CN85104928A - Silicophosphoaluminaand and relevant crystalline oxides - Google Patents

Abstract

Silicophosphoaluminaand is by crystallizing out in the biphasic reaction mixture that comprises silica source, alumina source and phosphorous oxide source and a kind of suitable directing agent.The silicon of this Silicophosphoaluminaand, phosphorus and aluminium can be separately at random substituted by the element of other positive tetravalence attitudes, positive pentavalent attitude and positive three valence states.The crystalline oxides that is generated has ion exchange property, and is easy to be transformed into the material with catalytic activity.

Description

Silicophosphoaluminaand and relevant crystalline oxides

The invention relates to synthesis silicon phosphorus aluminate crystallization from the reaction medium that two kinds of liquid phases constitute, this reaction medium contains organic or inorganic directing agent and specific reaction agent.A kind of Silicophosphoaluminaand crystalline texture of this synthetic generation with ion exchange property, and be transformed into material at an easy rate with catalytic activity.Silicon in this material, phosphorus, aluminium component can replace with other element.

For example talked about aluminum phosphate in the United States Patent (USP) 4310440 and 4385994, the aluminum phosphate material has the electroneutral lattice, therefore can not be used as ion-exchanger, perhaps as catalyst component.The aluminum phosphate of micropore has following combining form:

XR∶Al ₂O ₃∶（1.0±0.2）P ₂O ₅∶YH ₂O

Wherein: R is organic amine or the quaternary amine that is mixed in the aluminum phosphate, plays a part crystalline forming; X and Y represent required R of filling micropore hole and H ₂The amount of O.Because the aluminium in these materials/phosphorus atoms ratio approximately is one, so they can not show ion exchange property, and the structure positive charge of phosphorus is by the respective negative electric charge institute balance of aluminium:

AlPO ₄＝（AlO ^- ₂）（PO ⁺ ₂）

Canadian Patent 911416; 911417 and 911418 replacement phosphorus zeolite is considered to " alumo-silicate " zeolite.Some phosphorus seemingly is mixed in the inside, rather than structural chemical combination.These a kind of materials that contain silicon, aluminium and phosphorus in back show the feature of following general formula:

Wherein: M is a monovalent cation, and X is about 0.125-1.5, and Y is 0.05-1.0, and Z is the molecular number of hydrate water.Finish the structural silicon of replacement with phosphorus, these materials are known as the clathrate (DRP 3128988) of silicon.

United States Patent (USP) 4363748 has been described a kind of silicon and the phosphatic composition of aluminium-calcium-cerium, as a kind of low acid activity catalyst of oxidation deoxidation hydrogen.BP 2068253 has been revealed the composition of a kind of silicon and aluminium-calcium-tungsten phosphate, as a kind of low acid activity catalyst of oxidative dehydrogenation.United States Patent (USP) 3801704 is talked about and is someways handled aluminum phosphate and give acidity.United States Patent (USP) 4228036 is talked about a kind of aluminium-aluminum phosphate-silicon substrate, mixes being used as Cracking catalyst with zeolite as a kind of armorphous body.United States Patent (USP) 3213035 is spoken of with phosphoric acid and is handled the hardness of improving the aluminosilicate catalyst, and these catalyst are unbodied.

United States Patent (USP) 2876266 has been described the armorphous material of a kind of activated silica phosphoric acid or salt face, and it utilizes preformed silicate or the preparation of aluminosilicate absorption phosphoric acid.

Other wording of aluminum phosphate and its preparation also has in following United States Patent (USP): 4365095; 4361705; 4222896; 4210560; 4179358; 4158621; 4071471; 4014945; 3904550 and 3697550.Because their neutral backbone structure does not have ion exchange property, so be used as catalyst carrier or matrix.

United States Patent (USP) 4440871 has been described the various crystal formation micropore materials that it is characterized by " silicoaluminophosphate ", these materials are by containing reactive phosphorus, and the hydrogel of silicon and aluminium compound and organic forming agent carries out hydrothermal preparation.

Therefore, synthetic crystal formation Silicophosphoaluminaand is molecular sieve or other skeleton structures that present ion exchange property, and be easy to convert to easily the material with real catalytic activity, it is particularly useful for synthetic these crystal formation Silicophosphoaluminaands and their replacement analog that the technology of synthetic zeolite of being said in the prior art or phosphate aluminium is not considered to.

Therefore, the invention provides a kind of no aquosity crystalline oxides aspect the most wide combinations of substances, shown in it is composed as follows:

Wherein: X represents the element of one or more positive trivalents; Y represents the element of one or more positive pentavalents; Z represents the element of one or more positive tetravalences; Wherein the atomicity of representing by Z less than the atomicity of representing by X and Y and; Wherein or X be not aluminium, Y is not a phosphorus, perhaps Z is not silicon or titanium; M is that valence mumber is the cation of m; N is that valence mumber is the anion of n; X and y are the numbers that arrives less than+1 greater than-1, are satisfied with following relation:

(1) if x is 0, that y is not 0 just,

(2) if y is 0, that x is not 0 just,

(3) if the atom ratio of X/Y greater than 1, that (x+y) just greater than 0, x+0.6x is less than 0.4,

(4) if the atom ratio of X/Y less than 1, that (x+y) just greater than 0,0.5 just greater than 0.5y+x,

Said crystal formation oxide has the ion exchange capacity that is at least about 0.002 milliequivalent/gram.

Utilize calcining, i.e. heating can form this crystal-form substances, just as described in this article, is a kind of anhydrous state combination thing with the synthetic crystal formation oxide that forms, and is shown below:

Wherein: A is organic directing agent, and v is the molal quantity of A, X, Y, Z, M, N, x, y, z, m and n such as this paper above-mentioned definition.

Aspect it the most wide synthetic, the invention provides a kind of method of synthetic crystal formation oxide.This method step is as follows:

1) preparation contains the two-phase reaction mixture of special component, and is to be made of liquid organic facies and liquid water; 2) reactant mixture is heated to 80 °～300 ℃ temperature with 5～200 ℃ heating rate per hour; 3) stirred reaction mixture is mixed with each other fully liquid organic facies and water; 4) keep stirred reaction mixture at 80 °～300 ℃, pH value 2-9 is till the crystal of crystal formation oxide material forms; 5) the crystal formation oxide material in the recovery reactant mixture.

The main component of two-phase reaction mixture comprises water, a) source of the X element oxide of one or more positive trivalents; B) source of the Y element oxide of one or more positive pentavalents; C) source of the Z element oxide of one or more positive tetravalences; D) organic directing agent A source; E) inorganic cation M and f) anion N; Substantially water-fast organic solvent.

