CN1143727C - Synthetic porous crytalline material, its synthesis and use for catalytic conversion - Google Patents

Abstract

This invention relates to a composition of matter comprising an inorganic, porous crystalline phase material exhibiting, after calcination, an X-ray diffraction pattern with at least one peak at a d-spacing greater than 1.8 nm and having a benzene adsorption capacity of greater than 15 grams benzene per 100 grams of said material at 6.7 kPa (50 torr) and 25 DEG C. Preferably, the crystalline phase material has a hexagonal arrangement of uniformly-sized pores at least 1.3 nm in diameter and exhibiting, after calcination, a hexagonal electron diffraction pattern that can be indexed with a d100 value greater than 1.8 nm.

Description

Use synthetic porous crystalline material to carry out the method for catalyzed conversion

The present invention is Chinese patent application number 91103656.3 divides an application.

The present invention relates to a kind of method of using synthetic porous crystalline material to carry out catalyzed conversion.

Have been found that the porous inorganic solid has very multipurpose industrial as catalyst and separating medium.The opening of their micro-structurals makes various molecules can touch the sizable surface area of this class material, thereby has promoted their catalysis and sorption activity.The porous material that uses can be divided into three major types as basis of classification roughly with the details of their micro-structurals at present.Here it is amorphous and para-crystal material, crystalline molecular sieve and modified layer laminate materials.The details difference of these materials on microstructure shows as the gross differences of material catalysis and sorption property, also show as and be used for the difference of various observability matter of exosyndrome material, as their surface area, size of their holes and change conditions thereof, whether X ray diffracting spectrum exists the details with collection of illustrative plates, and the difference of each side such as viewed phenomenon when coming the research material microstructure with transmission electron microscopy and electronic diffraction.

The important porous, inorganic solid of one class of amorphous and para-crystal material representative industrial application for many years.The exemplary of this class material is to be generally used for preparing the amorphous silica of catalyst and through being usually used in the excessive property of the para-crystal aluminium oxide of solid acid catalyst and petroleum reforming catalyst carrier.

Here " amorphous " this speech is meant and does not have long-range order, thereby its pore-size tends to be distributed in the material of broad range.Another speech that is used for describing this class material is " adiaphorous to X ray ", also finds expression in the X ray diffracting spectrum in default of order, can make it not have feature usually.The porous of non-crystalline material (for example amorphous silica) is generally caused by the space between each particulate.

As the para-crystal material of transitional aluminium oxide and so on, its pore size distribution is also wide, but clearer and more definite X ray diffracting spectrum is arranged, and comprises a few broad peak usually.The microstructure of this class material is made of the small crystal region of cohesion aluminium oxide phase, and its porous is caused by the irregular cavity between these crystal regions.(K.Wrfers ﹠amp; Chanakya Misra, " oxide of aluminium and hydroxide ", Technical Paper No.19 Revised, Alcoa ResearchLaboratories, P.54-59,1987).

The size of amorphous and para-crystal material mesopore is in and is called in " mesopore " scope (mesoporous), and in this application, this scope is 1.3 to 20nm.

What do not have that the solid of clear and definite structure becomes sharp-pointed contrast with these is the very narrow material of pore size distribution, because its pore-size is to be controlled by the crystal unit of the accurate repetition of material three-dimensional skeleton.This class material is called " molecular sieve ", and wherein most important example is a zeolite.The accurate crystallization microstructure of most of zeolites shows in clear and definite X ray diffracting spectrum, generally contains many sharp-pointed very big peaks in the figure, can be used to determine uniquely this material.Equally, because the microstructural accurate repetition of crystallization, the size of this class material mesopore is very regular.The pore-size of whole zeolites of having found so far is all at " micropore ", and (microp-orous) in the scope, this scope refers generally to 0.2 to 2nm, but the full-size of report is about 1.2nm.

In stacking material, the interatomic bond cooperation on the both direction of lattice use with the 3rd direction on essential distinction is arranged, the structure like laminar unit of getting together in causing containing closely.Usually, interatomic bonding is a height covalency bonding in these thin slices, and is interacted and combined by ionic forces or Van der Waals between contiguous slices.These back two kinds of power usually can be offset by more weak relatively chemical action, and the bonding action in the thin layer between the atom then is kept perfectly and is unaffected.

Therefore in some stacking material, can force adjacent layer separately, by inserting pillar they are fixed on this separation point position then, have highly porous material thereby make with certain swelling agent.For example, some clay can water make its expand, and each of its medium clay soil layer separated by hydrone.Some other stacking material can not expand by water, but it is expanded.The example of the non-water expandable layer of this class laminate materials is at United States Patent (USP) 4,859, has in No. 648 illustratedly, comprises stacked silicate, Ma Jiadi river natural stone (magadiite), kenyaite, three titanates and perovskite.Another example of non-water expandable layer laminate materials is titanium hydrochlorate (titanometallate) material that contains the cavity that can make its expansion with some organic expander, sees United States Patent (USP) 4,831, No. 006.

The X ray diffracting spectrum of the stacking material of various struttings can have significant change, depends on that expansion and strutting are for the stacked microstructural destructiveness that is in good order state usually.In some strutting stacking material, microstructural regularity is seriously like that destroyed, so that can only observe a peak that is in the low angle zone in the X-ray diffraction figure.Its interval-d is corresponding to the interlayer repeat distance that adds in the column material.Destroy not that serious material can in this zone, present several peaks, the general and same order of magnitude of this basic repeat distance.Sometimes also can be observed X ray reflection by the crystal structure generation of each layer.Add narrower than in amorphous and the para-crystal material of pore size distribution in the column material at these, but wide than in the crystal frame material.

Stacking material is usually taked like laminar form, and it has reflected the asymmetry of the bonding action that is present in atom level.Such morphological properties can show with transmission electron microscopy.

The present invention relates to a kind of synthetic that comprises inorganic porous non-stacked crystalline phase material, after calcining, the X ray diffracting spectrum of this synthetic at interval has a peak at least greater than 1.8nm place at d-, and in the benzene adsorption capacities of 6.7KPa (50 torr) and 25 ℃ times these materials greater than 15g benzene/100g material.

In preferred embodiment, the present invention relates to a kind of synthetic inorganic, porous crystalline phase material that comprises, it have into hexagonal array, diameter is at least 1.3nm and the uniform array of apertures of size, and after calcining, it shows a d who can be used for 1.8nm ₁₀₀The hexagonal electron diffraction pattern spectrum that value indicates.

Here the pore-size of mentioning not is strict crystallography yardstick, but measures the active porosity size that is determined by sorption.The better method of measuring pore-size adopts the argon physisorphtion, and this is a kind of known technology and describes in detail in embodiment 21 (a) and 21 (b).In this method, record the quality of argon adsorbed under the sample condition that relative pressure changes in steady temperature and on the sample, and be used for drawing a constant temperature absorption line.Hole corresponding to the rapid dot mark that changes of gradient on the constant temperature absorption line and fill, and can decide pore-size with it according to the relation of the known mathematical described in the embodiment 21.

Crystalline material of the present invention (refer to here have sufficient order, making provides the material of the diffracting spectrum that has a peak at least in available X ray, electronics or neutron diffraction after the calcining) can be with the structure that comprises very large hole window unknown before it and high sorptive power as feature.Material of the present invention generally is " mesopore ", that is to say that material has diameter at 1.3 holes of uniform size to the 20mm scope.Under better situation, material of the present invention has diameter at 1.8 holes of uniform size to the 10nm scope.In this respect, pore-size is considered to the yardstick in the maximum perpendicular cross section of hole.

Material of the present invention can make a distinction with its regularity and other porous, inorganic solid of big open space, the size of this material hole more is similar to amorphous or para-crystal material, but hole regularly arranged and big or small evenly (for example, single phase inner pore Size Distribution this phase hole average-size ± 25%, usually be ± 15% or littler) then more be similar to the such crystal frame material of zeolite.

In preferable arrangement, the porosity of crystalline material of the present invention is to be provided by the array that is the open slot of hexagonal arrangement substantially, and this character can easily be observed with electronic diffraction and transmission electron microscopy.Particularly, the sample of the suitable orientation of material presents the hexagonal of vat to be arranged, and corresponding electronogram then provides the diffraction maximum point that approximate hexagonal is arranged.The d of electronogram ₁₀₀Spacing is exactly the distance between adjacent 2 in the hexagonal lattice hko projection, and passes through formula $d_{}$ ${}_{100}=a_0\sqrt{3}/2$ And the repeat distance a on the electron microscopic figure between viewed two grooves ₀Link mutually.Observed this d on electronogram ₁₀₀At interval, at interval corresponding to the d-at a low angle peak on the material X ray diffracting spectrum.The product of the highest order that this material makes so far can be observed 20-40 point clearly on electronogram.These figures can be with 100,110, and the hexagonal hko subclass of the reflection that the reflection of 200,210 uniquenesses such as grade and symmetry thereof are relevant indicates.

In this respect, when should be appreciated that the hexagonal array that mentions groove, not only comprise perfect hexagonal symmetry on the mathematics, and comprise such array that most of grooves are surrounded with the essentially identical arest neighbors groove of its distance by six in material.Defective and imperfection will make the groove of quite a lot of quantity run counter to this criterion in varying degrees.Adjacent slot presents up to ± 25% random sample that departs from average repeat distance, still can clearly provide the identifiable image of super big hole material of the present invention.

The most regular product of preferred materials of the present invention provides a hexagonal X ray diffracting spectrum that a few clear maximal point is arranged in the low angular regions of extreme.But X-ray diffractogram is the sufficient sign that exists of this class material always not, because the degree that alignment degree in microstructure and individual particle inner structure repeat can influence the number at observable peak.In fact, it is found that and have only a product at peak clearly in the X ray diffracting spectrum low angle zone, also contain quite a lot of quantity material of the present invention.

Crystalline material of the present invention, in its form after calcining, can be further with such X-ray diffraction figure as feature: this collection of illustrative plates have at least a peak be in d-at interval greater than about 1.8nm (for the K-α radiation of Cu, 2 θ be 4.909 the degree) the position, this position is corresponding to the d of described material electronics diffraction pattern ₁₀₀Value.

Under better situation, burnt crystalline material of the present invention be characterised in that its X ray diffracting spectrum have at least two peaks be in d-at interval greater than about 1nm (for the K-α radiation of Cu, 20 be 8.842 the degree) the position, wherein have at least one to be in d-, and do not have about 20% the peak of relative intensity less than the position of 1nm at interval greater than highest peak at d-at interval greater than the position of 1.8nm.Under situation more specifically, the X ray diffracting spectrum of burnt material of the present invention does not have about 10% the peak of relative intensity greater than highest peak less than the position of 1nm at interval at d-.In preferable hexagonal is arranged, have the d of the d-interval at a peak in the X ray diffracting spectrum at least corresponding to this material electronics diffraction pattern ₁₀₀Value.

The X ray diffracting data is here gathered with the automatic diffraction system of Scintag PAD X, and this system adopts θ-θ geometrical relationship, Cu K-α radiation and energy dispersion X-ray detector.Use the energy dispersion X-ray detector just not need incident or diffraction beam monochromator.Incident and diffraction X-ray beam all collimate with double slit incident and diffraction colimated light system.The size of used slit from the X-ray tube source, is respectively 0.5,1.0,0.3 and 0.2mm.Different slit systems can make each peak that varying strength is arranged.The material that has the maximum pore size among the present invention will need the more highly incident X beam of collimation, comes so that the incident X-rays bundle of low angle peak and transmission is differentiated.

