CN1678393A - Process for the preparation of catalysts comprising a pentasil-type zeolite - Google Patents

Process for the preparation of catalysts comprising a pentasil-type zeolite Download PDF

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CN1678393A
CN1678393A CNA038205815A CN03820581A CN1678393A CN 1678393 A CN1678393 A CN 1678393A CN A038205815 A CNA038205815 A CN A038205815A CN 03820581 A CN03820581 A CN 03820581A CN 1678393 A CN1678393 A CN 1678393A
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type zeolite
aforementioned
aluminium
zeolite
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CN1320960C (en
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P·奥康纳
D·施塔米雷斯
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Albemarle Netherlands BV
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    • 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
    • B01J21/12—Silica and alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8609—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • 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
    • 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
    • B01J21/16—Clays or other mineral silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/007—Mixed salts
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

Process for the preparation of a composition comprising a pentasil-type zeolite, which process comprises the following steps: a) hydrothermally treating an aqueous slurry comprising an aluminium source, a silicon source, a seeding material, and optionally a divalent metal source, thereby forming a pentasil-type zeolite and at least one other compound, and b) shaping the product of step a). Examples of the at least one other compound are anionic clay, cationic clay, Si-Al cogel, and (pseudo)boehmite.

Description

The Preparation of catalysts method that comprises pentasil type zeolite
The present invention relates to the method that a kind of preparation comprises the carbon monoxide-olefin polymeric of pentasil type zeolite and at least a other catalytic components.
EP 0 156 595 discloses a kind of method for preparing the carbon monoxide-olefin polymeric that comprises 60 weight % or pentasil type zeolite still less in porous matrix as follows: (i) mixed zeolite crystal seed, aluminium source and silicon source in water, form slurry, (ii) with this slurry moulding, form discrete particle, (iii) these particles are mixed in aqueous reaction mixture with the alkali metal cation source, (iv) these particles of hydrothermal treatment consists form zeolite in particle.Therefore, form slurry in the method, with the slurry moulding, once more with the particulate slurriesization and the hydrothermal treatment consists of moulding.
The inventive method provides a kind of preparation more easily to comprise the method for the carbon monoxide-olefin polymeric of pentasil type zeolite.
The inventive method comprises the following steps:
A) hydrothermal treatment consists comprises the aqueous slurries of aluminium source, silicon source, seed crystal material and optional divalent metal source, thus form pentasil type zeolite and at least a other compounds and
B) with the product moulding of step a).
Therefore, opposite with the method for prior art, the inventive method does not relate to the slurryization again of shaped granule.Do not form zeolite in the methods of the invention on the spot,, but form zeolite non-at-scenely, promptly before forming particle, form zeolite promptly not at the inner formation of shaped granule zeolite.In addition, this method provides for example easy mode of composition, ZSM-5 and the kaolinic composition of composition, ZSM-5 and the hydrotalcite of ZSM-5 and boehmite of a kind of formation.
The aluminium source that can be suitable in the inventive method comprises aluminum oxide and hydroxide such as transitional alumina (transition alumina), aluminum trihydrate (BOC, gibbsite, bayerite) and treated forms (aluminum trihydrate that comprises quick burning), alumina sol, alumina gel, amorphous alumina and (vacation) boehmite, aluminium chloride hydrogel (aluminium chlorohydrol), aluminum nitrate hydrogel (aluminium nitrohydrol), aluminium salt such as aluminum nitrate, aluminium chloride, aluminium chlorohydrate, sodium aluminate, aluminum phosphate, contain aluminium clay (comprising its calcinated form), and composition thereof.Preferred aluminium source is above-mentioned aluminum oxide and hydroxide, because these materials are more cheap.In addition, these materials can not stay the anion of must flush away or emitting with the harmful gas of environment when heating in carbon monoxide-olefin polymeric.
Suitable silicon source comprises the Ludox, silica gel of sodium metasilicate, sodium metasilicate, stabilisation, poly-silicic acid, tetraethyl orthosilicate, pyrogenic silica, precipitated silica and composition thereof.
