crystallite powder load additive precursor, the cellulose crystallite powder is had an effect with airborne oxygen in roasting process, generates carbonic acid gas and water, and the precursor of additive precursor and aluminum oxide becomes the oxide compound of high dispersing.
Said aluminium salt compound can be the salt that all can be water-soluble, comprises aluminum nitrate, sodium metaaluminate, aluminum chloride etc., preferably nitrate;
Said rare earth, alkaline-earth metal, transition metal salt compounds can be the salt that all can be water-soluble, comprise carbonate, muriate, nitrate, organic acid salt etc., preferably nitrate;
Said cellulose crystallite powder is a kind of compound that is made of carbon, hydrogen, oxygen element, comprises various methylcellulose gum microcrystal powders, has commercially available.
According to the present invention, the total concn of the metal ion of dipping salts solution is 10～60% (weight), and preferred version is 35～45%; The temperature of dipping is 10～50 ℃, and preferred version is 15～30 ℃; Dipping time is 0.5～5h, and preferred version is 1.5～2.5h.
According to the present invention, the dipping back is aging in air at room temperature, and the time is 1～48h, and preferred version is 10～14h; Then at air drying, temperature is 100～120 ℃, and the time is 10～30h; Move into retort furnace, carry out roasting according to following speed:
150℃0.5h，200℃0.5h，250℃0.5h，300℃0.5h，350℃1h，400℃1h，450℃1h，500℃1h，550℃6h。
Adopt U.S. Micrometeritics ASAP-2400 measurement the specific area, condition determination is N
2Be adsorbate, adsorption temp-196 ℃, H
2Do carrier gas, 300 ℃ of degassing temperature.Adopt Japanese Rigaku D.max/RB type x-ray diffractometer to carry out the sample material phase analysis, adopting CuK α is gamma ray source (λ=1.54A).Working conditions: 40KV * 60mA, scanning speed is 4 °/min.
Carry out pre-treatment according to follow procedure before the performance test: 800 ℃ of roasting 6h in air; 900 ℃ of roasting 6h; 1050 ℃ of roasting 15h and 30h; In water content is 10% wet air, be warmed up to 1050 ℃ of roasting 15h and 30h, obtain the sample of differing temps, different atmosphere roasting.Behind 1050 ℃ of roasting 15h, the aluminum oxide specific surface area that contains various additives is at 76～110m
2/ g, behind 1050 ℃ of roasting 30h, specific surface area is at 65～90m
2/ g; Under corresponding maturing temperature and roasting time, the aluminum oxide specific surface area of roasting in containing the air of steam is respectively 76～93m
2/ g and 50～86m
2/ g, behind 1250 ℃ of roasting 5h, specific surface area can remain on 22～56m
2/ g, concrete the results are shown in Table 1.
Material phase analysis to above-mentioned alumina sample learns, after 1050 ℃ of roasting 30h, is the θ phase basically in containing the air of steam, and the auxiliary agent oxide compound thing of interpolation does not show mutually, shows that these oxide compounds exist with the high dispersing state.What deserves to be mentioned is that behind 1050 ℃ of roasting 30h of air atmosphere, the diffraction peak that is very easy to the agglomerating cerium oxide is very faint; After the roasting under relevant temperature in air contained water, not sharp-pointed though its diffraction peak has increase, show cerium oxide in the composite oxides of body series, also be stable.Behind 1250 ℃ of roasting 5h, the aluminum oxide of most of sample is α-phase, small portion be θ with δ mutually, the diffraction peak of the auxiliary agent oxide compound crystalline phase of interpolation has shown.
This shows that aluminum oxide of the present invention has very high thermostability and hydrothermal stability.The preparation method of the present invention's narration is simple, and good reproducibility is easy to realize suitability for industrialized production.
Embodiment
Embodiment 1
Contain the preparation of Ba-La alumina sample.