Note by step-scan with per 2 θ, 0.04 degree for diffraction data, and wherein θ is a Bragg angle, and the gate time in per step is 10 seconds.Interplanar distance is calculated with millimicron (nm) from d, and the relative intensity I/I of each line ₀(I wherein ₀Be the strongest line at one of percentage of the above intensity of background) then be to derive with a linear fitting program.Each intensity is not revised Luo Lunzi and polarization effect.Relative intensity is with VS=very strong (75-100), S=strong (50-74), and m=medium (25-49), the weak symbols such as (0-24) of W=provides.Should be appreciated that in the diffraction data and list, may contain multiple superimposed spectral line as single line, they under certain condition (for example test resolution ratio very high or when crystallographic change takes place) can be rendered as each bar differentiate hold or part differentiate the line of holding.Typically crystallographic change can comprise the variation of the minor variations and/or the crystal symmetry of cell parameter, and does not have substantial variation on the structure.The effect that these are less important, comprise the variation of relative intensity, also the history that can use because of nature and extent, heat or hydro-thermal that the composition of cations, framework, hole are filled, cause by the difference of the other factors known to the caused peak width of particle size/shape effect/peak shape variation, structure disturbance or the X-ray diffraction technical staff.

Material of the present invention in the benzene adsorption capacity of 6.7KPa (50 torr) and 25 ℃ of demonstrations greater than in about 15g benzene/100g crystal.Certainly, the equilibrium adsorption ability of benzene must be the sample determination that hole is not subjected to accidental contaminants clog.For example, water can use dehydration technique (as heat treatment) to remove, and inorganic non-crystalline material (as silica) and organic matter can be by with acid, alkali or other chemical reagent contact and/or remove by physical method (as calcining), make chipped material be removed and not to material production deleterious effects of the present invention.

Crystalline material of the present invention generally has following composition:

M _N/q(W _aX _bY _cZ _dO _h) wherein W be a kind of diad, as divalence first row transition metal, for example manganese, cobalt, nickel, iron and/or magnesium are preferably cobalt; X is a kind of triad, as aluminium, boron, chromium, iron and/or gallium, is preferably aluminium; Y is a kind of quadrivalent element, as silicon and/or germanium, is preferably silicon; Z is a kind of pentad, as phosphorus; M is one or more ions, ammonium for example, IA, IA and VIIB family ion, normally hydrogen, sodium and/or fluorine ion; N is that mentioned component is removed M and is expressed as the electric charge of oxide; Q is the weighting mole flat fare of M; N/q is molal quantity or the molar fraction of M; A, b.c and d are respectively W, X, the molar fraction of Y and Z; H equals a number of 1 to 2.5; And (a+b+c+d)=1.

A preferred embodiment of above-mentioned crystalline material, be (a+b+c) greater than d, and h=2.Be more preferably h=2, a=0 and d=0.

Synthesize good form just, the composition of material of the present invention (by anhydrous calculating) can be expressed as with empirical equation:

RRM _N/q(W _aX _bY _cZ _dO _h) wherein R be synthetic and be not included in whole organic materials within the M as an ion with helping material, and r is the coefficient of R, i.e. the molal quantity of R or molar fraction.

M and R component are combined in the material owing to they are present in crystallization process, and they are removed easily, and perhaps (in the situation of M) replaces with the post crystallization method that the back more specifically illustrates.For example, the original M ion (as sodium or chlorion) in the just synthetic back of material of the present invention can be by replacing with the ion-exchange of other ion.Preferable displacement ion comprises metal ion, hydrogen ion, hydrogeneous parent ion (as ammonium) and their mixture.Especially good ion is that those can make catalytic activity satisfy the ion that some hydrocarbon conversion reactions requires.These ions comprise hydrogen, IA family (as K) on the rare earth metal and the periodic table of elements, IIA family (as Ca), VIIA family (as Mn), VIIIA family (as Ni), IB family (as Cu), IIB family (as Zn), IIIB family (as In), IVB family (as Sn) and VIIB family metal and their mixtures (referring to Sargent-Wclch Scientific Co.Cat.No.S-18806,1979) such as (as F).

Material with composition that following formula defines can be made by the reactant mixture with following composition, and the composition range of representing with oxide mol ratio of this mixture is:

The useful scope preferred range of reactant

X ₂O ₃/ YO ₂0 to 0.5 0.001 to 0.5

X ₂O ₃/ (YO ₂+ Z ₂O ₅) 0.1 to 100 0.1 to 20

X ₂O ₃/ (YO ₂+ WO+Z ₂O ₅) 0.1 to 100 0.1 to 20

Solvent/

(YO ₂+ WO+Z ₂O ₅+ X ₂O ₃) 1 to 1,500 5 to 1000

OH ^-/ YO ₂0 to 10 0 to 5

(M _2/eO+R _2/fO)/

(YO ₂+ WO+Z ₂O ₅+ X ₂O ₃) 0.01 to 20 0.05 to 5

M _2/eO/

(YO ₂+ WO+Z ₂O ₅+ X ₂O ₃) 0 to 10 0 to 5

R _2/fO/

(YO ₂+ WO+Z ₂O ₅+ X ₂O ₃) 0.01 to 2.0 0.03 to 1.0

Wherein e and f are respectively the weighted average chemical valences of M and R, and solvent wherein is a kind of C ₁To C ₆Alcohol or glycol, perhaps be more preferably water, and R comprises that general formula is R ₁R ₂R ₃R ₄Q ⁺Organic directing agent, wherein Q is nitrogen or phosphorus, and R ₁, R ₂, R ₃And R ₄In have at least one to be aryl or alkyl with 6 to 36 carbon atoms, as-C ₆H ₁₃,-C ₁₀H ₂₁,-C ₁₆H ₃₃With-C ₁₈H ₃₇, remaining R ₁, R ₂, R ₃And R ₄The alkyl that each all is selected from hydrogen and has 1 to 5 carbon atom.Derive above-mentioned An with the compound of Phosphonium ion can be hydroxide, halide, silicate or their mixture.

The special validity of above-mentioned directing agent, when compare with directing agent of directed synthetic one or more other crystal structures of known other, it is believed that be since it the nucleus of required super big hole material form and growth in play the ability of model effect.The nonrestrictive example of this class directing agent comprises cetyltrimethyl ammonium, octadecyl San Jia Ji Phosphonium, benzyltrimethylammon.um, cetyl pyridinium, the myristyl trimethyl ammonium, decyl trimethyl ammonium, compounds such as dodecyl trimethyl ammonium and dimethyl two (dodecyl) ammonium.

Be present in the total organic matter R in the reactant mixture, preferably include additional organic directing agent of the An Huo Phosphonium ionic species that a kind of above-mentioned directing agent molecular formula represents, but R wherein ₁, R ₂, R ₃, R ₄Each all is the alkyl (alkyl can two couple together constitute cyclic compound) that is selected from hydrogen and has 1 to 5 carbon atom.The example of additional organic directing agent comprises tetramethyl-ammonium, tetraethyl ammonium, tetrapropyl ammonium, compounds such as TBuA and pyrrolidines.Organic directing agent of at first mentioning can be in 100/1 to 0.01/1 scope with the mol ratio of additional organic directing agent.When existence adds organic directing agent, R in the reactant mixture _2/fO/ (YO ₂+ WO+Z ₂O ₅+ X ₂O ₃) mol ratio be advisable preferably 0.12 to 1.0 with 0.1 to 2.0.

In addition, in order to change the pore-size of final crystalline phase material, can outside above-mentioned organic directing agent, comprise a kind of auxiliary organic matter in the reactant mixture.Should auxiliary organic matter be to be selected from aromatic hydrocarbon and amine and replacement of their halogen and the C that (1) has 5-20 carbon atom ₁-C ₁₄Alkyl-substituted derivatives, (2) have ring-type and many cycloaliphatic hydrocarbon and amine and the replacement of their halogen and the C of 5-20 carbon atom ₁-C ₁₄Alkyl-substituted derivatives, (3) have straight chain and branched aliphatic hydrocarbons and the amine and their the halogen substitutive derivative of 3-16 carbon atom.

In above-mentioned auxiliary organic matter, halogenic substituent is bromine preferably, C ₁-C ₁₄Alkyl substituent can be the aliphatic chain of straight or branch, for example methyl, ethyl, propyl group, isopropyl, butyl, amyl group and their combination.The auxiliary organic example of this class comprises paraxylene, trimethylbenzene, triethylbenzene and triisopropylbenzene.

In reactant mixture, be mingled with when assisting organic matter (auxiliary organic matter)/YO ₂Mol ratio will be 0.05 to 20, preferably 0.1 to 10, and the mol ratio of (auxiliary organic matter)/(organic directing agent) will be preferably 0.05 to 35 0.02 to 100.

When in synthetic method, using a silicon source, preferably use a kind of organosilicate, for example quaternary ammonium silicate to small part.The nonrestrictive example of this silicate comprises tetramethyl-ammonium silicate and tetraethyl orthosilicate.

Imagination is used for the various of above-mentioned reactant mixture, W, and X, Y, the non-limitative example of Z combination comprises:

W X Y Z

- Al Si -

- Al - P

- Al Si P

Co Al - P

Co Al Si P

--Si-comprise that W is a kind of element (as Mn, Co and Ni) of Mg or first row transition metal that is selected from divalence; X is B, Ga or iron; And Y is the various combinations of Ge.

In order to make crystalline material of the present invention, above-mentioned reactant mixture is the temperature at 25 to 250 ℃, is preferably at 50 to 175 ℃, pH is preferably under 9 to 14 the condition, it is maintained to the required crystal of generation, and the general duration is 5 minutes to 14 days, preferably 1 to 300 hour.

When crystalline material of the present invention was a kind of alumina silicate, synthetic method can may further comprise the steps easily:

(1) organic directing agent (R) is mixed with solvent or mixed solvent, make solvent/R _2/fThe O mol ratio in 50 to 800 scope, preferably 50 to 500." original pattern " of this mixture constructive method.

(2) in the original pattern mixture of step (1), add silica and aluminium oxide, make R _2/fO/ (SiO ₂+ Al ₂O ₃) ratio in 0.01 to 2.0 scope.

(3) mixture of whipping step (2) gained under 20 to 40 ℃ temperature, mixing time is with better in 5 minutes to 3 hours.

(4) allow this mixture in stirring or not, put 10 minutes to 24 hours with stirring, be preferably under 20 to 50 ℃ temperature.

(5) under 50 to 150 ℃ temperature, make the product crystallization 1 to 72 hour of step (4).

When effect sorbent or catalytic component, synthetic of the present invention should be through handling, partly or wholly to remove its organic component.This synthetic also can be combined closely with a hydrogenation component in the place that needs are carried out hydrogenation-dehydrogenation function and as catalytic component, the example of hydrogenation component is a kind of noble metal or its mixture of tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese or platinum, palladium and so on.Such component can be passed through cocrystallization, exchanges within the composition so that reach the degree that IIIB family metal (as aluminium) exists in the structure, is impregnated into its inside, with it closely physics mode such as be blended together and enter within the synthetic.Such component (under the situation of platinum) for example can by handle with the ion solution that contains platinum metal that silicate is impregnated within the synthetic or on.The platinum compounds that is fit to this purpose comprises chloroplatinic acid, platinous chloride and all cpds that contains platinum and amine complex compound.

Above-mentioned crystalline material, particularly its metal, hydrogen and ammonia form can advantageously be converted into another form by heat treatment (calcining).This heat treatment was generally carried out 1 minute under 400-750 ℃ temperature at least, was no more than 20 hours usually, preferably 1 to 10 hour.Though can adopt pressure below atmospheric pressure during heat treatment, for convenience's sake, more be willing to use atmospheric pressure, for example in air, nitrogen and ammonia.Be specially adapted to some hydrocarbon conversion reactions of catalysis through heat treated product.