These components present following relation:

Wherein: a, b, c, d, e, f, g and h are the numbers that satisfies following relation:

A/(c+d+e) less than 4,

B/(c+d+e) less than 2,

D/(c+e) less than 2,

F/(c+d+e) be 0.1-15,

G/(c+d+e) less than 2,

H/(c+d+e) be 3-150,

When the initial preparation reactant mixture, wherein a kind of in X, Y or the Z oxide source is to be dispersed or dissolved in the organic facies.

The crystal formation oxide material that reclaims from reactant mixture is characterized by anhydrous state combination thing, as shown in the formula:

Wherein v is the molal quantity of A, and m is the valence mumber of cation M, and n is that the valence mumber x and the y of anion N is the number that arrives less than+1 greater than-1, and satisfies following relation:

(1) if x is 0, that y is not 0,

(2) if y is 0, that x is not 0,

(3) if the atom ratio of X/Y greater than 1, that (x+y) greater than 0, y+0.6x is less than 0.4,

(4) if the atom ratio of X/Y less than 1, that (x+y) greater than 0,0.5 greater than 0.5y+x,

Said crystal formation oxide has the ion exchange capacity that is at least about 0.002 milliequivalent/gram.

When X/Y(is Al/P) ratio is greater than 1 the time, and the prepared synthetic crystal formation Silicophosphoaluminaand of this method and other oxide are effective cation-exchanger and acidic catalyst.These catalyst have the spectral line of acid intensity, and are different from the spectral line of zeolite, and this is a significant benefit to some catalytic process.Ratio for X/Y is lower than at 1 o'clock, and the anion exchange characteristic is preponderated, and contributes the activity of these materials for base catalyzed reactions.They also present a kind of novel catalyst carrier, are very useful in this respect, because they have very high ion exchange capacity, can be detained quite high metal load.Under latter event, they present the catalysis toughness identical with the catalyst of other carrier band metal oxide.Characterization of adsorption points out that the Silicophosphoaluminaand of micropore is selectively to molecular shape, and as known in the zeolite catalysis technology, this selectivity benefits for many catalytic process.

The crystal formation oxide that synthesizes as the result (as, Silicophosphoaluminaand) X/Y(as, atom ratio Al/P) greater than 1, then show X/Z(as, atom ratio Al/Si) is greater than 1.5, usually between 1.6-600.As X/Y(as, ratio Al/P) less than 1, can show Y/Z(as, atom ratio P/Si) is greater than 1, usually between 1.2-600.

Phosphorus/al atomic ratio the rate that can identify aluminum phosphate well is 1 substantially, and not siliceous substantially.

Replace the phosphorus zeolite compositions and also be referred to as " alumo-silicate " zeolite sometimes, wherein silicon/al atomic ratio rate is greater than 1, and generally between 0.66-8.0, phosphorus/al atomic ratio rate is less than 1, usually greater than 0 to 1.

Use two-phase synthesis reaction mixture system, and got rid of solid, one or more reactants are remained in the organic facies with the solution form, they generally are insoluble or unsettled at aqueous phase under this synthesis condition.This method can prepare as Silicophosphoaluminaand, and we believe and utilize other technologies to be difficult to synthesize.In addition, in the presence of the organic or inorganic directing agent, carry out the inorganic synthetic crystal formation Silicophosphoaluminaand that also can obtain to have microporous properties.Organic directing agent also can play surfactant except playing the moulding effect, therefore the organic facies and the water that can help to contain reagent is divided into diffusing.

Such just as what above point out, with synthetic method of the present invention, reactant mixture contains enough Z sources (as silicon), Y source (as phosphorus) and X source (as aluminium) directing agent and organic solvent.

Organic directing agent can be by choosing in the following compound: organically single, and 21, or polyamine and compounds, have following general formula:

Wherein R and R ' are the alkyl of 1-20 carbon atom, the assorted alkyl of 1-20 carbon atom, aryl, heteroaryl, the cycloalkyl of 3-6 carbon atom, the ring of 3-6 the carbon atom alkyl of mixing, or they in conjunction with base, M is four coordination valence elements (as nitrogen, phosphorus, arsenic, antimony or bismuth) or has alicyclic ring, the hetero atom of heterolipid ring or assorted aromatic hydrocarbons structure (as N, O, S, Se, P, As etc.); X is anion (as fluoride, chloride, bromide, iodide, hydroxide, acetate, sulfate, a carboxylate etc.).When M has alicyclic ring, the hetero atom of heterolipid ring or assorted aromatic hydrocarbons structure, this structure can be non-limiting, following example:

Wherein: R ' is the alkyl of 1-20 carbon atom, the assorted alkyl of 1-20 carbon atom, aryl, heteroaryl, the ring of the cycloalkyl of 3-6 carbon atom or the 3-6 carbon atom alkyl of mixing.

The organic directing agent of the best of the present invention comprises alkylamine, wherein alkyl be 1-3 carbon atom and compounds, as defined above, wherein R is the alkyl of 1-4 carbon atom, R ' is the olefin(e) of 1-6 carbon atom, M is a nitrogen, X is halide or hydroxide.These non-limiting examples comprise two-n-propylamine, tetrapropylammonium hydroxide, tetraethyl ammonium hydroxide, the hydroxide or the bromide of tetrapropylammonium bromide and hexamethyl-hexane diamines.Also can play the auxiliary directional agent as inorganic hydroxide or the salt of regulating pH value.The non-limiting example of these compounds is KOH, NaOH, CsOH, CsBr, NaCl, Ca(OH) ₂And the like compound.

The organic solvent that is used to form two-phase reaction mixture can be any organic liquor, and is water insoluble substantially under the crystallization condition of this method.The non-limiting example of this solvent comprises C ₅-C ₁₀Alcohol and phenol naphthols; Or other water-fast organic solvent.The organic facies solvent is polar organic compound preferably.

The inorganic cation and the anion that mainly are present in the reactant mixture generally can not provide to dose component separately.On the contrary, these cations and anion be constantly from the compound of dosing in the reactant mixture, so that other main component to be provided, and as silicon, aluminium and/or phosphorus source or picture directing agent, perhaps PH conditioning agent, these can utilize.

One of X, Y or Z oxide source must be present in the organic facies of reactant mixture at the beginning.Therefore water will comprise directing agent, cation and anion, and PH conditioning agent and those intrinsic Main Ingredients and Appearances, these are not dosed in the organic facies.