Preferred use can not introduced sodium the Ludox in the carbon monoxide-olefin polymeric, as the ammonium Ludox.
Randomly in step (a), add divalent metal source.Suitable divalent metal source comprises magnesium, zinc, nickel, copper, iron, cobalt, manganese, calcium, barium and combination thereof.Preferred divalent metal is a magnesium.
Suitable zinc, nickel, copper, iron, cobalt, manganese, calcium and barium source are its oxide, hydroxide, carbonate, nitrate, chloride, phosphate, titanate and zirconates separately.
Suitable magnesium source comprises magnesium oxide or hydroxide, as MgO, Mg (OH) 2, hydromagnesite, magnesium salts such as magnesium acetate, magnesium formate, glycolic acid magnesium, magnesium carbonate, basic magnesium carbonate, magnesium bicarbonate, magnesium nitrate and magnesium chloride contain magnesium clay such as dolomite, talcum powder, hectorite, hectorite (laponite), sepiolite and composition thereof.
Suitable seed crystal material comprises crystal seed and template, as faujasite-type seeds (X zeolite or Y), pentasil type crystal seed (for example ZSM-5 crystal seed), amorphous crystal seed (for example amorphous Si-Al is cogelled), clay (for example bentonite, kaolin), crystal grain is too little and can not and contain organic directed template such as the colloidal sol or the gel of tetrapropylammonium hydroxide (TPAOH) or bromination tetrapropylammonium (TPABr) by the milled zeolite of X-ray diffraction technology for detection.This colloidal sol example that contains template is the Si-Al colloidal sol that contains 0.1-10 weight % bromination tetrapropylammonium.
If need, can in the process of step (a), have additive.These additives can add separately in this mixture.On the other hand, can also use aluminium source, silicon source, seed crystal material and/or the divalent metal source that is doped with this class additive.
Term " doping " is meant that desired additives (being also referred to as adulterant) for example mixed in silicon source, aluminium source, divalent metal source or the seed crystal material by these source metal of preparation or seed crystal material in the presence of required adulterant before carrying out said method.
Suitable adulterant is the compound that comprises the element that is selected from rare earth metal (for example La and Ce), Si, P, B, VI family metal, group VIII noble metals, alkaline-earth metal (for example Ca and Ba) and/or transition metal (for example Mn, Fe, Nb, Zn, Cr, Ti, Zr, Cu, Ni, Zn, Mo, W, V, Sn).Suitable compound is oxide, hydroxide, carbonate, subcarbonate, chloride, nitrate, sulfate and the phosphate of above-mentioned element.
In the process of step (a), can add bronsted lowry acids and bases bronsted lowry and regulate pH.Required pH for example depends on the type of other compounds that expectation forms.For example, if anionic clay is other required compounds, then slurry preferably has the pH above 6.On the other hand, if boehmite is other required compounds, then pH is preferably about 4-8.
Normally used catalytic component can be before the hydrothermal treatment consists of step a) or among add in the slurry.This will cause formed body to comprise the homogeneous mixture of these catalytic compounds and pentasil type zeolite and other compounds.Preferably after step a) is finished, after promptly hydrothermal treatment consists is finished and forming step b) do not add this class catalytic component before.
The example of appropriate catalyst component is zeolite, aluminium oxide-titanium dioxide, titanium dioxide, zirconia, clay, slaine and alkaline-earth metal (hydrogen) oxide beyond metal trapping agent, combustion improver, the pentasil type zeolite.
It should be noted that these " the normally used catalytic components " that can add in the slurry are not as " other compounds " according to claim 1 step a)." other compounds " according to claim 1 formed in the hydrothermal treatment consists process by aluminium source, silicon source and/or divalent metal source, is not directly to add in the slurry simply.
The hydrothermal treatment consists slurry.Hydro-thermal is meant in temperature and surpasses under the aqueous conditions of atmospheric pressure with pressure above 100 ℃.The suitable temperature scope of the inventive method is 100-300 ℃, preferred 100-200 ℃.Most convenient be to use self-generated pressure.
If need, use a more than hydrothermal treatment consists.
Aluminium source, silicon source and optional divalent metal source are reacted in the presence of suitable seed crystal material, form pentasil type zeolite and at least a other compounds.
If only use silicon source and aluminium source except seed crystal material, excessive aluminium source will cause forming (vacation) boehmite as other compounds as (heat treated) aluminum trihydrate (for example aluminum trihydrate of quick burning).
