WO2001012554A1 - Process for the preparation of quasi-crystalline boehmites - Google Patents
Process for the preparation of quasi-crystalline boehmites Download PDFInfo
- Publication number
- WO2001012554A1 WO2001012554A1 PCT/EP2000/007792 EP0007792W WO0112554A1 WO 2001012554 A1 WO2001012554 A1 WO 2001012554A1 EP 0007792 W EP0007792 W EP 0007792W WO 0112554 A1 WO0112554 A1 WO 0112554A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- quasi
- process according
- crystalline boehmite
- boehmite
- crystalline
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/30—Preparation of aluminium oxide or hydroxide by thermal decomposition or by hydrolysis or oxidation of aluminium compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/44—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water
- C01F7/447—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by wet processes
- C01F7/448—Dehydration of aluminium oxide or hydroxide, i.e. all conversions of one form into another involving a loss of water by wet processes using superatmospheric pressure, e.g. hydrothermal conversion of gibbsite into boehmite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/34—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/34—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
- C01F7/36—Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts from organic aluminium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/021—After-treatment of oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/04—Compounds with a limited amount of crystallinty, e.g. as indicated by a crystallinity index
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
Definitions
- the present invention pertains to a process for the preparation of quasi- crystalline boehmites.
- Alumina, alpha-monohydrates or boehmites and their dehydrated and or sintered forms are some of the most extensively used aluminum oxide-hydroxides materials. Some of the major commercial applications involve one or more forms of these materials and these are, for example, ceramics, abrasive materials, fire- retardants, adsorbents, catalysts, fillers in composites and so on. Also, a major portion of the commercial boehmite aluminas is used in catalytic applications such as refinery catalysts, catalyst for hydroprocessing hydrocarbon feeds, reforming catalysts, pollution control catalysts, cracking catalysts.
- hydroprocessing in this context encompasses all processes in which a hydrocarbon feed is reacted with hydrogen at elevated temperature and elevated pressure.
- aluminas are also used as catalysts for specific chemical processes such as ethylene-oxide production, and methanol synthesis.
- Relatively newer commercial uses of boehmite type of aluminas or modified forms thereof involve the transformation of environmentally unfriendly chemical components such as chlorofluorohydrocarbons (CFC's) and other undesirable pollutants.
- Boehmite alumina types are further used as catalytic material for the treatment of exhaust gases of gas turbines for reducing nitrogen oxide.
- Some of the main properties which determine the suitability of commercial applications involving gas-solid phase interactions are pore volume, pore size distribution, pore texture, specific density, surface areas, density and type of active centers, basicity and acidity, crushing strength, abrasion properties, thermal and hydrothermal aging (sintering) and long term stability.
- the desired properties of the alumina product can be obtained by selecting and carefully controlling certain parameters which usually involve: raw materials, impurities, precipitation or conversion process conditions, aging conditions and subsequent thermal treatments (calcination/steaming) and mechanical treatments.
- boehmite is used in the industry to describe alumina hydrates which exhibit XRD patterns close to that of the aluminum oxide-hydroxide [AIO(OH)], naturally occurring boehmite or diaspore.
- AIO(OH) aluminum oxide-hydroxide
- boehmite usually is used to broadly describe a wide range of alumina hydrates which contain different amounts of water of hydration, have different surface areas, pore volumes, specific densities, and exhibit different thermal characteristics upon thermal treatments.
- their XRD patterns although they exhibit the characteristic boehmite [AIO(OH)] peaks, usually vary in their widths and can also shift in their location. The sharpness of the XRD peaks and their location have been used to indicate degree of crystal unity, crystal size, and amount of imperfections.
- boehmite aluminas there are two categories of boehmite aluminas.
- Category I in general, contains boehmites which have been synthesized and/or aged at temperatures close to 100°C and most of the time under ambient atmospheric pressures. In the present specification, this type of boehmite is referred to as quasi-crystalline boehmites.
- the second category of boehmite consists of so- called micro-crystalline boehmites.
- category I boehmites, quasi-crystalline boehmites are referred to, interchangeably as: pseudo-boehmites, gelatinous boehmites or quasi-crystalline boehmites (QCB).
- pseudo-boehmites gelatinous boehmites or quasi-crystalline boehmites (QCB).
- QCB aluminas have very high surface areas, large pores and pore volumes, lower specific densities than microcrystalline boehmites, disperse easily in water or acids, they have smaller crystal sizes than micro-crystalline boehmites, and contain a larger number of water molecules of hydration.
- the extent of hydration of the QCB can have a wide range of values, for example from about 1.4 up and about 2 moles of water per mole of AlO, intercalculated usually orderly or otherwise between the octahedral layers.
