CN1070822C

CN1070822C - Preparation of aluminosilicate zeolites

Info

Publication number: CN1070822C
Application number: CN93119870A
Authority: CN
Inventors: S·J·米勒
Original assignee: CHEVENTION RESEARCH AND TECHNOLOGY Co
Current assignee: CHEVENTION RESEARCH AND TECHNOLOGY Co; Chevron USA Inc
Priority date: 1993-10-21
Filing date: 1993-12-14
Publication date: 2001-09-12
Anticipated expiration: 2013-12-14
Also published as: CN1101892A

Abstract

A method is disclosed for preparing a crystalline aluminosilicate zeolite from a reaction mixture containing only sufficient water so that the reaction mixture may be shaped if desired. In the method, the reaction mixture is heated at crystallization conditions and in the absence of an external liquid phase, so that excess liquid can be removed from the crystallized material prior to drying the crystals.

Description

The preparation of aluminosilicate zeolites

The present invention relates to produce a kind of method of crystalline aluminosilicate zeolites, only contain enough water in this reaction mixture, just make reaction mixture make the shape of wanting from a kind of reaction mixture.

Molecular sieve is important a kind of in a kind of crystalline material of industrial use.They have different crystalline structure to be accompanied by orderly pore structure, and the structure in this hole can show with different X-ray diffraction figures.Crystalline structure shows empty and different types of crystal is represented in the hole.Natural is used as catalyzer and sorbent material with synthetic crystal molecule sieve.The absorption property of each molecular sieve and catalytic performance partly are to be determined by its hole and empty size.Thereby the usability that sieves in the special occasions particular molecule depends in part on its crystalline structure at least.Because they have unique sieve performance, and their catalysis characteristics, make molecular sieve especially apply to the occasion as gas drying, separation and the hydrocarbon conversion." molecular sieve " this term refers to a kind of material prepared in accordance with the present invention, it has fixed, porous, network structure, crystal normally, be used to separating hydrocarbons or other mixtures by one or more components of occlusion selectively, perhaps in catalytic conversion process, be used as catalyzer.

The method for preparing the crystal zeolite in the prior art generates tiny isolating crystal usually, and this crystal must be separated from the liquid that excessive zeolite is crystallized out.Conversely, must handle so that utilize again or discard liquid, they have the potential harmful effect to environment.Prepare the industrial suitable catalyzer that contains zeolite powder and also need additional bonding and forming step usually.Usually, crystalline zeolite powder and jointing material must be mixed, make the particle or the molectron of definite shape then, the method for use such as extruding, sintering, spraying drying or the like.These bondings and forming step have greatly increased produces this complicacy that contains the catalyzer of zeolitic material.These additional steps also may produce opposite influence to the catalytic performance of the zeolite of bonding like this and shaping.

According to crystalline structure, the crystalline zeolite can be divided into common two types.One type is SiO in crystal lattices ₂/ Al ₂O ₃Mol ratio usually less than 12 zeolite, they are not normally having to prepare under the condition of organic formwork agent.Many this zeolites also contain the sodalite substructure, and the tetrahedron atom is arranged, and density is approximately less than 15TO ₂/ 1000 ³Zeolite with these general characteristics comprises as zeolite A, N-A, ZK-4, faujusite, X, Y, ZK-5 and p.

Some processing methodes of the crystal zeolite of this loose granule form have been proposed to prepare.For example people such as Howell is at United States Patent (USP) the 3rd, 119, set forth a kind of method by producing crystalline metallic aluminium silicate zeolite in the reaction of the aqueous solution medium clay soil molding particles body of reaction mixture in 660, above-mentioned reaction mixture comprises alkali-metal oxide compound.At people's such as Pryor United States Patent (USP) the 4th, 424,144, people's such as Brown United States Patent (USP) 4,235,753, people's such as Rundell United States Patent (USP) 3,777,006, people's such as Taggart United States Patent (USP) 3,119,659, people's such as Heinze United States Patent (USP) 3,773,690, people's such as Sakurada United States Patent (USP) the 4th, 977,120 and English Patent 2,160, a kind of similar approach for preparing zeolite in basic solution from molding is all disclosed among the 517A, can contain the crystal seed of zeolite in the above-mentioned molding.United States Patent (USP) 3,094,383 have described and have not a kind ofly contacted with the aqueous solution liquid phase of outside by aging homogeneous reaction mixture, but will make the method for the molded zeolite of A type under the condition that prevents the mixture dehydration.English Patent 1,567,856 disclose and have a kind ofly prepared the method for A type zeolite by heating a kind of pressure by metakaolin powder and sodium hydroxide (squeezing) mixture that goes out.

Make the method for crystallization of zeolites in the shaped particles that discloses a kind of zeolite that is containing additional powder in people's such as Chi the United States Patent (USP) 4,058,586, the particle of Cheng Xinging provides all crystallizations needed liquid herein.Adopt people's such as chi method need in alkaline aqueous solution, not make the particle crystallization.

Verduijn has instructed in a kind of deionized water solution that is containing hydroxide ion the zeolite by the bonding extrusion of ageing silica to prepare method without the zeolite compositions of tackiness agent in world patent WO92/12928.According to the description of Verduijn, the existence that zeolite crystal is arranged in extrudate is the key of the strong crystalline zeolite extrudate of preparation.People such as Verduijn are at European patent EP O A1/0,284, a kind of method for preparing the zeolite L of adhesive-free by the silica shaping has been described in 206, preferably make the finished product zeolite L crystal of the roughing that contains 10～50wt% become particulate state, make these particles and the basic solution phase reaction that contains the alumina source then, with the preparation zeolite L.

Recently, the someone has proposed the method for the high silica zeolite of similar preparation goods.Traditional preparation SiO ₂/ Al ₂O ₃Mol ratio approximately greater than 10, more typical is approximately greater than 20, the method for high silica goods generally includes and make crystallization of zeolites from the aqueous solution.For example in No. the 3rd, 702,886, people's such as Argauer United States Patent (USP), instructed a kind of from containing tetrapropylammonium hydroxide, sodium oxide, the oxide compound of aluminium or gallium prepares the method for ZSM-5 in the oxide compound of silicon or germanium and the solution.The dissolving of gel particle is just finished up to crystal formation.This crystal is separated from liquid, then reclaimed.

A kind of variation of preparation technology is to adopt clay as the alumina source when the high silica zeolite of preparation.For example United States Patent (USP) the 4th, 091, disclose for No. 007 and a kind ofly make the weight percent content of alumina be at least about 70%, the method for preparation crystalline aluminosilicate zeolite, especially ZSM-4 or ZSM-5 from a kind of like this reaction mixture by in reaction mixture, adding the clay contain alumina.European patent EP OA2/0,156,595 disclose a kind of like this method for preparing the crystal zeolite, this method is configured as the particle of definite shape by making the mixture that contains crystal seed, silica source, alumina source and water, crystallization in the reacting mixture solution that contains the alkaline kation source then, the mol ratio for preparing silica and alumina is greater than 12, and rejection coefficient is 1～12 crystal zeolite.It has also set forth the clay that contains alumina can be used as the alumina source.United States Patent (USP) the 4th, 522 has been described a kind of containing for No. 705 to make European patent EP OA2/0, the clay molectron of describing in 156,595 at the scene crystallization as the catalytic cracking catalyst of additive.United States Patent (USP) the 5th, 145 has been instructed a kind of method that increases the silica content of the zeolite of appendix on matrix in No. 659, and matrix can be clay herein.

The somebody has proposed to prepare from the reaction mixture that zeolite can be crystallized out the special methods of zeolite.At United States Patent (USP) the 4th, 560, a kind of like this method has been described in No. 542, the liquid medium that hydrogel and that an exsiccant contains silica and alumina contains organic formwork agent is contacted, remain under definite crystallization condition, with preparation aluminosilicate crystal.

At United States Patent (USP) the 5th, 240, the method for describing in No. 892 is to adopt comprise alumina and the sedimentary silica solid reaction mixture that contain about 30% weight percent at least to prepare zeolite.This method when the preparation feedback mixture no matter in the mixture solids content how highly have, in crystallisation process, can stir mixture.

" material engineering " " crystalline zeolite from dense system " people such as R.Aiello, 1992, Vol.3.n.3.P.407-416 has described the method that contains crystalline zeolite the reaction mixture that similar gels and excessive liquid phase balance each other from initial in one literary composition.