If have divalent metal source and excessive aluminium source, then other compounds will be anionic clay and amount, divalent metal source and reaction condition-(hydrogen) aluminium oxide and/or divalent metal (hydrogen) oxide that choose wantonly-depends on the aluminium source.The character that depends on divalent metal can form various anionic clays.Typical example is Mg-Al anionic clay, Zn-Al anionic clay and Fe-Al anionic clay.It should be noted that term " anionic clay " is equal to is usually used in term of the prior art " hydrotalcite-like material " and " layered double-hydroxide ".
If use divalent metal source and reaction condition to make the aluminium source become pentasil type zeolite (for example by regulating Si-Al ratio, crystal seed amount and reaction time) with the incomplete reaction of silicon source, then can form the composition that comprises cationic clay.The example of cationic clay is that terre verte (Al-Mg-Si clay) is as talcum powder and imvite.
Comprising the cogelled composition of zeolite and Si-Al can obtain by using silicon source, aluminium source and suitable seed crystal material, wherein control Si-Al than the amount of, seed crystal material and reaction time in case silicon source and aluminium source change into zeolite fully.
Hydrothermal treatment consists can be carried out with a step or multistep.As if carrying out, then before the beginning hydrothermal treatment consists, aluminium source, silicon source, seed crystal material and optional divalent metal source, additive and other catalytic components are all added in the reactor with a step.As if carrying out, then in the hydrothermal treatment consists process or between two hydrothermal treatment consists, add one or more components with two steps.The example of two-step method is will comprise the slurry hydrothermal treatment consists certain hour of aluminium source, silicon source and seed crystal material in the first step, thereby partial reaction to become pentasil type zeolite at least.Next add divalent metal source and continue the hydrothermal treatment consists of extra time, thus form anionic clay and-Ruo reacts incomplete words-make to react completely, forms the pentasil zeolite.
Hydrothermal treatment consists can be carried out in a reaction vessel or in a series of two reaction vessels at least.Preferably carry out with continuity method.If use a more than reaction vessel, then aluminium source, silicon source, seed crystal material and optional divalent metal source, additive and other catalytic components all can be added in first container, but the adding in these sources can also be distributed on the available reaction vessel.For example, can in first reaction vessel, aluminium source and silicon source be mixed, it is cogelled to form Si-Al, should cogelledly introduce second reaction vessel with zeolite seed crystal and make they at least partial reaction become pentasil type zeolite, and the slurry and the divalent metal source that contain zeolite the most at last introduce in the 3rd reaction vessel, and the reaction of any excessive aluminium source and divalent metal source obtains anionic clay in this container.
Aluminium source, silicon source and crystal seed can also be mixed in first reaction vessel and hydrothermal treatment consists, thereby form at least a portion in the zeolite of all measuring, and in second conversion vessel, extra aluminium source (for example aluminum trihydrate of aluminum trihydrate or quick burning) added in this mixture.The hydrothermal treatment consists of gained mixture will cause forming the composition that comprises pentasil type zeolite and (vacation) boehmite.
The product moulding that will in the hydrothermal treatment consists process, form.Suitable forming method comprises spray-drying, granulation, extrudes (optional with mediate combination), become pearl or any other to be used for the conventional forming method in catalyst and absorbent field or its combination.Be used for the amount of liquid that the suspension of moulding exists and be fit to pending specific forming step.Maybe advantageously part is removed liquid used in the suspension and/or is added extra or other liquid, but and/or changes the pH of precursor mixture so that this suspension gelling and therefore be suitable for moulding.The additive that is usually used in different forming methods can be added the precursor mixture that is used for moulding as extruding additive.