Ba (NO
3)
2, La (NO
3)
3NH
2O, Al (NO
3)
3XH
2The preparation of the dipping solution of O:, get Ba: La: Al=1 by Ba, La actual in the various salt, the content of Al: 1: 3 1.3 (gram), put into the beaker that contains 50ml water, be stirred to salt and all dissolve; 30g cellulose crystallite powder is put into above-mentioned salts solution, dipping 1h, ageing 24h, 100 ℃ of dry 12h place the interior speed with 50 ℃ of every 30min intensifications of retort furnace to be warming up to 500 ℃ of insulation 4h.800 ℃ of roasting 6h in air, 900 ℃ of roasting 6h, 1050 ℃ of roasting 15h and 30h, 1250 ℃ of roasting 6h; And in water content is 10% wet air, be warmed up to 1050 ℃ of roasting 15h and 30h, and obtaining the alumina sample that contains Ba-La of differing temps, different atmosphere roasting, the content of Ba and La respectively is 3% (weight).Specific surface area sees Table 1.
Embodiment 2
Contain the preparation of Ba-La-Ce alumina sample.
Ba (NO
3)
2, La (NO
3)
3NH
2O, Ce (NO
3)
3MH
2O, Al (NO
3)
3XH
2The preparation of the dipping solution of O: by Ba, La actual in the various salt, the content of Ce, Al, get Ba: La: Ce: Al is 1: 1: 1: 30.3 (grams), put into the beaker that contains 50ml water, and be stirred to salt and all dissolve; 30g cellulose crystallite powder is put into above-mentioned salts solution, dipping 1h, ageing 24h, 100 ℃ of dry 12h place the interior speed with 50 ℃ of every 30min intensifications of retort furnace to be warming up to 500 ℃ of insulation 4h.800 ℃ of roasting 6h in air, 900 ℃ of roasting 6h, 1050 ℃ of roasting 15h and 30h, 1250 ℃ of roasting 6h; And in water content is 10% wet air, be warmed up to 1050 ℃ of roasting 15h and 30h, and obtaining the alumina sample that contains Ba-La-Ce of differing temps, different atmosphere roasting, the content of Ba, La and Ce respectively is 3% (weight).Specific surface area sees Table 1.
Embodiment 3
Contain the preparation of Ba-La-Zr alumina sample.
Ba (NO
3)
2, La (NO
3)
3NH
2O, ZrOCl
2, Al (NO
3)
3XH
2The preparation of the dipping solution of O is by Ba, La actual in the various salt, the content of Zr, Al, and get Ba: La: Zr: Al is 1: 1: 1: 1: 30.3 (gram), put into the beaker that contains 50ml water, be stirred to salt and all dissolve; 30g cellulose crystallite powder is put into above-mentioned salts solution, dipping 1h, ageing 24h, 100 ℃ of dry 12h place the interior speed with 50 ℃ of every 30min intensifications of retort furnace to be warming up to 500 ℃ of insulation 4h.800 ℃ of roasting 6h in air, 900 ℃ of roasting 6h, 1050 ℃ of roasting 15h and 30h, 1250 ℃ of roasting 6h; And in water content is 10% wet air, be warmed up to 1050 ℃ of roasting 15h and 30h, and obtaining the alumina sample that contains Ba-La-Zr of differing temps, different atmosphere roasting, the content of Ba, Zr and La respectively is 3% (weight).Specific surface area sees Table 1.
Embodiment 4
Contain the preparation of Ba-La-Zr-Ce alumina sample.
Ba (NO
3)
2, La (NO
3)
3NH
2O, ZrOCl
2, Ce (NO
3)
3MH
2O, Al (NO
3)
3XH
2The preparation of the dipping solution of O: by the content of Ba, La actual in the various salt, Zr, Ce, Al, get Ba: La: Zr: Ce: Al is 1: 1: 1: 1: 29.3 (gram), put into the beaker that contains 50ml water, be stirred to salt and all dissolve; 30g cellulose crystallite powder is put into above-mentioned salts solution, dipping 1h, ageing 24h, 100 ℃ of dry 12h place the interior speed with 50 ℃ of every 30min intensifications of retort furnace to be warming up to 500 ℃ of insulation 4h.800 ℃ of roasting 6h in air, 900 ℃ of roasting 6h, 1050 ℃ of roasting 15h and 30h, 1250 ℃ of roasting 6h; And in water content is 10% wet air, be warmed up to 1050 ℃ of roasting 15h and 30h, and obtaining the alumina sample that contains Ba-La-Zr-Ce of differing temps, different atmosphere roasting, the content of Ba, La, Zr, Ce respectively is 3% (weight).Specific surface area sees Table 1.
