CN1223602A - Metal-containing zeolite catalyst, preparation thereof and use for hydrocarbon conversion - Google Patents

Abstract

The invention provides a zeolite bound zeolite catalyst which does not contain significant amounts of non-zeolitic binder and a process for utilizing the zeolite bound zeolite catalyst to convert hydrocarbons. The catalyst comprises first zeolite crystals, a binder comprising second zeolite crystals and a hydrogenation/dehydrogenation metal. The zeolite bound zeolite catalyst is prepared by converting the silica binder of a silica bound aggregate containing the first crystals of said first zeolite and at least a portion of the hydrogenation/dehydrogenation metal to said second zeolite. The zeolite bound zeolite catalyst has excellent performance when used in hydrocarbon conversion processes such as naphtha reforming and xylenes isomerization/ethylbenzene conversion.

Description

Metallic zeolite catalyst, its preparation method and the application in hydrocarbon transforms thereof

Invention field

The present invention relates to improve the preparation method through a kind of zeolite catalyst of zeolite agglutinating of hydrogenation/dehydrogenation metal dispersion, this catalyst themselves, and the application of this catalyzer in hydrocarbon conversion process.

Background of invention

No matter the crystalline microporous molecular sieve is natural or synthetic, all has been proved to be various types of hydrocarbon conversion process are had catalytic performance.In addition, these crystalline microporous molecular sieves also have been used as sorbent material, the support of the catalyst in various types of hydrocarbon conversion process, and some other purposes.These molecular sieves are orderly, porous, measure the crystalline material with clear and definite crystalline structure through X-ray diffraction, and a large amount of less cavitys is contained in its inside, and these cavitys can be interconnected by a large amount of littler passage or holes.The size in these passages or hole is allowed the molecule of some size and is forbidden that large-sized molecule adsorbs.These by the formed clearance space of crystalline network or passage make such as the molecular sieve of crystalline silicate, crystal aluminosilicate, crystalline silicoaluminophosphate salt and crystalline aluminium phosphoric acid salt in sepn process with can serve as sieving and the effect of support of the catalyst of molecule widely in the hydrocarbon conversion process respectively.

Zeolite is made up of silicon oxide and nonessential being combined with such as the lattice of tradable cationic, oxidized aluminium such as basic metal or alkaline-earth metal ions.Though comprise the material of silicon oxide-containing and nonessential aluminum oxide in the definition of " zeolites ", be to be appreciated that silicon oxide and aluminum oxide part can be completely or partially with other oxide compound replacement.Such as replacing the silicon oxide part with germanium oxide, stannic oxide, phosphorus oxide and composition thereof.Can replace the aluminum oxide part with boron oxide, ferric oxide, titanium oxide, gallium oxide, Indium sesquioxide and composition thereof.And, here used " zeolite ", " zeolites " and terms such as " zeolitic materials " not only are meant the material of silicon atoms in its crystal lattices and nonessential aluminium atom, also refer to contain the material of the replacement atom of suitable silicon and aluminium, such as aluminosilicophosphate (SAPO) and aluminate or phosphate (ALPO).Terminology used here " aluminosilicate zeolites " is meant in its crystalline network it mainly is the zeolitic material of Siliciumatom and aluminium atom.

Zeolite (as the ZSM-5) past that is combined with group VIII metal has been used as catalyzer in hydrocarbon conversion process.Such as, USP3, disclose in 856,872 a kind of preferably contain a kind of binding agent (as aluminum oxide) through dipping or ion-exchange and the zeolite of load platinum.Through dipping or ion-exchange and the problem that the zeolite catalyst of load platinum is followed is that metal can not disperse well.If metal is the dispersive words well, then the selectivity of zeolite catalyst, activity and/or active reservation may affect adversely.

USP4 discloses another kind of method at load platinum on the zeolite of alumina bound in 312,790.This method is after zeolite crystallization but before roasting precious metal is added in the zeolite.The catalyzer prepared by this method is not applied in commerce, because as USP4, reported in 683,214, makes to have caused relatively poor platinum to disperse in this way and the catalyzer of bigger platinum crystal grain.

Synthetic zeolite normally becomes zeolite to prepare a kind of oversaturated synthetic mixture crystallization.Then with resulting crystallized product through super-dry and roasting so that make a kind of zeolite powder.Though this zeolite powder has absorption property preferably, its practical application is subjected to strict restriction, operates because zeolite powder is difficult in the fixed bed.Therefore, business process bonds these zeolite crystals before using this powder usually.

Usually zeolite powder is bonded to the zeolite aggregate of a kind of sheet, spherical or extrudate shape.Extrudate normally pushes zeolite and drying and the resulting extrudate of roasting and forms in the presence of the nonzeolite binding agent.Used matrix material ability temperature and other condition, such as, the normal mechanical wear that takes place in various hydrocarbon conversion process.The example of matrix material comprises amorphous material, as aluminum oxide, silicon oxide, titanium oxide and various clay.Usually require zeolite ability mechanical wear, promptly form small particle powder, such as the particle that is lower than 20 microns sizes.

Though this have physical strength preferably through agglutinating zeolite aggregate than zeolite powder, when this when the agglutinating zeolite uses in catalytic conversion process, the performance of zeolite catalyst, such as activity, selectivity, the active reservation, or their combination meeting reduces because of the existence of binding agent.Such as, because the content of binding agent reaches about 50wt.% of zeolite consumption usually, binding agent has diluted the absorption property of zeolite aggregate.And, owing to normally prepare by zeolite and the dry and roasting extrudate that extruding or other method moulding contain binding agent through the agglutinating zeolite, unformed binding agent may enter in the hole of zeolite or block the inlet of zeolite pore, or the rate of mass transfer of the zeolite pore that slows down, thereby will lower the efficient of zeolite when being used for xylene isomerization.And when when the agglutinating zeolite is used in the catalytic conversion process, binding agent may influence the chemical reaction that carries out in the zeolite, and himself also may catalysis those do not wish the reaction carried out, generate and do not wish the product that obtains.

Relate in the hydrocarbon conversion process of hydrogenation and dehydrogenation reaction at some, wish that usually employed zeolite catalyst becomes aromatic hydrocarbons to metal catalysed reaction such as paraffin conversion in this process, the generation effect.For catalyzer is worked to the reaction of metal catalytic, need usually a kind of metal with catalytic activity is added in the catalyzer.Must be with this metal homodisperse with catalytic activity.If this metal disperses uneven words, will have a negative impact to activity of such catalysts, selectivity and/or active the reservation.

Therefore, wish to be prepared into hydrogenation/dehydrogenation metal homodisperse and do not contain the zeolite catalyst of obvious amount nonzeolite binding agent.

Summary of the invention

Provide a kind of among the present invention through zeolite agglutinating zeolite catalyst and this preparation method through zeolite agglutinating zeolite catalyst.This kind catalyzer comprises first kind of crystal of first kind of zeolite, a kind of second kind of crystalline binding agent that contains second kind of zeolite, and a kind of hydrogenation/dehydrogenation metal.This method is also to contain first kind of crystal of first kind of zeolite and the silica binder in silicon oxide agglutinating extrudate of hydrogenation/dehydrogenation metal changes into second kind of zeolite with a kind of.

The present invention provides in another program and used this method of coming the convert hydrocarbons raw material through zeolite agglutinating zeolite catalyst in the process of using hydrogenation/dehydrogenation metal (such as group VIII metal) or anabolic process.The example of these processes comprises that hydrogenation, dehydrogenation, dehydrocyclization, isomerization, cracking, dewaxing, reformation, alkylaromatic hydrocarbon conversion, oxidation, synthetic gas conversion, carbonylation, dimerization, polymerization and alcohol transform.

In the time of in being used in, have the very high hydrogenation/dehydrogenation activity that can generate desirable product, in these processes, show undesirable less cracking activity simultaneously through zeolite agglutinating zeolite catalyst such as processes such as naphtha reforming and xylene isomerizations.

Brief Description Of Drawings Fig. 1 is the electron microscopic picture of the catalyzer for preparing in embodiment 1. I.Fig. 2 is the electron microscopic picture of the catalyzer for preparing in embodiment 1. II.

Detailed description of the Invention

Comprise the first crystal of the first zeolite, a kind of binding agent that contains the second crystal of the second zeolite, and a kind of hydrogenation/dehydrogenation metal through the zeolite catalyst of zeolite bonding. Prepare thisly in the zeolite catalyst process of zeolite bonding, before silica binder is changed into the second zeolite, first the hydrogenation/dehydrogenation metal is added in the extrudate of silica bonding. Resulting zeolite catalyst through the zeolite bonding has improved the dispersive property of hydrogenation/dehydrogenation metal. In addition, adopt the second crystal of the second zeolite to cause a kind of catalyst as binding agent, this catalyst provides on a kind of outer surface that is controlled at the first zeolite crystal or near the method for the undesirable reaction of generation, and can improve hydrocarbon molecule to and from the mass transfer in the hole of the first zeolite.