Other also is included in this zeolite of preparation in the anhydrous basically environment with the synthetic relevant method of lenticular zeolite.These anhydrous methods were described, and as at " zeolite " 1992, Vol 12, and April/May P.343; " zeolite " 1990, Vol 10, November/December, P.753, and " zeolite " 1989, Vol9, November, P.468; " nature " Vol 317 (12), September, 1985, P.157; And J.Chem.Soc., Chem.Commun., 1988, P.1486, at J.Chem.Soc., Chem.Commun., 1993, P.659 described in a kind of in anhydrous system the blending means of synthetic ZSM-35, the quantity not sufficient of liquid that wherein is used to prepare crystalline mixture is with drenched all solids, makes the reactant of conglomerate be actually the mixture of exsiccant powder and little dough shape agglomerate.

Although some method described above has reduced the number of the step that makes crystallization of zeolites, but do not have one piece in the above-mentioned patent documentation of quoting a kind of like this crystallization method is provided, raw material that this method will be shaped easily and minimum water are combined in the particle of shaping, when eliminating the outside liquid crystallization phases, in shaped particles, make crystallization of zeolites, after crystallisation process is finished, the crystallization phases of outside liquid state is handled or removed.

Therefore an object of the present invention is to provide a kind of method for preparing the crystal zeolite with setting particulate form.

Another object of the present invention provides a kind of method of using minimum crystallization to prepare the crystal zeolite with liquid.

A further object of the present invention provides and a kind ofly prepares the crystal zeolite and waste liquid is reduced to minimum method.

A further object of the present invention provides a kind of method for preparing zeolite under the situation of not adding binding agent.

A further object of the present invention provides the method for the industrial suitable zeolite of a kind of preparation without any follow-up crystallization forming step.

A further object of the present invention provides a kind of method for preparing the little zeolite of crystalline size.

A further object of the present invention provides a kind of method that the template usage quantity prepares zeolite that lowers.

A further object of the present invention provides a kind of method for preparing zeolite that reduces raw materials cost.

These purposes and advantage and other purpose and advantage will be clearly concerning those skilled in the art.These purposes and advantage have been realized by the present invention.The method for preparing the lenticular zeolite described in the invention comprises a kind of reaction mixture of preparation, this reaction mixture contains at least a active silica source, a kind of organic formwork agent that can form above-mentioned crystal zeolite, with the enough water that said mixture is shaped: this method also is included in crystallization condition under and is not having under the situation of external liquid phase above-mentioned reaction mixture to be heated time enough to generate a kind of crystalline material that contains above-mentioned zeolite crystal, and the mol ratio of silica/alumina is greater than 12 in the wherein above-mentioned zeolite crystal.This reaction mixture can comprise at least a activated alumina source arbitrarily.

In the reaction mixture of preparation present method, importantly the water yield in the reaction mixture will prepare enough to make the water yield of mixture shaping for crystallisation step.Though and do not require that before mixture experience crystallization condition just make mixture be configured as the particle of setting, but hope is done so in many cases.The water yield of wanting required for the present invention is less than traditional needed water yield of the method for preparing zeolite.Thereby, in crystallisation process of the present invention, must from crystalline material, not remove at the terminal point of crystallisation process, for example before to the crystalline drying, exist by only liquid phase of filtering or decantation is removed.

Present method is the general method of the mol ratio of preparation silica/alumina greater than 12 zeolite.It still adopts organic formwork agent to prepare the general method of zeolite.It still prepares the general method of rejection coefficient greater than 1 zeolite.

Except that other factors, the present invention is based on found a kind of from reaction mixture the method for crystalline zeolite, contain in this reaction mixture and only enough make mixture be configured as the water of desired shape.Except that the particulate needs of this generation setting, crystallization be need not additional water.In addition, I find that also with respect to traditional crystallization of zeolites method, prepared according to the methods of the invention crystal zeolite needs the template of lower aq, has reduced crystallization time.In addition to my surprise, the zeolite with method for preparing appears in the shaped particles with very little crystal grain.

Zeolite therefrom and therein crystalline reaction mixture comprises at least a active silica source, a kind of organic formwork agent, and enough make mixture become the water of desired shape.The water yield is less than traditional required water yield of the method for preparing zeolite significantly.

Needed amount of liquid is the needed amount of enough blended mixture in mixture of the present invention, and liquid wherein can be the aqueous solution and organic liquid arbitrarily.Like this by making water mix to come the preparation feedback mixture mutually, so that generate a kind of homogeneous substance with thick paste denseness with the activated feedstock of zeolite.This activated feedstock is the form that is mixed into homogeneous substance easily, and for example it can be a powder, hydration particle, or the spissated aqueous solution.In mixing and whipping process, add and enough make the wetting water of all powder.Perhaps, add the water of q.s, can make powder be stirred into single and usually uniform mixture, the particle that this mixture can be made into to formalize.In whipping process, need not to make all activated feedstocks all to be dissolved in the water rapidly, because be added to the mixture that water in the activated feedstock is not enough to prepare flow-like.The add-on of water depends on the kind of mixing device and the activated feedstock that is adopted.Those those skilled in the art need not to test too much, just can easily determine the suitably needed amount of liquid of mixed zeolite activated feedstock.For example the required water yield of the hydration raw material of zeolite relatively can be less, and the required water yield of exsiccant raw material can be some more relatively.Although preferably will mix with stirring up to mixture mixture consistent, a uniform outward appearance are arranged, in the present invention, the stirring time length of mixture is not crucial.

Water content after mixing and the stirring in the reaction mixture can also further be adjusted, for example by dry or interpolation water, so that the particulate shaping.

Solid content depends on needed zeolite in the reaction mixture.Its silica of zeolite made with the inventive method and the mol ratio of alumina are greater than 12.Zeolite with very high silica and alumina ratio comprises that silica and alumina mol ratio are greater than 100 zeolite in the scope of present method.It also comprises the zeolite that is substantially free of aluminium.Especially when using industrial silica raw material, almost always there is aluminium more or less.Therefore " do not contain aluminium " and promptly mean and in reaction mixture, intentionally do not add aluminium, for example: as a kind of alumina or aluminate reagent, and the aluminium that in some scope, exists, a kind of pollutent of its appearance in the reagent.Other metal component that can join in the reaction mixture comprises, for example, and titanium, chromium, germanium, gallium, iron, boron and alkali and alkaline-earth metal.

Common silicon oxide (SiO ₂) raw material comprises silicate, silicone-hydrogel, silicic acid, colloidal state silicon, fused silica, tetraalkylphosphoniuhydroxide hydroxide ortho-silicate silica, precipitated silica and clay.Be generally used for the aluminum oxide (Al of reaction mixture ₂O ₃) raw material comprises aluminate, alumina, and aluminiferous compound such as AlCl ₃, Al ₂(SO ₄) ₃, kaolinton and other zeolites.Can be to add titanium, chromium, germanium, gallium, iron and boron corresponding to their aluminium and the form of silicon counterpart.Salt, especially alkali-metal halogenide such as sodium-chlor can be added in the reaction mixture, or generate in reaction mixture.They are described to prevent that as the auxiliary of crystallization of zeolites silica from blocking lattice in the literature.

The organic formwork agent that can form zeolite can be included in the reaction mixture.Usually, template is a kind of organic compound that contains nitrogen or phosphorus.The material that contains organic azonia can be the primary, and the second month in a season, or tertiary amine, or quaternary ammonium compound, this depends on the special zeolite product that obtains from the crystallization of reaction mixture.The example of quaternary ammonium compound indefiniteness comprises tetramethyl-ammonium, tetraethyl ammonium, tetrapropyl ammonium, TBuA, diethyl ammonium, triethyl ammonium, the debenzylation ammonium, dibenzyl Dimethyl Ammonium, dibenzyl diethyl ammonium, the salt of benzyltrimethylammon.um and 2-(hydroxyalkyl) trialkyl ammonium, wherein alkyl is methyl or ethyl or their combination.The example of amine that is applicable to the indefiniteness of the inventive method comprises Trimethylamine 99, triethylamine, tripropyl amine, 1, propylene diamine, butanediamine, pentamethylene diamine, hexanediamine, methylamine, ethamine, propylamine, butylamine, dimethylamine, diethylamine, dipropyl amine, benzylamine, aniline, pyridine, the compound of piperidines and tetramethyleneimine.Here the amine of Shi Yonging is the amine of pH value between about 7 and 12.The amount that an important feature of the present invention is exactly the required template of crystallisation process has reduced with respect to traditional crystallization of zeolites method.Like this, the mol ratio of template and silica is from 0 in about 0.5 scope in reaction mixture, and better in 0.01～about 0.5 scope, best is in 0.01～about 0.3 scope.