The atom example that X represents comprises aluminium, iron, chromium, vanadium, copper, arsenic, calcium halophosphate activated by antimony andmanganese, gallium and boron, and every kind shows positive trivalent.The atom example that Y represents comprises phosphorus, arsenic, antimony and vanadium, and every kind shows positive pentavalent.The atom example that Z represents comprises silicon, germanium and titanium, and every kind shows positive tetravalence.

Water can comprise the synthetic mixture as aluminium and phosphorus component.By giving molten Jie of aluminum phosphate material who forms the solid crystal formation or being partly dissolved in aqueous phase, make these components be incorporated into aqueous phase.Finishing of this dissolving is to remain under the effective alkaline PH by water.As mentioned above, mix the alkaline matter of q.s at aqueous phase.Also can be at random with aluminium and/or phosphorus source, as Al ₂O ₃And/or H ₃PO ₄Be incorporated into aqueous phase.

Carefully the reactant mixture with above-described composition heats, be heated to about 80 °-300 ℃ temperature per hour to increase about 5 °-200 ℃ speed, and keep this temperature range till the crystal of required crystal formation oxide forms, usually with about 5 hours to about 500 hours.The PH of crystallization reaction mixture carefully maintains about 2-9.This point can be finished by regulating the concentration that adds alkali.

When crystallisation step heats, common stirred reaction mixture, be enough to make largely insoluble organic facies and water finally fully to mix, the technology that organic facies and water are disperseed each other is well-known technology, in order to increase the inner surface between these liquid phases, even wish to make organic facies and water to form emulsion state.

Crystallization goes out after the required oxide (as Silicophosphoaluminaand), filters the reactant mixture that contains oxide, and the crystallization of washing and recycling, for example washes with water, and is dry then, as be heated to about 150 ℃ from about 25 ℃ under normal pressure.

According to method of the present invention, aluminium in the synthetic mixture and phosphorus source can be dissolving or part dissolving phosphoric acid aluminium.This aluminum phosphate can be with amorphous material, and the form of crystal-form substances or its mixture is used.The crystal formation aluminum phosphate can have structure closely knit or open cell type, and the example of the crystal formation aluminum phosphate of a kind of pattern in back is described in United States Patent (USP) 4310440 and 4385994.

The alkaline matter example that can mix aqueous phase comprises the hydroxide and the alkali carbonate of I family metal in the periodic table, the hydroxide of silicate and tetraalkyl ammonium ion.

The additional source of aluminium comprises (non-limiting example), the oxide of the aluminium of any form known or hydroxide, organic or inorganic salt or compound.

The additional source of phosphorus comprises (non-limiting example), the phosphoric acid of any form known or the oxide of phosphorus, the organic derivative of phosphate and phosphite and phosphorus.

Used silicon source comprises (non-limiting example), the silicic acid of any form known or the dioxide of silicon, the alkoxide compound of silicon or other compounds.

According to the present invention, a kind of special synthetic method more clearly is described, water contains the component of phosphorus and aluminium.The organic facies of making solvent with hexanol contains the silicon source, as four-positive alkyl-silicate.Organic directing agent as tetraalkylammonium hydroxides or a kind of amine, also plays the effect of surfactant, makes water and organic facies latexization, and makes the inner surface optimization.In synthesized gel rubber, the hydrolysis of the organic compound by silicon, and hydrolysate transferred to the process of water by inner surface, silicon little by little is provided.

Because Z(such as silicon), X(such as aluminium) and Y(such as phosphorus) must reach formation nucleus and crystallization simultaneously and go out needed oxide (as, Silicophosphoaluminaand), the speed that provides of these three kinds of elements must be complementary.This just means that when doing aluminium and phosphorus source with aluminum phosphate the dissolving of aluminum phosphate should be consistent with the hydrolysis of organo-silicon compound.Therefore, give molten at least a portion aluminum phosphate and just seem very important.Even more crucial be the speed that provides of silicon, this will depend on various factors, as, the size of inner surface, temperature, the pH value of water, the character of concentration and organic solvent and silica reagent.

Because the hydrolysis alkoxide compound of alkoxide compound Z(such as silicon) and transfer rate are subjected to the control of inner surface size.As early stage discussion, increase mixing is to help Z(such as silicon) combination.

As early stage mentioned, PH is an important synthetic parameter.In the process that oxide (as Silicophosphoaluminaand) forms, pH value should maintain about neutrality or above (that is, and be approximately 6 or more than, maximum is about 9).When the alkaline stability of wishing Silicophosphoaluminaand was between aluminum phosphate and zeolite, pH value was preferably in about 8 or be higher than 8 slightly.Because the hydrolysis of silica reagent plays a major role, need to control it in this method, so need the pH value of a near constant during crystallization.This can be before adding other reagent, and utilization is given molten aluminum phosphate and obtained.

In order to obtain and to keep higher pH value (PH=8 or more than), even after organic hydroxide partly decomposes, can dose inorganic base.This inorganic base also can play the above-mentioned effect of pointing out as the auxiliary directional agent.

By synthesis mode of the present invention, utilize Z(such as silicon) molar fraction be about 1-20%, X(is as, aluminium) molar fraction be about 35-50% and Y(as, phosphorus) molar fraction be about 35-50% and can prepare oxide.Therefore, by synthetic method of the present invention, the oxide for preparing the formula that sees service is possible, needn't calculate according to the pentagon combination region (pentagonal composition al areas) of Fig. 1 and Fig. 2 in people's such as LOK the United States Patent (USP) 4440871, especially about this point, X(such as aluminium) can represent with the molar fraction of 30-44%, Y(such as phosphorus) can represent with the molar fraction of 43-50%, Z(such as silicon) can represent that clearly the molar fraction summation of X, Y and Z is 100 with the molar fraction of 6-20%.

Micropore crystal formation oxide material of the present invention (as Silicophosphoaluminaand) has ion-exchange capacity and catalytic activity.Otherwise, only contain aluminium, phosphorus and oxygen, the respective substance of not having the crystalline structure of the same race of silicon in the lattice structure that is made of them substantially has very little or does not have ion-exchange capacity and catalytic activity.Therefore, as the α value of Silicophosphoaluminaand at least with 100%, or even at least with 1000%, greater than the α value of the respective substance of crystalline structure of the same race.Said respective substance only has aluminium, phosphorus and oxygen, does not have silicon substantially in the lattice structure that they constitute.People such as Wilson has briefly discussed the example of this respective substance in United States Patent (USP) 4310440.

Here prepared oxide (as Silicophosphoaluminaand) can be molecule or other skeleton structure.When they are molecular sieve or closely knit material, will have certain differentiable crystalline structure, this structure presents the feature that the X-ray powder comes diffraction pattern.