Not as the zeolite catalyst that usually bonds to strengthen the mechanical strength of zeolite through silica or aluminium oxide or other unformed binding agent commonly used that is used for hydrocarbon conversion process, the zeolite catalyst among the present invention does not contain the nonzeolite binding agent of significant quantity usually. Preferably, this in the zeolite catalyst of zeolite bonding the content of nonzeolite binding agent be lower than the 10wt. % of the first zeolite and the second zeolite total amount, be more preferably and be lower than 5wt.%, most preferably be to be substantially free of the nonzeolite binding agent in the catalyst. Preferably, the second zeolite crystal is by being bonded to the surface of the first zeolite, thereby forms a kind of matrix that the first zeolite crystal particle is fixed together or bridge construction the first zeolite crystal that bonds. More preferably, so that form one deck coating or local coating the first zeolite that bonds outside the first zeolite crystal of larger particles, and most preferably to be the second zeolite crystal form the wear-resisting attached growth of crystal the first zeolite crystal that bonds by crystal stock between crystal at the first zeolite crystal to the second zeolite by crystal stock between crystal.

Although the present invention does not attempt to be confined to any theory of operation, but believe that except improving metal disperses another advantage through the zeolite catalyst of zeolite bonding among the present invention is that the second zeolite crystal can be controlled the acid site of the first zeolite crystal outer surface for the accessibility of reactant. Because the acid site that is present in the zeolite catalyst outer surface does not have shape selectivity, these acid sites may be left in the hole of zeolite for the hole neutralized reaction product that reactant enters zeolite and produce negative effect. Briefly, owing to can select carefully acidity and the structure type of the second zeolite, the second zeolite not only can not produce to the hole that reactant leaves the first zeolite significant negative effect (this negative effect may occur for the zeolite catalyst through the generality bonding), but also may produce favorable influence to the hole that reactant leave the first zeolite. Have again, because the second zeolite is not unformed but a kind of molecular sieve, in hydrocarbon conversion process, can make hydrocarbon more easily reach the hole of the first zeolite. No matter be theoretical supposition, when being used for catalytic process, the zeolite catalyst of zeolite bonding will have the improvement on one or more performances disclosed herein.

Employed term " acidity ", " lower acidity " and " higher acidity " are well-known for the people who is familiar with this field in the zeolite.The acidity of zeolite is well-known.Yet, must be distinguished strength of acid and acid site density for the present invention.The acid site of zeolite can be Bronsted acid or Lewis acid.Acid site density and acid site number the decision zeolite acid the time very important.The factor that directly influences strength of acid is the chemical constitution of (ⅰ) zeolite framework, relative concentration and type such as the tetrahedron atom, (ⅱ) the outer species of the concentration of skeleton outer cationic and formed skeleton, (ⅲ) local structure of zeolite, such as in the crystal of zeolite or the hole size of surface/near surface and position, and (ⅳ) existence of pretreatment condition and co-adsorption molecule.The acid amount is relevant with the degree of isomorphous substitution, yet this acidity is confined to the loss in acid site for the pure silica component.Here employed term " acidity ", " lower acidity " and " higher acidity " refer to the concentration in the acid site of being measured by ammonia absorption and do not consider the intensity in these acid sites.

Be suitable in the present invention in zeolite agglutinating zeolite catalyst, use first kind and second kind of zeolite and comprise large pore zeolite, mesopore zeolite and pore zeolite.These zeolites are at " Atlas ofZeolite Structure Types ", editor W.H.Meier and D.H.Olson, and Butterworth-Heineman publishes, and the third edition had description in 1992, quoted here and was used as reference.The hole of large pore zeolite comprises the zeolite (IUPAC zeolite NK) of LTL, VFI, MAZ, MEI, FAU, EMT, OFF, BEA and MOR structure type usually greater than 7 .The example of large pore zeolite comprises mazzite, mordenite, offretite, L-zeolite, VPI-5, Y-zeolite, X-zeolite, Ω-zeolite, beta-zeolite, ZSM-3, ZSM-4, ZSM-18 and ZSM-20.The hole size of mesopore zeolite is about 5 -7 usually, comprises the zeolite (IUPAC zeolite NK) of MFS, MFS, MEL, MTW, EUO, MTT, HEU, FER and TON structure type.The example of mesopore zeolite comprises ZSM-5, ZSM-12, ZSM-22, ZSM-23, ZSM-34, ZSM-35, ZSM-38, ZSM-48, ZSM-50, silicite and silicite 2.The hole size of pore zeolite is about 3 -5 usually, comprises the zeolite (IUPAC zeolite NK) of CHA, ERI, KFI, LEV and LTA structure type.The example of pore zeolite comprises ZK-4, SAPO-24, SAPO-35, ZK-14, SAPO-42, ZK-21, ZK-22, ZK-5, ZK-20, A-zeolite, erionite, chabazite, T-zeolite, gemlinite, ALPO-17 and clinoptilolite.

Usually, first kind of zeolite and the second kind of zeolite through zeolite agglutinating zeolite catalyst comprises the composition with following molar relationship:

X ₂O ₃: (n) YO ₂Wherein X is a kind of trivalent element, and such as titanium, boron, aluminium, iron and/or gallium, Y is a kind of quadrivalent element, and such as silicon, tin and/or germanium, it is 1 value at least that n is one, and said value depends on the trivalent element that exists in the particular type of zeolite and the zeolite.

When any zeolite is mesopore, comprise composition usually in the zeolite with following molar relationship:

X ₂O ₃: (n) YO ₂Wherein X is a kind of trivalent element, and such as aluminium, boron, titanium and/or gallium, Y is a kind of quadrivalent element, such as silicon, tin and/or germanium; N be one greater than 10 numerical value, said value depends on the trivalent element that exists in the particular type of zeolite and the zeolite.When first kind or second kind of zeolite had the MFI structure, n was preferably greater than 10.

As be familiar with this area the people understood, can adopt the many kinds of technology (such as dealuminzation and steam treatment) to reduce the acidity of zeolite.In addition, the acidity of zeolite depends on that the form of this zeolite, h-type zeolite have the highest acidity and the zeolite (such as the sodium type) of other form has the acidity lower than acid type zeolite.And the silicon oxide that disclosed herein is: aluminum oxide and silicon oxide: the mol ratio of gallium oxide not only comprises the zeolite that discloses mol ratio, also comprises the zeolite that does not disclose mol ratio but have catalytic activity of equal value simultaneously.

When silicic acid gallium zeolite that first kind of zeolite is a kind of mesopore, this kind zeolite comprises the composition with following molar relationship usually:

Ga ₂O ₃: ySiO ₂Wherein the about 10-of y about 1000.Can only contain gallium and Siliciumatom in the zeolite framework or also can contain a kind of combination of gallium, aluminium and silicon.When silicic acid gallium zeolite that first kind of zeolite is a kind of MFI structure type, second kind of zeolite be a kind of silicon oxide preferably: the gallium oxide mol ratio is greater than 100 mesopore zeolite.Second kind of zeolite also can have higher silicon oxide: the gallium oxide mol ratio, and such as greater than 200,500,1000 or the like.

When first kind of zeolite in zeolite agglutinating zeolite catalyst is a kind of aluminosilicate zeolites, its silicon oxide: alumina molar ratio depends on the structure type and the applied particular hydrocarbon process of catalyzer of first kind of zeolite usually, therefore is not limited to any specific ratio.Yet, depending on the structure type of zeolite, the silicon oxide of common first kind of zeolite: alumina molar ratio is 2: 1 at least, is 4 in some cases: about 7: 1 of 1-.For many zeolites, silicon oxide: alumina molar ratio is about 10: between about 1000: 1 scope of 1-.Using such as catalyzer at some is to be used for acid catalyzed reaction, isomerization such as the raw material that contains dimethylbenzene and ethylbenzene, first kind of zeolite will be tart, and when mesopore zeolite (especially a kind of) preferably has higher silicon oxide: alumina molar ratio, and such as 70: about 700: 1 of 1-.If catalyzer is to be used for not wishing to be the hydrocarbon conversion process of acid catalyzed reaction, when reforming such as the L-zeolite, first kind of zeolite will preferably have lower acid activity, and more preferably will have very little or do not have acid activity.For the process of these types, can adopt high oxidation silicon: alumina molar ratio is that well-known technology reduces acid activity by ion-exchange or other for the people who is familiar with this area.

The structure type of first kind of zeolite will depend on the applied specific hydrocarbon process of zeolitic catalyst system.Such as, if catalyzer is that being used for naphtha reforming is aromatic hydrocarbons, zeolite type is LTL (example is the L-zeolite) preferably.If first kind of zeolite is to be used for xylene isomerization, first kind of preferably a kind of mesopore zeolite of zeolite then is such as MFI structure type (example has ZSM-5).If catalyzer is to be used for the cracking paraffinic hydrocarbons, then preferred hole size and structure type will depend on cleaved bulk of molecule and the desired product that obtains.For hydrocarbon conversion process choice structure type is well-known for the people who is familiar with this area.

When first kind of zeolite was a kind of LTL structure type, zeolite was preferably a kind of by the following aluminosilicate zeolites of forming (mol ratio with the anhydrous oxide component is represented):

(0.9-1.3) M _2/nO: Al ₂O ₃: xSiO ₂Wherein M is the positively charged ion of n valency, and x is 4-7.5, preferably 5-7.5.

When being when being used to contain the isomerization of alkylaromatic hydrocarbon raw material through zeolite agglutinating zeolite catalyst, first kind of preferably a kind of aluminosilicate zeolites of zeolite or a kind of silicic acid gallium zeolite, and the silicon oxide of zeolite: alumina molar ratio is 70: 1-700: 1 or silicon oxide: the gallium oxide mol ratio is 24-500.

Terminology used here " mean particle size " refers to crystal diameter distribution arithmetical av by volume.