Reaction mixture can also comprise the activated feedstock of one or more alkalimetal oxides.The raw material of lithium, sodium and potassium preferably.Anyly can here all not be suitable for the deleterious alkali metal compound of crystallisation process.The example of indefiniteness comprises oxide compound, oxyhydroxide, nitrate, vitriol, halogenide, oxalate, Citrate trianion and acetate.In reaction mixture, in 0～about 0.5 the scope, best is in 0.05～0.3 scope to the mol ratio of basic metal and silica more fortunately.Alkali metal compound can also provide OH ^-Usually, in reaction mixture, OH is being arranged ^-OH under the situation about existing ^-/ SiO ₂Mol ratio about 0.05～0.4, preferably approximately from 0.05～0.3, help the synthetic of zeolite.

In the preferred approach of present zeolite synthesis, reaction mixture comprises one or more alkalimetal oxides, nitrogenous organic cation, hydrogen ion, the oxide compound of silicon, water and the raw material of the oxide compound of aluminium arbitrarily.Usually, the pH value of reaction mixture is at least 7, preferably between 8～14.

Advantage of the present invention is before crystallisation step, reaction mixture of the present invention can be made required shape, reduces the required step of catalytic material that preparation contains the zeolite for preparing with mixture thus.Before the preparation feedback mixture, may need to change the content liquid in the reaction mixture, change by drying or by adding more liquid, so that a kind of material of shapable its shape of maintenance is provided.Usually, to most of manufacturing process, the common content of water is account for the reaction mixture weight percent about 20%～60%, preferably accounts for about 30%～50%.

In the preliminary shaping step, reaction mixture is made into certain shape.Preparation particulate method is well-known in the prior art, and it comprises extruding, spraying drying, granulation, the method for caking or the like.To final catalyst, particle preferably reaches required size and shape, and for example they can be extrudates, and sphere is cylindrical, particle, agglomerate and piller.The common cross-sectional diameter of particle is between 0.40-12.70 millimeter (1/64-1/2 inch); preferably between 0.79～6.35 millimeter (1/32-1/4 inch); that is to say; particle has such size; be retained in 0.40 millimeter; preferably on 0.79 millimeter the screen cloth, pass 12.70 millimeters, preferably 6.35 millimeters screen cloth.

In the method, the particle from the shaping of reaction mixture preparation will contain enough water to keep required shape.In mixture, need not to add water, so that in the particle that is shaped, impel or keep crystallization.From the particle that is shaped, remove some excessive water before being preferably in crystallization in fact.For the moistening solid traditional method of drying can be used for the particle of dry forming, these methods are included in the air or in a kind of rare gas element such as nitrogen or helium and are being lower than under about 200 ℃ temperature, carry out drying in negative pressure under the pressure of about 505 kPas (5 normal atmosphere).

Naturally occurring clay, as wilkinite, kaolin, polynite, sepiolite and attapulgite are unwanted, but also can be added in before crystallization in the particle of shaping, so that make particle have good crush strength.These clays use with the original original form of being exploited or are initial through calcining, acid treatment or chemical modification.Microcrystalline cellulose can be used for improving the particulate physicals.

According to the inventive method, in reaction mixture, or crystallization goes out zeolite in by the shaped particles of reaction mixture preparation.Under each situation, the component of mixture that crystallization goes out zeolite all has following mole composition scope:

SiO ₂/Al ₂O ₃=5～∞

M ⁺/SiO ₂=0～1

R/SiO ₂=0～0.5

OH ^-/SiO ₂=0.05～0.4

H ₂O/SiO ₂=0.5～5

M wherein ⁺Be alkali-metal positively charged ion, R is a template.Best molar constituent scope is as follows:

SiO ₂/Al ₂O ₃=12～∞

M ⁺/SiO ₂=0.03～0.5

R/SiO ₂=0.01～0.3

OH ^-/SiO ₂=0.05～0.3

H ₂O/SiO ₂=1～4

M wherein ⁺Be alkali metal cation, R is a template.That especially best is H ₂O/SiO ₂Molar constituent in 1～3 scope.Especially Zui Jia SiO ₂/ Al ₂O ₃Mol ratio be in 12～5000 scope.

As mentioned above, the liquid that (can be the form of shaped particles) in reaction mixture can be that the aqueous solution and organic liquid are combined, as long as there is true quantitative water to exist.Because for example total content liquid may influence the physical strength of shaped particles, in crystallisation process in the reaction mixture total content of volatile matter better in the scope of 20%～60% (W/W), preferably in the scope of about 30%～60% (W/W), the total content of volatile matter is a volatile liquid in the reaction mixture, comprises the total content of water.Characteristics of present method are except the liquid that shaping particles needs, concerning need not additional liquid particle intercrystalline zeolite.

The crystallization of zeolite occurs under the situation that does not have the external liquid phase existence, and that is to say does not have liquid phase to separate from reaction mixture.Usually, in crystallisation process, if there is some liquid water to exist, and contact, or contact, can not produce adverse influence method of the present invention with the particle that is shaped with reaction mixture.Can reckon with in crystallisation process, may have some water on the surface of shaped particles.Yet one object of the present invention just provides a kind of handle needing after the crystallization and/or the depleted water yield is reduced to the method for MIN crystallization of zeolites.Be this purpose, present method provides a kind of method of synthetic zeolite, and this method is except needs form the liquid of the required q.s of particle, and crystallization need not additional water.In fact under certain conditions, the water that exists in crystallisation process may change the shaping coating of particles, and under egregious cases, and they also can make the particle of shaping lose their integrity or dissolvedly fall.Therefore, the amount of liquid that adopts in crystallisation process depends on the required amount of liquid of generation shaped particles from the activated feedstock of crystalline zeolite to a great extent.

The knot product are to carry out under the condition of an elevated temperature, carry out in an autoclave usually, make reaction mixture can bear an autogenous pressure process up to the crystal that generates zeolite.The temperature of hydrothermal crystallization process remains between about 80 ℃～200 ℃ usually, better is about between 90 ℃～180 ℃, preferably in about 100 ℃～170 ℃ scope.

The crystallization phases of zeolite often is acceleration for traditional crystallization method, and this is a key character of the inventive method.Therefore, form the required crystallization time of crystal usually from about 1 hour～about 10 days, more frequent is from about 3 hours to about 4 days.In some cases, in order to prepare the crystalline material of high-crystallinity, require crystallization time less than 24 hours.In the method, the material of the crystallization of collecting after the crystallization will contain the crystal of 50wt% at least usually.Can also contain crystal with present method preparation at least about 80wt%, even at least about the crystalline crystalline material of 90wt%.

In case generated zeolite crystal, just can crystal be washed water, dry then, for example under 90 ℃～150 ℃ temperature dry 8～24 hours.Drying process can under atmospheric pressure or under the negative pressure be carried out.

The crystallization in reaction mixture of the zeolite of the inventive method forms, and it contains reagent unbodied, noncrystalline shape.Can add crystalline material (i.e. " seed " crystal) before the crystallization in mixture, the method that improves crystallization of zeolites by adding " crystal seed " is well-known.Yet present method does not but need to add crystal seed.Really, before crystallisation step, under the situation that does not add crystal seed, zeolite just can form in reaction mixture in crystallization, and this is a key character of the present invention.

In the most general embodiment, the present invention goes for silica/alumina mol ratio synthetic greater than 12 zeolite.One than special embodiment in, present method is used for preparing rejection coefficient approximately greater than 1 silicate and aluminosilicate zeolites.With the rejection coefficient here is at J.Catalysis67, when defining among the P218 also at United States Patent (USP) the 4th, 481, disclosed rejection coefficient in 177.

Concrete, the example with the crystal zeolite of present method preparation of indefiniteness comprises ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38, β, SSZ-32 and other similar material.