Embodiment 5
Contain the preparation of Mg-Ba-La alumina sample.
Mg (NO
3)
2, Ba (NO
3)
2, La (NO
3)
3NH
2O, Al (NO
3)
3XH
2The preparation of the dipping solution of O: by Mg, Ba actual in the various salt, the content of La, Al, get Mg: La: Ba: Al is 1: 1: 1: 30.3 (grams), put into the beaker that contains 50ml water, and be stirred to salt and all dissolve; 30g cellulose crystallite powder is put into above-mentioned salts solution, dipping 1h, ageing 24h, 100 ℃ of dry 12h place the interior speed with 50 ℃ of every 30min intensifications of retort furnace to be warming up to 500 ℃ of insulation 4h.800 ℃ of roasting 6h in air, 900 ℃ of roasting 6h, 1050 ℃ of roasting 15h and 30h, 1250 ℃ of roasting 6h; And in water content is 10% wet air, be warmed up to 1050 ℃ of roasting 15h and 30h, and obtaining the alumina sample that contains Mg-Ba-La of differing temps, different atmosphere roasting, the content of Mg, Ba and La respectively is 3% (weight).Specific surface area sees Table 1.
Embodiment 6
Contain the preparation of Mg-Ba-La-Ce alumina sample.
Mg (NO
3)
2, Ba (NO
3)
2, La (NO
3)
3NH
2O, Ce (NO
3)
3MH
2O, Al (NO
3)
3XH
2The preparation of the dipping solution of O: by the content of Mg, La actual in the various salt, Ba, Ce, Al, get Mg: Ba: La: Ce: Al is 1: 1: 1: 1: 29.3 (gram), put into the beaker that contains 50ml water, be stirred to salt and all dissolve; 30g cellulose crystallite powder is put into above-mentioned salts solution, dipping 1h, ageing 24h, 100 ℃ of dry 12h place the interior speed with 50 ℃ of every 30min intensifications of retort furnace to be warming up to 500 ℃ of insulation 4h.800 ℃ of roasting 6h in air, 900 ℃ of roasting 6h, 1050 ℃ of roasting 15h and 30h, 1250 ℃ of roasting 6h; And in water content is 10% wet air, be warmed up to 1050 ℃ of roasting 15h and 30h, and obtaining the alumina sample that contains Mg-Ba-La-Ce of differing temps, different atmosphere roasting, the content of Mg, Ba, La and Ce respectively is 3% (weight).Specific surface area sees Table 1.
Embodiment 7
Contain the preparation of Mg-Ba-La-Zr alumina sample.
Mg (NO
3)
2, Ba (NO
3)
2, La (NO
3)
3NH
2O, ZrOCl
2, Al (NO
3)
3XH
2The preparation of the dipping solution of O: by the content of Mg, Ba actual in the various salt, La, Zr, Al, get Mg: Ba: La: Zr: Al is 1: 1: 1: 1: 29.3 (gram), put into the beaker that contains 50ml water, be stirred to salt and all dissolve; 30g cellulose crystallite powder is put into above-mentioned salts solution, dipping 1h, ageing 24h, 100 ℃ of dry 12h place the interior speed with 50 ℃ of every 30min intensifications of retort furnace to be warming up to 500 ℃ of insulation 4h.800 ℃ of roasting 6h in air, 900 ℃ of roasting 6h, 1050 ℃ of roasting 15h and 30h, 1250 ℃ of roasting 6h; And in water content is 10% wet air, be warmed up to 1050 ℃ of roasting 15h and 30h, and obtaining the alumina sample that contains Mg-Ba-La-Zr of differing temps, different atmosphere roasting, the content of Mg, Ba, La and Zr respectively is 3% (weight).Specific surface area sees Table 1.