- the DTG (differential thermographimetry) curves which are the water release from the QCB materials as function of temperature, show that the major peak appears at much lower temperatures as compared to that of the much more crystalline boehmites.
- the XRD Patterns of QCBs show quite broad peaks and their half-widths are indicative of the crystal sizes as well as degree of crystal perfection.
- the broadening of the widths at half-maximum intensities varies substantially and typical for the QCB's could be from about 2° - 6° to 2 ⁇ . Further, as the amount of water intercalated into the QCB crystals is increased, the main (020) XRD reflection moves to lower 2 ⁇ values corresponding to greater d- spacings.
- Some typical, commercially available QCB's are; Condea Pural ®, Catapal ® and Versal ® products.
- the category II of the boehmites consists of microcrystalline boehmites (MCB), which are distinguished from the QCBs due to their high degree of crystallinity, relatively large crystal sizes, very low surface areas, and high densities. Contrary to the QCB's the MCB's show XRD patterns with higher peak intensities and very narrow half-peak line widths. This is due to the relatively small number of water molecules intercalated, large crystal sizes, higher degree of crystallization of the bulk material and to lesser amount of crystal imperfections present. Typically, the number of molecules of water intercalated can vary in the range from about 1 up to about 1.4 per mole of AlO.
- the main XRD reflection peaks (020) at half-length of maximum intensities have widths from about 1.5 down to about 0.1 degrees 2-theta (2 ⁇ ).
- quasi-crystalline boehmites to have 020 peak widths at half-length of the maximum intensity of 1.5 or greater than 1.5 °.
- Boehmites having a (020) peak width at half-length of the maximum intensity smaller than 1.5 are considered micro-crystalline boehmites.
- a typical MCB commercially available product is Condea's P-200 ® grade of alumina. Overall, the basic, characteristic differences between the QCB and
- MCB types of boehmites involve variations in the following: 3-dimensional lattice order, sizes of the crystallites, amount of water intercalated between the octahedral layers and degree of crystal imperfections.
- boehmite aluminas are most commonly manufactured via processes involving: Neutralization of aluminum salts by alkalines, acidification of aluminate salts, hydrolysis of aluminum alkoxides, reaction of aluminum metal (amalgamated) with water and rehydration of amorphous rho-alumina obtained by calcining gibbsite.
- the MCB type of boehmite aluminas in general are commercially produced with hydrothermal processes using temperatures usually above 150°C and autogeneous pressures. These processes usually involve hydrolysis of aluminum salts to form gelatinous aluminas, which are subsequently hydrothermally aged in an autoclave at elevated temperatures and pressures. This type of process is described in US 3,357,791. Several variations of this basic process exist involving different starting aluminum sources, additions of acids or salts during the aging, and a wide range of process conditions.
- MCB's are also prepared using hydrothermal processing of gibbsite. Variations of these processes involve; addition of acids, alkaline and salts during the hydrothermal treatment, as well as the use of boehmite seeds to enhance the conversion of gibbsite to MCB. These types of processes are described in Alcoa's US 5,194,243, in US 4,117,105 and in US 4,797,139.
- boehmite materials are characterized by reflections in their powder X-ray.
- the ICDD contains entries for boehmite and confirms that reflections corresponding to the (020) , (021) and (041) planes would be present. For copper radiation, such reflections would appear at 14, 28 and 38 degrees two theta..
- the various forms of boehmite would be distinguished by the relative intensity and width of the reflections.
- Various authors have considered the exact position of the reflections in terms of the extent of crystallinity. Nevertheless, lines close to the above positions would be indicative of the presence of one or more types of boehmite phases.
- EP-A1-0 597 738 describes the thermal stabilization of alumina by addition of lanthanum, optionally combined with neodymium.
- This material is prepared by aging rehydrateble alumina (i.e. flash calcined gibbsite) in a slurry at a pH between 8 and 12 with a lanthanum salt at a temperature between 70 and 110 °C, followed with thermal treatment at a temperature between 100 and 1000°C.
- EP-A-0 130 835 describes a catalyst comprising a catalytically active metal supported on a lanthanum or neodymium- ⁇ - AI 2 O 3 carrier.
- Said carrier is obtained by precipitation of aluminum nitrate solution with ammonium hydroxide in the presence of a lanthanum, praseodymium or neodymium salt solution.
- the precipitated amorphous material is directly washed with water and filtered, the alumina is not allowed under the usual conditions and certain pH, concentration and temperatures to age with time so that it crystallizes to a boehmite alumina structure.
- the present invention is directed to an improved process for the preparation of quasi-crystalline boehmite.
- a quasi-crystalline boehmite precursor is aged at a pH below 7, preferably under hydrothermal conditions.