According to present method, the reaction mixture that is produced has a prescription, represents recently that with mole its mol ratio is in following scope:

Generalized is best

YO ₂/W ₂O ₃ 12～∞ 12～∞

M ⁺/YO ₂ 0～1 0.04～0.7

R/YO ₂ 0～0.5 0.01～0.3

OH ^-/YO ₂ 0.05～0.4 0.05～0.3

H ₂O/YO ₂ 0.5～5 1～4

Y is a silicon, gallium or the two, and W is an aluminium, boron, gallium, iron, or their mixture, M ⁺Be alkalimetal ion, sodium preferably, and R is a template.The zeolite type that goes out from the reaction mixture crystallization depends on that several factors comprises the concrete prescription of crystallization condition, reaction mixture and the type of used template.

At United States Patent (USP) the 3rd, 702, zeolite ZSM-5 and traditional preparation method have been described in No. 886, its scheme is here by with reference to having quoted.The reaction mixture that can be applicable to preparation ZSM-5 is raw material and a template by silica and alumina, the raw material of tetrapropylammonium hydroxide and alkalimetal oxide preferably, and preferably sodium oxide mixes.

Zeolite SSZ-35, and traditional preparation method discloses in No. the 959th, 205, pendent U.S. Patent application is here by with reference to having quoted.The raw material that contains a kind of alkali-metal oxide compound in the method in the aqueous solution of the reaction mixture of being prepared for preparation zeolite SSZ-35, a kind of comparison inflexible polycyclic ring system template with four nitrogen heteroatoms (as, N, the N-dimethyl-[5.2.2.0 (2 for 4-nitrogen three rings, 6)] 11-8-alkene positively charged ion), aluminium, boron, gallium, the oxide compound of iron, or their mixture, silicon oxide or germanium oxide, the perhaps mixture of these two kinds of materials.

β zeolite and its traditional preparation method are documented in United States Patent (USP) the 3rd, 308, and in No. 069, its disclosed content is here with reference to having quoted.The reaction mixture that is applicable to preparation β zeolite is that preferably sodium oxide mixes by the raw material of silica and alumina and the template raw material of tetraethyl ammonium hydroxide (TEAOH) and alkalimetal oxide preferably.

In about 75 ℃～200 ℃ temperature range, crystallisation process can carry out satisfactorily.Under autogenous pressure, heat, up to generating desirable zeolite crystal.

Zeolite ZSM-12 with and traditional preparation method be documented in United States Patent (USP) 3,832, in 449, its content is here by with reference to having quoted.Contain tetraethylammonium cation by preparation, sodium oxide, aluminum oxide or gallium oxide, silicon oxide or germanium oxide, and the reaction mixture of water goes for preparing zeolite ZSM-12.After this, from liquid, isolate crystal and reclaiming.Common reaction conditions comprises that the temperature with above-mentioned reaction mixture is heated in about 80 ℃～180 ℃ scope, is about 1 hour heat-up time～10 days.Best temperature range is about 150 ℃～170 ℃, heat-up time of this temperature range in 3 hours～4 days scope.

Zeolite ZSM-22 and traditional preparation method thereof are documented in United States Patent (USP) the 4th, 556, and in No. 477, its content is here by with reference to having quoted.Zeolite ZSM-22 can prepare by preparing a kind of reaction mixture, contain a kind of alkalimetal oxide in this reaction mixture, a kind of raw material of silica, the organic compound of a kind of IVB family element, the nitrogenous or phosphorus of this organic compound comprises a kind of alkyl or aryl that has 2 carbon atoms at least at least.Reaction mixture is remained under the crystalline state, up to the crystal that generates zeolite.After this, from liquid, isolate these crystal and reclaiming.Usually reaction conditions comprises above-mentioned reaction mixture is heated to about 80 ℃～200 ℃ temperature, is about 1 hour heat-up time～10 days.

Silicite and traditional preparation method are documented in United States Patent (USP) the 4th, 073, and in 865, its content is here by with reference to having quoted.In addition, the reaction mixture that is used for preparing silicite does not add the activated alumina raw material.Like this, the content of alumina raw is just very low in the reaction mixture, promptly is equivalent to the content of impurity.The template that is used to prepare silicite preferably has molecular formula and is (R ₄X) ⁺The quaternary positively charged ion, wherein each R represents hydrogen or contains the alkyl group of 2～6 carbon atoms, and X represents phosphorus or nitrogen.The reaction mixture that is provided is heated in 100 ℃～200 ℃ temperature range, up to generating crystalline hydration primary particle, usually the time be about 1 hour～10 days, isolate above-mentioned crystalline primary particle, and at these primary particles of temperature lower calcination of 400 ℃～1000 ℃.

Zeolite ZSM-11 and traditional preparation method thereof are documented in United States Patent (USP) the 3rd, 709, and in No. 979, its content is here by with reference to having quoted.Zeolite ZSM-23 and traditional preparation method thereof are documented in United States Patent (USP) the 4th, 076, and in No. 842, its content is here by with reference to having quoted.Zeolite ZSM-35 and traditional preparation method thereof are documented in United States Patent (USP) the 4th, 016, and in No. 245, its content is here by with reference to having quoted.Zeolite ZSM-38 and traditional preparation method thereof are documented in United States Patent (USP) the 4th, 046, and in No. 859, its content is here by with reference to having quoted.The method of zeolite SSZ-32 and traditional preparation thereof is documented in United States Patent (USP) the 5th, 053, and in No. 373, its content is documented in here by with reference to having quoted.

A key character of the present invention is exactly that the crystalline size of the zeolite crystal that generates of present method is very little.Usually, use scanning electronic microscope to determine that the diameter of zeolite crystal is less than 10 microns.Because little crystal wishes that crystallization condition can satisfy the requirement of generation diameter less than 1.0 microns zeolite crystal as in some catalyzer use.The crystalline size of zeolite can be measured to isolate one crystal by for example pulverizing the particle that is shaped.Can prepare the high-resolution electron microscopic picture of single crystalline then, by with reference to the length standard of demarcating, determine the mean size of single zeolite crystal then.Calculate the size of average crystal grain then according to well-known method, comprising:

Wherein ni is the number that drops on the zeolite crystal in the Li scope when minimum length.For the purpose of describing, average crystalline size is defined as mean value.It should be noted that and be purpose of the present invention, zeolite crystal size and some producers' term " zeolite granular size " is distinguishing, what the latter represented is all particulate mean sizess when producing zeolite powder, has both comprised that one crystal also comprised a plurality of crystalline agglomerates.

Usually, obtain the diameter of zeolite crystal less than 10 microns by scanning electronic microscope.Because for being used as Application of Catalyst, wish that crystal is less, so can be by for example reducing Tc, increase the content of aluminium in the reaction mixture, and/or in the reduction reaction mixture or before crystallization in the shaped particles content of water change crystallization condition so that generate diameter less than 1.0 microns zeolite crystal.

A kind of crystallisate mass-energy that contains zeolite crystal prepares as stated above.The synthetic zeolite can directly use or be used by thermal treatment (calcining) back.Usually, wish to remove alkali metal cation, and use hydrogen by ion-exchange, aluminium, or the metal ion of any hope replaces alkali metal cation.Zeolite can with sequestrant for example the acid solution of EDTA or dilution leach, to increase the mol ratio of silica and alumina.These methods also comprise use (NH ₄) ₂SiF ₆Or tart ion exchange resin treatment.Zeolite can also be steamed; Help the stability of the lattice of crystalline state with steam to acid corrosion.Zeolite can also be used to closely combining with the hydrogenation composition, as tungsten, and vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or noble metal such as palladium or platinum use for those hope have the occasion of hydrogenation-dehydrogenation effect.Usually replace positively charged ion and comprise for example rare earth of various metallic cations, I A family, the metal of II A family and VIII family, and their mixture.In the metallic cation that replaces, metallic cation is rare earth for example, Mn, and Ca, Mg, Zn, Ga, Cd, Pt, Pd, Ni, Co, Ti, Al, Sn, Fe and Co are especially preferable.

Hydrogen, ammonium and metal ingredient can exchange and enter in the zeolite.Zeolite also can flood with metal, perhaps uses standard method well known in the prior art that metal is mechanically closely mixed with zeolite.Can appear in the reaction mixture of preparation zeolite with ionic species by making desired metal, make metal block lattice.

Usually ion exchange technique is to make synthetic zeolite and contain one or more cationic salts solutions that are hopeful to replace and contact.Although can adopt all salt, muriate and other halogenide, nitrate and vitriol are especially best.In various patents, comprise United States Patent (USP) the 3rd, 140,249; 3,140,251; With 3,140,253 all disclose this representational ion exchange process.Carry out ion-exchange at zeolite before or after being calcined.