When oxide of the present invention (as Silicophosphoaluminaand) is measured X-ray value, no matter be molecular sieve or other structure, all utilize the K-α duplet ray of copper, diffractometer and parallel computer of scintillation counter is housed.Utilization is being associated with computing measurable peak height on the computer of spectrometer, I and the method for drawing number as 2 θ, and the θ here is angle, Prague (Bragg).With respect to call wire, can measure relative intensity 100 I/I., wherein I from these capacity _OIntensity for the strongest line or peak.Observe with interplanar distance d() (A °).Contrast is taken as 100 the strongest line can obtain relative intensity, and various cationic particular oxides (as Silicophosphoaluminaand) demonstrate identical style, just some skew and some variation of relative intensity of interplanar distance.Other variation may take place, and this will depend on the Z(such as the silicon of specific sample) with X(such as aluminium) and Y(such as phosphorus) and X(such as aluminium) ratio, and to its heat treated degree.

Oxide of the present invention (as Silicophosphoaluminaand) is material micropore or closely knit, has the Z(of containing such as silicon), Y(such as phosphorus) and X(such as aluminium) the tetrahedral skeleton of Atomic coordinate (by oxygen).If micropore, will present ion-exchange, acid and characteristic catalysis, the characteristic of this and zeolite is similar.Yet because their different acid intensity spectrum, as the catalyst of acidic catalyst conversion, they have potential advantages greatly.All can produce unnecessary secondary response because acidity is too high or too low in conversion.With skeleton X(such as aluminium) relevant acidity is by Z(such as silicon) replace Y(such as phosphorus) and bring.Otherwise, when with Z(such as silicon) replace skeleton X(such as aluminium) time can produce and skeleton Y(such as phosphorus) relevant basicity.

The ionic radius of X, Y and Z should be enough to guarantee to form the peculiar skeleton structure that contains tetrahedral coordination.Especially, we think that the ion " radius ratio " of these elements should be approximately between the 0.15-0.73.

Term " radius ratio " is defined as the crystal ionic radius and the negative oxygen ion O of M element ^-2The ratio of crystal ionic radius.

Radius ratio=(the crystal ionic radius of M element)/(O ^-2The crystal ionic radius)

The crystal ionic radius of various elements is listed in " CRC Chemical Physics handbook " the 61st edition, and 1980, CRC published Co., Ltd, F-216 and F-217 page or leaf.Enroll tabulation here for your guidance.When measuring radius ratio, need utilize M atom and negative oxygen ion (O ^-2) the crystal ionic radius, these data are measured with Same Way.

The following various elements example of " radius ratio " under various valence states of having listed:

Element valence mumber radius ratio

As????+3????0.44

B????+3????0.17

Bi????+3????0.73

Co????+2????0.55

Cu????+2????0.54

Fe????+2????0.56

Fe????+3????0.48

Ge????+2????0.55

Ge????+4????0.40

Mn????+2????0.61

Sb????+3????0.57

Ti????+3????0.58

Ti????+4????0.52

V????+3????0.56

V????+4????0.48

Zn????+2????0.56

V????+5????0.45

B????+1????0.26

Ba????+1????1.16

Ba????+2????1.02

Ce????+3????0.78

Cd????+1????0.86

Cd????+2????0.73

Cr????+1????0.61

Cr????+2????0.67

Cu????+1????0.73

La????+1????1.05

Mg????+1????0.62

Mg????+2????0.50

Mo????+1????0.70

Sn????+2????0.70

Sr????+2????0.85

Th????+4????0.77

Ti????+1????0.73

Ti????+2????0.71

Zn????+1????0.67

Thus He Cheng oxide (as Silicophosphoaluminaand) also can with metal component as Ag, W, V, Mo, Re, Cr, Mn, or the metal of VIII family combines closely as Pt or Pd, as catalyst, carries out oxidation-dehydrogenation or oxidation reaction.A kind of like this component can be undertaken in the composition by ion-exchange, wherein can or carry out closely physical mixed by dipping.For example, as the situation of Pt, utilize and contain Pt metal ion solution processing crystal, then this component can be impregnated into inside the crystal face or above it.So far, suitable platinum compounds comprises chloroplatinic acid, platinum chloride and the various compound that contains the platinum ammonium complex compound.

According to prior art, utilize other cations or anion to replace, replace the original cationic or the anion of synthesis oxide (as Silicophosphoaluminaand) to small part.Desirable replacement cation comprises metal ion, hydrogen ion, and the primary of hydrogen, as ammonium, ion and their mixture, best cation comprises hydrogen, II A in the rare earth metal and the periodic table of elements, III A, IV A, I B, II B, III B, IV B, the metal of VI B and VIII B.

Typical ion exchange technique should be that the salt of required substitution ion and synthetic crystal formation oxide (as Silicophosphoaluminaand) are contacted.The example of these cationic salts comprises halide, as, chloride, nitrate and sulfate.

Synthesis oxide prepared in accordance with the present invention (as Silicophosphoaluminaand) utilizes heat treatment to be easy to convert to another kind of pattern.This heat treatment normally at least under 300 ℃ with the oxide of a certain pattern heating at least 1 minute, generally be no more than 20 hours, can utilize the pressure that is lower than atmosphere during heat treatment, owing to reason easily, the most desirable is to adopt normal pressure.Under up to about 1000 ℃, heat-treat.Be specially adapted to catalysis hydrogen conversion reaction through heat treated product.

In addition, no matter be as adsorbent, the ion-exchanger or the catalyst of organic compound transfer process, this oxide should dewater, at least partial dehydration.This process can be in 200 °-600 ℃ air or inert atmosphere (as nitrogen etc.), and normal pressure is lower than normal pressure or is higher than under the normal pressure heating 30 minutes and finished by 48 hours.Also can be near under the room temperature, oxide (as Silicophosphoaluminaand) placed under the vacuum finish dehydration.But, obtain to dewater preferably, just need the long time.Therefore, according to dehydration or heat treatment degree, oxide can be placed about 200 °-1000 ℃ to heat 1 minute to 48 hours down to oxide (as Silicophosphoaluminaand).

Can be processed into the particulate of all size with oxide (as the Silicophosphoaluminaand) crystal of the present invention's preparation.Usually get on very well, particulate can exist with the form of powder, particle or mechanograph, and such as a kind of extrudate, it has and can sieve and can not pass through 400 orders (Tyler) by the granularity of 2 orders (Tyler) sieve.When composition molding, as adopting extrusion, crystal can extruding or part dry back extruding before dry.