- FIGURE 1 is an X-ray diffractogram (XRD) for the spectrum of Catapal A® of Vista Chemicals.
- FIGURE 2 is the XRD pattern of the QCB formed in the procedure of Example 2.
- FIGURE 3 is the XRD pattern of the QCB formed in the procedure of Example 3.
- FIGURE 4 is the XRD pattern of the QCB formed in the procedure of Comparative Example 4.
- Suitable quasi-crystalline boehmite precursors are aluminum alkoxide, soluble aluminum salts such as aluminum sulfate, aluminum nitrate, aluminum chloride and sodium aluminate, thermally treated aluminum trihydrate such as flash calcined aluminum trihydrate (CP ® alumina), amorphous gel alumina, QCBs with relatively low crystallinity, aluminum trihydrate such as gibbsite, BOC and bayerite and mixtures thereof,
- additives may be added to the quasi- crystalline boehmite precursor. This results in a high quality QCB with additives in a homogeneously dispersed state. It was found that when using a pH below 7 the additives in the resulting QCB are even more homogeneously dispersed than when using the higher pH and thermal aging of the prior art processes. In fact, it was found that some additives can only be added in a homogenously dispersed state at these low pHs such as lanthanum nitrate and nickel salts. At higher pHs, the additives precipitate readily as a separate phase.
- Additives present in QCB aid to adjust the QCBs physical, chemical and catalytic properties such as thermal stability,specific density, surface area, pore volume, pore size distribution, density and type of active centers, basicity and acidity, crushing strength, abrasion properties etcetera, and so determine the boehmite's suitability for use in catalytic or absorbent material.
- the fact that the additive is homogeneously dispersed within the QCB distinguishes the QCBs according to the invention from QCBs which have been impregnated with additives, and renders these new QCBs extremely suitable for catalytic purposes or as starting materials for the preparation of catalysts for heterogeneous catalytic reactions.
- a homogenous dispersion of the additive is present in the QCB if the X-ray diffraction pattern has no reflections of the additive, and thus the additive is not present as a separate phase. It is, of course, possible to incorporate different types of additives in the QCB according to the invention.
- Suitable additives are compounds containing elements selected from the group of rare earth metals, alkaline earth metals, alkaline metals, transition metals, actinides, noble metals such as Pd and Pt, silicon, gallium, boron, titanium, and phosphorus.
- the presence of silicon increases the amount of acidic sites in the boehmite, transition metals introduce catalytic or absorbing activity such as SO x captivation, NO x captivation, hydrogenation, hydroconversion, and other catalytic systems for gas/solid interactions.
- Suitable compounds containing the desired elements are nitrates, sulfates, chlorides, formates, acetates, carbonates, vanadates etctera.
- the use of compounds with decomposable anions is preferred, because the resulting QCBs with additive may directly be dried, without any washing, as undesirable anions for catalytic purposes are not present.
- the QCBs according to the invention may be prepared in several ways as long as the aging step is conducted at a pH below 7.
- the process is preferably conducted under hydrothermal conditions.
- a quasi-crystalline boehmite precursor and optionally additive are aged, preferably under hydrothermal conditions, to form a quasi-crystalline alumina.
- the aging may be conducted hydrothermally, which means in the presence of a protic liquid or gas such as water, ethanol, propanol or steam and under pressure, i.e. with increased pressure such as aging in water at a temperature above 100 °C under autogeneous pressure. Examples of suitable preparation processes are described below: 10
- the QCB can be prepared by hydrolyzing and aging an aluminum alkoxide, preferably under hydrothermal conditions. Any additive can be incorporated during the hydrolysis step or added at the end before the aging step.
- the QCB may be prepared by hydrolysis and precipitation as hydroxides of soluble aluminum salts and aged, preferably hydrothermally, to form a QCB.
- suitable alumnium salts are aluminum sulfate, aluminum nitrate, aluminum chloride, sodium aluminate, and mixtures thereof.
- the additive(s) may be added simultaneously during hydrolysis and coprecipitation or at the end in the aging step.
- the QCB can also be prepared by aging a slurry containing a thermally treated form of aluminum trihydrate and optionally additive for a time sufficient to form QCB.
- Thermally treated forms of aluminum trihydrate are calcined aluminum trihydrate and flash calcined aluminum trihydrate (CP ® alumina).
- This preparation method has the advantage that no ions are introduced into the QCB besides ions of an optional additive compound. That means that with the appropriate choice of additive compounds washing steps can be reduced or avoided altogether. For instance, when additive compounds are used with decomposable anions (such as carbonates, nitrates and formates), the QCB containing additive may be dried directly, since undesirable cations for catalytic purposes will not be present.