With contain to some extent the cationic salts solution that requires to replace and contact after, water washs zeolite usually, and carries out drying in 65 ℃～about 315 ℃ temperature range.After the washing, can in about 200 ℃～820 ℃ temperature range, in air or rare gas element, zeolite be calcined 1～48 hour, perhaps longer, to generate a kind of active result that catalytic effect is arranged that is particularly useful for hydrocarbon conversion process.

No matter positively charged ion appears at the synthesized form in the zeolite, the atom spatial arrangement that forms the zeolite elementary cell should remain unchanged basically.Cationic exchange has seldom influence to the crystalline network of zeolite, even influential words.

When the size of the shaped particles that generates from above-mentioned reaction mixture and shape all are final catalyst desired the time, zeolite can be used as catalyzer, and does not have additional form.On the other hand, use as spraying drying, extrude or the like technology, zeolite can also combine with other temperature-resistant material and needed other material of organic transformation process.These base materials comprise active and inactive material, synthetic or naturally occurring zeolite, and inorganic substance such as clay, silica and metal oxide.The latter can be naturally occurring or with gel precipitate, and the form of colloidal sol or gel comprises the mixture of silica and metal oxide.Use a kind of active substance to add synthetic zeolite,, can in some organic transformation process, improve the conversion performance and the selectivity of catalyzer even they combine.Inactive substance is applicable to as thinner, with control conversion values in the given process otherwise do not control speed of reaction so that do not make, just can obtain product economically.Usually, zeolite material is mixed naturally occurring clay, in wilkinite and kaolinton.These materials, clay for example, oxide compound or the like, its partial function is intended for the binding agent of catalyzer.Be desirable to provide the catalyzer with good crush strength, because in the petroleum refining process, catalyzer often will experience rough disposal, and this will make catalyzer be ground into powder, thereby in use have problems.

The naturally occurring clay that can combine with synthetic zeolite of the present invention comprises polynite and kaolin group, these families comprise inferior wilkinite and kaolin, the common Dixie that is called, McNamee, Georgia and Florida clay or other essential mineral composition are halloysites, kaolin, dickite, nakrite, or the clay of anauxite.Fibrous clay such as sepiolite and attapulgite also can be used as carrier.This clay can use with the original states of matter of being exploited, perhaps at first through calcining, acid treatment or chemical modification.

Except above-mentioned substance, zeolite with present method preparation can also combine with the mixture of porous matrix material and these substrate substances, these substrate substances such as silica, alumina, titanium dioxide, magnesium oxide, silica-alumina, silica-magnesium oxide, silicon-dioxide-zirconium white, silica-thorium oxide, silica-beryllia, silica-titania, titanium dioxide titania-zirconia and ternary composition such as silica-alumina-Thorotrast, silica-alumina-zirconium white, silica-alumina-magnesium oxide and silicon oxide-magnesium oxide-zirconium white.Matrix can be with cogelled form.

Zeolite can also be combined with other zeolite such as synthetic and natural all directions zeolite (as X and Y), erionite and mordenite.They can also with isozygoty into zeolite such as zeolite ZSM, zeolite EU, zeolite FU and zeolite NU series are combined.Zeolite facies are in conjunction with being combined into the porous inorganic matrix.

Zeolite with present method preparation can be used for hydrocarbon conversion process.The conversion reaction of hydrocarbon is chemistry and catalytic process, and wherein carbon compound is transformed into the different carbon compounds that closes.The embodiment of hydrocarbon conversion reaction comprises catalytic cracking, and hydrocracking and alkene and aromatics formation reaction comprise the formation reaction from oxide treatment.Catalyzer also can be used in other petroleum refinings and the hydrocarbon conversion reaction as n-paraffin and naphthenic isomerization, the polymerization of alkene and acetylene hydrocarbon compound and oligomerization, polymerization and oligomerization as iso-butylene and 1-amylene, the aromatic substance that many alkyl replace (as-dimethylbenzene) reformation, alkylation, isomerization, the disproportionation of aromatic substance (as toluene) is to provide the mixture of benzene, dimethylbenzene and senior methylbenzene.

Embodiment 1

In 100 gram silicas (Hi-Sil 233, by the hydration silica of PPG production), add 8 gram kaolinton powder (53.7wt%SiO ₂, 4.5wt%Al ₂O ₃) and tetrapropylammonium hydroxide (TPAOH) aqueous solution of 60 gram 40wt%, in the Baker-Perkins mixing tank, mixed one hour.Then with the 0.34 boric acid (H that restrains ₃BO ₃) be dissolved in the water of 25 grams, and be added in the said mixture with the NaOH aqueous solution of 5.8 gram 50wt%.Continue again to mix 30 minutes.Mol ratio in synthetic mixture is as follows:

TPA ⁺/SiO ₂=0.074

OH ^-/SiO ₂=0.12

Na ⁺/SiO ₂=0.045

SiO ₂/Al ₂O ₃=48

H ₂O/SiO ₂=2.6

Mould by one 1/16 inch pushes mixture then.Extrudate is placed in tetrafluoroethylene (plastics) bottle of a sealing, under spontaneous (autogenous) pressure, under 100 ℃ temperature, heated four days.In a vacuum drying oven under 110 ℃ temperature with extrudate dry night, under 538 ℃ temperature, calcining is 8 hours in air then.Use X-ray diffraction analysis, differentiate that this product is about 100% ZSM-5, when proving when determining that with scanning electronic microscope (SEM) it is to be approximately 0.2 micron granulometric composition by diameter.The content of sodium is 1.5wt%, and the crush strength of extrudate is 2.1 pounds/millimeter (1b/mm).

Embodiment 2

In 50 gram Hi-Sil233, add 4 gram kaolinton powder, in the Baker-Perkins mixing tank, mixed 5 minutes.The NaOH aqueous solution that adds 4 gram 50wt% again, remix 10 minutes.The TPAOH aqueous solution that in this mixture, adds 45 gram 40wt%, remix 15 minutes.Mould by one 1/16 inch pushes mixture then, before putting into tetrafluoroethylene (plastics) bottle that is arranged in the sealing of stainless steel pressure container, air drying 1 hour, in heating four days under 100 ℃ temperature under the spontaneous pressure.Then under 110 ℃ temperature, dry night in a vacuum drying oven, and in air was 538 ℃ temperature lower calcinations 8 hours.Differentiate that with X-ray diffraction analysis this product is about 100% ZSM-5.When determining with SEM, its median size is about 0.1 micron.

Embodiment 3

In 50 gram Hi-Sil233, add the NaOH of 2 grams 50%, in the Baker-Perkins mixing tank, mixed 5 minutes.In this mixture, add 3 gram microcrystalline Mierocrystalline celluloses (Avicel is produced by FMC Corp.) and restrain 40% the TPAOH aqueous solution, and mixed 15 minutes with 30.Dissolving 0.17 gram H in 15 gram water ₃BO ₃, this solution is added in the said mixture remix 10 minutes.Mol ratio is as follows in synthetic mixture:

TPA ⁺/SiO ₂=0.074

OH ^-/SiO ₂=0.11

Na ⁺/SiO ₂=0.033

H ₂O/SiO ₂=2.5

Mould by one 1/16 inch pushes mixture then.Extrudate is divided into two equal portions, and every part all is placed on tetrafluoroethylene (plastics) bottle that is arranged in the stainless steel pressure container, and heating is four days under autogenous pressure.First sample heats under 100 ℃ temperature, and second sample heats under 120 ℃ temperature.In a vacuum drying oven, under 110 ℃ temperature, with product dry night, and in air 538 ℃ temperature lower calcination 8 hours.The content that obtains silicite with X-ray diffraction analysis is about 100%.The median size that SEM is presented at 100 ℃ of zeolites that make is about 0.2 micron, and is about 0.4 micron in the median size of 120 ℃ of zeolites that make.The crush strength of first kind of extrudate is 1.3 pounds/millimeter, and the crushing strength of second kind of extrudate is 0.9 pound/millimeter.