With regard to a lot of catalyst, people wish oxide (as Silicophosphoaluminaand) and can sustain in addition that the material of temperature and other condition combines in the organic matter conversion process.This material comprises active and the inorganic active material, synthesize or natural zeolite and inorganic matter, as clay, silica/or metal oxide.The latter is not natural existence, exists with gel precipitation or with the gel form of the mixture that contains silica and metal oxide exactly.A kind of material uses together with new oxide (as Silicophosphoaluminaand), promptly with activated new oxide chemical combination, is to help to improve its conversion reaction and/or selection of catalysts in some organic matter conversion process.Non-viable material is suitable for doing the inversion quantity of diluent control assignment procedure, so that can obtain product to very economical, and need not to use other method just can control the speed of reacting.In order to improve the compression strength of catalyst under the commercialization operating condition, these materials can and natural clay, as bentonite and kaolin, combine use.Said material, promptly clay, oxide etc. play a part adhesive concerning catalyst.Because total hope prevents that catalyst is broken into powder in commercialization is produced, be attracting so require the catalyst of high compressive strength is provided.Usually using clay adhesive is exactly in order to improve the compression strength of catalyst.

Can and the natural clay of new oxide combination montmorillonite is arranged and comprises the kaolin group of pair bentonite, the clay that it is halloysite, kaolinite, dickite, nacrite or anauxite that kaolin group is considered to Dixie, Mcnamee, Georgia and Floria clay or its main inorganic component usually.These clays can use with the crude state of initial mining, or re-use after biscuit firing, acid treatment or chemical modification.Also comprise the inorganic chlorine oxide with the useful adhesive of crystal combination of the present invention, it should be noted that aluminium oxide or silica.

Except above-mentioned material, the host material combination of new oxide (as Silicophosphoaluminaand) crystal energy and porous, as aluminium silicophosphate, silica, an aluminium oxide, silica one magnesia, silica one zirconia, silica one thorium oxide, silica one beryllium oxide, silica-titania and ternary composition, as silica one aluminium oxide one thorium oxide, silica one aluminium oxide one zirconia, silica one aluminium oxide, one magnesia and silica one magnesia one zirconia.The crystalline oxides matter of telling at last (as Silicophosphoaluminaand) alters a great deal with the relative scale of inorganic oxide gel matrix, its crystalline content scope is about 1-90%(weight) and generally also some more, particularly when composition was made pearl, crystal was about 2-80 in the percentage range of composition.

Crystalline material of the present invention changes at an easy rate and is applicable to various organic matters, as hydrocarbon, and the catalytic active substance in the conversion process.These conversion processes comprise the hydrocarbon cracking as non-limiting example, its reaction condition: temperature is about 300-700 ℃, and pressure is about the 0.1-30 crust, and the weight hourly space velocity is about 0.1-20 hour ^-1; Dehydrogenation of hydrocarbons, its reaction condition: temperature is about 300-700 ℃, and pressure is about the 0.1-10 crust, and the weight hourly space velocity is about 0.1-20 hour ^-1; Paraffin conversion becomes aromatic compounds, its reaction condition: temperature is about 100-700 ℃, and pressure is about the 0.1-60 crust, and the weight hourly space velocity is about 0.5-400 hour ^-1, hydrogen/hydrocarbon mol ratio is about 0-20; Olefines changes into aromatic compounds, and as benzene, toluene and dimethylbenzene, its reaction condition: temperature is about 100-700 ℃, and pressure is about the 0.1-60 crust, and the weight hourly space velocity is about 0.5-400 hour ^-1, hydrogen/hydrocarbon mol ratio is about 0-20; Alcohols, as methyl alcohol, or ethers, as ether, or its mixture changes into the hydro carbons that comprises aromatic compounds, its reaction condition: temperature is about 275-600 ℃, and pressure is about the 0.5-50 crust, and the liquid hourly space velocity is about 0.5-100 hour ^-1; The isomerization of dimethylbenzene material component, its reaction condition: temperature is about 230-510 ℃, and pressure is about the 3-235 crust, and the weight hourly space velocity is about 0.1-200 hour ^-1And hydrogen/hydrocarbon mol ratio is about 0-100; Toluene disproportionation, its reaction condition: temperature is about 200-760 ℃, and pressure is about the 1-60 crust, and the weight hourly space velocity is about 0.08-20 hour ^-1; The alkylation of aromatic hydrocarbons, as benzene and alkylbenzene, in the presence of alkylating agent, as alkene, formaldehyde, halogenated alkyl thing and alcohols, its reaction condition: temperature is about 340-500 ℃, and pressure is about the 1-200 crust, and the weight hourly space velocity is about 2-2000 hour ^-1, aromatic hydrocarbons/alkylating agent mol ratio is about 1/1-20/1; The transalkylation of aromatic hydrocarbons in the presence of many alkylaromatic hydrocarbons, its reaction condition: temperature is about 340-500 ℃, and pressure is about the 1-200 crust, and the weight hourly space velocity is about 10-1000 hour ^-1And aromatic hydrocarbons/many alkylaromatic hydrocarbons mol ratio is about 1/1-16/1.

For the catalyst that contains activating oxide (as Silicophosphoaluminaand), the condition of its catalyzed conversion generally comprises temperature and is about 100-760 ℃, and pressure is about the 0.1-200 crust, and the weight hourly space velocity is about 0.08-2000 hour ^-1, hydrogen/organic matter, as hydrocarbon, mol ratio is about 0-100.

For the more abundant mode that illustrates character of the present invention and implement like this, list following embodiment.

When analyzing the α value, merit attention the α value and be catalytic pyrolysis active aspect the approximate representation of employed catalyst and fiducial mark catalyst comparing result, and also can obtain relative velocity constant (catalyst of unit volume transforms the speed of hexane in the unit interval) according to the α value.The active alpha value of highly active silica-alumina catalyst for cracking is decided to be 1(velocity constant=0.016 second ^-1).With regard to zeolite HZSM-5, only need the aluminium oxide of the four sides ligand of 174ppm, its α value just can reach 1.U.S. Patent number 3,3543,078 and the assorted Chi (The Journal of Catalysis) of catalysis, the IV volume, 522-529 page or leaf (August nineteen sixty-five) has been narrated the α test.

For this specification and following claim, by in the temperature programming process, decomposing the ammonia of emitting, in order to measure its ion exchange capacity with the ammonium in the sulfamic acid solution titration oxide (as Silicophosphoaluminaand).This method is described in heat chemistry (Thermochimica Acta), 111 volumes,, Kerr and A, M, Chester, 124 pages of 113-in 1971.Oxide of the present invention to the exchange capacity of iron be at least about 0.002 in addition minimum be 0.35 milliequivalent/gram.