About 15 microns of the preferably about 0.1-of the crystalline mean particle size of first kind of zeolite.In some applications, mean particle size preferably is at least about 6 microns of about 1-.In other application (such as the hydrocarbon pyrolysis), preferred mean particle size is littler, and 0.1-is about 3.0 microns according to appointment.

The structure type of second kind of zeolite can be identical or different with first kind of zeolite.The structure type of second kind of zeolite depends on the application through zeolite agglutinating zeolite catalyst.Such as, if catalyst system is as a kind of dual-function catalyst, can select and make first kind of zeolite and second kind of zeolite so that carry out desired response.

When second kind of zeolite is aluminosilicate zeolites, the silicon oxide of second kind of zeolite: alumina molar ratio will depend on the structure and the applied particular hydrocarbon process of catalyzer of second kind of zeolite usually, thereby not limit to any specific ratio.Yet, depend on the structure type of zeolite, usually silicon oxide: alumina molar ratio be at least 2: 1 to＞1000.In some applications, it is less acid or even almost do not have acidity to wish that second kind of zeolite has.When zeolite was a kind of mesopore zeolite (such as ZSM-5), the silicon oxide of second kind of zeolite: alumina molar ratio was generally 200: 1 or is bigger in these are used, such as 300: 1,500: 1,1000: 1 or the like.In some applications, second kind of zeolite will be a kind of silicite, promptly a kind of salic hardly MFI structure type, or silicite 2 are a kind of salic hardly MEL structure type.The hole size of second kind of zeolite does not preferably stop the molecule of desirable hydrocarbon feed to lead to the hole of first kind of zeolite.Such as, in the time will being 5 -6.8 by the size of the raw material of first kind of zeolite conversion, second kind of zeolite preferably will be a kind of large pore zeolite or a kind of mesopore zeolite.Second kind of zeolite content in catalyst system usually is the 10-60wt.% of first kind of zeolite.The content of second kind of zeolite depends on the applied hydrocarbon process of catalyzer usually.More preferably, the content of second kind of zeolite is about 20-50wt.%.

The granular size of common second kind of zeolite crystal is littler than first kind of zeolite granular, and its mean particle size is preferably less than 1 micron, such as, about 0.1-0.5 micron.First kind of zeolite crystal of second kind of zeolite crystal bonding and preferably at crystal stock between crystal and form a kind of be coated in or part is coated in attached growth on first kind of zeolite.Preferably, this coating is wear-resistant.

Contain the hydrogenation/dehydrogenation metal through zeolite agglutinating zeolite catalyst.Mention that one or more hydrogenation/dehydrogenation metals are intended to comprise metal or some other catalytic activity forms of this or these several element state (being zeroth order), such as oxide compound, sulfide, halogenide, carboxylate salt and so on.These metals are well-known for the people who is familiar with this area, comprise such as, III A in one or more metals and the periodic table of elements, IV A, V A, VI A, VII A, VIII, I B, II B, III B, IV B, and V B family metal.Suitable metal example comprises VIII family metal (such as Pt, Pd, Ir, Rh, Os, Ru, Ni, Co and Fe), IV A family metal (such as Sn and Pb), V B family metal (such as Sb and Bi), and VII B family metal (such as Mn, Tc and Re).Precious metal (such as Pt, Pd, Ir, Rh, Os and Ru) is preferred metal sometimes.

The content of the metal significant quantity of about 0.001-10wt.% usually is preferably 0.05-3.0wt.% in zeolite agglutinating zeolite catalyst.Metal content changes with the character of metal, and high activity metal content is less than low activity metal (particularly Pt).

This kind of preparation contain the hydrogenation/dehydrogenation metal during zeolite agglutinating zeolite catalyst, metal just has been present in through the silicon oxide agglutinating before silica binder being changed into second kind of zeolite and has contained in the aggregate of first kind of zeolite.Can metal be added in silicon oxide agglutinating aggregate in any stage before silica binder being changed into second kind of zeolite, such as before forming through silicon oxide agglutinating aggregate, during or afterwards.

Such as, preferably can adopt following steps to prepare through zeolite agglutinating zeolite catalyst: 1. adopt first kind of zeolite of well-known program preparation.2. form the pressurizing medium of a kind of silicon oxide-containing and first kind of zeolite.3. it is a kind of through silicon oxide agglutinating aggregate to form to push this material.4. roasting is this through silicon oxide agglutinating aggregate.5. in a kind of suitable aqueous solution, wear out through silicon oxide agglutinating aggregate this.6. by aging this silica binder in silicon oxide agglutinating aggregate is changed into second kind of zeolite.

Can be before step 6 whenever, such as during step 1-5, metal is added this in silicon oxide agglutinating aggregate.Such as, can be before step 2 beginning by metal and first kind of zeolite cocrystallization or adopt as ion-exchange or impregnating technology with metal load on first kind of zeolite with in first kind of zeolite of metal adding.Also can or through between silicon oxide agglutinating aggregate aging time, metal added during pressurizing medium forms, after silicon oxide agglutinating aggregate forms, before the roasting, after the roasting.In a kind of preferred version, but be during step 2, to add metal in the pressurizing medium by metal is included in.After silica binder changed into second kind of zeolite, metal may be present in the surface of any one or two kinds of zeolites, also may reside in the crystal of any one or two kinds of zeolites in the matrix.

At least have a kind of in the following advantage by the prepared catalyzer of the method among the present invention: improve the dispersiveness of metal, reduce cracking activity and keep high hydrogenation/dehydrogenation activity simultaneously, or theirs is comprehensive.

This contain the hydrogenation/dehydrogenation metal preferably adopt a kind of three step procedure to prepare through zeolite agglutinating zeolite catalyst.The first step relates to first kind of zeolite synthetic of mesopore size.First kind of prepare zeolite method is well-known for the people who is familiar with this area.Such as, with regard to aluminosilicate zeolites or silicic acid with MFI structure type are sowed prepare zeolite, a kind of method comprises a kind of oxyhydroxide of tetrapropyl ammonium or solution of bromide, alkalimetal oxide, a kind of aluminum oxide or a kind of gallium oxide, a kind of silicon oxide and water of containing of preparation, reaction mixture is heated to 80-200 ℃ temperature in about 4 hours-8 days time.The crystal grain that resultant gel formation is solid-state separates it with reaction medium, wash with water and drying.With product under 400-550 ℃ in air roasting 10-40 hour time so that remove tetrapropyl ammonium (TPA) positively charged ion.

In second step, by with a kind of first kind of zeolite crystal, a kind of silicon gel or colloidal sol, water and hydrogenation/dehydrogenation metal or a kind of compound that contains these metals of containing, and the mixture of a kind of extrusion aid of selectivity mixes, and prepares through silicon oxide agglutinating zeolite up to forming a kind of mashed prod that can push uniformly.Be used for preparing this through silicon oxide agglutinating zeolite aggregate preferably a kind of silicon sol of silicon oxide and can contain the trivalent element of various amounts, such as aluminium or gallium.The consumption of silicon oxide is to make content at the dried extrudate mesolite in this stage between the scope of about 40-90wt.%, is more preferably about 50-80wt.%, and all the other materials mainly are silicon oxide, such as the silicon oxide of about 20-50wt.%.

Then with made mashed prod moulding, such as extruding and be cut into little, such as the extrusion of general 2 mm dias, with its 100-150 ℃ dry 4-12 hour down, under about 400-550 ℃ temperature in air the about 1-10 of roasting hour then.

Thisly not necessarily make very little particle through silicon oxide agglutinating aggregate, this small-particle is applied in fluid process (such as catalytic cracking).Preferably but this relates to zeolite and a kind of silicon oxide and the metal that contains matrix solution being mixed so that form and a kind ofly sprayablely is dried to little fluidizing through the zeolite of silicon oxide agglutinating aggregate particle and the aqueous solution of silica binder.The preparation procedure of this aggregate particle is well-known for the people who is familiar with this area.Scherzer described an example (Octane-Enhancing Zeolitic FCC Catalysts, Julius Scherzer, Marcel Dekker, Inc.New York, 1990) of this program.That crosses as described above is the same through silicon oxide agglutinating extrudate, but then this fluidizing is carried out following described final step so that silica binder is changed into second kind of zeolite through silicon oxide agglutinating aggregate particle.

Final step in this three step method for preparing catalyst is to change into second kind of zeolite that first kind of zeolite crystal bonded together with being present in this silicon oxide in silicon oxide agglutinating zeolite.

In order to prepare second kind of zeolite, at first will be through silicon oxide agglutinating aggregate in a kind of suitable aqueous solution, wearing out under the high temperature.Secondly selective aggregation body carries out the composition of aged solution and temperature so that unformed silica binder is changed into the desired second kind of zeolite that obtains.The new second kind of zeolite that forms is crystal.These crystal can and/or be bonded on first kind of zeolite crystal in growth on first kind of zeolite crystal, also can form new crystal stock crystal, and they are more much smaller than first kind of zeolite crystal usually, such as sub-micron.The crystal of these new formation can be grown together and be connected each other.

Silicon oxide to second time of zeolite in synthetic the conversion character of formed zeolite with the composition and synthetic aging condition different and different of the resulting solution second time.Preferably a kind of aquo ion solution that is enough to silicon oxide is changed into the hydroxyl ion source of desirable zeolite that contains of the resulting solution second time.Yet it also is very important that the composition of this aged solution will can not cause in agglutinating zeolite extrudate existing silicon oxide to dissolve from this kind extrudate.