Embodiment 4

In 50 gram Hi-Sil233, add 4 gram sepiolite clay powder (Tolsa), in the Baker-Perkins mixing tank, mixed 5 minutes.And then add the TPAOH aqueous solution of 30 gram 40wt%, and mixed 15 minutes.Then dissolving 0.17 restrains H in 9 gram water ₃BO ₃, this solution is added in the said mixture remix 10 minutes with the 4 NaOH aqueous solution that restrain 50wt%.Mould by one 1/16 inch pushes mixture.The mole of extrudate is composed as follows:

TPA ⁺/SiO ₂=0.074

OH ^-/SiO ₂=0.13

Na ⁺/SiO ₂=0.066

SiO ₂/Al ₂O ₃=310

H ₂O/SiO ₂=2.3

Extrudate is placed on tetrafluoroethylene (plastics) bottle that is arranged in the stainless steel pressure container, and under 100 ℃ temperature, heating is four days under autogenous pressure.Then in a vacuum drying oven under 110 ℃ temperature with extrudate dry night, and calcining 8 hours in air under 538 ℃ temperature.X-ray diffraction analysis shows that product is about 100% ZSM-5.SEM shows that median size is below 0.1 micron.The crush strength of extrudate is 4.4 pounds/millimeter.

Embodiment 5

In 800 gram Hi-Sil233, add the NaOH aqueous solution of 64 gram 50wt% and the kaolinton powder of 64 grams, in a Baker-Perkins mixing tank, mixed 30 minutes.With 2.4 gram H that are dissolved in the 200 gram water ₃BO ₃Solution is added in the said mixture with the TPAOH aqueous solution of 480 gram 40wt%, mixes about 90 minutes.Under mixing, in 3 hours, add 300 gram water gradually.Be heated in mixer wall under 100 ℃ the condition and continue to mix half an hour, reduce to 52.5% with volatile component (under about 427 ℃ temperature, measuring small amount of sample) with this mixture.Mould by 1/16 inch of a porous pushes mixture then.At ambient temperature, making 1/3rd extrudate is 44.7% at air drying to the content of volatile constituent.The molar constituent of extrudate is as follows:

TPA ⁺/SiO ₂=0.074

OH ^-/SiO ₂=0.12

Na ⁺/SiO ₂=0.063

SiO ₂/Al ₂O ₃=48

H ₂O/SiO ₂=2.2

Two portions are put into a tetrafluoroethylene bottle that is arranged in the stainless steel pressure container, heating four days under 100 ℃ temperature under autogenous pressure.In a vacuum drying oven under 110 ℃ temperature to extrudate dry night, and calcining 8 hours in air under 538 ℃ temperature.X-ray diffraction analysis shows that the content of ZSM-5 in two samples is about 100%.Found that with SEM less than the median size at the sample of air drying be about 0.2 micron crystallization before, the crush strength of extrudate is 1.0 pounds/millimeter.And in the median size of air drying less than 0.1 micron, the crush strength of extrudate is 3.1 pounds/millimeter.

Embodiment 6

In this embodiment, without high pressure (steam and press) still, zeolite is forced out crystallization, makes 50 Hi-Sil233 that restrain and the 4 kaolinton powder mixes that restrain 5 minutes in a Baker-Perkins mixing tank.Add the TPAOH aqueous solution of 30 gram 40wt% then, and mixed 15 minutes.H with 0.17 gram ₃BO ₃Be dissolved in the solution that obtains in the 15 gram water and be added in the said mixture remix 10 minutes with the 4 NaOH aqueous solution that restrain 50wt%.Mixture is pushed, extrudate is placed on the filter screen, steam passes filter screen from the bottom.After four days, in a vacuum drying oven, under 110 ℃ temperature with extrudate dry night, then calcining 8 hours in air under 538 ℃ temperature.Divide plate to determine that product is ZSM-5 with X-ray diffraction.Find that with SEM median size is about 0.3 micron.

Embodiment 7

By the filling perforation method, with the Pt (NH of 0.8wt%Pt ₃) ₄(NO ₃) ₂The aqueous solution floods the extrudate that the method that is similar to embodiment 1 makes.In a vacuum drying oven under 110 ℃ temperature to catalyzer dry night, and calcining 4 hours in dry air under 204 ℃ temperature is 260 ℃ temperature lower calcinations 4 hours, 288 ℃ temperature lower calcinations 4 hours.The catalyzer research octane value (RON) that is used to reform is 100.6 reformate (table 1), at 70 pounds/inch ²(gauge pressure), the ratio (H of 1.3 liquid hourly space velocitys (LHSV) and hydrogen and the hydro carbons that increases newly ₂/ HC) be to carry out under 1 the condition.Unvulcanised with two kinds of conditions of sulfurized under detecting catalyst.When unvulcanised, obtaining the RON value when catalyst temperature is 770 °F is 107, and the productive rate of C5+ is 85.7wt%, and after the sulfuration, the RON value is 107 o'clock, and required catalyst temperature is elevated to 915 °F, but the productive rate of C5+ is brought up to 93wt%.

Embodiment 8

In 50 gram Hi-Sil 233, add 4 gram kaolinton powder, in the mixing tank of a Baker-Perkins, mixed 5 minutes.Adding under the thermal conditions 6 gram NaAlO ₂Be dissolved in tetraethylammonium hydroxide (TEAOH) aqueous solution of 30 gram 40wt%, the NaOH with 1 gram 50wt% is added in the said mixture then, mixes about 15 minutes.The TEAOH aqueous solution that adds 15 grams 40% again adds 3.2 NaNO that restrain then ₃With 5 gram water, remix 30 minutes.Mol ratio in the synthetic mixture is as follows:

TEA ⁺/SiO ₂=0.15

OH ^-/SiO ₂=0.18

Na ⁺/SiO ₂=0.17

SiO ₂/Al ₂O ₃=15

H ₂O/SiO ₂=2.7

The mould of mixture with one 1/16 inch pushed, be placed on tetrafluoroethylene (plastics) bottle that is arranged in the stainless steel pressure container then, heating four days under 150 ℃ temperature under autogenous pressure.Wash extrudate with water, in a vacuum drying oven under 110 ℃ temperature a dry night, then in air 538 ℃ temperature lower calcination 8 hours.X-ray diffraction analysis shows that this extrudate contains β (position) zeolite, does not have other crystallization phasess.By comparing with commercial peak area with reference to sample from 20 to 24 degree 2 θ, degree of crystallinity is determined and is about 92%.Determine that with SEM median size is about 0.4 micron.The crush strength of extrudate is 1.6 pounds/millimeter.

Embodiment 9

In 100 gram Hi-Sil233, add 8 gram kaolinton powder, in a Baker-Perkins mixing tank, mixed 5 minutes.Adding under the thermal conditions 12 gram NaAlO ₂Be dissolved in the TEAOH aqueous solution of 120 gram 40wt%, be added in the said mixture with the 2 NaOH aqueous solution that restrain 50wt%.Mix after 30 minutes, and then add the TEAOH aqueous solution of 30 grams 40%, this solution is dissolved with the NaNO of 6.4 grams ₃Remix 30 minutes pushes mixture by one 1/16 inch mould, and extrudate is placed on tetrafluoroethylene (plastics) bottle that is arranged in the stainless steel pressure container, heats 4 days under 100 ℃ temperature under autogenous pressure.With by NH ₄It is that 10 water washs extrudate that OH is adjusted to the pH value, in a vacuum drying oven under 110 ℃ temperature a dry night, calcining 8 hours in air under 538 ℃ temperature then.X-ray diffraction analysis shows that extrudate contains the β zeolite, does not have other crystallization phasess, and degree of crystallinity is about 82%, obtains median size by SEM and is about 0.1 micron.

Embodiment 10

In 100 gram Hi-Sil233, add 3 gram NaAlO ₂With 12 gram kaolinton, mixed 5 minutes.In this mixture, add the TEAOH aqueous solution of 90 gram 40wt% and the NaOH aqueous solution of 2 gram 50wt%, mixed about 15 minutes.In said mixture, add the TEAOH solution of 30 grams 40% and the NaNO of 6.4 grams again ₃, remix 30 minutes.Mixture is pushed, under ambient temperature,, and then push dry 1 hour again air drying 2 hours.The mol ratio of extrudate is as follows:

TEA ⁺/SiO ₂=0.20

OH ^-/SiO ₂=0.21

Na ⁺/SiO ₂=0.08

SiO ₂/Al ₂O ₃=24

Then extrudate is placed on tetrafluoroethylene (plastics) bottle that is arranged in the stainless steel pressure container, heating four days under 150 ℃ temperature under autogenous pressure.Wash extrudate with water, in a vacuum drying oven under 110 ℃ temperature a dry night, under 538 ℃ temperature in air the calcining 8 hours.X-ray diffraction analysis shows that this extrudate is β (position) zeolite near 100%.