Embodiment 8
Contain the preparation of Mg-Ba-La-Zr-Ce alumina sample.
Mg (NO
3)
2, Ba (NO
3)
2, La (NO
3)
3NH
2O, ZrOCl
2, Ce (NO
3)
3MH
2O, Al (NO
3)
3XH
2The preparation of the dipping solution of O is by the content of Mg, La actual in the various salt, Ba, Zr, Ce, Al, and get Mg: Ba: La: Zr: Ce: Al is 1: 1: 1: 1: 1: 28.3 (gram), put into the beaker that contains 50ml water, be stirred to salt and all dissolve; 30g cellulose crystallite powder is put into above-mentioned salts solution, dipping 1h, ageing 24h, 100 ℃ of dry 12h place the interior speed with 50 ℃ of every 30min intensifications of retort furnace to be warming up to 500 ℃ of insulation 4h.800 ℃ of roasting 6h in air, 900 ℃ of roasting 6h, 1050 ℃ of roasting 15h and 30h, 1250 ℃ of roasting 6h; And in water content is 10% wet air, be warmed up to 1050 ℃ of roasting 15h and 30h, and obtaining the alumina sample that contains Mg-Ba-La-Zr-Ce of differing temps, different atmosphere roasting, the content of Mg, Ba, La, Zr, Ce respectively is 3% (weight).Specific surface area sees Table 1.
Embodiment 9
Contain the preparation of Co-Ba-La alumina sample.
Co (NO
3)
2YH
2O, Ba (NO
3)
2, La (NO
3)
3NH
2O, Al (NO
3)
3XH
2The preparation of the dipping solution of O is by Co, Ba actual in the various salt, the content of La, Al, and get Co: Ba: La: Al is 1: 1: 1: 30.3 (grams), put into the beaker that contains 50ml water, and be stirred to salt and all dissolve; 30g cellulose crystallite powder is put into above-mentioned salts solution, dipping 1h, ageing 24h, 100 ℃ of dry 12h place the interior speed with 50 ℃ of every 30min intensifications of retort furnace to be warming up to 500 ℃ of insulation 4h.800 ℃ of roasting 6h in air, 900 ℃ of roasting 6h, 1050 ℃ of roasting 15h and 30h, 1250 ℃ of roasting 6h; And in water content is 10% wet air, be warmed up to 1050 ℃ of roasting 15h and 30h, and obtaining the alumina sample that contains Co-Ba-La of differing temps, different atmosphere roasting, the content of Co, Ba and La respectively is 3% (weight).Specific surface area sees Table 1.
Embodiment 10
Contain the preparation of Co-Ba-La-Ce alumina sample.
Co (NO
3)
2YH
2O, Ba (NO
3)
2, La (NO
3)
3NH
2O, Ce (NO
3)
3MH
2O, Al (NO
3)
3XH
2The preparation of the dipping solution of O is by the content of Co, Ba actual in the various salt, La, Ce, Al, and get Co: Ba: La: Ce: Al is 1: 1: 1: 1: 29.3 (gram), put into the beaker that contains 50ml water, be stirred to salt and all dissolve; 30g cellulose crystallite powder is put into above-mentioned salts solution, dipping 1h, ageing 24h, 100 ℃ of dry 12h place the interior speed with 50 ℃ of every 30min intensifications of retort furnace to be warming up to 500 ℃ of insulation 4h.800 ℃ of roasting 6h in air, 900 ℃ of roasting 6h, 1050 ℃ of roasting 15h and 30h, 1250 ℃ of roasting 6h; And in water content is 10% wet air, be warmed up to 1050 ℃ of roasting 15h and 30h, and obtaining the sample that contains the Co-Ba-La-Ce aluminum oxide of differing temps, different atmosphere roasting, the content of Co, Ba, La, Ce respectively is 3% (weight).Specific surface area sees Table 1.
Embodiment 11
Contain the preparation of Co-Ba-La-Zr alumina sample.