The relevant method that is called the Silicophosphoaluminaand material of MCM-2 by aluminum phosphate as feedstock production of following embodiment 1-8.These embodiment 1-8 also illustrate some Silicophosphoaluminaand and the aluminum phosphate difference aspect ion exchange capacity and catalytic activity simultaneously.

Example 1

With 138.3 gram H ₃PO ₄(85%), the water of 357.6 grams, the triethylamine of the Catapal aluminium oxide of 82.5 grams and 91.2 grams prepares synthesis reaction mixture.After suspension is stirred, this mixture is poured in 1 liter the steel autoclave, and under self-generated pressure, kept 24 hours in 200 ℃.Product after filtration, washing, down dry in 80 ℃ again.This product crystal after by analysis atomic percent: aluminium is 48.9, and phosphorus is 51.1, and silicon is less than 0.03.The sample of synthetic product is paid the x-ray analysis, found that according to gained sample is a crystalline material, and its diffract spectral line data are listed in table 1.

Table 1

d（A） 2θ I/I _O

11.7535????7.515????95.99

6.8016????13.005????16.08

5.8886????15.033????28.26

4.4534????19.921????60.53

4.2109????21.080????71.59

3.9417????22.538????100.00

3.5870????24.800????5.00

3.4042????26.155????28.27

3.0617????29.142????19.01

2.9523????30.248????18.94

2.6520????33.771????6.87

2.5750????34.810????15.00

Example 2

Repeat the synthetic reaction of embodiment 1, its result has generated the material with the listed feature diffract spectral line of table 1, the atomic percent of its component: aluminium is 47.95, and phosphorus is 51.70, and silicon is 0.35.

Example 3

The crystal phosphoric acid aluminium of a certain amount of example 2, under nitrogen, in 450 ℃ of roastings 4 hours, and twice 80 ℃ down with 1 mole the NH of PH=7 ₄Cl solution contact 3 hours.The ammonia that this product of employing titration is later on emitted in 25-600 ℃ of heating process is in order to estimate the cation exchange property of above-mentioned product.Experimental result shows that surpassing 250 ℃ does not also have ammonia to emit, thereby points out not exist the cation exchange position.

Example 4

The end product of embodiment is paid the α test.The α value is less than 0.1.

Example 5

With the Si(OC that contains 60 gram 1-hexanols and 10 grams ₂H ₅) ₄Organic facies and by 71 gram water and under nitrogen, in the product of 4 hours 24 grams of 450 ℃ of roastings example 1, and the water formed of 37 gram tetraethyl ammonium hydroxides (40%), co-production two-phase synthesis reaction mixture.After mixture is stirred, mixture transferred in 0.3 liter the copper autoclave, be heated to 180 ℃ and under this temperature, kept 7 days.PH value is between 6-8 when beginning and end.With filtration method crystallized product and reactant mixture are separated, washing, dry down at 80 ℃ again.The product crystal gets atomic percent by analysis: aluminium is 41.1, and phosphorus is 42.8, and silicon is 16.1.Aluminium/phosphorus ratio is 0.96.The sample of synthetic product Silicophosphoaluminaand is paid the x ray analysis, and finds that sample is a crystalline texture, and its diffract spectral line data are listed in table 2, it be by MCM-2 peculiar.

Table 2(MCM-2)

d（A） 2θ I/I _O

9.2777????9.525????100.00

6.8832????12.851????17.26

6.2774????14.097????15.85

5.5276????16.021????80.96

4.9185????18.020????15.09

4.6701????18.987????2.66

4.3119????20.581????98.58

3.9922????22.249????4.58

3.8475????23.098????4.35

3.5163????25.308????19.04

3.4447????25.843????19.47

3.0224????29.530????2.98

2.9248????30.539????35.79

2.8587????31.264????35.38

2.6051????34.396????6.06

Example 6

The product of use-case 2 roastings repeats the synthetic of example 5 as aluminium source and phosphorus source.Crystallized product separates with crystalline mixture by filtering, and washing is dry down in 80 ℃ again.The product crystal gets atomic percent by analysis: aluminium is 44.9, and phosphorus is 41.6, and silicon is 13.5.Aluminium/phosphorus ratio is 1.08.The sample of synthetic product Silicophosphoaluminaand is paid the x ray analysis again, finds that product is a crystalline texture, and its diffract spectral line data are listed in table 3, it be for MCM-2 peculiar.

Table 3(MCM-2)

d（A） 2θ I/I _O

9.2698????9.533????100.00

6.8803????12.856????15.13

6.2784????14.094????14.22

5.5226????16.035????77.00

4.9233????18.002????12.78

4.6787????18.952????5.80

4.3088????20.596????96.57

3.9959????22.228????5.61

3.8416????23.133????4.54

3.5131????25.331????29.89

3.4435????25.852????21.11

3.3408????26.661????15.04

3.1505????28.304????6.42

3.0239????29.515????4.06

2.9234????30.555????39.38

2.8602????31.247????38.68

2.6071????34.369????6.26

Example 7

The crystallized product of a certain amount of example 6 under blanket of nitrogen in 450 ℃ of roastings 4 hours, and 1 mole of NH of twice and PH=7 ₄Cl solution contacts 3 hours down in 80 ℃.Be warmed up to the ammonia of being released 600 ℃ the process by the titration product from 25 ℃, in order to estimate its cation exchange property.The gained result shows has two kinds of ammonia to emit.Be equivalent to 1.45 milliequivalent/grams to 250 ℃ of low temperature ammonia of being emitted, be equivalent to 1.14 milliequivalent/grams, and the maximum desorption rate of observing high temperature ammonia is at 375 ℃ corresponding to the high temperature ammonia of cation position.

Example 8

Example 7 end products are paid the α test.Its α value is 4.8, and it has shown and the product material comparison of embodiment 2, has improved 48 times on catalytic activity, even higher.

Following embodiment 9-24 further specifies the preparation method and the character of various Silicophosphoaluminaands.

Example 9

Si(OC with 1-hexanol that contains 60 grams and 10 grams ₂H ₅) ₄Organic facies and by 13.7 the gram Al ₂O ₃, 23.1 gram H ₃BO ₄The water that the water of the TPAOH (TPAOH) of (85%) 8.4 gram 25% and 30 grams is formed, preparation two-phase synthesis reaction mixture.Reactant mixture is done as a whole, its atomic percent: silicon is 9.3%, phosphorus be 38.8% and aluminium be 51.9%.Directing agent is a TPAOH.