Embodiment 11

Prepare a kind of β extrudate with the method that is similar to embodiment 8.Under 82 ℃ temperature with the CsNO of one or four times of excessive 15wt% ₃The aqueous solution exchanges 2 hours.Filter extrudate then, water washs.And then same Pt (NH ₃) ₄(NO ₃) ₂Solution exchanges, and the content that makes Pt in the extrudate is to 0.6wt%.In a vacuum drying oven, under 110 ℃ temperature, make extrudate dry night, calcining 2 hours in air under 149 ℃ temperature is 204 ℃ temperature lower calcinations 2 hours, 288 ℃ temperature lower calcinations 4 hours.Catalyzer is used at 482 ℃, 1.0LHSV, 30Psig and HC/H ₂Be normal hexane to be reformed in 2 o'clock.In 10 hours operational process, the transformation efficiency that is converted into benzene is 24wt%, to the selectivity of aromatics, is 54% in the percentage ratio of C6 paraffin conversion.

Embodiment 12

In 600 gram Hi-Sil233, add 26 gram NaAlO ₂, in a Baker-Perkins mixing tank, mixed 5 minutes.In a mixture, add the TEAOH aqueous solution of 412 gram 35wt% then, add the NaOH aqueous solution that 100 gram water and 48 restrain 50wt% again.Mix after 3.5 hours,, uniform humidity is arranged up to mixture while mix the water that in 25 minutes, slowly adds 240 grams.And then add 36 gram kaolinton powder, be heated under about 60 ℃ condition in mixer wall and slowly mix continuously, up to 1/32 inch mould, at 2500～3000 pounds/inch by a single hole ²Carver extruding down, a spot of blend sample is forced out.The mould that passes 1/16 inch of a porous is pushed mixture, be placed on then on the filter screen, at room temperature drying is 45% for the content of volatile constituent.Mol ratio is as follows in extrudate:

TEA ⁺/SiO ₂=0.11

OH ^-/SiO ₂=0.17

Na ⁺/SiO ₂=0.10

SiO ₂/Al ₂O ₃=24

H ₂O/SiO ₂=2.3

Then extrudate is put into tetrafluoroethylene (plastics) bottle that is arranged in the stainless steel pressure container, heating 3.5 days under 150 ℃ temperature under autogenous pressure.Wash extrudate then with water, in a vacuum drying oven under 120 ℃ temperature a dry night, under 593 ℃ temperature in air the calcining 7 hours.X-ray diffraction analysis shows that having an appointment in the extrudate 90% is the β zeolite.

Embodiment 13

In a Baker-Perkins mixing tank, in 600 gram Hi-Sil233, add 18 gram NaAlO ₂And 38.4NaNO ₃, mixed one hour.In this mixture, add 72 gram kaolinton powder again, and then add the TEAOH aqueous solution of 600 gram 40wt% and the NaOH aqueous solution of 12 gram 50wt%.Continue to mix 4 hours, after 110 gram water are slowly added and mix, formed thick paste.The wall of mixing tank is heated to about 70 ℃, and continues slowly to modulate under pushing at 1500 pounds/inch at Carver ²The mould that passes one 1/32 inch under the pressure obtains extrudate from small amount of sample.Volatile content at this point is 52%.And then by the mould of 1/16 inch of a porous mixture is pushed, be placed on then and at room temperature carry out drying on the filter screen, be 45% up to the content of volatile matter.Mol ratio is as follows in extrudate:

TEA ⁺/SiO ₂=0.18

OH ^-/SiO ₂=0.20

Na ⁺/SiO ₂=0.09

SiO ₂/Al ₂O ₃=23

H ₂O/SiO ₂=2.1

/ 4th of an extrudate is placed on tetrafluoroethylene (plastics) bottle that is arranged in the stainless steel pressure container, in heating four days under 150 ℃ temperature under the autogenous pressure.Another part sample of extrudate also heats in the same way, but is to heat 6 days under 100 ℃ temperature.Wash the extrudate sample with water, at a dry night in a vacuum drying oven, under 593 ℃ temperature, in air, calcined 8 hours.X-ray diffraction analysis confirms that two kinds of samples approximately all are 100% β zeolite.Two kinds of samples are carried out SEM obtain the average crystallite particle diameter less than 0.2 micron.The crush strength of two kinds of extrudates all surpasses 2 pounds/millimeter.

Embodiment 14

In 100 gram Hi-Sil233, add 1.0 gram NaAlO ₂With 6.0 gram sepiolite clay powder.Under mixing, add the TEAOH aqueous solution of 90 gram 40wt% and the NaOH aqueous solution of 2 gram 50wt% then.Mix after 15 minutes, with 11.4 gram NaNO ₃Be dissolved in the 15 gram water, this solution be added in the said mixture remix 2.5 hours.This mixture 1/3rd in add 5 gram water, mixed about 15 minutes.Mould by one 1/16 inch pushes this mixture then.Mol ratio is as follows in this mixture:

TEA ⁺/SiO ₂=0.16

OH ^-/SiO ₂=0.18

Na ⁺/SiO ₂=0.11

SiO ₂/Al ₂O ₃=160

H ₂O/SiO ₂=2.9

Extrudate is placed on tetrafluoroethylene (plastics) bottle that is arranged in the stainless steel pressure container, heating 3 days under 150 ℃ temperature under autogenous pressure.With through NH ₄OH adjusts to 10 water with pH extrudate is washed, in a vacuum drying oven under 120 ℃ temperature a dry night, calcining 8 hours in air under 593 ℃ temperature then.X-ray diffraction analysis shows that extrudate mainly comprises ZSM-12.

Embodiment 15

150 gram Hi-Sil233 are put into a Baker-Perkins mixing tank.Add 6.5 gram NaNO ₃, 3.0 gram kaolinton powder and 2.2 gram alumina powder (Reheis F, the Al of 52.3wt% ₂O ₃, the water of 47.7wt%), mixed 5 minutes.Add 1,3,3,8 of 130 gram 1.4M in this mixture, 8-pentamethyl--3-nitrogen two encircles [3.2.1] octane oxyhydroxide, adds the NaOH aqueous solution of 12 gram 50wt% then, mixes 3 hours.After adding the organic formwork solution of 30 grams again, in 25 minutes, add entry lentamente, up to generating uniformly wet piece.Mixer wall is heated to about 60 ℃, slowly mixes continuously, and the content of volatile matter reduces to about 62% in mixture.Mould by one 1/16 inch pushes mixture then, and it is 50% up to the content of volatile matter that extrudate is carried out dry air.Mol ratio in the extrudate is as follows:

R/SiO ₂=0.098

OH ^-/SiO ₂=0.16

Na ⁺/SiO ₂=0.10

SiO ₂/Al ₂O ₃=100

H ₂O/SiO ₂=3.7

Extrudate is placed on tetrafluoroethylene (plastics) bottle that is arranged in the stainless steel pressure container, and heating is four days under autogenous pressure.Use is by NH ₄OH is adjusted to 10 water with the pH value extrudate is washed, in a vacuum drying oven, and a dry night under 120 ℃ temperature, calcining 8 hours in air under 593 ℃ temperature then.X-ray diffraction analysis confirms that crystallization phases is the crystallization phases of SSZ-35.

Claims

1. method for preparing crystalline zeolite, this method comprises:

But a. prepare the reaction mixture that a kind of extrusion molding also can keep shape, at least contain a kind of first oxide compound activated feedstock in this mixture, this first oxide compound is selected from silicon, germanium or both oxide compounds, the optional at least a second oxide compound activated feedstock, this second oxide compound is selected from oxide compound or its mixture of aluminium, boron, gallium, iron, a kind of enough water that can generate the organic formwork agent of above-mentioned crystalline zeolite and said mixture is shaped; And

B. under crystallization condition, under the situation that the external liquid phase that does not have to add exists, to above-mentioned reaction mixture heating time enough, so that generate a kind of crystalline material that contains above-mentioned zeolite crystal, the mol ratio of first oxide compound in the wherein above-mentioned zeolite crystal/second oxide compound is greater than 12.

2. the method for claim 1, wherein in crystallisation process, the mol ratio of the water of above-mentioned reaction mixture/first oxide compound is between 0.5～5.

3. method as claimed in claim 2, wherein in crystallisation process, the mol ratio of water in the above-mentioned reaction mixture/first oxide compound is between 1～4.