Crystalline material of the present invention should be through dehydration when being used as adsorbent or being used as the catalytic component of organic compound conversion process, dehydration at least in part.This can be by in atmosphere such as air, nitrogen, under normal pressure, decompression and pressurized conditions, and heating 30 minutes to 48 hours in 200-595 ℃ the temperature range and reaching.Dehydration also can at room temperature only be placed on this synthetic in the vacuum to be carried out, but will obtain the longer time of dehydration needs of quantity sufficient.

Various composition useful as catalysts component of the present invention, transform (as oxide and hydro carbons) by acid catalyzed reaction catalysis organic compound.The size of hole be make in reactions such as cracking specific selectivity with respect to the space of transition state animal kind be minimum (Chen etc. " shape in the commercial Application selects catalysis " 3 6CHEMICAL INDUSTRIES 41-61 page or leaf (1989)).Because material of the present invention mesopore is very big, thereby diffusion-restricted also is reduced to minimum.Owing to these reasons, synthetic of the present invention is specially adapted to the following reaction of catalysis: these are reflected under the condition that there is acid position in catalyst surface and take place, and relate to reactant with big molecular dimension, product and transition state species, its molecular dimension too big so that can not with conventional macrovoid solid catalyst (as X zeolite, Y, L, ZSM-4, macrovoid zeolites such as ZSM-18 and ZSM-20) similar reaction takes place.

So, catalyst component of the present invention is specially adapted to have the conversion of the organic compound of big molecular dimension, as have a hydro carbons that replaces or do not replace the height aromatics of polycyclic aromatic component, huge naphthenic compound or have the compound that the height of huge spatial configuration replaces, for example molecular dimension is 1.3nm or bigger compound.The molecular weight that this catalyst component is particularly useful for raw material is reduced to the reaction (being cracking or hydrocrack) of smaller value.Cracking can be 200-800 ℃ in temperature, pressure be atmospheric pressure to 100psig (100-800KPa), be to carry out under 0.1 second to 60 minutes the condition time of contact.Hydrocracking can be 150-550 ℃ in temperature, and pressure is 100-3000psig (800-20800KPa), and weight per hour space velocity is 0.1-100, and hydrogen/hydrocarbon mol ratio is to carry out under the condition of 0.1-100.

The reaction of the reaction that raw material rose, particularly residuum feedstocks that this catalyst component is particularly useful for using HMW, higher boiling maybe can not distill (i.e. the raw material that can not distill basically or play the raw material of bubble point (5% point) more than 1050 (565 ℃)).Can comprise that api gravity is lower than about 20 with the residuum feedstocks that this catalyst composition uses, be usually less than 15, representative value is 5-10, and Conradsen Kang Laxun carbon residue content (CCR) is at least 1% weight, more generally be at least 5% or more, as the raw material of 5-10%.CCR can be up to 20% weight even higher in some residual oil fraction.The arene content of these raw materials is also correspondingly high, and the content of hetero atom (as sulphur and nitrogen) and metal also is correspondingly high.The arene content of these raw materials generally is at least 50% weight, and much higher in typical case (usually being at least 70-80% weight), all the other mainly are cycloalkanes and heterocyclic compound.Such oil plant feedback material is typically and comprises normal pressure and vacuum column Residual oil, pitch is by the aromatics extract that solvent extraction process (as phenol or furfural extraction) obtains, deasphalting oil, waste oil, and make residual cut in the class process of lubricating oil, coking.Can comprise gas oil (as normal pressure gas oil) with the high boiling fraction that this catalyst component uses; Vacuum gas oil; Recycle oil, especially heavy-cycle oil; Deasphalted oil; Solvent extract is as bright stock; And heavy gas oil, as heavy coking gas oil.This catalysis material also can be applicable to the feedback material of non-petroleum sources, the artificial oil that for example coal liquefaction produced, cured and its heavy oil fraction and other materials similar that obtain in the Fischer-Tropsch building-up process.

Also can be used for the selective conversion of inorganic compound according to catalyst composition of the present invention, for example make and contain nitrogen oxide (NO _x) admixture of gas (as industrial waste gas and hydro carbons is processed catalyst system therefor in the operation of catalytic pyrolysis particularly carry out the gas that generates in the oxidative regeneration process) in nitrogen oxide transform, this porous crystalline material can be used for this purpose with the form that matrix is arranged or do not have a matrix, and can suitably form extrudate, ball sheet or other shape are passed through catalyst thereby allow gas to fall with the pressure of minimum.Crystalline material preferably is Hydrogen at least in part, but also can advantageously contain small amount of precious metals (particularly using metal, the especially platinum in periodic table VIIIA family the 5th and the 6th cycle, palladium, rubidium, rhodium, iridium or their mixture) as catalyst component.The typical amounts of noble metal is below 1% weight, but the most handy lower quantity, for example below 0.1 or 0.5% weight.

NO _xReduction, be that the gas that contains nitrogen oxide by catalyst is undertaken improving under the temperature (typical temperature is 200 ℃, generally 200-600 ℃ of scope) at least.This admixture of gas can mix with ammonia promoting the reduction of nitrogen oxide, and premixed can be carried out under the temperature of height to 200 ℃.The quantity of the ammonia that mixes mutually with admixture of gas, it generally is 0.75 to 1.25 scope in stoichiometric, and stoichiometric quantity itself also is that the ratio according to various nitrogen oxide in the admixture of gas becomes, shown in following reaction equation:

Crystalline material of the present invention also can be used for nitrogen oxide in the reducing gas mixture under the condition that other reducing agent (as carbon or carbon monoxide) exists.The nitrogen oxide that reduces by this way has special purposes for the regeneration of fluid catalytic cracking (FCC) catalyst, to produce the carbon monoxide of desired concn because regenerate under proper condition, it will be used to reduce NO in the regeneration gas under the condition that catalyst exists _xRatio.

Composition of the present invention also can be used as adsorbent and separate medium body in pharmaceutical chemistry or fine chemistry application.For example, these super large hole synthetics can be used to purify medicine of insulin and so on or solid carrier that discharges as medicine control.It is waste disposal that the another kind of these super big hole gap materials is used, and this has developed its unusual pore volume.Therefore, the mixture that has the difference sorption properties with respect to super large hole synthetic of the present invention for each component, by mixture is contacted with said composition,, just a kind of component partially or substantially all can be separated from mixture at least with a certain component of sorption optionally.The example of this separation comprises and contacting with composition with the mixture of at least a hydrocarbon component containing water that this at least a hydrocarbon component is with regard to selected sorption.Another example is to select at least a hydrocarbon component of sorption from the mixture that comprises hydrocarbon component and at least a additional hydrocarbons component.

When as catalyst, may wish the material of used temperature and other condition in crystal composition of the present invention and the another kind of anti-anti-organic transformation technology is combined.These materials comprise activity and non-active material, synthetic and natural zeolite, and the metal oxide of the inorganic material of clay, silica and so on and/or aluminium oxide, titanium oxide, zirconia and so on.The latter can be natural, also can be the form (mixture that comprises silica and metal oxide) of gum deposit or colloid.Use and new crystal combination material together,, the conversion ratio and/or the selectivity of catalyst in some organic transformation process are changed promptly with its chemical combination or be present in new crystal building-up process (new crystal is active).Non-active material can be suitably as diluent, controlling the inversion quantity in the given process, thereby obtains product economically and regularly and need not adopt other method to control reaction rate.These materials can combine with natural clay (as bentonite and kaolin), to improve the crushing strength of catalyst under the commercial operation condition.Described material (being clay, oxide etc.) plays a part the adhesive of catalyst.People wish to provide a kind of catalyst with good crushing strength, because wish to prevent catalyst breakage powdering material on commerce is used.Usually these clay adhesives just adopt for the crushing strength of improving catalyst.

Can comprise imvite family and kaolin group with the natural clay of new crystal combination, this two family comprises sub-Ben (Subbentonite), the common Dixie of being called clay, McNamee clay, Georgia clay, the lourie that boils reach clay or essential mineral composition be halloysite (hal-loysite) kaolinite, open other various kaolin of face (dickite), nacrite (nacrite) or anauxite (an  ux-ite).These clays can use in the rough that exploitation is come out, and perhaps at first re-use through calcining, acid treatment or chemical modification.

Outside above-mentioned material, new crystal also can with as silica-alumina, silica-magnesia, silica-zirconia, silica-thorium oxide, silica-beryllia, silica-titanium oxide and ternary complex such as silica-alumina-thorium oxide, silica-alumina-zirconia, certain porous matrix material of silica-alumina-magnesia and silica-magnesia-zirconia etc. combines.

Above-mentioned matrix material preferably can have at least a part to provide with colloidal form, so that the easy extrusion molding of the catalyst various ingredients of combination.

The crystalline material that separates subtly and the relative scale of inorganic oxide matrix can have a great difference, and crystalline content is at the 1-90% weight range, and (particularly compound is made under the situation of pearl) more generally is at the 2-80% of complex weight range.

Hereinafter with reference to embodiment and accompanying drawing the present invention is described more specifically, wherein:

Fig. 1-14 is respectively the X ray diffracting spectrum of the product of embodiment 1-13 and 15.

Figure 15 is the isothermal adsorption curve that physical absorption is measured among the embodiment 21.

Figure 16 is the figure that gained is measured in physical absorption among the embodiment 21, shows the pore-size of various crystalline materials.

Figure 17 is the electronic diffraction collection of illustrative plates of the product of embodiment 4.

Figure 18 is the transmission electron microscopy figure of the product of embodiment 4.

Figure 19 is the transmission electron microscopy figure of the product of embodiment 5.

Figure 20 is the transmission electron microscopy figure of the product of embodiment 18.

Figure 21 is the X ray diffracting spectrum of the product of embodiment 23.

Figure 22 shows d-at interval the influence of auxiliary organic matter to first X-ray diffraction maximum of embodiment 23-31.

Figure 23 is embodiment 23,25, the pore-size of 26,28,29,31 product and X ray d-graph of a relation at interval.

Figure 24 is embodiment 23,25, the pore volume of 26,28,29,31 product and X ray d-graph of a relation at interval.

Figure 25-28 is respectively the X ray diffracting spectrum of the product of embodiment 46-49.

In each embodiment, when providing the sorption data with relatively to the sorptive power of water, cyclohexane, benzene and/or n-hexane the time, they are equilibrium adsorption values of measuring by the following method:

With a load weighted sample of sorbent, calcined at least about 1 hour at about 540 ℃, handle through other more in case of necessity, to remove the pollutant of any block pores, in adsorption chamber, contact again with pure absorbate gas to be measured.The increase of adsorbent weight is the adsorption capacity that unit is calculated as sample with g/ (100g adsorbent) just, is benchmark with the weight of adsorbent after about 540 ℃ of calcinings during calculating.This synthetic in the balance benzene adsorption capacity of 50 torrs (6.7KPa) and 25 ℃ greater than about 15g/100g, preferably greater than about 17.5g/100g, better greater than about 20g/100g.

Measuring the better method of adsorption capacity, is in being evacuated to the adsorption chamber that pressure is lower than 1mm material of the present invention to be contacted with pure absorbate gas to be measured.Making pressure keep constant by a barostat control adding absorbate gas between adsorption cycle (stablizes extremely approximately ± 0.5mm).When the new crystal absorption of adsorbed material quilt, the reduction of pressure will make barostat open a valve, make more adsorbate inlet chamber interior to recover above-mentioned controlled pressure.When the pressure deficient change when starting barostat, adsorption process has just been finished.