In the preferred version in the present invention, thisly will carry out the aqueous solion of aged through silicon oxide agglutinating aggregate and contain a kind of hydroxyl ion source (preferably sodium hydroxide).When preparing a kind of zeolite of MFI structure type, OH: the initial molar ratio of silicon oxide preferably is to be no more than about 1.2 level at least, is more preferably about 0.05-1.2, most preferably is about 0.07-0.15.This processing makes the silica binder major part change into the zeolite of MFI structure type, but because silicon oxide: aluminum oxide is than suitable height and acidity is lower.Also comprise a kind of template (such as the tetraalkyl ammonium ion source that is used for MFI structure type zeolite synthesis) in this kind solution, and not necessarily comprise a kind of alumina source and a kind of Na ion source.Therefore control the silicon oxide of the binding agent that is transformed by the composition of the control aqueous solution: the aluminum oxide ratio.

The pH value of this aged solution is not that alkalescence is too strong also very important.When a kind of zeolite agglutinating zeolite through the MFI structure type of preparation, this can be by using a kind of initial OH: the silicon oxide mol ratio realizes as the solution of 0.05-1.2.Usually, preferred ratio is 0.07-0.15.Zeolite extrudate wearing out in aged solution preferably at high temperature carried out, and common temperature range is about 95-200 ℃, is more preferably about 130-170 ℃, most preferably is about 145-155 ℃.The about 20-140 of digestion time scope hour, be more preferably 60-140 hour, be most preferably 70-80 hour.After aging, separate from solution through zeolite agglutinating zeolite, wash, drying and roasting this.

Can resemble and first and second kinds of zeolites in the zeolite catalyst among the present invention be carried out further ion-exchange well known in the art, at least replace part primary basic metal in the zeolite with different positively charged ion (such as the ion in the 1B-VIII family in the periodic table of elements), by form acid stronger form with intermediate ammonium ion exchange basic metal, then prepare the tart h-type zeolite by roasting ammonium type zeolite.This acid type zeolite adopts a kind of suitable acid reagent (such as ammonium nitrate) to prepare by ion-exchange at an easy rate.Then with this zeolite catalyst 400-550 ℃ roasting temperature 10-45 hour so that remove deammoniation and form the tart hydrogen type catalyst.Preferably after forming, zeolite catalyst carries out ion-exchange.

Can be used for processing hydrocarbon feed through zeolite agglutinating zeolite catalyst among the present invention.The hydrocarbon feed carbon compound and the difference of may originating such as oil component, recycle stock component, coking oil, and may be any carbonaceous fluids that carries out the zeolite catalysis reaction easily usually.Depend on the type that hydrocarbon is processed, can containing metal in the raw material or containing metal not.Also can contain in the raw material or high or low impurity nitrogen or sulphur.

Can carry out the conversion of hydrocarbon feed with any mode easily, such as fluidized-bed, or fixed-bed reactor, this depends on desirable processing type.

Thisly can be used as many organism through zeolite agglutinating zeolite catalyst, catalyzer such as the hydrocarbon compound conversion process, comprise conversion, oxidation, reformation, synthetic gas conversion, carbonylation, dimerization, the polymerization of hydrogenation, dehydrogenation, dehydrocyclization, isomerization, hydrocracking, dewaxing, reformation, alkylaromatic hydrocarbon, alcohol conversion etc.

The catalyticing conversioning condition of raw material hydrogenation such as alkene, diolefine, polyene hydrocarbon, alkynes, cycloolefin, aromatic hydrocarbons, oxygenatedchemicals comprises about 0-1000 °F, temperature between preferred about 80-900, about 10-1000psia, pressure between preferred about 20-200psia, about 0.1-20, hydrogen/material molar ratio between preferred about 4-12, and about 0.1-20, the LHSV between preferably about 0.5-4.

Become corresponding alkene or ethylbenzene conversion to become processes such as vinylbenzene for resembling paraffin conversion, not necessarily have steam or such as rare gas elementes such as nitrogen under, dehydrogenation condition comprises about 400-1800 °F, temperature between preferred about 650-1000, about 10000-1500psia, raw material dividing potential drop between preferred about 2-20psia, and about 0.1-100, the LHSV between preferably about 0.5-4.

For become aromatic hydrocarbons (changing into ethylbenzene or dimethylbenzene) such as paraffin conversion such as octane, the dehydrocyclization condition comprises about 400-1800 °F, temperature between preferred about 600-1100, about 1-1500psia, raw material dividing potential drop between preferred about 2-20psia, and about 0.1-100, the LHSV between preferably about 0.5-4.

No matter have hydrogen still not have hydrogen, the straight-chain paraffin isomerization is at about 212-50 °F, the temperature between preferably about 400-900, and about 0.01-20, the LHSV between preferably about 0.25-5, and 0-5: the hydrogen between 1: hydrocarbon than under carries out.

For cracking, no matter do not have hydrogen and still do not have hydrogen, catalyticing conversioning condition comprises the temperature between about 1200-100, the pressure between about 25-2500psia, the hydrogen between about 0-80: material molar ratio, and the LHSV between about 0.1-10.

Catalyzer among the present invention also can be used for the dewaxing operation.Equally, the present invention can be used in the reforming catalyst or as the part of reforming catalyst.Dewaxing and reform and to carry out under the following conditions, to comprise about 500-1100, the temperature between preferably about 800-950, the pressure between about 1.5-1470psia, and about 0.01-100, the WHSV. between preferably about 0.1-10 there being hydrogen still not have under the hydrogen

Therefore, enumerated the special applications of some hydrocarbon conversion process below: (A) the feed naphtha catalytic cracking prepares light olefin.The example of reaction conditions comprises the temperature between about 500-750 ℃, is lower than normal atmosphere or normal atmosphere, usually to about 10 normal atmosphere (gauge pressure) and about 10 milliseconds of residence time of-10 seconds (volume of catalyzer, feeding rate).(B) the high molecular hydrocarbon catalytic cracking becomes low molecular weight hydrocarbon.The example of catalytic cracking reaction condition comprises the temperature between about 400-700 ℃, the pressure between about 0.1 normal atmosphere (crust)-Yue 30 normal atmosphere, and about 0.1-100 hour ^-1Between weight hourly space velocity (WHSV).(C) isomerization of aromatic hydrocarbons (such as dimethylbenzene) feed composition.The example of this process reaction condition comprises the temperature between about 230-510 ℃, the pressure between about 0.5 normal atmosphere-Yue 50 normal atmosphere, the WHSV between about 0.1-200, and the hydrogen between about 0-100: hydrocarbon mol ratio.(D) heavy oil feedstock, the hydrocracking of ring-type cut and other hydrocracking cut.At least a hydrogenation component that is used for hydrocracking catalyst that contains significant quantity in the zeolite catalyst systems.(E) light paraffins changes into alkene and/or aromatic hydrocarbons.The example of reaction conditions comprises temperature between about 425-760 ℃ and the pressure between about 10-2000psig.(F) light olefin changes into gasoline, the hydrocarbon of distillate and lube range.The example of reaction conditions comprises temperature between about 175-375 ℃ and the pressure between about 100-2000psig.(G) be used for and play that the about hydrocarbon steam upgrading more than 200 ℃ of initial boiling point becomes senior distillate and gasoline boiling range range product or as the two-stage hydrocracking of the raw material of other fuel or chemical process step.First section will be the zeolite catalyst that contains one or more catalytically-active metals (such as group VIII metal), and will react as catalyzer with second kind of zeolite (such as beta-zeolite) that contains one or more catalytic active substances (such as group VIII metal) second section from first section material that comes out.The example of reaction conditions comprises the temperature between about 315-455 ℃, the pressure between about 400-2500psig, about 1000-10, the hydrogen circulation between 000 SCFF/bbl, and the liquid hourly space velocity between about 0.1-10 (LHSV).(H) a kind of at the hydrocracking in the presence of the zeolite agglutinating zeolite catalyst/dewaxing combination process that contains a kind of hydrogenation component and a kind of zeolite (such as beta-zeolite).The example of reaction conditions comprises the temperature between about 350-400 ℃, the pressure between about 1400-1500psig, the LHSV between about 0.4-0.6, and about 3000-5, the hydrogen circulation between 000 SCFF/bbl.(I) alcohol prepares mixed ether with olefine reaction, such as methyl alcohol and iso-butylene and/or isopentene prepared in reaction methyl tert-butyl ether (MTBE) and/or tert pentyl methyl ether (TAME).The example of reaction conditions comprises the temperature between about 20-200 ℃, the pressure between about 2-200 normal atmosphere, the WHSV between about 0.1-200 hour-1 (gram alkene/hour gram zeolite), and the alcohol/olefin molar ratio between about 0.1/1-5/1.(J) with petroleum naphtha (such as C ₆-C ₁₀) and similar mixture change into high aromatic hydrocarbons mixture.Therefore, by the temperature between about 400-600 ℃ with hydrocarbon feed and zeolite, preferably 480-550 ℃, pressure between normal atmosphere-40 crust, and the contact down of the LHSV between the 0.1-15, can and the hydrocarbon of slight side chain be arranged with straight chain, preferably boiling spread about more than 40 ℃ and the hydrocarbon below 200 ℃ change into the quite high product of octane aromaticity content.(K) with oxygenatedchemicals, such as alcohol such as methyl alcohol, or ether such as dme or its mixture change into the hydrocarbon that comprises alkene and aromatic hydrocarbons.Reaction conditions comprises the temperature between about 275-600 ℃, the pressure between about 0.5-50 normal atmosphere, and the LHSV between about 0.1-100.(L) contain the straight chain of about 2-5 carbon atom and the oligomerisation of branched-chain alkene.The product oligopolymer of this process is the intermediate of heavy alkene, both can be used as the fuel as gasoline or gasoline blend component, also can be used as chemical products.The oligomerisation process is normally passed through the olefin feedstock of gaseous phase and a kind of through the temperature of zeolite agglutinating zeolite between 250-800 ℃, the LHSV between about 0.2-50, and contact is carried out under the pressure between about 0.1-50 normal atmosphere.When liquid starting material is come the oligomerisation raw material with can adopt about temperature below 250 ℃ when zeolite agglutinating zeolite catalyst contacts.Therefore, when olefin feedstock contacts with catalyzer, can adopt about 10-250 ℃ temperature under liquid state.(M) with C ₂Unsaturated hydrocarbons (ethene and/or acetylene) changes into C _6-12Aliphatic aldehyde and said aldehyde changed into corresponding C _6-12Alcohol, acid or ester.(N) conversion of alkylaromatic hydrocarbon becomes benzene such as ethylbenzene dealkylation.(O) contain alkene saturated of 2-20 carbon atom.(P) ethylbenzene isomerization is become dimethylbenzene.The example of conversion condition comprises the temperature between 600-800, the pressure between the 50-500psig, and the LHSV between about 1-10.