Co (NO
3)
2YH
2O, Ba (NO
3)
2, La (NO
3)
3NH
2O, ZrOCl
2, Al (NO
3)
3XH
2The preparation of the dipping solution of O is by the content of Co, La actual in the various salt, Ba, Zr, Al, and get Co: Ba: La: Zr: Al is 1: 1: 1: 1: 29.3 (gram), put into the beaker that contains 50ml water, be stirred to salt and all dissolve; 30g cellulose crystallite powder is put into above-mentioned salts solution, dipping 1h, ageing 24h, 100 ℃ of dry 12h place the interior speed with 50 ℃ of every 30min intensifications of retort furnace to be warming up to 500 ℃ of insulation 4h.800 ℃ of roasting 6h in air, 900 ℃ of roasting 6h, 1050 ℃ of roasting 15h and 30h, 1250 ℃ of roasting 6h; And in water content is 10% wet air, be warmed up to 1050 ℃ of roasting 15h and 30h, and obtaining the alumina sample that contains Co-Ba-La-Zr of differing temps, different atmosphere roasting, the content of Co, Ba, La, Zr respectively is 3% (weight).Specific surface area sees Table 1.
Embodiment 12
Contain the preparation of Co-Ba-La-Zr-Ce alumina sample.
Co (NO
3)
2YH
2O, Ba (NO
3)
2, La (NO
3)
3NH
2O, ZrOCl
2, Ce (NO
3)
3MH
2O, Al (NO
3)
3XH
2The preparation of the dipping solution of O is by the content of Co, La actual in the various salt, Ba, Zr, Ce, Al, and get Co: Ba: La: Zr: Ce: Al is 1: 1: 1: 1: 1: 28.3 (gram), put into the beaker that contains 50ml water, be stirred to salt and all dissolve; 30g cellulose crystallite powder is put into above-mentioned salts solution, dipping 1h, ageing 24h, 100 ℃ of dry 12h place the interior speed with 50 ℃ of every 30min intensifications of retort furnace to be warming up to 500 ℃ of insulation 4h.800 ℃ of roasting 6h in air, 900 ℃ of roasting 6h, 1050 ℃ of roasting 15h and 30h, 1250 ℃ of roasting 6h; And in water content is 10% wet air, be warmed up to 1050 ℃ of roasting 15h and 30h, and obtaining the alumina sample that contains Co-Ba-La-Zr-Ce of differing temps, different atmosphere roasting, the content of Co, Ba, La, Zr, Ce respectively is 3% (weight).Specific surface area sees Table 1.
Table 1. contains the specific surface area of aluminum oxide after different conditions is handled of various auxiliary agents
| Calcination atmosphere → | Air | 10% water+air |
| Maturing temperature/℃ → | ????500????800????1050??1050??1250 | ??1050????1050 |
| Roasting time/h → | ????4??????6??????15????30????5 | ??15??????30 |
| Additive ↓ | BET specific surface area/m 2/g↓ | BET specific surface area/m 2/g |
| Ba-La | ????270????200????96????78????54 | ??83??????70 |
| Ba-La-Ce | ????276????206????101???85????40 | ??80??????69 |
| Ba-La-Zr | ????275????198????87????65????23 | ??88??????80 |
| Ba-La-Zr-Ce | ????265????195????83????67????22 | ??83??????71 |
| Mg-Ba-La | ????276????199????110???90????56 | ??83??????76 |
| Mg-Ba-La-Ce | ????266????207????89????70????41 | ??85??????70 |
| Mg-Ba-La-Zr | ????240????205????85????78????31 | ??87??????76 |
| Mg-Ba-La-Zr-Ce | ????221????206????76????70????33 | ??76??????67 |
| Co-Ba-La | ????250????202????91????75????38 | ??89??????78 |
| Co-Ba-La-Ce | ????253????210????83????59????25 | ??78??????50 |
| Co-Ba-La-Zr | ????286????240????90????89????45 | ??93??????86 |
| Co-Ba-La-Zr-Ce | ????276????213????80????76????42 | ??85??????81 |
Claims (10)
1. the aluminum oxide of a high thermal stability comprises main component aluminum oxide and additive, it is characterized in that, said additive is two or more the combination in rare earth oxide, alkaline earth metal oxide and the transition metal oxide.