The another kind of method of measuring the absorption of benzene is to carry out with a suitable thermogravimetric analysis system, for example computer-controlled 990/951 du Pont TGA system.With sample of sorbent in the helium that flows about 350 ℃ or 500 ℃ of following thermal dehydrations to constant weight constant (removing the moisture of physical absorption).If sample is in just synthetic good form, for example contain organic directing agent, it be in air, dewater under about 540 ℃ constant rather than take above-mentioned 350 ° or 500 ℃ of processing to constant weight.The absorption isotherm of benzene is 25 ℃ of measurements, during measurement with the saturated helium flow of a branch of benzene and a branch of pure helium flow by the proper proportion fusion to obtain required benzene dividing potential drop.Try to achieve at the adsorptive value of 50 torrs (6.7KPa) benzene by absorption isotherm figure.

Embodiment 1

With 100g cetyltrimethyl ammonium (CTMA) hydroxide solution-this solution is with N, N, N-trimethyl-1-cetyltrimethyl ammonium muriatic 29% (weight) solution contact with a kind of ion exchange resin with hydroxyl ion exchange halogen ion and prepare-mix with the aqueous silicate solution (10% silica) of 100g tetramethyl-ammonium (TMA).Add 25gHisil (a kind of contain the free moisture of 6% weight of having an appointment and the precipitation water in conjunction with moisture of about 4.5% weight contains silica, its limit granular size is about 0.02 μ).The gained mixture is put into a polypropylene vial, and this bottle is placed in 95 ℃ the steam chest and spends the night.The ingredients of a mixture is corresponding to every mole of Al ₂O ₃Contain

2.7 mole Na ₂O

392 moles of SiO ₂

35.7 mole (CTMA) ₂O

61.7 mole (TMA) ₂O

6231 moles of H ₂O

Reclaim by filtering the solid product that will produce, and air drying at ambient temperature.Then product was calcined 1 hour the calcining in air that continues 6 hours in 540 ℃ of following nitrogen.

It is 475m that product after the calcining records surface area ²/ g, and have following equilibrium adsorption ability (unit is g/100g):

H ₂O8.3

Cyclohexane 22.9

N-hexane 18.2

Benzene 21.5

The X-ray diffractogram of present embodiment calcined product as shown in Figure 1.In Ben Tu and later each figure, the d-that please notes 10 dusts (1.0nm) is at interval corresponding to 8.842 20 (the K-α radiation of Cu) of spending, and 18 dusts (1.8mm) are corresponding to 4.909 degree.

The feature of present embodiment product is to be spaced apart 3.78 ± 0.2nm place at d-the very strong line of one relative intensity is arranged, and 2.16 ± 0.1 and 1.92 ± 0.1nm place weak line is respectively arranged.Present described super big hole material is present in this fact in the present embodiment product, is shown by transmission electron microscopy (TEM), and its produces resembling and d of even space that hexagonal arranges ₁₀₀Equal the hexagonal electron diffraction pattern of 3.9nm.

Embodiment 2

Hydroxide (25%) aqueous solution of 100g cetyltrimethyl ammonium (CTMA) hydroxide (prepared as embodiment 1) with 100g tetramethyl-ammonium (TMA) is mixed.Add 25gHisiL (a kind of contain the free moisture of 6% weight of having an appointment and the precipitation water in conjunction with moisture of about 4.5% weight contains silica, its limit granular size is about 0.02 μ).The mixture of gained is put into a fixing autoclave to spend the night at 150 ℃.This ingredients of a mixture is corresponding to every mole of Al ₂O ₃Contain:

2.7 mole Na ₂O

291 moles of SiO ₂

35.7 mole (CTMA) ₂O

102 moles (TMA) ₂O

6120 moles of H ₂O

Reclaim by filtering the solid product that will produce, and air drying at ambient temperature.Then product was calcined 1 hour the calcining in air that continues 6 hours in 540 ℃ of following nitrogen.

It is 993m that product after the calcining records surface area ²G, and have following equilibrium adsorption ability (unit is g/100g):

H ₂O7.1

Cyclohexane 47.2

N-hexane 36.2

Benzene 49.5

The X-ray diffractogram of present embodiment calcined product as shown in Figure 2.It is characterized in that being spaced apart 3.93 ± 0.2nm place at d-has the very strong line of a relative intensity, and 2.22 ± 0.1 and 1.94 ± 0.1nm place respectively have weak line, TEM to demonstrate this product to comprise super big hole material of the present invention.

Then the part in the above-mentioned product is contacted 2 hours with 100% water vapour at 790 ℃ (1450 °F), the surface area that records the material of this steaming is 440m ²/ g shows through about 45% of fierce boiling rear surface to remain.

Another part calcined product of this embodiment is contacted 2 hours at 680 ℃ (1250 °F) with 100% steam, and the surface area that records this material is 718m ²/ g shows that 72% of steam treatment rear surface under these conditions is retained.

Embodiment 3

With water, as embodiment 1 prepared cetyltrimethyl ammonium hydroxide solution, aluminum sulfate, HisiL and a kind of tetrapropyl ammonium (TPA) bromide (35%) aqueous solution produce a kind of mixture, and this ingredients of a mixture is with regard to every mole of Al ₂O ₃And opinion is:

0.65 mole Na ₂O

65 moles of SiO ₂

8.8 mole (CTMA) ₂O

1.22 mole (TMA) ₂O

1336 moles of H ₂O

The mixture of gained is placed in the polypropylene vial, this bottle is placed in 95 ℃ of steam chests 192 hours, mix with the sample cool to room temperature and with the TMA hydroxide solution of embodiment 1 prepared CTMA hydroxide solution and 25% (weight) then, mixing is by following weight ratio: 3 fens said mixtures, 1 part of CTMA hydroxide and 2 parts of TMA hydroxide, the mixture that this mixing is obtained is placed in the polypropylene vial then, and preserves in 95 ℃ of steam chests and spend the night.The composition of this mixture is with regard to every mole of Al ₂O ₃And opinion is:

0.65 mole Na ₂O

65 moles of SiO ₂

15 moles (CTMA) ₂O

1.22 mole (TPA) ₂O

35.6 mole (TMA) ₂O

2927 moles of H ₂O

Reclaim by filtering the solid product that will produce, and air drying at ambient temperature, then this product was calcined 1 hour in 540 ℃ nitrogen, that continues aloft calcined 6 hours.

It is 1085m that product after the calcining records surface area ²/ g, and have equilibrium adsorption ability (unit is g/100g) under several:

H ₂O11.5

Cyclohexane＞50

N-hexane 39.8

Benzene 62

The X-ray diffractogram of present embodiment calcined product as shown in Figure 3.The feature of present embodiment product is to be spaced apart 3.82 ± 0.2nm place at d-the very strong line of one relative intensity is arranged, and 2.22 ± 0.1 and 1.94 ± 0.1nm place respectively have weak line, TEM to demonstrate this product to comprise super big hole gap material of the present invention.

Embodiment 4

With 200g such as embodiment 1 prepared cetyltrimethyl ammonium (CTMA) hydroxide solution and 2gCatapal alumina (α-Al ₂O ₃-hydrate, 74%Al ₂O ₃) and 100 gram tetramethyl-ammonium (TAM) silicate (10%SiO ₂) aqueous solution mixes.Add 25g HisiL (a kind of free moisture of 6% weight of having an appointment and precipitated hydrated silica in conjunction with moisture of about 4.5% weight of containing, its limit granular size is about 0.02 μ).The gained mixture is put into a fixing autoclave, placed 48 hours at 150 ℃, the composition of this mixture is with regard to every mole of Al ₂O ₃And opinion is:

0.23 mole Na ₂O

33.2 mole SiO ₂

6.1 mole (CTMA) ₂O

5.2 mole (TMA) ₂O

780 moles of H ₂O

Reclaim by filtering the solid product that will produce, and in the air at ambient temperature in dry, then this product calcine 1 hour in 540 ℃ nitrogen, that continues calcined 6 hours in air.

It is 1043m that product after the calcining records surface area ²/ g, and have following equilibrium adsorption ability (unit is g/100g):

Water 6.3

Cyclohexane＞50

N-hexane 49.1

Benzene 66.7

The X-ray diffractogram of the burnt product of present embodiment as shown in Figure 4.It is characterized in that being spaced apart 4.08 ± 0.2nm place at d-has the very strong line of a relative intensity, and 2.31 ± 0.1 and 2.01 ± 0.1nm place weak line is respectively arranged.TEM shows that this product comprises super big hole gap material of the present invention (seeing example 22).

Embodiment 5

With 260g and 77g phosphoric acid (85%), 46g Catapal aluminium oxide (74% aluminium oxide) and 24g pyrrolidines (PYr) mix in stirring.The autoclave pressure that this first mixture is put into stirring is heated to 150 ℃ and kept 6 days.Filtration of material is come out, clean and the air drying.Product 50g and 200g water and 200g are made into slurry by the cetyltrimethyl ammonium hydroxide solution of embodiment 1 preparation.And then add 400g tetraethyl ammonium silicate solutions (10% silica) and form second mixture, this mixture is put into a polypropylene vial, and be placed in 95 ℃ the steam chest and spend the night.First the ingredients of a mixture is corresponding to every mole of Al ₂O ₃Contain:

1.0 mole P ₂O ₅

0.51 mole (PYr) ₂O

47.2 mole H ₂O

Reclaim by filtering the solid product that will produce, and dry under air at room temperature, and product was calcined 1 hour in 540 ℃ nitrogen then, calcined 6 hours in air again.

Recording burnt product, to record surface area be 707m ²/ g, and have following equilibrium adsorption ability (is unit with g/100g):

H ₂O33.2

Cyclohexane 19.7

N-hexane 20.1

Benzene 23.3

The X-ray diffractogram of the burnt product of present embodiment as shown in Figure 5.Its feature is to be spaced apart 2.54 ± 0.15nm place at d the very strong line of a kind of relative intensity is arranged.TEM shows that product contains super big hole gap material of the present invention (seeing embodiment 22).

Embodiment 6

With 1.35gNaAlO ₂(43.5%Al ₂O ₃, 30%Na ₂O) be dissolved in the solution and the 17.3g NaOH of 45.2g water gained, 40% aqueous solution of 125.3g cataloid (40%, Ludox HS-40) and 42.6g tetraethyl ammonium (TEA) hydroxide together.After stirring is spent the night, mixture is placed in the steam chest (95 ℃) heating 7 days.After the filtration, 151g solution and 31g are mixed by the cetyltrimethyl ammonium hydroxide solution of embodiment 1 preparation, and seasoning 13 days in 95 ℃ steam chest.Mixture has following relative mole and forms:

0.25 mole Al ₂O ₃

10 moles of Na ₂O

36 moles of SiO ₂

0.95 mole (CTMA) ₂O

2.5 mole (TEA) ₂O

445 moles of H ₂O

Reclaim by the solid product that filters gained, and water and ethanol cleaning.Then product was calcined 1 hour in 540 ℃ of nitrogen, in air, calcined 6 hours again.

The product that alkene burnt contains 0.14% weight Na, 68.5% weight SiO ₂With 5.1% weight Al ₂O ₃, and the equilibrium benzene adsorption capacity that records it is 58.6g/100g.

The X-ray diffractogram of the burnt product of present embodiment as shown in Figure 6.Its feature is to be spaced apart 3.14 ± 0.15nm place at d-a line that relative intensity is very strong is arranged.TEM shows that product contains super big hole gap material of the present invention.