Usually, the catalyticing conversioning condition on the zeolite catalyst among the present invention independently or associativity ground comprise temperature between about 100-760 ℃, the pressure between about 0.1 normal atmosphere (crust)-200 normal atmosphere (crust), about 0.08-2,000 hour ^-1Between WHSV.

Though second kind of zeolite crystal in many hydrocarbon conversion process preferably contains lower acidity, second kind of zeolite crystal preferably contains higher acidity in some processes.

Employing is those processes that two or more reactions take place in zeolite catalyst through the application-specific process of zeolite agglutinating zeolite catalyst.To contain two kinds of different zeolites through zeolite agglutinating zeolite catalyst, they are designed separately so that promote or suppress different reactions.Adopt the process of this catalyzer not only to benefit from bigger apparent catalyst activity, bigger zeolite accessibility, and reduce non-selective surface's acidity, also benefit from a kind of catalyst system of making as requested simultaneously.

Be specially adapted to and contain the C of ethylbenzene through zeolite agglutinating zeolite catalyst ₈One or more xylene isomer isomerization in the aroamtic hydrocarbon raw material, thus obtain neighbour near equilibrium concentration, or right-dimethylbenzene, also can transform a considerable amount of ethylbenzene simultaneously.Especially xylene isomerization is used in combination with a kind of sepn process and prepares right-dimethylbenzene.Such as, adopt the method known for this area people, as crystallization, absorption etc., can part is right-dimethylbenzene from a kind of mixed C ₈Reclaim in the aromatic hydrocarbons material.Material with gained reacts under the xylene isomerization condition so that with the neighbour then, and right-dimethylbenzene return near equilibrium concentration.Also wish under the very little situation of xylene loss the ethylbenzene conversion in the raw material simultaneously.Can select the first kind of zeolite in zeolite agglutinating zeolite catalyst and the acidity of second kind of zeolite, so that do not wish the side reaction carried out reducing as far as possible, ethylize and ethylbenzene/ethylbenzene or ethylbenzene/dimethylbenzene transalkylation such as dimethylbenzene, prerequisite get off balance xylene isomerization and ethylbenzene dealkylation.Isomerization process is by carrying out a kind of C8 aromatic hydrocarbons material that contains one or more xylene isomers or ethylbenzene or its mixture under isomerisation conditions with this contact through zeolite agglutinating zeolite catalyst.Catalyzer among the present invention be applicable to saturated in the ethylbenzene dealkylation process formed ethene and have and can reduce the saturated and naphthenic hydrocarbon cracked advantage of aromatic hydrocarbons.

Suitable isomerisation conditions comprises the temperature between 250-600 ℃, and preferably 300-550 ℃, the pressure between about 0.5-50 bar absolute pressure is preferably 10-25 bar absolute pressure, and the WHSV between the 0.1-100, is preferably 0.5-50.The isomerization of vapor phase not necessarily can exist under the 0.1-30.0 mol of hydrogen in every mole of alkylbenzene to be carried out.If use hydrogen, what should contain 0.1-2.0wt.% in the catalyzer is selected from hydrogenation/dehydrogenation component, the especially platinum in the VIII A family in the periodic table of elements, palladium, or nickel.VIII A family metal component is meant these metals and their compound, such as oxide compound or sulfide.

Be particularly suitable for relating to the reaction of aromizing and/or dehydrogenation through zeolite agglutinating zeolite catalyst.Dehydrocyclization and/or isomerization process especially for use in acyclic hydrocarbous, these processes are with the temperature of hydrocarbon at 370-600 ℃, preferred 430-550 ℃ down with through zeolite agglutinating zeolite catalyst (preferably through L-zeolite agglutinating L-zeolite, preferred contain at least 90% as tradable positively charged ions such as alkalimetal ions, and add the metal that a kind of VIII family has dehydrogenation activity at least) contact, so that change into aromatic hydrocarbons to major general's part acyclic hydrocarbous.

Aliphatic hydrocarbon can be the acyclic hydrocarbous of straight or branched, and especially as the paraffinic hydrocarbons of hexane, though also can use the mixture of hydrocarbon, such as the paraffin distillate of the alkane that contains certain limit that has a small amount of other hydrocarbon.Also can use cycloaliphatic hydrocarbon, as methylcyclopentane.In a preferred version, a kind of aromatic hydrocarbons for preparing especially contains hexane in the raw material in the method for benzene.The temperature of catalyzed reaction can be between 370-600 ℃, and preferably 430-550 ℃, and the preferred pressure that uses is higher than normal atmosphere, more than 2000KPa, is more preferably 500-1000KPa.Usually adopt hydrogen when forming aromatic hydrocarbons usually, hydrogen: raw material ratio is preferably less than 10.Following example is illustrated the present invention.

Example 1 is through zeolite agglutinating MFI type silicic acid gallium Preparation of catalysts.I. catalyst A-load platinum between synthesis phase

MFI structure silicic acid gallium crystal prepares according to following program:

The component that is used to prepare	Quality (gram)
		Solution A
Sodium hydroxide sheet (98.6%)	????18.82
		Ga 2O 3(99.999％)	????12.06
Water	????50.08
		Washing water	????189.80
		Solution B
Colloided silica (Ludox HS-40)	????773.06
Solution C
		The bromination tetrapropyl ammonium	????123.73
Water	????425.01
		Washing water	????124.97
		Solution D
		The aqeous suspension that contains the colloidal silicite of 0.0794wt.% crystal seed	?????2.39
Washing water	????100.0

The component of solution A is boiled dissolving until making transparent solution.Then solution A is cooled to room temperature and additional because of boiling the water that loses.

In the glass beaker with one 2 liters of solution B impourings.With in this beaker of solution C impouring and mix.To mix in the solution D impouring beaker and with component in the beaker then.In the stainless steel autoclave with one 2 liters of the component impourings in the beaker.Add in the autoclave with washing water washing beaker and with washings.Solution A is added in the autoclave.Component in the autoclave was mixed about 20 minutes.Make a kind of smooth gel that inclines.The available following pure-oxide mole form of the composition of this gel is represented:

0.45Na ₂O/0.90?TPA?Br/0.125?Ga ₂O ₃/10SiO ₂/147H ₂O

Then, the colloidal silicite crystal seed that adds 1.0wt.ppm is inoculated gel.

Autoclave is put into a baking oven, at 2 hours internal heating to 150 ℃ and under this temperature, kept 48 hours.

Product taken out from autoclave and be divided into 3 parts.Every part is restrained water washings 7 times with about 600.With product 120 ℃ of following dried overnight.Collected product is 333.70 grams.With product roasting 48 hours in air under 475 ℃.The character of product of roasting is as follows:

The pure MFI of XRD

The spherulite of 4 microns sizes of SEM

Ultimate analysis SiO ₂/ Ga ₂O ₃=80

A part of product of roasting is pressed the extrudate of following program formation through 2 millimeters of silicon oxide agglutinating:

The component that is used to prepare	Quality (gram)
		Silicon sol (Nyacol 2034 DI)	????128.59
Silicon gel (aerosil 300)	????12.26
		H 2PtCl 6.6H 2O	????2.47
Water	????35.01
		Washing water	????3.00
Silicic acid gallium MFI crystal	????130.00
		Extrusion aid (Vltra tears)	????0.87

Each component is mixed in a food mixer by above order.After adding extrusion aid and mixing about 7 minutes, obtain a thick and slick mashed prod.Mashed prod is squeezed into 2 millimeters extrudate and at room temperature dry 3 hours.With extrudate be broken into less than 5 millimeters sheet and in a baking oven 120 times dryings 16 hours.With the exsiccant extrudate 490 times roastings 8 hours.