2. aluminum oxide according to claim 1 is characterized in that additive counts 1%～15% with alumina weight.
3. aluminum oxide according to claim 1 and 2 is characterized in that, rare earth oxide comprises cerium oxide, lanthanum trioxide, Praseodymium trioxide, Yangization Nd; Alkaline earth metal oxide comprises magnesium oxide, barium oxide; Transition metal oxide comprises zirconium white, titanium oxide, cobalt oxide, chromic oxide.
4. aluminum oxide according to claim 3 is characterized in that, additive is lanthanum trioxide, barium oxide, cerium oxide, zirconium white, magnesian combination, preferably is combined as: barium oxide, lanthanum trioxide, magnesium oxide.
5. aluminum oxide according to claim 1 is characterized in that rare earth oxide: alkaline earth metal oxide: transition metal oxide: aluminum oxide=0.1～1: 0.1～1: 0.1～1: 0.1～1.
6. according to the preparation method of each described aluminum oxide of claim 1～5, it is characterized in that, comprise the steps:
The cellulose crystallite powder is flooded in the salts solution of rare earth, alkaline-earth metal, transition metal salt and aluminium, after aging, drying, roasting, can obtain the aluminum oxide of high thermal stability of the present invention.
7. the preparation method of aluminum oxide according to claim 6 is characterized in that, said aluminium salt can be the salt compounds that all can be water-soluble.
8. the preparation method of aluminum oxide according to claim 6 is characterized in that, said rare earth, alkaline-earth metal, transition metal salt can be the salt compounds that all can be water-soluble.
9. the preparation method of aluminum oxide according to claim 6 is characterized in that, the total concn of the metal ion in the steeping fluid is 10～60% (weight), and the temperature of dipping is 10～50 ℃, and dipping time is 0.5～5h.
10. the preparation method of aluminum oxide according to claim 6 is characterized in that, carries out roasting according to following speed:
150℃0.5h，200℃0.5h，250℃0.5h，300℃0.5h，350℃1h，400℃1h，
450℃1h，500℃1h，550℃6h。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583271B (en) * | 2004-06-15 | 2011-07-27 | 宜兴市宜浦催化剂有限公司 | Porous alumina catalyst carrier |
| CN104860341A (en) * | 2015-05-26 | 2015-08-26 | 华东理工大学 | Preparation method of high-temperature-resistant and high-specific-surface-area alumina |
| CN105585313A (en) * | 2016-01-14 | 2016-05-18 | 深圳市商德先进陶瓷有限公司 | Alumina ceramic powder, alumina ceramic and preparation method of alumina ceramic |
| CN107362790A (en) * | 2017-07-21 | 2017-11-21 | 广东科远高新材料有限责任公司 | A kind of modified gamma-alumina powder and preparation method thereof |
-
2003
- 2003-05-14 CN CNB031169058A patent/CN100522348C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583271B (en) * | 2004-06-15 | 2011-07-27 | 宜兴市宜浦催化剂有限公司 | Porous alumina catalyst carrier |
| CN104860341A (en) * | 2015-05-26 | 2015-08-26 | 华东理工大学 | Preparation method of high-temperature-resistant and high-specific-surface-area alumina |
| CN104860341B (en) * | 2015-05-26 | 2018-10-19 | 华东理工大学 | A kind of preparation method of high temperature resistant and high specific surface aluminium |
| CN105585313A (en) * | 2016-01-14 | 2016-05-18 | 深圳市商德先进陶瓷有限公司 | Alumina ceramic powder, alumina ceramic and preparation method of alumina ceramic |
| CN105585313B (en) * | 2016-01-14 | 2018-03-16 | 深圳市商德先进陶瓷股份有限公司 | Aluminium oxide ceramics powder, aluminium oxide ceramics and preparation method thereof |
| CN107362790A (en) * | 2017-07-21 | 2017-11-21 | 广东科远高新材料有限责任公司 | A kind of modified gamma-alumina powder and preparation method thereof |
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| Publication number | Publication date |
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| CN100522348C (en) | 2009-08-05 |
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