Embodiment 7

With 150g by the mixture (initial pH is 12.64) of cetyltrimethyl ammonium (CTMA) hydroxide of embodiment 1 preparation and 21g cataloid (40%Ludox HS-40) in-300cc autoclave under 150 ℃ with 200rpm agitating heating 48 hours.The ingredients of a mixture is to contain corresponding to every mole of SiO:

0.5 mole (CTMA) ₂O

4 6.5 moles of H ₂O

Reclaim by filtering the solid product that will produce, water cleans, and calcines 6 hours in 540 ℃ air then.

Record 0.01% weight sodium that consists of of burnt product, 93.2% weight SiO ₂With 0.016% weight Al ₂O ₃, its surface area is 992m ²/ g, and have following equilibrium adsorption ability (is unit with g/100g):

Water 4.6

Cyclohexane＞50

N-hexane＞50

Benzene 62.7

The X-ray diffractogram of the burnt product of present embodiment its feature as shown in Figure 7 is to be spaced apart 4.36 ± 0.2nm place at d-the very strong line of one relative intensity is arranged, and 2.51 ± 0.15 and 2.17 ± 0.1nm place weak line is respectively arranged.TEM shows that this product comprises super big hole gap material of the present invention.

Embodiment 8

The 4.15g sodium aluminate slowly is added to 100g water contains 16g myristyl trimethylammonium bromide (C ₁₄TMABr) in the solution.And then in this mixture, add tetramethyl-ammonium silicate (100g-10%SiO ₂), HiSil (25g) and tetramethyl-ammonium hydroxide (14.2g-25% solution).This mixture has following relative mol composition:

1.9 mole Al ₂O ₃

3.0 mole Na ₂O

54 moles of SiO ₂

2.4 mole (C ₁₄TMA) ₂O

6.1 mole (TMA) ₂O

628 moles of H ₂O

Mixture was placed in the inherent 120 ℃ of stirrings of autoclave crystallization 24 hours.Products therefrom is filtered, clean and the air drying.Elementary analysis shows that product contains 53.3% weight SiO ₂, 3.2% weight Al ₂O ₃, 15.0% weight C, 1.88% weight N, 0.11% weight Na, and 1000 ℃ ash content is 53.5% weight.Fig. 8 calcines 1 hour X ray diffracting spectrum of 6 hours material of calcining in air again through 540 ℃ in nitrogen.This diffraction pattern d-is spaced apart 3.53 ± 0.2nm place the very strong line of a relative intensity, and be spaced apart 2.04 ± 0.1 and 1.77 ± 0.1 places at d weak line is arranged.TEM shows that product contains super big hole gap material of the present invention.

Burnt again product has 827m after washing also at room temperature exchanges with the 1N ammonium nitrate solution ²The surface area of/g and following equilibrium adsorption ability (unit is that g/100g does not have water absorbent):

Water 30.8

Cyclohexane 33.0

N-hexane 27.9

Benzene 40.7

Embodiment 9

The 8.3g sodium aluminate slowly is added to the water-reducible 184g dodecyl trimethyl ammonium of 480g hydroxide (C ₁₂TMAOH, 50%) in the solution.In this mixture, add Ultra Sil (50g) and tetramethyl-ammonium silicate (200g-10%SiO again ₂) aqueous solution and tetramethyl-ammonium hydroxide (26.38g-25% solution).Mixture has following relative mol composition:

0.36 mole Al ₂O ₃

0.55 mole Na ₂O

11 moles of SiO ₂

1.9 mole (C ₁₂TMA) ₂O

1.2 mole (TMA) ₂O

394 moles of H ₂O

11.1 mole isopropyl alcohol

Mixture is put into autoclave crystallization 24 hours under 100 ℃ of stirrings.Products therefrom is filtered, clean and the air drying.Fig. 9 is the X ray diffracting spectrum that 6 hours material was calcined in calcining in 1 hour then in air in 540 ℃ of nitrogen.Being spaced apart 3.04 ± 0.15nm place at d on the X ray diffracting spectrum has the very strong line of a relative intensity, and d be spaced apart 1.77 ± 0.1 and 1.53 ± 0.1nm place weak line is arranged.TEM shows that product contains super big hole material of the present invention.

Through cleaning, burnt again sample has 1078m after at room temperature exchanging with the 1N ammonium nitrate solution ²The surface area of/g and following equilibrium adsorption ability (unit is that g/100 does not have water absorbent):

Water 32.6

Cyclohexane 38.1

N-hexane 33.3

Benzene 42.9

Embodiment 10

With 4.9g NaAlO ₂(43.5%Al ₂O ₃, 30%NaO ₂) solution in 37.5g water and 40% aqueous solution of 46.3cc tetraethyl ammonium hydroxide and 96g cataloid (40%, Ludox HS-40) mixing.With gel vigorous stirring 0.5 hour, mixes by the cetyltrimethyl ammonium hydroxide solution of embodiment 1 preparation with isopyknic (150ml) again, reacted 168 hours down at 100 ℃.The composition of this mixture is corresponding to every mole of Al ₂O ₃Contain:

1.1 mole Na ₂O

30.6 mole SiO ₂

3.0 mole (TEA) ₂O

3.25 mole (CTMA) ₂O

609 moles of H ₂O

Reclaim by filtering the solid product that will produce, water cleans, and calcines 6 hours in 540 ℃ of air then.

Burnt product has 1352m ²The surface area of/g and following equilibrium adsorption ability:

Water 23.6

Cyclohexane＞50

N-hexane 49

Benzene 67.5

The X ray diffracting spectrum of the burnt product of present embodiment as shown in figure 10.It is characterized in that being spaced apart 3.85 ± 0.2nm place at d-has the very strong line of a relative intensity, and one weak line is arranged at 2.03 ± 0.1nm place.TEM shows that product contains super big hole gap material of the present invention.

Embodiment 11

Cetyltrimethyl ammonium (CTMA) hydroxide solution of 200g being pressed embodiment 1 preparation under agitation mixes with 4.15g sodium aluminate and 100g tetramethyl-ammonium TMA aqueous silicate solution (10% silica).Add 25g HiSiL (a kind of have an appointment 6% weight percent free moisture and about 4.5% weight of containing is in conjunction with moisture, and limit particle size is the precipitated hydrated silica of 0.02 μ m).The mixture of gained is put into static autoclave pressure to be put 24 hours down at 150 ℃.The composition of mixture is corresponding to every mole of Al ₂O ₃Contain:

1.25 mole Na ₂O

27.8 mole SiO ₂

5.1 mole (CTMA) ₂O

4.40 mole (TMA) ₂O

650 moles of H ₂O

Reclaim by filtering the solid product that will produce, and dry under the environment temperature in air.Then product was calcined 1 hour in 540 ℃ of nitrogen, in air, calcined 6 hours again.TEM shows that this product contains super big hole material of the present invention.The X-ray diffractogram of the burnt product of present embodiment as shown in figure 11.It is characterized in that being spaced apart 4.42 ± 0.2nm place at d has the very strong line of a relative intensity, and 2.52 ± 0.15 and 2.2 ± 0.1nm place weak line is arranged.

The product that records calcining has 932m ²The surface area of/g and following equilibrium adsorption ability (unit is g/100g):

Water 39.3

Cyclohexane 46.6

N-hexane 37.5

Benzene 50

Then with the product and the 1N NH of present embodiment ₄NO ₃Solution is made ammonium ion exchange, calcines 10 hours under 540 ℃ in air again.

Embodiment 12

Cetyltrimethyl ammonium (CTMA) hydroxide solution of 200g being pressed embodiment 1 preparation under agitation mixes with the aqueous solution (10% silica) of 4.15g sodium aluminate and 100g tetramethyl-ammonium (TMA) silicate.Add 25g HiSiL (a kind of close have an appointment 6% weight free moisture and about 4.5% weight be the precipitated hydrated silica of about 0.02 μ) in conjunction with moisture limit particle size.The mixture of gained was put 48 hours under 100 ℃ in steam chest.The composition of mixture is corresponding to every mole of Al ₂O ₃Contain:

1.25 mole Na ₂O

27.8 mole SiO ₂

5.1 mole (CTMA) ₂O

4.4 mole (TMA) ₂O

650 moles of H ₂O

Reclaim by filtering the solid product that will produce, and air drying at ambient temperature.Then product was calcined 1 hour in 540 ℃ of nitrogen, in air, calcined 6 hours again.

Record burnt product and have following equilibrium adsorption ability (unit is g/100g):

Water 35.2

Cyclohexane＞50

N-hexane 40.8

Benzene 53.5

The X ray diffracting spectrum of the burnt product of present embodiment as shown in figure 12.It is characterized in that being spaced apart 3.91 ± 0.2nm place at d has the very strong line of a relative intensity, and 2.24 ± 0.1 and 1.94 ± 0.1nm place weak line is arranged.TEM shows that this product contains super big hole gap material of the present invention.

Then with the product and the 1N NH of present embodiment ₄NO ₃Solution is made ammonium ion exchange, calcines 10 hours in 540 ℃ of air again.

Embodiment 13

With muriatic 29% aqueous solution of 125g CTMA, 200g water, 3g sodium aluminate (in the 50g water), 65g UltraSiL (the amorphous precipitated silica of buying from Pq Corp.) and the mixture of 21gNaOH (50g water) fully stir, and 150 ℃ of crystallizations 168 hours.Reactant mixture has following relative mol composition corresponding to every mole of silica:

0.10 mole (CTMA) ₂O

21.89 mole H ₂O

0.036 mole NaAlO ₂

0.53 moles of NaOH

By filtering solid product is separated, water cleans, and at room temperature dry 16 hours, calcines 10 hours in 540 ℃ of air again.

Record burnt product and have 840m ²The surface area of/g and following equilibrium adsorption ability (unit is g/100g):

Water 15.2

Cyclohexane 42.0

N-hexane 26.5

Benzene 62

The X ray diffracting spectrum of the burnt product of present embodiment is characterized in that being spaced apart 4.05 ± 0.2nm place at d has the very strong line of a relative intensity as shown in figure 13.TEM shows that product contains super big hole gap material of the present invention.

Embodiment 14

In order to contrast, take out a kind of overstable zeolite Y of industrial preparation.Its equilibrium benzene adsorption capacity is 20.7g/100g.Its X-ray diffractogram has the line of whole zeolite Y, and the top is spaced apart the 1.40nm place about d.

Embodiment 15

In order to prepare the original pattern mixture of present embodiment, 240g water is added to 92g contains 50% dodecyl trimethyl ammonium hydroxide, in the solution of 36% isopropyl alcohol (IPA) and 14% water, make (solvent)/(R _2/fO) mol ratio is 155.Water/R in this mixture _2/fThe O mol ratio is 149, and IPA/R _2/fThe O mol ratio is 6.In this original pattern mixture, add 4.15g sodium aluminate, 25g HiSiL, the aqueous solution (10%SiO of 100gTMA silicate ₂) and 25% aqueous solution of 13.2g TMA hydroxide.The R of this solution _2/fO (SiO ₂+ Al ₂O ₃) mol ratio is 0.28.

This mixture was stirred 1 hour at 25 ℃.Then the gained mixture being put into autoclave stirred 24 hours with 100rpm for inherent 100 ℃.Mixture in the autoclave is corresponding to every mole of SiO ₂Have following relative mol composition:

0.05 mole Na ₂O

0.036 mole Al ₂O ₃

0.18 mole (C ₁₂TMA) ₂O

0.12 mole (TMA) ₂O

36.0 mole H ₂O

1.0 mole IPA

Reclaim by the solid product that filters gained, water cleans and is dry under air at room temperature.Then product was calcined 1 hour in 540 ℃ of nitrogen, in air, calcined 6 hours again.