- a further advantage of this preparation method is 11
- a slurry containing a thermally treated form of aluminum trihydrate and optionally additive reslurry the shaped bodies, and subsequently age the shaped bodies to form QCB.
- Shaping is defined in this specification as any method of obtaining particles with the appropriate size and strength for the specific purpose. Suitable shaping methods are spray-drying, extrusion (optionally with intermediate spray-drying, filterpressing, or kneading), pelletizing, beading or any other conventional shaping method used in the catalyst field.
- the QCB can also be prepared by aging a slurry containing amorphous gel alumina and optionally additive(s)for a time sufficient to form QCB.
- this preparation method has also the advantage that no ions are introduced into the QCB beside optionally any ions of the additive compound. That means that with the appropriate choice of additive compounds washing steps can be reduced or avoided altogether.
- QCBs according to the invention may also be prepared by aging, preferably by hydrothermal treatment, a relatively amorphous QCB , optionally in the presence of compounds of a desired additive.
- the crystallinity increases to some extend, but the resulting product is still a QCB according to the definition of the present description.
- This process also allows shaping of the QCB-additive mixture before the thermal treatment. Further, no additional ions besides the optional ions of the additive compound are introduced in the QCB.
- QCBs may also be prepared by aging, preferably by hydrothermal treatment alumina trihydrates such as gibbsite, BOC and bayerite, with the help of suitable boehmite seeds in the presence of compounds of the desired additives.
- suitable seeds are the known seeds to make microcrystalline boehmite such as commercially available boehmite (Catapal ®, Condea ⁇ Versal, P-200 ® etcetera), amorphous seeds, miled boehmite seeds, boehmite prepared from sodium aluminate solutions, etcetera.
- quasi-crystalline boehmites prepared by one of the processes described here can suitably be used as a seed.
- processes 5 and 6 described-above are known for the preparation of microcrystalline boehmites, we found that aging at a pH below 7 favors the production of QCBs over MCBs. Further, the process can be adapted to form QCBs by adjusting the seed and the conditions used.
- boehmite seed is also claimed to produce finer particle size boehmite product which is easier to disperse in water.
- the use of boehmite seeds in the hydtrothermal conversion of gibbsite has been described in US 4,797,139, filed on December 16, 1987, and in US 5,194,243, filed on September 30, 1985.
- All the processes described above may be conducted batch-wise or in a continuous mode, optionally in a continuous multy step operation.
- the processes may be conducted partly continuous, partly batchwise.
- more than one type of QCB precursor may be used, although care must be taken that the reaction conditions employed enable the conversion of the precursor to QCB.
- Said mixture of QCB precursors may be prepared before introduction of the additive or the various types of precursors may be added in any of the further stages of the reaction.
- more than one aging step may be applied, wherein for instance the aging temperature and/or condition (thermally or hydrothermally, pH, time) is varied.
- reaction products of the processes for the preparation of the QCBs according to the invention may also be recycled to the reactor.
- the various additives may be added simultaneously or sequentially in any of the reaction steps.
- the processes for the preparation of the quasi-crystalline boehmites according to the invention allow shaping into shaped bodies during preparation. It is also possible to shape the final QCB, optionally with the help of binders and/or fillers.
- the invention is also directed to shaped bodies obtained with the process according to the invention.
- the QCBs according to the invention are extremely suitable as components or starting material for catalyst compositions or catalyst additives. To this end the QCB is combined with, optionally, binders, fillers (e.g.
- catalyst compositions and catalyst additives comprising the QCB according to the invention.
- the QCB may be mixed with other metal oxides or hydroxides, binders, extenders, activators, pore regulating additives, etcetera in the course of further processing to produce absorbents, ceramics, refractories, substrates, and other carriers.
- boehmites are generally used at temperatures between 200 and 1000°C. At these high temperatures the boehmites are usually converted into transition-aluminas. Therefore, the present invention is also directed to transition alumina which is obtainable by thermal treatment of the quasi-crystalline boehmite prepared with the process according to the invention
- transition aluminas catalyst compositions or catalyst additives can be made, optionally with the help of binder materials, fillers, etcetera.
- a quasi-crystalline boehmite was prepared from hydrolysis of aluminum isopropoxide and aged at 65 °C for 5 days.
- the XRD pattern is given in Figure 2.
- a quasi-crystalline boehmite was produced using the process of Wachowski containing 5 wt% lanthanum ions (calculated at the oxide).
- the XRD pattern is given in Figure 4.
- Comparative example 4 The product of Comparative example 4 was re-slurried in water, the pH was adjusted to 4 and the slurry was hydrothermally treated at 198 °C for 1 hour. Comparison of the XRD of the product of example 4 and the XRD of the product of example 5 shows that when using the hydrothermal conditions and low pH according to the process of the invention, an improved crystallinity is obtained.