The pentasil type zeolite that obtains in the inventive method process is preferably ZSM section bar material, more preferably ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, beta-zeolite or β-borosilicate zeolite, and they are described in U.S. patent 3,308,069; 3,702,886; 3,709,979; 3,832,449; 4,016,245; 4,788,169; 3,941,871; 5,013,537; 4,851,602; 4,564,511; 5,137,706; 4,962,266; 4,329,328; 5,354,719; 5,365,002; 5,064,793; 5,409,685; 5,466,432; 4,968,650; 5,158,757; 5,273,737; 4,935,561; 4,299,808; 4,405,502; 4,363,718; 4,732,747; 4,828,812; 5,466,835; 5,374,747; In 5,354,875.
Can use the example of the composition that the inventive method obtains to be: to comprise the cogelled composition of ZSM-5 and Si-Al, comprise the cogelled composition of beta-zeolite and Si-Al, the composition that comprises ZSM-5 and Mg-Al anionic clay, the composition that comprises beta-zeolite and Mg-Al anionic clay, the composition that comprises ZSM-5 and (vacation) boehmite, the composition that comprises beta-zeolite and (vacation) boehmite, comprise ZSM-5, the composition of Mg-Al anionic clay and (vacation) boehmite, comprise beta-zeolite, the composition of Mg-Al anionic clay and (vacation) boehmite, the composition that comprises ZSM-5 and terre verte comprises the composition of beta-zeolite and terre verte etc.
Above-mentioned composition can contain one or more additives, as phosphorus compound, or metallic compound.Preferred metal is Ce, La, Mn, Fe, Nb, Zn, Cr, Ti, Zr, Cu, Ni, Zn, Mo, W, V, Sn, Pt and Pd.
Said composition preferably contains 5-95 weight %pentasil type zeolite, more preferably 20-80 weight %pentasil type zeolite, even more preferably 40-80 weight %pentasil type zeolite.
Carbon monoxide-olefin polymeric obtained by the method for the present invention can be chosen wantonly by hydrothermal treatment consists (for example to stablize this zeolite), calcine and/or exchange with for example rare earth ion.
Carbon monoxide-olefin polymeric obtained by the method for the present invention can be at 200-1000 ℃, preferred 300-500 ℃ temperature lower calcination.If in carbon monoxide-olefin polymeric, there is an anionic clay, then calcining this anionic clay is changed into solid solution and the spinelle chosen wantonly mutually.This solid solution can change into anionic clay once more by the composition of rehydrated calcining in aqueous slurries.If need, this aqueous slurries can contain the additive of dissolving, for example the salt of metal such as Ce, La, Mn, Fe, Nb, Zn, Cr, Ti, Zr, Cu, Ni, Zn, Mo, W, V, Sn, Pt and Pd.
The gained carbon monoxide-olefin polymeric can be suitably as catalyst or additive in the FCC method.Composition of the present invention is suitable for removing the SO in the flue gas xAnd/or NO x, reduce sulphur in fuel such as gasoline and the diesel oil and nitrogen amount, catch metal, increase olefin(e) centent and reduce the aromatic content etc. of gasoline and light cycle oil.
When being used for the FCC method, the composition that comprises pentasil type zeolite (for example ZSM-5, ZSM-11, beta-zeolite) and anionic clay (for example Mg-Al anionic clay) may cause product to have the aromatics yield of reduction and the olefinicity of increase.
Embodiment
Embodiment 1
With 4.6 weight % aluminum sulfate solutions (2792g) and 30.3 weight %H 2SO 4Solution (441g) adds in 30 liters of autoclaves that stir.In 15 minutes, slowly in this solution, add 2467g waterglass.In reinforced process, form gel.
Prepare seed slurry (300g, 14.1 weight % solids) by mixing commercially available ZSM-5 and water.Grinding this slurry is 0.89 μ m up to the particle mean size of ZSM-5.Under 10 minutes vigorous stirring, this seed slurry is slowly added in aluminum sulfate/waterglass mixture.With the gained slurry 170 ℃ of following hydrothermal treatment consists 4 hours.
Then will be in 10 minutes by mixing 95.7g Catapal TMBoehmite/MgO slurry that the 1500g of (Sasol, 73 weight % solids), 112.4g MgO (Nedgem, 98 weight % solids) and the preparation of 1291.9g water has 12 weight % solids pumps in the autoclave.The gained mixture was heated extra 1 hour down and last spray-drying at 170 ℃.
The PXRD pattern displaying of spray-dired product exists ZSM-5 and hydrotalcite.
Embodiment 2
With 4.6 weight % aluminum sulfate solutions (2792g) and 30.3 weight %H 2SO 4Solution (441g) adds in 30 liters of autoclaves that stir.In 15 minutes, slowly in this solution, add 2467g waterglass.In reinforced process, form gel.
Prepare seed slurry (300g, 14.1 weight % solids) by mixing commercially available ZSM-5 and water.Grinding this slurry is 0.89 μ m up to the particle mean size of ZSM-5.Under 10 minutes vigorous stirring, this seed slurry is slowly added in aluminum sulfate/waterglass mixture.With the gained slurry 170 ℃ of following hydrothermal treatment consists 4 hours.
Then in 10 minutes with aluminium gibbsite (the Alcoa CP-3 of 1500g quick burning ) aqueous slurries (12 weight % solid) pump in the autoclave.The gained mixture was heated extra 1 hour down and last spray-drying at 170 ℃.
The PXRD pattern displaying of spray-dired product exists ZSM-5 and boehmite.