Record burnt product and have 1223m ²The surface area of/g and following equilibrium adsorption ability (unit is g/100g):

Water 25.5

Cyclohexane 41.1

N-hexane 35.1

Benzene 51

The X ray diffracting spectrum of the burnt product of present embodiment as shown in figure 14.It is characterized in that being spaced apart 3.08 ± 0.15nm place at d has the very strong line of a relative intensity, and 1.79 ± 0.1 and 1.55 ± 0.1nm place weak line is arranged.TEM shows that this product contains super big hole gap material of the present invention.

Embodiment 16

50.75g decyl trimethyl ammonium hydroxide (be by concentration the decyl trimethyl ammonium bromide solution of about 29% weight contact with a kind of ion exchange resin with hydroxide ion exchange halogen ion make) is mixed with the 8.75g tetraethyl orthosilicate.The mixture stirring was transferred in the polypropylene jar after 1 hour, again it was put in steam chest 24 hours.The ingredients of a mixture is corresponding to every mole of SiO ₂Contain:

0.81 mole (C ₁₀TMA) ₂O

47.6 mole H ₂O

The gained solid product is leached, clean several times with (60-70 ℃) distilled water of temperature with acetone.With end product at N ₂Being calcined to 538 ℃ in the/air mixture placed 8 hours in air then.

Record burnt product and have 915m ²The surface area of/g, its balance benzene adsorption capacity is 35g/100g.Argon physical absorption data show that the argon soakage is 0.34cc/g, and pore-size is 1.5nm.

The feature of the X-ray diffractogram of the burnt product of present embodiment is to be spaced apart 2.75 ± 0.15nm place at d the very strong line of one relative intensity is arranged, and 1.58 ± 0.1 and 1.37 ± 0.1nm place weak line is arranged.TEM shows that this product contains super big hole gap material of the present invention.

Embodiment 17

In pressing cetyltrimethyl ammonium (CTMA) hydroxide solution of embodiment 1 preparation, 80g adds 1.65g NaAlO ₂At room temperature stir this mixture until NaAlO ₂Dissolving.The aqueous solution (the 10% weight SiO that in this solution, adds 40g tetramethyl-ammonium (TMA) silicate ₂), 10g HiSiL, 200g water and 70g 1,3,5-trimethylbenzene (TMB).The gained mixture is at room temperature stirred some minutes.Then gel is packed in the 600cc autoclave 105 ℃ of heating 68 hours, the speed with 150rpm stirs simultaneously.The composition of mixture is corresponding to every mole of Al ₂O ₃Contain:

1.25 mole Na ₂O

27.8 mole SiO ₂

5.1 mole (CTMA) ₂O

2.24 mole (TMA) ₂O

2256 moles of H ₂O

80.53 mole TMB

Products therefrom is leached, clean several times with (60-70 ℃) distilled water of temperature with acetone.End product is at N ₂Be fired to 538 ℃ in the/air mixture, in air, placed about 10 hours then.

Record burnt product to have＞the balance benzene adsorption capacity of 25g/100g.

The feature of the X-ray diffractogram of the burnt product of present embodiment, be to be about the 10.2nm place at interval at d the very strong wide line of one relative intensity is arranged, but be difficult to accurately measure the position that is positioned at X-ray diffractogram utmost point low angle zone spectral line with conventional X-ray diffractometer.And, differentiate at the peak at these low 2 θ angles, need thinner collimating slit.Used slit in the present embodiment from X-ray tube, is respectively 0.1,0.3,0.5 and 0.2mm.TEM shows that the product of present embodiment comprises different materials, and these materials are observed d on their electron diffraction diagrams ₁₀₀Value is different.Observe the d of these materials ₁₀₀Value be 8.5 and 12nm d at interval between.

Embodiment 18

In pressing cetyltrimethyl ammonium (CTMA) hydroxide solution of embodiment 1 preparation, 80g adds 1.65g NaAlO ₂At room temperature stir this mixture until NaAlO ₂Dissolving.The aqueous solution (the 10% weight SiO that in this solution, adds 40g TMA silicate ₂), 10gHiSil, 200g water and 120g 1,3,5-trimethylbenzene (TMB).The gained mixture is at room temperature stirred some minutes.Then gel is packed in the 600cc autoclave 105 ℃ of heating 90 hours, the speed with 150rpm stirs simultaneously.The ingredients of a mixture is corresponding to every mole of Al ₂O ₃Contain:

1.25 mole Na ₂O

27.8 mole SiO ₂

5.1 mole (CTMA) ₂O

2.24 mole (TMA) ₂O

2256 moles of H ₂O

132.7 mole TMB

Products therefrom is leached, and clean several times with (60-70 ℃) distilled water of temperature with acetone.End product is at N ₂Be fired to 538 ℃ in the/air mixture, in air, placed about 10 hours then.

The surface area that records burnt product is 915m ²/ g, and balance benzene adsorption capacity＞25g/100g.Argon physical absorption data show that the argon soakage is 0.95cc/g, and the central value of pore-size is 7.8mm (the Dollimore-Heal method is seen embodiment 21 (b)), but is distributed to greater than 10.5nm from 7.

The feature of the X-ray diffractogram of the burnt product of present embodiment is the scattering strength that enhancing is only arranged in X-ray diffraction utmost point low angle district, can be observed by the intensity of the incident X-rays bundle of transmission in this district usually.But TEM shows the product of present embodiment and comprises different materials that these materials are observed d on their electron diffraction diagrams ₁₀₀Value is different.Observe the d that these materials have ₁₀₀Value be 8.5 and 11nm d at interval between.

Embodiment 19

In pressing cetyltrimethyl ammonium (CTMA) hydroxide solution of embodiment 1 preparation, 80g adds 1.65g NaAlO ₂At room temperature stir this mixture up to NaAlO ₂Dissolving.The aqueous solution (the 10% weight SiO that in this solution, adds 40g tetramethyl-ammonium (TMA) silicate ₂), 10g HiSiL, and 18g1,3,5 trimethylbenzenes (TMB).The gained mixture is at room temperature stirred some minutes.Then gel is packed in the 300cc autoclave 105 ℃ of heating 4 hours, the speed with 150rpm stirs simultaneously.The composition of mixture is corresponding to every mole of Al ₂O ₃Contain:

1.25 mole Na ₂O

27.8 mole SiO ₂

5.1 mole (CTMA) ₂O

2.24 mole (TMA) ₂O

650 moles of H ₂O

19.9 mole TMB

Products therefrom is leached, and clean several times with (60-70 ℃) distilled water of temperature with propyl alcohol.End product is at N ₂Be fired to 538 ℃ in the/air mixture, in air, placed about 8 hours then.

The surface area that records burnt product is 975m ²/ g, and balance benzene adsorption capacity＞40g/100g.Argon physical absorption data show that the argon soakage is 0.97cc/g, and pore-size is 6.3nm (the Dollimore-Heal method is seen embodiment 21 (b)), and peak value is at P/P _o=0.65.

The feature of the X-ray diffractogram of the burnt product of present embodiment is to be spaced apart 6.3 ± 0.5nm place at d the very strong line of one relative intensity is arranged, and 3.64 ± 0.2,3.13 ± 0.15 and 2.38 ± 0.1nm d interval weak line is arranged.TEM shows that the product of present embodiment contains super big hole gap material of the present invention.

Embodiment 20

In order to estimate catalytic performance of the present invention, for being that the performance of two 2-methyl-2-phenylpropanes is assessed with three 2-methyl-2-phenylpropanes (TTBB) dealkylation with each end product of embodiment 1-14.Assessment is to carry out under a kind of in two set conditions or two kinds: (i) temperature is 225 ℃, and weight per hour space velocity is 100hr ^-1(ii) temperature is 200 ℃, and weight per hour space velocity is 200hr ^-1Pressure is atmospheric pressure.Charging is made of the TTBB/ toluene of 6.3/93.7.Conversion ratio is to measure 30 minutes the time in materials flow.

The result is as follows:

The conversion ratio of preparation catalyst, (weight %)

Embodiment numbers 225 ℃/100hr ^-1200 ℃/200hr ^-1

1 0 --

2 6.2 --

3 53.9 --

4 10.4 --

5 68.9 --

6 100.0 --

7 5.3 --

8 -- 61.2

9 -- 58.9

10 86.3 --

11 96.7 --

12 92.8 --

13 -- 37.7

14 12.0 0

Embodiment 21 (a)

The argon physical absorption of the pore system that the about 6.0nm of diameter is following

In order to measure the pore diameter that pore diameter of the present invention is lower than the product of 6.0nm, the product sample 0.2g of embodiment 1-16 is put into the hyaloid QC, be connected to United States Patent (USP) 4,762, on No. 010 described physical adsorption appearance.

Sample was heated 3 hours for 300 ℃ times in a vacuum, to remove the moisture of absorption.Then sample cell is immersed in the liquid argon, sample is cooled to 87 ° of K.Again will be through the argon gas of metering, according to United States Patent (USP) 4,762, No. 010 the 20th the described method in hurdle is progressively introduced in the sample.According to argon gas quantity of leading to sample and the quantity of staying the argon gas in the gas compartment above the sample, just can be regarded as the argon gas quantity that is adsorbed.Used during calculating perfect gas law and through the sample volume of calibration (also can be referring to S.J.Gregg etc., " absorption, surface area and porosity ", second edition, Academic Press, 1982).For each example, the quantity of adsorbing when making balance and the graph of a relation of relative pressure above the sample constitute shown in Figure 15 to the such constant temperature adsorption curve of embodiment 4 product samples.Usually use relative pressure, it is the vapour pressure P by equalizing pressure and absorbate under the temperature of listing measurement constant temperature absorption line _oRatio obtain.The argon gas quantity introduced of each step will be small enough to produce 168 data points in relative pressure is 0 to 0.6 scope.To determine fully at length that constant temperature absorption line needs 100 points at least.

Transition point (flex point) on the constant temperature absorption line, (product of embodiment 4) is about P/P in this example _o=0.4, the filling of control hole slot sytem.The size of transition is represented the quantity of adsorbing, and with P/P _oThe transition point position of expression, then the size of the hole of absorption takes place in expression.Bigger hole is at bigger P/P _oFill.In order to determine the position of transition point on the constant temperature line better, calculated (P/P with respect to log _o) derivative.This is illustrated in Figure 16.Also listed among Figure 16 with the same manner obtain by United States Patent (USP) 4,880, the crystalline material of making for No. 611 and the data of other several crystalline materials.Also have a physical scale on axle, it will be with log (P/P _o) expression the adsorption peak position be converted to tangible pore diameter.Conversion is tried to achieve with following formula:

$\log (P/P_o)=\frac{K}{d-0.38}(\frac{{\mathrm{<figure-callout\; id="4"\; label="S"\; filenames="C9610101800771.png"\; state="\{\{state\}\}">S</figure-callout>}}^4}{3{(L-D/2)}^3}-\frac{{\mathrm{<figure-callout\; id="10"\; label="S"\; filenames="C9610101800571.png,C9610101800581.png"\; state="\{\{state\}\}">S</figure-callout>}}^{10}}{9{(L-D/2)}^9}-\frac{{\mathrm{<figure-callout\; id="4"\; label="S"\; filenames="C9610101800771.png"\; state="\{\{state\}\}">S</figure-callout>}}^4}{3{(D/2)}^3}+\frac{{\mathrm{<figure-callout\; id="10"\; label="S"\; filenames="C9610101800571.png,C9610101800581.png"\; state="\{\{state\}\}">S</figure-callout>}}^{10}}{9{(D/2)}^9})$

D=pore diameter (is unit with nm) wherein, K=32.17, S=0.244 6, L=d+0.19, D=0.57.