The component through silicon oxide agglutinating extrudate after the roasting is:

Silica binder: 30.1wt.%

MFI:??????????????69.4wt.％

Pt?????????????????0.5wt.％

Change into through zeolite agglutinating zeolite by following program through silicon oxide agglutinating extrudate this:

The component that is used to prepare	Quality (gram)
		Solution A
Sodium hydroxide sheet (98.6%)	????1.36
		Water	????29.08
Washing water	????11.78
		Solution B
The bromination tetrapropyl ammonium	????9.28
		Water	????30.35
Washing water	????22.16

With in the autoclave of one 1 liter of solution A and B impouring and mix.At last, 70.0 grams are added in the autoclave through silicon oxide agglutinating extrudate.The mole of synthetic mixture consists of:

0.48Na ₂O/1.00TPABr/10SiO ₂/149H ₂O

Autoclave is put into a baking oven.Baking oven was heated to 150 ℃ and kept 80 hours from room temperature under this temperature in 2 hours.The product that is obtained is washed 4 times with 1700 ml waters down at 60 ℃.The electric conductivity of last washing water is 49 little Siemens/cm.With this extrudate 120 ℃ of down dry and roastings 16 hours in air under 490 ℃.

Product is as follows through XRD and sem analysis result:

The degree of crystallinity that XRD is good

SEM is surrounded by 4 microns sizes of the littler crystalline of size

Crystal.Do not observe unformed silicon oxide

Ultimate analysis central crystal: SiO ₂/ Ga ₂O ₃=80

Binding agent crystal=silicite

Central crystal=70wt.%

Pt=0.5wt.％

Measuring platinum by a Philips CM12 TEM by transmission electron microscope (TEM) qualitative detection one product sample distributes and the platinum grain size.Fig. 1 has provided the electron microscopic picture of a catalyst A.Image in the picture shows that platinum disperses better.The granular size of most of platinum is the 5-10 nanometer.II. catalyst B-fill load platinum by the hole.

The silicic acid gallium through the MFI of roasting structure type that a part is used for preparing catalyst A by following program forms the extrudate through 2 millimeters of silicon oxide agglutinating:

The component that is used to prepare	Quality (gram)
		Silicic acid gallium MFI crystal	????130.05
Water	????37.70
		Silicon gel (aerosil 300)	????45.26
Silicon sol (NALCOAG 1034A)	????128.57
		Extrusion aid (Vltra tears)	????0.89

Above each component is mixed in a food mixer by above order.After adding extrusion aid and mixing about 14 minutes, obtain a thick and slick mashed prod.Mashed prod is squeezed into 2 millimeters extrudate and at room temperature dry 3 hours.With extrudate 150 ℃ of down roastings 8 hours in air under 510 ℃ then in dry 7 hours.

Consisting of after the roasting through silicon oxide agglutinating extrudate:

MFI:??????????????70.0wt.％

Silica binder: 30.0wt.%

Change into through zeolite agglutinating zeolite by following program through silicon oxide agglutinating extrudate this:

The component that is used to prepare	Quality (gram)
		Solution A
Sodium hydroxide sheet (98.6%)	????2.44
		Water	????51.91
Washing water	????21.08
		Solution B
The bromination tetrapropyl ammonium	????16.56
		Water	????54.20
Washing water	????39.54

With in the stainless steel autoclave of one 300 milliliters of solution A and B impourings and mix.At last, 125.00 grams are added in the autoclave through silicon oxide agglutinating MFI extrudate.The mole of synthetic mixture consists of:

0.48Na ₂O/0.99TPABr/SiO ₂/ 148H ₂O is in this mixture, and silicon oxide is present in the binding agent of extrudate.

Autoclave is put into baking oven under the room temperature, at 2 hours internal heating to 150 ℃ and under this temperature, kept 72 hours.With the product that obtained at 60 ℃ down with 7 parts 2000 milliliters water washings.The electric conductivity of last washing water is 25 little Siemens/cm.With this extrudate 150 ℃ of down dry and roastings 16 hours in air under 500 ℃.

Products therefrom is as follows through X-ray diffraction (XRD) and scanning electron microscope (SEM) analytical results:

The degree of crystallinity that XRD is good

SEM is surrounded by 4 microns sizes of the littler crystalline of size

Crystal.Do not observe unformed silicon oxide

Ultimate analysis central crystal: SiO ₂/ Ga ₂O ₃=80

Binding agent crystal=silicite

Central crystal=70wt.%

Binding agent crystal=30wt.%

The Pt (based on the weight of product) of 0.31wt.% is carried in the catalyzer.This process at first is the ammonium chloride solution exchange of using 1N down at 65 ℃.Will be through the catalyzer with water washing of exchange, drying is then 530 ℃ of following roastings 8 hours.By the Pt (NH of hole fill method with appropriate amount ₃) ₄Cl ₂The aqueous solution comes load platinum.After the load, with the catalyzer drying and 480 ℃ of following roastings 8 hours.

Measuring platinum by a Philips CM12 TEM through transmission electron microscope (TEM) qualitative detection one product sample distributes and the platinum grain size.Fig. 2 has provided the electron microscopic picture of a catalyst B.Image in the picture shows that the granular size of most of platinum is the 10-30 nanometer, and platinum is good not as dispersive in the catalyst A.

Example 2 I. the xylene isomerization of catalyst A-combination/ethylbenzene dealkylation test

Xylene isomerization/ethylbenzene dealkylation test of adopting catalyst A to carry out a series of combination by a kind of raw material that is rich in dimethylbenzene being passed fixed-bed reactor.With catalyst A pre-treatment 2 hours in hydrogen under 850 and 250psig.After temperature is reduced to 700 °F, with catalyzer under 250psig with the prevulcanized of 500ppm hydrogen sulfide to penetrating.Then under different condition, carry out the on-oil test.Condition and the results are shown in the table I in:

The table I
							The experiment number
??1	??2	??3	??4	??5
					Temperature (°F)		750	?750	?750	?795	?750
HC dividing potential drop (inlet)	163	?118	?118	?118		?163
					H 2Dividing potential drop (inlet)		81	?118	?118	?118	?81
WHSV(#/#/Hr)	10	?3.7	?10	?20		?10
					H 2: oil (mol ratio)		0.5	?1.0	?1.0	?1.0	?0.5
On-Oil experiment hour	155	?431	?481	?621		?748
					Raw material EB Wt.%		11.4	?12.6	?12.6	?12.6	?12.6
Raw material dimethylbenzene Wt.%	86.8	?85.3	?85.3	?85.3		?85.3
					Raw material PX Wt.%		2.7	?1.1	?1.1	?1.1	?1.1
The EB% of reaction	73.7	?93.5	?73.0	?74.3		?74.7
					Aromatic ring loss (% of aromatic ring in the raw material)		0.1	? *-0.1	? *-0.1	? *-0.2	? *-0.2
Xylene loss (dimethylbenzene % in the raw material)	2.0	?5.9	?2.3	?2.5		?2.5
					PX during near balance (%) *		103	?101	?101	?98	?100

^*It is believed that negative value is because less gas-chromatography changes.

The EB percentage ratio % of reaction is according to formula: %EB transformation efficiency=100 * (in the raw material in mole number-product of EB the mole number of EB)/(mole number of EB in the raw material) measured; Aromatic ring loss % is according to formula: 100 * (in the raw material in the mole number-product of aromatic hydrocarbons the mole number of aromatic hydrocarbons)/(mole number of aromatic hydrocarbons in the raw material) measure.Xylene loss is according to formula: 100 * (in the raw material in the mole number-product of dimethylbenzene the mole number of dimethylbenzene)/(mole number of dimethylbenzene in the raw material) measure, and the PX during near balance is according to formula: (product P X/Xs-raw material PX/Xs)/(balance PX/Xs-raw material PX/Xs) * 100 are measured.II. the xylene isomerization of catalyst B-combination/ethylbenzene dealkylation test

Xylene isomerization/ethylbenzene dealkylation test of adopting catalyst B to carry out a series of combination by a kind of artificial raw material being passed fixed-bed reactor.Adopt with same program described in the example II with catalyst B pre-treatment and carry out prevulcanized in hydrogen.Then under different condition, carry out the on-oil test.Condition and the results are shown in the table II in:

The table II
							The experiment number
?????1	???2	???3	???4	???5
					Temperature (°F)		????736	?750	?710	?786	?736
HC dividing potential drop (inlet)	????163	?118	?118	?118		?118
					H 2Dividing potential drop (inlet)		????81	?118	?118	?118	?118
WHSV(#/i#/Hr)	????10	?10	?5	?20		?10
					H 2: oil (mol ratio)		????0.5	?1.0	?1.0	?1.0	?0.5
On-Oil experiment hour	????160	?233	?633	?656		?714
					Raw material EB Wt.%		????12.3	?12.6	?12.6	?12.6	?12.6
Raw material dimethylbenzene Wt.%	????85.3	?85.3	?85.3	?85.3		?85.3
					Raw material PX Wt.%		????7.2	?1.1	?1.1	?1.1	?1.1
The EB% of reaction	????72	?78.3	?75.8	?74.0		?69.4
					Aromatic ring loss (% of aromatic ring in the raw material)		????0.1	?1.3	?1.2	?0.6	?1.0
Xylene loss (dimethylbenzene % in the raw material)	????3.3	?4.2	?3.7	?3.4		?2.9
					PX during near balance (%) *		????102	?101	?101	?99	?101

Data show in the table, and under comparable ethylbenzene conversion, loss of the ring of catalyst A and xylene loss are more much lower than catalyst B.Catalyst A and catalyst B are all effective to isomerization of xylenes and conversion ethylbenzene.