4. the method for claim 1, wherein the rejection coefficient of above-mentioned zeolite is greater than 1.

5. the method for claim 1, wherein in above-mentioned crystalline material, the grain-size of zeolite crystal is less than 10 microns.

6. method as claimed in claim 5, wherein in above-mentioned crystalline material, the grain-size of zeolite crystal is less than 1.0 microns.

7. the method for claim 1 contains the crystalline zeolite greater than 50wt% in the wherein above-mentioned crystalline material.

8. method as claimed in claim 7 contains the crystalline zeolite greater than 90wt% in the wherein above-mentioned crystalline material.

9. the method for claim 1 does not wherein contain the crystal seed of interpolation in the reaction mixture.

10. the method for claim 1, wherein crystalline zeolite is ZSM-5.

11. the method for claim 1, wherein crystalline zeolite is the β zeolite.

12. the method for claim 1, wherein crystalline zeolite is ZSM-12.

13. the method for claim 1, wherein crystalline zeolite is silicite.

14. the method for claim 1, wherein crystalline zeolite is SSZ-35.

15. the method for claim 1, wherein the mole of above-mentioned reaction mixture is formed in following scope:

SiO ₂/Al ₂O ₃=5～∞

M ⁺/SiO ₂=0～1

R/SiO ₂=0～0.5

OH ^-/SiO ₂=0.05～0.4

H ₂O/SiO ₂=0.5～5

M wherein ⁺Be alkali metal cation, R is a template.

16. method as claimed in claim 15, wherein the molar constituent of above-mentioned reaction mixture is in following scope:

SiO ₂/Al ₂O ₃=12～∞

M ⁺/SiO ₂=0.03～0.5

R/SiO ₂=0.01～0.3

OH ^-/SiO ₂=0.05～0.3

H ₂O/SiO ₂=1～4

M wherein ⁺Be alkali metal cation, R is a template.

17. the method for claim 1, wherein above-mentioned reaction mixture further also comprises the activated feedstock of at least a aluminum oxide.

18. method as claimed in claim 17 is wherein in the scope of mol ratio 12～5000 of its silica/alumina of zeolite crystal of above-mentioned reaction mixture being carried out generated in the heat-processed.

19. the method for claim 1, wherein above-mentioned reaction mixture further comprise the activated feedstock of at least a VIII family metal.

20. method as claimed in claim 19, wherein above-mentioned VIII family metal is selected from platinum, palladium and their combination.

21. a method for preparing the crystalline zeolite of shaping, this method comprises:

But a. prepare reaction mixture a kind of extrusion molding and that can keep shape, at least contain a kind of first oxide compound activated feedstock in this mixture, this first oxide compound is selected from silicon, germanium or both oxide compounds, the optional at least a second oxide compound activated feedstock, this second oxide compound is selected from oxide compound or its mixture of aluminium, boron, gallium, iron, a kind of water that can generate the organic formwork agent of above-mentioned crystalline zeolite and make the q.s of said mixture shaping;

B. above-mentioned reaction mixture is made shaped particles;

C. under crystallization condition, under the situation that the external liquid phase that does not have to add exists, to above-mentioned shaped particles heating time enough, to generate the crystal of above-mentioned zeolite in above-mentioned shaped particles, wherein the mol ratio of first oxide compound of above-mentioned zeolite crystal/second oxide compound is greater than 12.

22. method as claimed in claim 21, wherein the mol ratio of first oxide compound of above-mentioned shaped particles/second oxide compound is not more than 5 during crystallization.

23. method as claimed in claim 22, wherein in crystallisation process, the mol ratio of first oxide compound of above-mentioned shaped particles/second oxide compound is between 1～4.

24. method as claimed in claim 21, wherein the rejection coefficient of above-mentioned zeolite is greater than 1.

25. method as claimed in claim 21, wherein in the size of the crystal grain of above-mentioned zeolite crystal less than 10 microns.

26. method as claimed in claim 25, wherein in the grain-size of above-mentioned zeolite crystal less than 1.0 microns.

27. method as claimed in claim 21 wherein, contains the crystalline zeolite that contains in the above-mentioned shaped particles of above-mentioned crystalline zeolite greater than 50wt%.

28. method as claimed in claim 27 wherein, contains the crystalline zeolite that contains in the above-mentioned shaped particles of above-mentioned crystalline zeolite greater than 90wt%.

29. method as claimed in claim 21 wherein need not add crystal seed in the reaction mixture.

30. method as claimed in claim 21, wherein above-mentioned crystalline zeolite is ZSM-5.

31. method as claimed in claim 21, wherein above-mentioned crystalline zeolite is the β zeolite.

32. method as claimed in claim 21, wherein above-mentioned crystalline zeolite is ZSM-12.

33. method as claimed in claim 21, wherein above-mentioned crystalline zeolite is silicite.

34. method as claimed in claim 21, wherein above-mentioned crystalline zeolite is SSZ-35.

35. method as claimed in claim 21, wherein the molar constituent of above-mentioned reaction mixture is in following scope:

SiO ₂/Al ₂O ₃=5～∞

M ⁺/SiO ₂=0～1

R/SiO ₂=0～0.5

OH ^-/SiO ₂=0.05～0.4

H ₂O/SiO ₂=0.5～5

M wherein ⁺Be alkali metal cation, R is a template.

36. method as claimed in claim 35, wherein the molar constituent of above-mentioned reaction mixture is in following scope:

SiO ₂/Al ₂O ₃=12～∞

M ⁺/SiO ₂=0.03～0.5

R/SiO ₂=0.01～0.3

OH ^-/SiO ₂=0.05～0.3

H ₂O/SiO ₂=1～4

M wherein ⁺Be alkali metal cation, R is a template.

37. method as claimed in claim 21, wherein the crystalline zeolite of Cheng Xinging is spheric or columniform particle, and the diameter of its cross section is between 0.40～12.70 millimeter.

38. method as claimed in claim 35, wherein the crystalline zeolite of Cheng Xinging is spheric or columniform particle, and the diameter of its cross section is between 0.79 millimeter～6.35 millimeters.

39. method as claimed in claim 21 comprises a kind of activated feedstock of aluminum oxide at least in the wherein above-mentioned reaction mixture, wherein the mol ratio of silica/alumina in reaction mixture is in 12～5000 scope.

40. method as claimed in claim 21 is wherein in the scope of mol ratio 12～5000 of its first oxide compound of zeolite crystal/second oxide compound that above-mentioned reaction mixture is carried out generated in the heat-processed.

41. method as claimed in claim 21, wherein above-mentioned reaction mixture further comprise the activated feedstock of at least a VIII family metal.

42. method as claimed in claim 41, wherein above-mentioned VIII family metal is to be selected from platinum, palladium and their combination.

43. crystalline zeolite with the described method preparation of claim 42.

44. method as claimed in claim 1, the composition of wherein said reaction mixture is calculated in molar ratio as following scope:

YO ₂/W ₂O ₃ 12-∞

M ⁺/YO ₂ 0～1

R/YO ₂ 0～0.5

OH/YO ₂ 0.05-0.4

H ₂O/YO ₂ 0.5-5

Wherein Y is silicon, germanium or both, and W is aluminium, boron, gallium, iron or its mixture, M ⁺Be alkali metal cation, R is a template.

45. method as claimed in claim 1, the composition of wherein said reaction mixture is calculated in molar ratio as following scope:

YO ₂/W ₂O ₃ 12-∞

M ⁺/YO ₂ 0.04～0.7

R/YO ₂ 0.01～0.3

OH/YO ₂ 0.05-0.3

H ₂O/YO ₂ 1-4

46. method as claimed in claim 1, wherein crystalline zeolite is ZSM-11.

47. method as claimed in claim 1, wherein crystalline zeolite is ZSM-22.

48. method as claimed in claim 1, wherein crystalline zeolite is ZSM-23.

49. method as claimed in claim 1, wherein crystalline zeolite is ZSM-38.

50. method as claimed in claim 1, wherein crystalline zeolite is SSZ-32.

51. as the method for claim 15, wherein crystalline zeolite is ZSM-11.

52. as the method for claim 15, wherein crystalline zeolite is ZSM-22.

53. as the method for claim 15, wherein crystalline zeolite is ZSM-23.

54. as the method for claim 15, wherein crystalline zeolite is ZSM-38.

55. as the method for claim 15, wherein crystalline zeolite is SSZ-32.