This formula be according to the method for Horvath and Kawazoe derive (G.Horvath etc., J.Chem.Eng.Japan, 16 (6) 470 (1983)).Required constant when setting up this formula is to determine according to constant temperature absorption line that ALPO-5 is recorded and known pore-size thereof.This method is specially adapted to the poromerics that pore diameter is lower than 6.0nm.

As shown in figure 16, the pore-size of the material of embodiment 4 is 3.96nm, and peak value is at log (P/P _o)=-0.4 or P/P _o=0.4, and press United States Patent (USP) 4,880, the pore-size of the material of No. 611 manufacturings is 1.2nm, or P/P _o=0.02.In other material, at P/P _o=0.015 observes a peak, represents with asterisk (*) in Figure 16.This peak is reflected in the absorption on the pore wall, does not resemble the pore-size of indicating given material other.P/P _oNumerical value be 0.03 to be 1.3nm corresponding to pore-size.

With the results are shown in following table of this method to the sample gained of embodiment 1-16.Embodiment 9,12 and 15 sample provide two peaks that separate, and it is believed that it is owing in the product two super large hole phases of separating are arranged.

Embodiment numbers pore diameter, nm

1 3.22

2 3.54

3 4.25

4 3.96

5 1.69

6 2.73

7 4.26

8 2.83

9 2.28，3.08

10 3.68

11 3.61

12 3.50，4.21

13 4.0

14 0.83

15 2.24，3.04

16 1.50

Embodiment 21 (b)

The argon physical absorption of the pore system that the about 6.0nm of diameter is above

In the aperture ranges of diameter, can use the Kelvin equation greater than 6.0nm.This equation generally is expressed as:

$\ln \left({P/P}_o\right)=\frac{-2\mathrm{V\&gamma;}\cos \mathrm{\&theta;}}{r_K\mathrm{RT}}$ Wherein:

The surface tension of γ=absorbate

The molal volume of V=absorbate

θ=contact angle (in fact generally get and do zero)

The R=gas constant

T=absolute temperature

r _K=capillary condensation (hole) radius

P/P _o=relative pressure (taking from the physical absorption constant temperature line)

The Kelvin equation is handled the absorption of pore system as a kind of capillary condensation phenomenon, and the surface tension by absorbate (being argon under this situation) and contact angle will adsorb the pressure and the pore-size that take place and link.The principle of Kelvin equation institute basis is applicable to the hole of diameter in the 5-100nm scope.Under this scope, this equation no longer reflects physical reality, because in littler hole real capillary condensation can not take place; On this scope,, can not when measuring pore-size, obtain enough precision because equation is a logarithmic function character.

Usually selecting and specifically using the Kelvin equation is method (the D.Dollimore ﹠amp of Dollimore and Heal report with what measure pore-size; G.R.Heal, J, Applied Chem., 14,108 (1964)).Correction has been done in influence that this method is not considered usually to the Kelvin equation, the superficial layer of absorbate on pore wall, thereby pore diameter measured value more accurately is provided.Though the method for Dollimore and Heal is to derive to be used for constant temperature desorb line, as long as simply data the other way around, it also can be applied to adsorb constant temperature line equally well.

Embodiment 18 and 19 product just as point out handle the argon adsorpting data with Dollimore and Heal method.

Embodiment 22

Transmission electron microscopy

In order to further specify the character of hex crystal product of the present invention, to embodiment 1-13,15-19, the sample of 23-31 and 36-38 products therefrom has been done research as the usefulness transmission electron microscopy of pointing out (TEM).TEM is a kind of microstructural technology of various materials (comprising crystalline material) that is used for showing.

In order to illustrate the microstructure of material, sample must be thinned to is enough to allow electron beam pass through it, and normally about 50-100nm is thick.Generally all requirement can be for deliberation with its preparation by ultramicrotomy for the crystal habit of material of the present invention.Though it is more time-consuming.The electron microscope technique personnel are very familiar to this sample preparation methods.Material is embedded in a kind of resin, is a kind of commercially available low viscosity propionic acid resin L.R.White (firmly) under this situation, then it is solidified 1.5 hours at 80 ℃.On ultramicrotome, cut out thin slice from sample blocks, the thin slice of thickness in the 50-100nm scope is collected on the detailed catalogue electron microscope support mesh with diamond tool.For these samples, used a LKB type ultramicrotome of being furnished with 45 ° of diamond blades; Support mesh is 400 order copper mesh.Charge in microscope preventing at skim carbon on the evaporation on the sample, (at this moment, the blank sheet of paper that is placed on the sample next door in the evaporation platform manifests light gray), sample just is ready to observe in TEM.

If only want to confirm the existence of material of the present invention, can adopt a kind of better simply sample preparation technology to most of synthetic products.This method is to allow the dispersion thing of material be deposited on the lacery Formvar electron microscopic mirror support of carbon coated, and support is in advance through polishing and the ultrasonic processing in propyl alcohol.Usually the enough thin fragment and the zone that can obtain electron diffraction diagram and lattice image can found near the place at crystal edge.The sample that is used for analyzing among embodiment 23-31 and the 36-38 prepares with this dispersion technology.

High-resolution TEM micrograph display structure is along the projection of sample direction of observation.Therefore, in order to observe microstructural some details of material, just need the sample of specific orientation.For crystallized sample, these orientations are the easiest to be to choose by observing with the produced simultaneously electronic diffraction collection of illustrative plates of electronic microscopic image (EDP).The selection area visual field snoot technology that such EDP can use the electron microscope technique personnel to be familiar with produces on modern TEM instrument.When observing when showing the EDP that required point diffraction arranges, the resembling of the crystal of corresponding this EDP of generation will demonstrate the details of the projection on the direction that its microstructure points out along EDP.Like this, with regard to the projection on available tem observation and the identification crystal different directions.

In order to observe the prominent features of crystallized product of the present invention, need on such orientation, observe this material, EDP corresponding on this direction can provide into the point diffraction that hexagonal is arranged from individual other monocrystalline.If have polycrystalline in the snoot of visual field, the overlapping diffraction pattern of explaining will take place extremely to be difficult to.Figure 17 has provided the example of the hexagon figure that the single crystal grain of the product of embodiment 4 produces.The number of viewed point diffraction is outside other thing, also at the regularity that only depends on that to a certain degree crystallization is arranged in the material.But what obtain resembles, and should observe the bright spot of inner ring at least.Individual other crystal can be regulated by the sample inclination adjusting device on the TEM, up to obtaining this orientation.More common situation is, utilizes more easily to comprise many these facts of randomly-oriented crystal in the sample, seeks everywhere at sample simply, up to finding the crystal that provides required EDP (thereby being required orientation).Back one technology is used to produce electron micrograph discussed below.

With the ultrathin section sample, of above-mentioned technical checking embodiment 1-13 and 15-19 gained material, electron microscope is done at 200,000 couchers in JEOL 200CX transmission electron microscope, and an effective 0.2nm object lens light is housed explains.The resolution ratio of putting in order of instrument is 0.45nm.Other EE mode that also can use high-resolution (phase contrast) TEM technical staff to be familiar with produces of equal value resembling, as long as note the minimum contrast lens current setting value of object lens is remained on focusing less than one side (underfocus side).Figure 18 be embodiment 4 crystallized products cut out the electron micrograph of thin slice with slicer.On scheming, can find out a quite regular vat array that becomes hexagonal to arrange.Repeat distance between the groove is about 4.5nm unit, the position at first peak on it and this material X-ray diffractogram ( $4.1\mathrm{nm}/\sqrt{3}/2$ ) be consistent.Owing to wall must be arranged between each groove, this observed result also with among the embodiment 16 is measured the hole that obtains according to the argon physical absorption of this material and is estimated that the about 3.96nm of size conforms to.

Figure 19 be embodiment 5 crystallized products cut out the electron micrograph of thin slice with slicer.Can see the quite regular array of the smaller slightly groove that hexagonal is arranged on scheme.Repeat distance between the groove is about 3.0nm, the position at first peak on it and this material X-ray diffractogram ( $2.5\mathrm{nm}/\sqrt{3}/2$ ) be consistent.The less argon physical absorption of also being reported by embodiment 21 (a) of this material pore-size is measured and is confirmed, calculates to such an extent that the numerical value among the embodiment 5 is 1.69nm there.

Figure 20 is embodiment 18 crystallized products cut out thin slice with slicer a electron micrograph.Groove during this resembles is very big but than irregularity, but the feature that material hexagonal of the present invention is arranged is still significantly.

Embodiment 23

In 80g cetyltrimethyl ammonium hydroxide (CTMAOH) solution-this solution is with N, N, N-trimethyl-1-cetyltrimethyl ammonium muriatic 29% (weight) solution contact with a kind of exchanger resin with hydroxyl exchange halogen ion and make-add 1.65gNaAlO ₂Stir this mixture until NaAlO ₂Dissolving fully.In this solution, add 40.0g tetramethyl-ammonium silicate solutions (10% weight SiO ₂) and 10.0g HiSiL (90% weight SiO ₂).With the gained mixture in stirring at room a few minutes.Then this gel is packed into-stir and be heated to 105 ℃ with 150RPM in the 300ml autoclave pressure.After heating about 4 hours, make the reaction quenching, the material in the still is taken out with cold water.Wash several times with the product filtration with warm (60-70 ℃) distilled water and acetone.At N ₂In/the air mixture end product was calcined 8 hours at 538 ℃.

The composition of gel reactant mixture is corresponding to every mole of Al ₂O ₃Have:

1.25 mole Na ₂O

27.8 mole SiO ₂

5.1 mole (CTMA) ₂O

2.24 mole (TMA) ₂O

650 moles of H ₂O

The surface area that records the calcined product of present embodiment is 1187m ²/ g, the benzene adsorption capacity is 66g/100g.

The X-ray diffractogram of the calcined product of present embodiment is gone up by figure and can be found out that this product is spaced apart 3.68 ± 0.2nm place at d-a line that relative intensity is very strong as shown in figure 21, and 2.12 ± 0.1 and the existence of 1.83 ± 0.1nm place a little less than line.Check the product of present embodiment with transmission electron microscopy (TEM), provided resembling that even hole hexagonal arranges, and d ₁₀₀Approximate the hexagonal electron diffraction diagram of 3.8nm.

Embodiment 24-31

Carry out other experiment of 8 branches by the method for embodiment 23, but in initial reactant mixture, added a kind of auxiliary organic matter.In each experiment all is 1,3, and 5-trimethylbenzene (TMB) adds in the reactant mixture as auxiliary organic matter becomes last component.The concentration of TMB changes between each experiment, shown in Table A.Also having listed the product pore-size in the Table A, is the pore volume and the equilibrium benzene adsorptive value of unit with cc/g.Embodiment 24,27 and 30 pore-size and pore volume numerical value be by other embodiment d-at interval and the pore-size that records and the extrapolation of the graph of a relation between the pore volume and (seeing Figure 23 and 2 4).For the ease of relatively, also pointed out the strongest X-ray diffraction spectral line.Figure 22 is by the TMB molal quantity/mole SiO in each reactant mixture ₂Show that the auxiliary organic matter of TMB is to first great d-influence at interval of X-ray diffractogram.Along with auxiliary organic concentration in the reactant mixture increases, the pore-size of crystalline material product and volume increase.