Reactant mixture is heated to 150 ℃ with the speed that per hour increases by 50 ℃, and under this temperature insulation 65 hours up to forming Silicophosphoaluminaand.The beginning pH value is between 5 and 7.

Crystallized product separates with filtration method and reactant mixture, and is dry down at 80 ℃ after the washing.The product crystal analysis gets atomic percent: silicon is 15.7, and phosphorus is 34.8, and aluminium is 49.5.Its result of sample payment x ray analysis who is called as the synthesis silicon phosphorus aluminate of MCM-1 shows that sample is a crystalline texture, and the diffract spectral line data are listed in table 4.

Table 4(MCM-1)

The 2 θ relative intensity I/Io that interplanar crystal spacing (A) is observed

9.6677????9.140????29.97

6.8569????12.900????100.00

6.4870????13.639????77.56

5.6000????15.812????5.00

4.8729????18.190????51.07

4.8414????18.310????50.26

4.2482????20.893????85.10

3.9700????22.375????5.00

3.6099????24.641????9.67

3.4401????25.877????6.62

3.3900????26.267????41.66

3.0597????29.162????77.25

2.9312????30.471????15.08

2.8927????30.886????16.69

2.7777????32.199????10.96

2.6781????33.432????41.21

Example 10

The MCM-1 silicon metal aluminophosphates of a certain amount of example 9 in 450 ℃ of roastings 4 hours, is used the x-ray analysis afterwards under the nitrogen fluorine.The results are shown in table 5.

Table 5

The 2 θ relative intensity I/I that interplanar distance (A) is observed _O

6.8339????12.944????94.83

4.8477????18.286????11.21

4.7900????18.507????10.00

4.5300????19.579????8.00

4.2731????20.770????100.00

4.1441????21.424????43.10

3.6246????24.539????9.98

3.5438????25.108????1.54

3.4200????26.032????10.00

3.2900????27.079????5.00

3.0823????28.944????11.86

3.0427????29.329????13.57

2.6961????33.202????2.87

Example 11

Si(OC with 60 gram 1-hexanols and 10 grams ₂H ₅) ₄The organic facies of forming and by 23.1 gram H ₃PO ₄(85%), 10 gram Al ₂O ₃, 84 gram TPAOH(25%) and the water formed of 30 gram water, the mixture of co-production two-phase synthetic reaction.Reactant mixture is done as a whole, its atomic percent: silicon is 10.8, and phosphorus is 45.0, and aluminium is 44.2.Directing agent is a TPAOH.

With 50 ℃ programming rate per hour, reactant mixture is heated to 150 ℃, and insulation 168 hours under this temperature, up to forming the Silicophosphoaluminaand crystal.The pH value of beginning is between 5 and 7.

With filtration method crystalline product and reactant mixture are separated, washing, dry down in 80 ℃ afterwards.The product crystal contains atomic percent by analysis: silicon is 17.5, and phosphorus is 37.2, and aluminium is 45.4, and its crystal size is big.The sample of synthetic Silicophosphoaluminaand is paid the x ray analysis, finds that sample is the MCM-2 crystalline molecular sieve of Chabazite-type, and its diffract spectral line data are listed in table 6.

Table 6(MCM-2)

The 2 θ relative intensity I/I that interplanar distance (A) is observed _O

9.2412????9.563????99.21

6.8600????12.894????24.93

6.4808????13.640????7.48

6.2515????14.155????14.65

5.5144????16.059????72.90

4.8868????18.138????21.38

4.8257????18.370????11.67

4.3030????20.624????100.00

4.2584????20.843????23.57

4.0000????22.205????5.00

3.8400????23.142????5.00

3.5075????25.373????21.42

3.4376????25.897????22.89

3.3947????26.230????7.27

3.12393????28.550????1.77

3.0495????29.262????14.07

3.0160????29.594????5.90

2.9190????30.601????33.97

2.8492????31.370????25.06

Example 12

Repeat the synthetic reaction of example 11, just water contains the Al of 17.0 grams ₂O ₃The crystal size of resulting product MCM-2 silicon metal aluminophosphates is little, its atomic percent: silicon is 13.2, and phosphorus is 36.3, and aluminium is 50.5.

Example 13

The MCM-2 silicon metal aluminophosphates of a certain amount of example 11 in 450 ℃ of roastings 4 hours, is used the x-ray analysis afterwards under blanket of nitrogen.Gained the results are shown in table 7.

Table 7

The 2 θ relative intensity I/I that interplanar distance (A) is observed _O

9.2476????9.556????100.00

6.8414????12.929????23.34

6.2800????14.090????2.00

5.5050????16.087????16.61

4.9465????17.918????5.05

4.6200????19.194????2.00

4.2923????20.676????35.99

3.8415????23.134????4.72

3.5423????25.119????6.97

3.4266????25.982????7.73

3.2100????27.768????2.00

3.1600????28.216????2.00

2.9086????30.174????15.30

2.8621????31.226????8.93

Example 14

By 60 gram 1-hexanols and 10 gram Si(OC ₂H ₅) ₄The organic facies of forming and by 7 gram Al ₂O ₃, 23.1 gram H ₂PO ₄(85%) co-production two-phase synthesis reaction mixture, 84 gram TPAOH(25%) and the water formed of 30 gram water.Reactant mixture is made its as a whole mixture, its atomic percent: silicon is 12.4, and phosphorus is 52.0, and aluminium is 35.6, and directing agent is a TPAOH.The pH value of beginning is between 5 and 7.

Per hour to increase by 50 ℃ programming rate, reactant mixture is heated to 150 ℃, and insulation 65 hours under this temperature, up to forming the Silicophosphoaluminaand crystal.PH value during the reaction beginning is between 5 and 7.

Crystallized product separates with filtration method and reactant mixture, and washing is dry down in 80 ℃ afterwards.Synthetic Silicophosphoaluminaand sample is paid the x-ray analysis, and discovery is the crystalline texture that is called MCM-3, and its diffract spectral line data are listed in table 8.