- Example 7 5 wt% lanthanum nitrate (calculated as the oxide) in solution was added to a slurry containing fine particle Gibbsite and 20% Catapal A alumina ® as a seed. The pH was adjusted between 4 and 6 and homogenized. In an autoclave the resulting slurry was heated to 180 °C for 2 hours under autogeneous pressure.
- Example 7 5 wt% lanthanum nitrate (calculated as the oxide) in solution was added to a slurry containing fine particle Gibbsite and 20% Catapal A alumina ® as a seed. The pH was adjusted between 4 and 6 and homogenized. In an autoclave the resulting slurry was heated to 180 °C for 2 hours under autogeneous pressure.
- Example 7 5 wt% lanthanum nitrate (calculated as the oxide) in solution was added to a slurry containing fine particle Gibbsite and 20% Catapal A alumina ® as a seed.
- Example 1 was repeated using finely ground BOC. 10 wt% of Catapal A, strongly peptized with nitric acid, was used as a seed. The pH was adjusted to 6, and 10 wt% lanthanum nitrate (calculated as oxide) in solution was added. The resulting slurry was homogenized in a blender and transferred to an autoclave where it was heated under autogeneous pressure to 175 °C for 2 hours.
- Example 6 was repeated using sodium aluminate (10 wt% calculated as alumina) as a seed. The pH was adjusted between 6 and 7 with nitric acid, and 5 wt% lanthanum nitrate (calculated as oxide) in solution was added. The resulting slurry was homogenized in a blender and transferred to an autoclave where it was heated under autogeneous pressure to 165 °C for 2 hours.
Abstract
Description
Claims
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE60015345T DE60015345T2 (en) | 1999-08-11 | 2000-08-11 | PROCESS FOR THE PREPARATION OF QUASI CRYSTALLINE BOEHMITEN |
DK00960436T DK1200350T3 (en) | 2000-08-11 | 2000-08-11 | Process for the preparation of quasi-crystalline boehmites |
AT00960436T ATE280738T1 (en) | 1999-08-11 | 2000-08-11 | METHOD FOR PRODUCING QUASI-CRYSTALLINE BOEHMITE |
CA002381301A CA2381301C (en) | 1999-08-11 | 2000-08-11 | Process for the preparation of quasi-crystalline boehmites |
BR0013135-0A BR0013135A (en) | 1999-08-11 | 2000-08-11 | Processes for the preparation of quasi-crystalline boehmite and transition alumina |
EP20000960436 EP1200350B1 (en) | 1999-08-11 | 2000-08-11 | Process for the preparation of quasi-crystalline boehmites |
JP2001516859A JP2003507299A (en) | 1999-08-11 | 2000-08-11 | Method for producing pseudocrystalline boehmite |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US37255799A | 1999-08-11 | 1999-08-11 | |
US09/372,557 | 1999-08-11 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001012554A1 true WO2001012554A1 (en) | 2001-02-22 |
Family
ID=23468656
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2000/007792 WO2001012554A1 (en) | 1999-08-11 | 2000-08-11 | Process for the preparation of quasi-crystalline boehmites |
Country Status (12)
Country | Link |
---|---|
US (1) | US6506358B1 (en) |
EP (1) | EP1200350B1 (en) |
JP (1) | JP2003507299A (en) |
KR (1) | KR100711342B1 (en) |
CN (1) | CN1174922C (en) |
AT (1) | ATE280738T1 (en) |
BR (1) | BR0013135A (en) |
CA (1) | CA2381301C (en) |
DE (1) | DE60015345T2 (en) |
ES (1) | ES2231252T3 (en) |
PT (1) | PT1200350E (en) |
WO (1) | WO2001012554A1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005051845A2 (en) | 2003-11-26 | 2005-06-09 | Albemarle Netherlands B.V. | Hydrothermal process for the preparation of quasi-crystalline boehmite |
DE102004018336A1 (en) * | 2004-04-15 | 2005-11-10 | Albemarle Corporation | Flame retardant filler for plastics |
US6964934B2 (en) | 2002-08-28 | 2005-11-15 | Albemarle Netherlands B.V. | Process for the preparation of doped pentasil-type zeolite using doped seeds |
US6969692B2 (en) | 2002-08-28 | 2005-11-29 | Albemarle Netherlands B.V. | Process for the preparation of doped pentasil-type zeolites using a doped reactant |
EP1604951A1 (en) * | 2003-03-10 | 2005-12-14 | Kawai-Lime Ind. Co., Ltd. | Heat-resistant aluminum hydroxide and method for preparation thereof |