TEM check to each burnt product of embodiment 24-31 is done all provides an even hole and is resembling and d of hexagonal arrangement ₁₀₀Value is corresponding to the d-hexagonal electron diffraction diagram at interval at some peaks in the X-ray diffractogram.

Table A

Embodiment TMB TMB/SiO ₂TMB/ d-is pore-size benzene adsorption rate at interval

Numbering molal quantity mol ratio CTMA+ (nm) is (g/100g (nm);

Mol ratio is 6.7

KPA)

23 0 0 0 3.68 3.2，3.77 66

24 0.025 0.12 0.32 4.03 4.15 61

25 0.050 0.23 0.65 4.53 4.51 62

26 0.075 0.35 0.97 4.81 5.25 48

27 0.100 0.46 1.30 5.48 5.80 37

28 0.150 0.70 1.95 6.22 6.30 43

29 0.150 0.70 1.95 6.22 6.90 36

30 0.183 0.85 2.38 6.37 6.81 32

31 0.216 1.00 2.80 6.51 7.02 38

Embodiment 32-45

Be suitable as auxiliary organic matter among the present invention in order to illustrate which organic compound, repeated embodiment 23, but in each experiment before joining HiSiL in the reactant mixture, directly add the auxiliary organic matter that 10g may use earlier.The results are shown in Table B, from showing to see n-octadecane (embodiment 40), 1-amylalcohol (embodiment 43) and phenol (embodiment 44) can not cause marked change at interval or produce amorphous product the d-of the strongest X-ray diffraction spectral line.All other materials of listing at table B all make the position of the strongest X ray spectral line that marked change takes place, thereby are suitable auxiliary organic matters.

To the check that each burnt product of embodiment 36-38 is done, all provide an even hole and be resembling and d of hexagonal arrangement ₁₀₀The value cardinal principle is corresponding to the d-hexagonal electron diffraction diagram at interval at some peaks in the X-ray diffractogram.

Table B

The auxiliary organic assistant of the auxiliary organic matter of embodiment/d-is the benzene adsorption rate at interval

Numbering thing molal quantity SiO ₂(rub (nm) (g/100g,

That ratio) 6.7KPA)

23 do not have 00 3.68 66

32 paraxylene 0.094 0.44 4.98 39

33 1,3,5-trimethylbenzene 0.083 0.39 5.12 38

34 1,3,5-triethylbenzene 0.062 0.29 4.81 36

35 1,3,5-triisopropylbenzene 0.049 0.23 4.49 43

36 1,3-dimethyladamantane 0.061 0.28 4.89 42

37 pentanes 0.139 0.64 4.72 31

38 n-decanes 0.070 0.33 4.64 48

39 dodecanes 0.059 0.27 4.28 48

40 octadecanes 0.039 0.18 3.70 54

41 1-phenyl nonanes 0.049 0.23 4.64 34

42 1,8-two bromooctanes 0.037 0.17 4.49 33

43 1-amylalcohols, 0.113 0.53 amorphous 28

44 phenol, 0.106 0.49 amorphous lacks

45 pyridines 0.126 0.59 4.64 lack

Embodiment 46

The 1.08g cabaltous nitrate hexahydrate is dissolved in the 10g water makes solution.29% (weight) aqueous solution that in this solution, under agitation adds 40g CTMAOH, 10g TBuA (TBA) silicate solutions (with 55% (weight) aqueous solution of 168g tetraethyl orthosilicate and 270g TBA hydroxide and make) and 5gHiSiL silica.The mixture of gained contains following composition corresponding to every mole of silica:

0.21 mole (CTMA) ₂O

0.07 mole (TBA) ₂O

0.04 mole CoO

25.7 mole H ₂O

Mixture is put into a polypropylene vial, and in steam chest, put 72 hours.Resulting solid product is leached, washing, the air drying was calcined 10 hours in 540 ℃ of air then.Burnt product has the balance benzene adsorption capacity of 40% weight, and its X-ray diffractogram as shown in figure 25.On scheming, can see that being spaced apart 3.7 ± 0.2nm at d-has a very strong line, and d-be spaced apart 2.1 ± 0.1 and 1.9 ± 0.1nm place weak line is arranged.

Embodiment 47

Repeat embodiment 46, but replace cobalt salt with the 1.08g Nickelous nitrate hexahydrate.The equilibrium benzene adsorption capacity of the burnt product of gained is 60% weight, and its X-ray diffractogram is (being spaced apart 3.7 ± 0.2nm place at d-has a very strong line, and be spaced apart 2.1 ± 0.1nm place at d-one weak line is arranged) as shown in figure 26.

Embodiment 48

4.5g hydration chromium sulfate is dissolved in the 20g water makes solution.29% (weight) aqueous solution that in this solution, stir to add 200g CTMAOH, 50g TBuA (TBA) silicate solutions (55% (weight) aqueous solution of 168g tetraethyl orthosilicate and 270g TBA hydroxide is made) and 25gHiSiL silica.The mixture of gained contains following composition corresponding to every mole of silica:

0.21 mole (CTMA) ₂O

0.07 mole (TBA) ₂O

0.02 mole Cr ₂O ₃

22.0 mole H ₂O

Mixture is put into a polypropylene vial, and in steam chest, placed 72 hours.The gained solid product is leached, washing, the air drying was calcined 10 hours in 540 ℃ of air again.The equilibrium benzene adsorption capacity of burnt product is 40% weight, and its X-ray diffractogram as shown in figure 27.As seen being spaced apart 3.9 ± 0.2nm at d-on scheme has a very strong line, and be spaced apart 2.1 ± 0.1nm place at d-one weak line is arranged.

Embodiment 49

50g is mixed in stirring with 5g tetraethyl orthosilicate and 14.5g tetramethyl-ammonium silicate (10% silica) by the cetyltrimethyl ammonium hydroxide of embodiment 1 preparation.Stir lasting 1 hour, and in gained solution, add gallium nitrate solution (with 1.2gGa (NO ₃) ₃XH ₂O is dissolved in the 10g water and makes).Suppose that surfactant exchanges fully, form by following corresponding to every mole of silica in the mixture:

0.5 mole (CTMA) ₂O

0.05 mole Ga ₂O ₃

66 moles of H ₂O

This mixture is put into a polypropylene vial, put into steam chest again and put 48 hours for inherent about 95 ℃.The gained solid is leached washing, air drying, calcining (6 hours subsequently in air in 540 ℃ of flowing nitrogens in 1 hour) again.The X-ray diffractogram of its burnt product as shown in figure 28, wherein being spaced apart 3.4 ± 0.2nm place at d-has a very strong line, and d-be spaced apart 2.1 ± 0.1 and 1.8 ± 0.1nm place weak line is arranged.The chemical analysis composition of just synthetic good product is: (percentage by weight)

40% carbon

2.5% nitrogen

15% silicon

2.8% gallium

0.07% aluminium

39.9% ash content (1000 ℃)

Claims (19)

1. method that makes the raw material that contains organic compound or inorganic-containing compound carry out catalyzed conversion, it is characterized in that raw material is contacted with a kind of catalyst of activity form of synthetic under catalyticing conversioning condition, this synthetic comprises a kind of inorganic, porous, non-stacked crystalline phase material, after calcining, the X ray diffracting spectrum that it presents have at least a peak at d-at interval greater than the 1.8nm place, and in the benzene adsorption capacity of 6.7KPa and 25 ℃ greater than this material of every 100g 15g benzene.

2. method that makes the raw material that contains organic compound or inorganic-containing compound carry out catalyzed conversion, it is characterized in that raw material is contacted with a kind of catalyst of activity form of synthetic under catalyticing conversioning condition, this synthetic comprises a kind of crystalline phase material inorganic, porous, it has by diameter and is at least the hexagonal array that the hole of uniform size of 1.3nm constitutes, and through after the calcining, the hexagonal electron diffraction pattern that it presents can be with a d greater than 1.8nm ₁₀₀Value indicates.

3. the method for catalyzed conversion as claimed in claim 2 is characterized in that described crystalline phase material through after calcining, and its X-ray diffractogram has the d-at two peaks at least at interval corresponding to the d that is obtained by electron diffraction diagram ₁₀₀Value.

4. the method for catalyzed conversion as claimed in claim 1 or 2, after it is characterized in that described crystalline phase material is through calcining, its X-ray diffractogram has two peaks at least in the position of d-interval greater than 1.0nm, at least wherein have a peak at d-at interval greater than the position of 1.8nm, and do not have 20% the peak of relative intensity less than the position of about 1.0nm at interval greater than highest peak at d-.

5. the method for catalyzed conversion as claimed in claim 4 is characterized in that described material does not have 10% the peak of relative intensity greater than highest peak less than the position of about 1.0nm at interval at d-.

6. the method for catalyzed conversion as claimed in claim 1 or 2 is characterized in that described crystalline phase has the composition shown in the following formula:

M _N/q(W _aX _bY _cZ _dO _h) wherein M be one or more ions; N is that synthetic is removed the charge number that M is expressed as oxide; Q is the weighting mole flat fare of M; N/q is molal quantity or the molar fraction of M; W is one or more diads; X is one or more triads; Y is one or more quadrivalent elements; Z is one or more pentads; A, b, c, d are respectively W, X, Y, the molar fraction of Z; H is the number between 1 to 2.5; And (a+b+c+d)=1.

7. the method for catalyzed conversion as claimed in claim 6 is characterized in that (a+b+c) this and value greater than d, and h=2.

8. the method for catalyzed conversion as claimed in claim 6 is characterized in that W comprises a kind of divalent transition metal or magnesium that is selected from first row in the periodic table of elements; X comprises aluminium, boron, chromium, gallium or iron; Y comprises silicon or germanium; And Z comprises phosphorus.

9. the method for catalyzed conversion as claimed in claim 8 is characterized in that W wherein comprises cobalt, and X comprises aluminium, and Y comprises silicon and Z comprises phosphorus.

10. the method for catalyzed conversion as claimed in claim 6 is characterized in that wherein a and d equal zero and h=2.

11. the method for catalyzed conversion as claimed in claim 10 is characterized in that wherein X comprises aluminium and Y comprises silicon.

12. the method for catalyzed conversion as claimed in claim 1 is characterized in that described synthetic has basically as Fig. 1 to 14, any one such X ray diffracting spectrum in 21 and 25 to 28.

13. as claim 1-3,5, the method for each described catalyzed conversion among the 7-11 and 12 is characterized in that raw material wherein comprises certain hydro carbons, relates to cracking or hydrocracking so that the molecular weight of this hydro carbons reduces and transform.

14. the method for catalyzed conversion as claimed in claim 4 is characterized in that raw material wherein comprises certain hydro carbons, relates to cracking or hydrocracking so that the molecular weight of this hydro carbons reduces and transform.

15. the method for catalyzed conversion as claimed in claim 6 is characterized in that raw material wherein comprises certain hydro carbons, relates to cracking or hydrocracking so that the molecular weight of this hydro carbons reduces and transform.

16. as claim 1-3,5, the method for each described catalyzed conversion among the 7-11 and 12 is characterized in that raw material wherein comprises certain nitrogen oxide, and transforms the electronation that relates to this kind nitrogen oxide matter.

17. the method for catalyzed conversion as claimed in claim 4 is characterized in that raw material wherein comprises certain nitrogen oxide, and transforms the electronation that relates to this kind nitrogen oxide matter.

18. the method for catalyzed conversion as claimed in claim 6 is characterized in that raw material wherein comprises certain nitrogen oxide, and transforms the electronation that relates to this kind nitrogen oxide matter.

19., it is characterized in that using this synthetic that a certain component in one blending ingredients is selected absorption as the application of a kind of synthetic used in arbitrary method in the claim 1 to 12.

Images