Claims (11)

1. one kind prepares the method for compositions that comprises pentasil type zeolite, and this method comprises the following steps:
A) hydrothermal treatment consists comprises the aqueous slurries of aluminium source, silicon source, seed crystal material and optional divalent metal source, thus form pentasil type zeolite and at least a other compounds and
B) with the product moulding of step a).
2. according to the process of claim 1 wherein that described at least a other compounds are selected from anionic clay, cationic clay, Si-Al is cogelled and (vacation) boehmite.
3. according to each method in the aforementioned claim, wherein pentasil type zeolite is ZSM type zeolite or beta-zeolite.
4. according to each method in the aforementioned claim, wherein the crystal seed of Can Zaing is used as seed crystal material in step a).
5. according to each method in the aforementioned claim, wherein step a) is included in aluminum mixture source in the slurry, silicon source, seed crystal material and divalent metal source, and wherein divalent metal source is the magnesium source.
6. according to the method for claim 6, wherein the magnesium source is selected from MgO, Mg (OH) 2, hydromagnesite, magnesium carbonate, basic magnesium carbonate, magnesium acetate, glycolic acid magnesium and composition thereof.
7. according to each method in the aforementioned claim, wherein the aluminium source is selected from aluminum trihydrate, boehmite, pseudobochmite, aluminium colloidal sol, amorphous alumina, alumina gel, transitional alumina of aluminum trihydrate, quick burning and composition thereof.
8. according to each method in the aforementioned claim, wherein the silicon source is (partially) sodium metasilicate, Ludox or its mixture.
9. according to each method in the aforementioned claim, wherein step a) is carried out at least in a series of two reaction vessels continuously.
10. according to each method in the aforementioned claim, wherein step a) is included in aluminum mixture source in the slurry, silicon source, seed crystal material and divalent metal source, thereby forms pentasil type zeolite and as the anion or the cationic clay of other compounds.
11. according to each method in the aforementioned claim, wherein step a) comprises and mixes silicon source, excessive aluminium source and seed crystal material, thereby forms pentasil type zeolite and as (vacation) boehmites of other compounds.
CNB038205815A 2002-08-28 2003-08-19 Process for the preparation of catalysts comprising a pentasil-type zeolite Expired - Fee Related CN1320960C (en)

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US40644502P 2002-08-28 2002-08-28
US60/406,445 2002-08-28
EP02079412 2002-10-24
EP02079412.9 2002-10-24

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CN1320960C CN1320960C (en) 2007-06-13

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JP (1) JP2005536342A (en)
CN (1) CN1320960C (en)
AU (1) AU2003273799A1 (en)
BR (1) BR0313746A (en)
CA (1) CA2496899A1 (en)
WO (1) WO2004020092A1 (en)

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EP1863588B1 (en) * 2004-12-21 2017-11-01 Albemarle Netherlands B.V. Fcc catalyst, its preparation and use

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CA1136112A (en) * 1979-01-05 1982-11-23 William J. Ball Method for producing aluminosilicates, their use as catalysts and catalytic compositions containing them
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AU2003273799A1 (en) 2004-03-19
BR0313746A (en) 2005-07-19
CN1320960C (en) 2007-06-13

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