WO2022155528A1 (en) | 2021-01-15 | 2022-07-21 | Albemarle Corporation | Fcc catalyst additive with pseudo solid state crsytallized zeolite |
Families Citing this family (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7208446B2 (en) * | 1999-08-11 | 2007-04-24 | Albemarle Netherlands B. V. | Quasi-crystalline boehmites containing additives |
US20030180214A1 (en) * | 1999-08-11 | 2003-09-25 | Dennis Stamires | Process for the preparation of quasi-crystalline boehmites |
ATE280130T1 (en) * | 1999-08-11 | 2004-11-15 | Akzo Nobel Nv | METHOD FOR PRODUCING QUASI-CRYSTALLINE BOEHMITE FROM CHEAP PRECURSORS |
EP1385622B1 (en) * | 2001-05-10 | 2014-07-09 | Albemarle Netherlands B.V. | Continuous process for the efficient conversion of inorganic solid particles |
US7090824B2 (en) * | 2001-07-27 | 2006-08-15 | Board Of Trustees Of Michigan State University | Mesostructured transition aluminas |
US20050227000A1 (en) * | 2004-04-13 | 2005-10-13 | Saint-Gobain Ceramics & Plastics, Inc. | Surface coating solution |
US20050124745A1 (en) * | 2002-04-19 | 2005-06-09 | Saint-Gobain Ceramics & Plastics, Inc. | Flame retardant composites |
CN1156336C (en) * | 2002-07-12 | 2004-07-07 | 清华大学 | Preparation method of titanium dioxide film photocatalyst loaded on surface of flexible base material |
CN1688508A (en) * | 2002-08-13 | 2005-10-26 | 英特凯特公司 | Flue gas treatments to reduce NOx and CO emissions |
US7431825B2 (en) * | 2003-12-05 | 2008-10-07 | Intercat, Inc. | Gasoline sulfur reduction using hydrotalcite like compounds |
TWI342335B (en) * | 2004-06-02 | 2011-05-21 | Intercat Inc | Mixed metal oxide additives |
US20060104895A1 (en) | 2004-11-18 | 2006-05-18 | Saint-Gobain Ceramics & Plastics, Inc. | Transitional alumina particulate materials having controlled morphology and processing for forming same |
DE102006012268A1 (en) | 2006-03-15 | 2007-09-27 | Nabaltec Ag | Fine crystalline boehmite and process for its preparation |
KR100885309B1 (en) * | 2007-08-24 | 2009-02-24 | 한국화학연구원 | Manufacturing method of high porous alo(oh) gel |
EP2190574B1 (en) | 2007-08-29 | 2019-08-28 | Pacific Industrial Development Corporation | Rare earth alumina particulate manufacturing method and application |
WO2009085870A2 (en) * | 2007-12-19 | 2009-07-09 | Saint-Gobain Ceramics & Plastics, Inc. | Aggregates of alumina hydrates |
WO2010077779A2 (en) | 2008-12-17 | 2010-07-08 | Saint-Gobain Ceramics & Plastics, Inc. | Applications of shaped nano alumina hydrate in inkjet paper |
CA2793668A1 (en) | 2011-10-31 | 2013-04-30 | Bradley J. Crosby | An apparatus and method for construction of structures utilizing insulated concrete forms |
USD713975S1 (en) | 2012-07-30 | 2014-09-23 | Airlite Plastics Co. | Insulative insert for insulated concrete form |
US20150299551A1 (en) * | 2012-11-06 | 2015-10-22 | KAWAI LIME INDUSTRY Co. Ltd. | High thermal conductive boehmite and method for manufacturing same |
CA2985438A1 (en) | 2016-11-14 | 2018-05-14 | Airlite Plastics Co. | Concrete form with removable sidewall |
EP3723900A1 (en) | 2017-12-11 | 2020-10-21 | BASF Corporation | Reactive silica-alumina matrix component compositions for bottoms cracking catalysts |
US11155995B2 (en) | 2018-11-19 | 2021-10-26 | Airlite Plastics Co. | Concrete form with removable sidewall |
CN116081668B (en) * | 2023-03-06 | 2023-07-25 | 成都超纯应用材料有限责任公司 | Boehmite sol dispersing agent, preparation method and application thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3739062A (en) * | 1970-10-05 | 1973-06-12 | Kaiser Aluminium Chem Corp | Direct conversion of dawsonite to pseudoboehmite |
US4332782A (en) * | 1980-07-28 | 1982-06-01 | Filtrol Corporation | Method of producing pseudoboehmite |
US4344928A (en) * | 1979-02-26 | 1982-08-17 | Rhone-Poulenc Industries | Process for preparing alumina particulates, at least a fraction of which being ultrafine boehmite |
EP0113796A1 (en) * | 1982-11-23 | 1984-07-25 | Degussa Aktiengesellschaft | Hydrous alumina essentially consisting of pseudoboehmite, process for producing it and its use |