Example 3 is through KL-zeolite agglutinating KL-prepare zeolite.I. catalyzer C-is load platinum between synthesis phase

LTL structure aluminosilicate crystal (KL-zeolite) prepares according to following program:

The component that is used to prepare	Quality (gram)
		Solution A
Potassium hydroxide pellets (87.0%)	????176.3
		?Al(OH) 3	????81.7
Water	????873.2
Solution B
		Colloided silica (LudoxHS-40)	????786.9
		Washing water	????104.8

The component of solution A is boiled dissolving until making transparent solution.Then solution A is cooled to room temperature and additional because of boiling the water that loses.

In the stainless steel autoclave with one 2 liters of solution B impourings.Solution A is added in the autoclave.Add in the autoclave with washing water washing beaker and with washings.Component in the autoclave is mixed up to making a kind of slick gel.The available following pure-oxide mole form of the composition of this gel is represented:

2.61K ₂O/1.0Al ₂O ₃/10SiO ₂/158H ₂O

With reinforced autoclave with pressurized with hydrogen to 65psig, does not have then to stir and time in 48 hours, wall temperature is heated to 79 ℃.Then autoclave is stirred under the rotating speed of 20rpm and with wall temperature at 56 hours internal heating to 150 ℃.Stop to stir and under 150 ℃ of temperature, keeping 56 hours.

Product is taken out from autoclave and wash 3 times with the cold mineral water that goes.The PH of washings is 12.3 for the first time, and the PH of washings is 11.7 for the second time, and the PH of last washings is 11.4.With product 150 ℃ of following dried overnight.Collected product is 310 grams.This desciccate of X-ray diffraction (XRD) analysis revealed is pure KL-zeolite.

A part of product of roasting is pressed the extrudate of following program formation through 2 millimeters of silicon oxide agglutinating:

The component that is used to prepare	Quality (gram)
		Silicon sol (Nalcoag 1034A) KL-zeolite crystal	????124.68
Silica hydrogel (Aerosil 200) water	????11.91
		H 2PtCl 6.6H 2O	????2.92
Water	????26.28
		Washing water	????9.72
Aluminosilicate LTL crystal (KL)	????126.2
		Additional water	????3.0
Methocel (Vltra tears extrusion aid)	????0.87

Above each component is mixed in a family expenses mixing tank by above order.After adding extrusion aid, obtain a thick and squeezable dough thing.Mixing time is about 30 minutes altogether.

Dough is squeezed into 2 millimeters extrudate and at room temperature dry 2 hours, then 120 ℃ dry 16 hours down, be broken into 5 millimeters sheet, and roasting 5 hours in 490 ℃ of following air.Collected product of roasting is 139.3 grams.

Consisting of after the roasting through silicon oxide agglutinating extrudate:

KL-zeolite: 69.5wt.%

Silica binder: 29.9wt.%

Pt?????????????????0.6wt.％

Change into through KL-zeolite agglutinating KL-zeolite through silicon oxide agglutinating KL-zeolite extrudate by following program with this:

Potassium aluminate solution prepares (chemical substance weight is by gram) from following component:

Potassium hydroxide pellets, purity 87.3%=8.44

Aluminium hydrate powder, purity 98.5%=6.40

Water=56.65

Aluminum oxide is boiled dissolving up to obtaining transparent solution.This solution is cooled to room temperature and replenishes the water that loses because of boiling.Aluminate solution is quantitatively changed in one 300 milliliters the stainless steel autoclave with 5.92 gram washing water.Then add in the autoclave 50.00 grams contain the 29.9wt.% silica binder through silicon oxide agglutinating extrudate (contain 0.20 in the extrudate and restrain planar water).The prior drying of extrudate is so that remove planar water.After correcting the water-content of extrudate, the consisting of of the mixture in the autoclave:

2.64K ₂O/1.62Al ₂O ₃/10SiO ₂/148H ₂O

Silicon oxide exists as the binding agent in the extrudate in the mixture.

With autoclave at 4.5 hours internal heating to 175 ℃ and under this temperature, kept 65 hours.Through behind this aging time with autoclave opening and collect the product extrudate.

The extrudate that is obtained is washed 2 times with 500 ml waters down at 60 ℃, and then wash with 60 ℃ 250 ml waters.The PH of last washing water is 10.8, and electric conductivity is 321 little Siemens/cm.With this extrudate 120 ℃ of following dried overnight.The product amount of collecting is 55.8 grams.

The product extrudate is as follows through XRD and sem analysis result:

XRD shows and has the L zeolite

SEM shows and has the L zeolite crystal, by new shape

The littler II that crystal bonds of size that becomes. catalyzer D-fills load platinum by the hole.

By following program a part is used for preparing the extrudate of the aluminosilicate through the LTL of roasting structure type (KL-zeolite) formation of catalyzer C through 2 millimeters of silicon oxide agglutinating:

The component that is used to prepare	Quality (gram)
		Silicon sol (Nalcoag 1034A)	????128.2
Silica hydrogel (Aerosil 300)	????12.26
		Water	????37.06
The KL-zeolite crystal	????130.01
		Methocel (HYDROXY PROPYL METHYLCELLULOSE extrusion aid)	????0.88

Each component is mixed in a family expenses mixing tank by above order.Obtain a thick and squeezable dough/pasta after adding extrusion aid.Mixing time is about 18 minutes altogether.

Dough/pasta is squeezed into 2 millimeters extrudate, and at room temperature dry 2 hours, then 120 ℃ dry 16 hours down, be broken into 5 millimeters sheets, roasting 5 hours under 490 ℃ of air then.The product of roasting of collecting is 147.39 grams.

Through consisting of of silicon oxide agglutinating extrudate:

KL-zeolite: 69.95wt.%

Silica binder: 30.05wt.%

Change into through KL-zeolite agglutinating KL-zeolite through silicon oxide agglutinating KL-zeolite extrudate by following program with this:

Potassium aluminate solution prepares (chemical substance weight is by gram) by following program:

Potassium hydroxide pellets, purity 87.3%=9.25

Aluminium hydrate powder, purity 98.5%=6.43

Water=56.99

Aluminum oxide is boiled dissolving up to obtaining transparent solution.This solution is cooled to room temperature and replenishes the water that loses because of boiling.Aluminate solution is quantitatively changed in one 300 milliliters the stainless steel autoclave with 5.94 gram washing water.Then add in the autoclave 50.00 grams contain the 30wt.% silica binder through silicon oxide agglutinating extrudate (contain 0.47 in the extrudate and restrain planar water).The prior drying of extrudate is so that remove planar water.After correcting the water-content of extrudate, the consisting of of the mixture in the autoclave:

2.88K ₂O/1.62Al ₂O ₃/10SiO ₂/148H ₂O

Silicon oxide exists as the binding agent in the extrudate in the mixture.

With autoclave at 5.5 hours internal heating to 175 ℃ and under this temperature, kept 65 hours.Through behind this aging time with autoclave opening and collect the extrudate product.

The extrudate that is obtained was washed one hour with 2000 ml waters down at 60 ℃, and then washed 2 hours with 60 ℃ 1000 ml waters.The PH of last washing water is 10.8, and electric conductivity is 662 little Siemens/cm.With this extrudate 120 ℃ of following dried overnight.The product amount of collecting is 52.6 grams.

The product extrudate is as follows through XRD and SEM characterization result:

XRD shows and has the L zeolite

SEM shows and has the L zeolite crystal, is newly formed

The littler crystal of size bond

The Pt (based on the weight of catalyzer) of 0.85wt.% is used the Pt (NH of appropriate amount by the hole fill method ₃) ₄Cl ₂The aqueous solution is carried among the catalyzer D.After the load, with the catalyzer drying.

Example 4

Adopt catalyzer C and catalyzer D to carry out two kinds of independent aromizing tests.Before the test beginning every kind of catalyzer is carried out redispersion program and reducing program according to following program:

With the 10 gram catalyzer internal diameter of packing into is in 1 inch the silica tube, puts into an electrically heated baking oven.In all treatment steps all be allow gas under the flow velocity of 500 ml/min by silica tube and catalyst sample.Originally catalyzer is used and consisted of the O that contains 10v% ₂Be heated to 450 ℃ with the air-flow of the helium of 90v%.Catalyzer was kept under 450 ℃ 1 hour.Then temperature is increased to 530 ℃ and gas composition and change the O of 20v% into ₂, the water of 2.2v% and the helium of 77.8v%.Catalyzer is exposed 67.5 hours under these conditions.Then catalyzer is cooled to 510 ℃ in the exsiccant helium.On this temperature, gas composition is changed into the O of 20v% ₂, the water of 2.2v% and the helium of 77.8v%.After 30 minutes, gaseous fraction is changed into the Cl of 0.8v% ₂, the water of 2.2v% and the helium of 70.0v%.Catalyzer is exposed 2 hours under these conditions.Then gas composition is changed into the O of 20v% ₂, the water of 2.2v% and the helium of 77.8v%.Under these conditions after 2 hours, with O ₂Remove and with the remaining O in the helium purge reactor of the water of 2.2v% and 97.8v% ₂Introduce hydrogen at that point so that gas composition is changed into the H of 20v% ₂, the water of 2.2v% and the helium of 77.8v%.Catalyzer was reduced 1 hour under these conditions.Then gas composition is changed into the exsiccant helium and catalyzer is cooled to room temperature, catalyzer is taken out from reactor.