JPH10109030A (en) * | 1996-10-04 | 1998-04-28 | Japan Energy Corp | Pseudo-boehmite for catalyst carrier and its production |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3357791A (en) | 1964-07-20 | 1967-12-12 | Continental Oil Co | Process for producing colloidal-size particles of alumina monohydrate |
US4089811A (en) * | 1976-11-01 | 1978-05-16 | Texaco Inc. | Preparation of catalyst support |
US4117105A (en) | 1977-03-21 | 1978-09-26 | Pq Corporation | Process for preparing dispersible boehmite alumina |
JPS5442399A (en) * | 1977-09-10 | 1979-04-04 | Mizusawa Industrial Chem | Superfine powdery hydrated alumina and its manufacturing method |
JPS5527830A (en) * | 1978-08-15 | 1980-02-28 | Chiyoda Chem Eng & Constr Co Ltd | Production of alumina carrier |
US4318896A (en) * | 1980-04-14 | 1982-03-09 | Uop Inc. | Manufacture of alumina particles |
DE3482094D1 (en) * | 1983-07-01 | 1990-06-07 | Hitachi Ltd | AT HIGH TEMPERATURE STABLE CATALYST, METHOD FOR THE PRODUCTION THEREOF AND METHOD FOR CARRYING OUT CHEMICAL REACTIONS USING THE SAME. |
JPS6022929A (en) * | 1983-07-15 | 1985-02-05 | Hitachi Ltd | Heat resistant carrier for catalyst |
US5194243A (en) | 1983-09-22 | 1993-03-16 | Aluminum Company Of America | Production of aluminum compound |
US4676928A (en) * | 1986-01-30 | 1987-06-30 | Vista Chemical Company | Process for producing water dispersible alumina |
US4797139A (en) | 1987-08-11 | 1989-01-10 | Norton Company | Boehmite produced by a seeded hydyothermal process and ceramic bodies produced therefrom |
FR2697832B1 (en) | 1992-11-12 | 1994-12-30 | Rhone Poulenc Chimie | Alumina stabilized by lanthanum and its preparation process. |
US5837634A (en) * | 1992-11-12 | 1998-11-17 | Condea Vista Company | Process for producing stabilized alumina having enhanced resistance to loss of surface area at high temperatures |
JPH08268716A (en) * | 1995-03-30 | 1996-10-15 | Japan Energy Corp | Method for controlling particle diameter of pseudo-boehmite powder |
US6027706A (en) * | 1998-05-05 | 2000-02-22 | Board Of Trustees Operating Michigan State University | Porous aluminum oxide materials prepared by non-ionic surfactant assembly route |
-
2000
- 2000-08-11 CN CNB00811448XA patent/CN1174922C/en not_active Expired - Fee Related
- 2000-08-11 BR BR0013135-0A patent/BR0013135A/en not_active Application Discontinuation
- 2000-08-11 AT AT00960436T patent/ATE280738T1/en not_active IP Right Cessation
- 2000-08-11 CA CA002381301A patent/CA2381301C/en not_active Expired - Fee Related
- 2000-08-11 EP EP20000960436 patent/EP1200350B1/en not_active Revoked
- 2000-08-11 PT PT00960436T patent/PT1200350E/en unknown
- 2000-08-11 DE DE60015345T patent/DE60015345T2/en not_active Revoked
- 2000-08-11 ES ES00960436T patent/ES2231252T3/en not_active Expired - Lifetime
- 2000-08-11 US US09/636,694 patent/US6506358B1/en not_active Expired - Fee Related
- 2000-08-11 KR KR1020027001567A patent/KR100711342B1/en not_active IP Right Cessation
- 2000-08-11 JP JP2001516859A patent/JP2003507299A/en active Pending
- 2000-08-11 WO PCT/EP2000/007792 patent/WO2001012554A1/en active IP Right Grant
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3739062A (en) * | 1970-10-05 | 1973-06-12 | Kaiser Aluminium Chem Corp | Direct conversion of dawsonite to pseudoboehmite |
US4344928A (en) * | 1979-02-26 | 1982-08-17 | Rhone-Poulenc Industries | Process for preparing alumina particulates, at least a fraction of which being ultrafine boehmite |
US4332782A (en) * | 1980-07-28 | 1982-06-01 | Filtrol Corporation | Method of producing pseudoboehmite |
EP0113796A1 (en) * | 1982-11-23 | 1984-07-25 | Degussa Aktiengesellschaft | Hydrous alumina essentially consisting of pseudoboehmite, process for producing it and its use |
JPH10109030A (en) * | 1996-10-04 | 1998-04-28 | Japan Energy Corp | Pseudo-boehmite for catalyst carrier and its production |
Non-Patent Citations (1)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 1998, no. 09 31 July 1998 (1998-07-31) * |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6964934B2 (en) | 2002-08-28 | 2005-11-15 | Albemarle Netherlands B.V. | Process for the preparation of doped pentasil-type zeolite using doped seeds |
US6969692B2 (en) | 2002-08-28 | 2005-11-29 | Albemarle Netherlands B.V. | Process for the preparation of doped pentasil-type zeolites using a doped reactant |
EP1604951A1 (en) * | 2003-03-10 | 2005-12-14 | Kawai-Lime Ind. Co., Ltd. | Heat-resistant aluminum hydroxide and method for preparation thereof |
EP1604951A4 (en) * | 2003-03-10 | 2012-03-14 | Kawai Lime Ind Co Ltd | Heat-resistant aluminum hydroxide and method for preparation thereof |
WO2005051845A2 (en) | 2003-11-26 | 2005-06-09 | Albemarle Netherlands B.V. | Hydrothermal process for the preparation of quasi-crystalline boehmite |
WO2005051845A3 (en) * | 2003-11-26 | 2006-06-15 | Albemarle Netherlands Bv | Hydrothermal process for the preparation of quasi-crystalline boehmite |
US8088354B2 (en) | 2003-11-26 | 2012-01-03 | Albemarle Netherlands B.V. | Hydrothermal process for the preparation of quasi-crystalline boehmite |
DE102004018336A1 (en) * | 2004-04-15 | 2005-11-10 | Albemarle Corporation | Flame retardant filler for plastics |
WO2022155528A1 (en) | 2021-01-15 | 2022-07-21 | Albemarle Corporation | Fcc catalyst additive with pseudo solid state crsytallized zeolite |
WO2022155523A1 (en) | 2021-01-15 | 2022-07-21 | Albemarle Corporation | Pseudo solid state crystallization of zeolites and uses therein |
WO2022155525A1 (en) | 2021-01-15 | 2022-07-21 | Albemarle Corporation | Fcc catalyst with pseudo solid state crsytallized zeolite |
Also Published As
Publication number | Publication date |
---|---|
EP1200350B1 (en) | 2004-10-27 |
ES2231252T3 (en) | 2005-05-16 |
CA2381301C (en) | 2009-01-20 |
DE60015345D1 (en) | 2004-12-02 |
JP2003507299A (en) | 2003-02-25 |
KR100711342B1 (en) | 2007-04-27 |
US6506358B1 (en) | 2003-01-14 |
ATE280738T1 (en) | 2004-11-15 |
BR0013135A (en) | 2002-04-30 |
PT1200350E (en) | 2005-03-31 |
KR20020026563A (en) | 2002-04-10 |
EP1200350A1 (en) | 2002-05-02 |
CA2381301A1 (en) | 2001-02-22 |
CN1174922C (en) | 2004-11-10 |
CN1368938A (en) | 2002-09-11 |
DE60015345T2 (en) | 2005-10-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2381301C (en) | Process for the preparation of quasi-crystalline boehmites | |
US6503867B1 (en) | Quasi-crystalline boehmites containing additives | |
US6555496B1 (en) | Micro-crystalline boehmites containing additives | |
US6689333B1 (en) | Process for the preparation of quasi-crystalline boehmites from inexpensive precursors | |
US7208446B2 (en) | Quasi-crystalline boehmites containing additives | |
EP1358129B1 (en) | Method of making doped anionic clays | |
JP2003517993A (en) | Aluminum oxide composites with high pore volume and high surface area derived from alumina trihydrate and methods of making and using same | |
EP1515912B1 (en) | Use of cationic layered materials, compositions comprising these materials, and the preparation of cationic layered materials | |
EP1689677B1 (en) | Hydrothermal process for the preparation of quasi-crystalline boehmite | |
US20030180214A1 (en) | Process for the preparation of quasi-crystalline boehmites |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): BR CA CN IN JP KR |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2000960436 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020027001567 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 00811448X Country of ref document: CN Ref document number: 2381301 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: IN/PCT/2002/213/CHE Country of ref document: IN |
|
WWP | Wipo information: published in national office |
Ref document number: 1020027001567 Country of ref document: KR |
|
WWP | Wipo information: published in national office |
Ref document number: 2000960436 Country of ref document: EP |
|
WWG | Wipo information: grant in national office |
Ref document number: 2000960436 Country of ref document: EP |