The test of first kind of aromizing is the C with a kind of 60wt.% of containing normal hexane 30wt.%3-methylpentane and 10wt.% methylcyclopentane ₆Mixing raw material is in 950 temperature, 1000psig pressure, 6.0w/w hour ^-1WHSV and in the presence of hydrogen, carry out hydrogen: the hydrocarbon ratio is 6.Be respectively the working time of catalyzer C and D 14.6 hours and 14.4 hours.The results are shown in Table 3:

Table 3

Product	Catalyzer C	Catalyzer D
			????C 1-C 2	????5.8	????13.5
????C 3-C 4	????6.6	????16.6
			????C 5-C 6	????21.3	????11.0
Benzene	????66.3	????58.4
			Toluene	????0.1	????0.3
????A 8 +	????0.0	????0.1

Data show that catalyzer C is higher by 14% than the benzene yield of catalyzer D in the table, and undesirable by the raw material cracking to C ₁-C ₄Product has reduced more than 50%.

Second kind of aromizing test is with the temperature of a kind of light naphthar raw material at 860,100psig pressure, 1.0w/w hour ^-1WHSV and in the presence of hydrogen, carry out hydrogen: the hydrocarbon ratio is 6.Be respectively the working time of catalyzer C and D 16.5 hours and 16.3 hours.Consisting of of LVN raw material:

Form	????wt.％
		????C 5	????0.26
????C 6	????5.85
		????C 7	????18.99
????C 8	????22.35
		????C 9	????21.60
????C 10	????10.37
		????C 11	????2.93
Benzene	????0.32
		Toluene	????3.13
????A 8	????5.33
		????A 9	????8.07
????A 10	????0.80

These tests the results are shown in Table 4:

Table 4

Product	Catalyzer C	Catalyzer D
			????C 1-C 2	????7.2	????12.0
????C 3-C 4	????3.3	????3.7
			????C 5-C 6	????30.9	????20.5
Benzene	????10.0	????14.3
			Toluene	????22.1	????31.5
????A 8	????20.0	????15.1
			????A 9	????5.8	????2.6
????A 10	????0.6	????0.3

Data show the clean A of catalyzer C than catalyzer D in the table ₈Yield is high by 50%, and by the raw material cracking C extremely ₁-C ₂Product reduces more than 40%.Catalyzer D produces more benzene and toluene than catalyzer C, but its part is to have sacrificed more to wish the dimethylbenzene that obtains.

Claims (29)

1. do not contain the nonzeolite binding agent of obvious amount and contain at least a hydrogenation/dehydrogenation metal through zeolite agglutinating zeolites hydrocarbon conversion catalyst, comprising: (a) first of first kind of zeolite kind of crystal (b) contains second kind of crystalline binding agent of second kind of zeolite; Reach (c) at least a hydrogenation/dehydrogenation metal of significant quantity; Wherein should can change into second kind of zeolite by the silica binder in silicon oxide agglutinating aggregate with a kind of first kind of crystal that contains first kind of zeolite and the said at least a hydrogenation/dehydrogenation metal of at least a portion through zeolite agglutinating zeolite catalyst prepares.

2. one kind prepares the nonzeolite binding agent that does not contain obvious amount, and the method through zeolite agglutinating zeolite catalyst that contains the hydrogenation/dehydrogenation metal that contains the second kind of crystal and the said hydrogenation/dehydrogenation metal of first kind of crystal of first kind of zeolite, second kind of zeolite, this method comprise and contain first kind of crystal of first kind of zeolite and the silica binder in silicon oxide agglutinating aggregate of the said at least a hydrogenation/dehydrogenation metal of at least a portion changes into second kind of zeolite with a kind of.

3. catalyzer described in the claim 1 or 2 or method, wherein second kind of crystal is crystal stock between crystal, and forms partial coating at least on first kind of crystal.

4. catalyzer or the method described in any claim in front, wherein the content of nonzeolite binding agent is lower than the 5wt.% of first kind of zeolite and second kind of zeolite gross weight in the catalyzer.

5. catalyzer or the method described in any claim in front, wherein the mean particle size of first kind of zeolite crystal is greater than 0.1 micron.

6. catalyzer or the method described in any claim in front, wherein the mean particle size of second kind of zeolite crystal is less than the granular size of first kind of zeolite crystal.

7. catalyzer described in the claim 5 and 6 or method, wherein first kind of crystalline mean particle size is the 1-6 micron, second kind of crystalline mean particle size is the 0.1-0.5 micron.

8. catalyzer or the method described in any claim in front, wherein second kind of crystal is wear-resistant to small part.

9. catalyzer or the method described in any claim in front, wherein second kind of zeolite has lower acidity than first kind of zeolite.

10. each described catalyzer or method among the claim 1-8, wherein second kind of zeolite has higher acidity than first kind of zeolite.

11. catalyzer or the method described in any claim in front, wherein first kind of zeolite and second kind of zeolite independently are aluminosilicate zeolites or silicic acid gallium zeolite separately.

12. catalyzer described in the claim 11 or method, wherein first kind of zeolite is a kind of silicon oxide: alumina molar ratio 70: 1-700: 1 aluminosilicate or a kind of silicon oxide: gallium oxide mol ratio 20: 1-500: 1 silicic acid gallium, and/or second kind of zeolite is a kind of silicon oxide: alumina molar ratio is greater than 200 aluminosilicate or silicon oxide: the gallium oxide mol ratio is greater than 100 silicic acid gallium.

13. catalyzer or the method described in any claim in front, wherein first kind of zeolite and second kind of zeolite independently of one another the hole be macropore or mesopore, preferred each mesopore naturally.

14. catalyzer or the method described in any claim in front, wherein the structure type of first kind of zeolite and second kind of zeolite independently is selected from OFF, BEA, MAZ, MEI, FAU, EMT, LTL, VFI, MOR, MFI, MFS, MEL, MTW, MTT, FER, EUO, HEU, TON, CHA, ERI, KFI, LEV and LTA separately.

15. catalyzer described in the claim 14 or method, wherein first kind of zeolite and second kind of zeolite have the LTL structure type.

16. catalyzer described in the claim 14 or method, wherein first kind of zeolite and second kind of zeolite have the structure type of MFI or MEL independently of one another.

17. catalyzer or the method described in any claim in front, wherein the hydrogenation/dehydrogenation metal contains VIII A family metal, or precious metal.

18. catalyzer or the method described in any claim in front, wherein the content of hydrogenation/dehydrogenation metal is 0.05-3.0wt.% in the catalyzer.

19. catalyzer or the method described in any claim in front, wherein the conversion of silica binder is that first kind of crystalline by will containing hydrogenation/dehydrogenation metal and first kind of zeolite at high temperature wears out in a kind of ionic aqueous solution that contains the hydroxyl ion source that is enough to silica binder is changed into second kind of zeolite through silicon oxide agglutinating aggregate and carry out.

20. catalyzer or the method described in any claim in front, be by forming first kind of squeezable material of crystalline of a kind of silicon oxide-containing and first kind of zeolite wherein through silicon oxide agglutinating aggregate, should kind of squeezable material extruding with form a kind of extrudate and optionally this extrudate of roasting prepare.

21. catalyzer described in the claim 20 or method, wherein metal had been present in first kind of zeolite before forming this squeezable material.

22. catalyzer described in the claim 20 or method, wherein metal is to be present in the silicon oxide of this squeezable material.

23. catalyzer described in the claim 20 or method wherein are with the extrudate roasting and after roasting metal is added in the extrudate.

24. catalyzer described in the claim 19 or method wherein are introduced in the aggregate by metal is added in the aqueous solution.

25. the method for convert hydrocarbons or oxygenatedchemicals, comprise with hydrocarbonaceous-or oxygenatedchemicals-raw material under the conversion condition of hydrocarbon or oxygenatedchemicals with claim 1 or be subordinated among the claim 3-24 of claim 1 described in any one through zeolite agglutinating zeolite catalyst, or a kind ofly adopt claim 2 or be subordinated to contacting that the method described in any one prepares among the claim 3-24 of claim 2 through zeolite agglutinating zeolite catalyst.

26. the method described in the claim 25, conversion wherein is selected from that hydrocarbon cracking, Alleyl aromatics isomerizating, hydrocarbon dewaxing, alkylaromatic hydrocarbon take off alkyl, naphtha reforming becomes aromatic hydrocarbons, paraffinic hydrocarbons and/or conversion of olefines to become aromatic hydrocarbons, and oxygenate becomes hydrocarbon product.

27. the method described in claim 25 or 26, conversion wherein are the pressure that comprises 100-760 ℃ temperature and/or 10.1kPa-10.1MPa (0.1-100 normal atmosphere) and/or 0.09-200 hour ^-1The condition of WHSV under carry out.

28. the method described in the claim 25,26 or 27, conversion process wherein is an xylene isomerization, a kind of C that contains ethylbenzene, xylene isomer or its mixture of isomerization ₈The aromatic hydrocarbons material, alkylaromatic hydrocarbon takes off alkyl, and fatty cpd is reformatted into aromatic hydroxy compound, paraffinic hydrocarbons dewaxing, or their combination.

29. the method described in the claim 25,26 or 27, comprising paraffinic hydrocarbons is reformatted into aromatic hydroxy compound, wherein, in zeolite agglutinating zeolite catalyst, first kind of zeolite is that L-zeolite and second kind of zeolite are the L-zeolites.

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