Table 8(MCM-3)

The 2 θ relative intensities that interplanar distance (A) is observed, I/I _O

5.1933????17.059????43.92

4.8933????18.114????15.90

4.5500????19.493????1.00

4.2976????20.650????100.00

3.9617????22.423????23.28

3.9145????22.697????63.05

3.8453????23.111????14.34

3.6884????24.109????28.92

3.5868????24.802????49.12

3.3852????26.305????4.70

3.0406????29.349????20.04

2.9094????30.705????12.74

2.8588????31.262????14.05

2.7565????32.454????12.24

Example 15

By 60 gram 1-hexanols and 10 gram Si(OC ₂H ₅) ₄The organic facies of forming and by 15.8 gram Al ₂O ₃, 42.3 gram H ₃PO ₄(85%) co-production two-phase synthesis reaction mixture, 84 gram TPAOH(25%) and the water formed of 30 gram water.Reactant mixture is made as a whole composition, its atomic percent: silicon is 6.6, and phosphorus is 50.6, and aluminium is 42.8.Directing agent is a TPAOH.Reactant mixture is heated to 150 ℃ with the programming rate that per hour increases by 50 ℃, and insulation 168 hours under this temperature, up to forming the Silicophosphoaluminaand crystal.PH value is between 5 and 7 during beginning.

By filtering, washing 80 ℃ of dryings, is isolated crystallized product then from reactant mixture.Then this synthetic Silicophosphoaluminaand sample is carried out the x-ray analysis, and show it is a kind of crystalline material of representing with MCM-4, and demonstrate diffraction as shown in table 9 (spectral line) figure.

Table 9(MCM-4)

The relative intensity of the observation between crystal face (plane)

D-spacing (A) 2x θ I/I _O

4.4626????19.879????13.77

4.3539????20.380????36.23

4.2694????20.788????100.00

4.0690????21.825????16.32

3.9834????22.299????3.43

3.7400????23.770????5.00

3.6516????24.355????31.12

3.3698????26.428????62.10

3.0467????29.289????7.84

2.9447????30.328????6.71

Example 16

A kind of two-phase synthesis reaction mixture be by 60 restrain oneself alcohol-(1) and 10 the gram Si(OC ₂H ₅) ₄The organic facies of forming and by 13.8 gram Al ₂O ₃, 23.1 the gram H ₃PO ₄(85%), 4.0 gram NaOH, the waters preparation that 26.0 gram TA TPABr and 100 gram water are formed.As a whole, the composition of reactant mixture is represented with atomic percentage, is 9.3%Si, 38.6%P and 52.1%Al.Directing agent is the tetrapropylammonium bromine.Initial pH value is between 5 and 7.

Reactant mixture is heated to 150 ℃, and remains on this temperature through 168 hours per hour to increase by 50 ℃ firing rate, up to generating the Silicophosphoaluminaand crystal.

From reactant mixture by filter, washing, then 80 ℃ of dryings, isolate crystalline product.Analyze crystalline product, each constituent content is expressed as with atomic percentage: 9.6%Si, 45.9%P and 44.5%Al.Then this synthetic Silicophosphoaluminaand sample is carried out the x-ray analysis, and show it is a kind of crystalline material of representing with MCM-5, and demonstrate diffraction as shown in table 10 (spectral line) figure.

Table 10(MCM-5)

The relative intensity of the observation between crystal face (plane)

D-spacing (A) 2x θ I/I _O

8.5984????10.279????100.00

6.7810????13.045????3.05

4.7545????18.647????4.65

4.6389????19.116????6.49

4.5429????19.524????1.58

4.4200????20.072????2.00

4.3500????20.398????3.00

4.2206????21.031????2.60

4.1134????21.586????2.37

3.8541????23.058????1.60

3.7092????23.971????6.80

3.6724????24.215????3.65

3.4981????25.441????1.08

3.3886????26.278????3.73

3.3331????26.723????0.48

3.2150????27.724????4.51

3.1616????28.202????2.87

3.0206????29.548????2.28

2.9090????30.709????1.12

2.8887????30.930????1.63

2.7450????32.594????1.07

2.7005????33.146????2.00

2.6774????33.441????0.84

2.6472????33.833????0.73

2.5890????34.618????1.34

2.5760????34.797????1.30

Example 17

For the sample of the MCM-2 crystalloid Silicophosphoaluminaand of calcining in the example 13, measured to further proving the absorption property of its property of the molecular sieve.The result who measures, percentage is represented as follows by weight:

Water (60 ℃) 10.3

N-hexane (90 ℃) 9.3

Paraxylene (90 ℃) 2.7

2-methyl-pentane (90 ℃) 1.1

Cyclohexane (90 ℃) 0.8

Ortho-xylene (120 ℃) 0.9

Example 18

The crystalloid MCM-2 Silicophosphoaluminaand product of a certain amount of example 11, before 900 ℃ heat treatment and after the heat treatment, measured its absorption property, showing its absorption property, is constant by this heat treatment, and the Silicophosphoaluminaand crystalline molecular sieve of this illustrative examples 11 has good heat endurance.

Example 19

Measure the acidity of example 11 and example 12 products, this mensuration is by from 25 to 600 ℃ of titration, and long-pending gaseous ammonia of emitting is carried out during heating ammonium type (salt).This experimental result shows that maximal rate that ammonia is emitted is that ion exchange capacities at 360 ℃ and every kind of product are 0.7～0.8 milliequivalent/gram.

Example 20

The product of example 11 converts to after the Hydrogen by heating ammonium type to 450 in nitrogen ℃～550 ℃, carries out the α test and detects.Its α value is indicated as 8.6.This identical product shows that to have a methyl alcohol conversion at 350 ℃ active, and the activity that makes alkylation of toluene with methyl alcohol is at 538 ℃, and the activity that makes alkylation of toluene with ethene is between 450 ℃ and 500 ℃.

Example 21～24

For synthetic four kinds of different Silicophosphoaluminaand crystalline materials, four kinds of two-phase back mixing compounds have been prepared.The composition of reactant mixture and reaction condition are listed in following table 11 and have suffered.Four kinds of products that obtain, every kind of product all has silicon, phosphorus and the al composition of tetrahedral coordination as shown in table 11.

The X-ray diffraction analysis result of every kind of Silicophosphoaluminaand of example 21,22,23 and 24 products is listed in respectively in the following table 12,13,14 and 15.These products have name code separately: MCM-6, MCM-7, MCM-2 and MCM-8.

The constraint indices of crystallographic plane (Constraint Index) (at United States Patent (USP) 4,385, in 195 definition) and the α value of example 21,22 and 23 product materials have been measured.It the results are shown in table 16 and has suffered.

Table 11

Product 21 22 23 24 in the example

Synthetic mixture component (gram)

H ₃PO ₄（85%） 23.1 23.1 23.1 23.1

H ₂O 71.0 59.6 71.0 70.0

Al ₂O ₃10.0 13.7 10.0 10.0

Si（OC ₂H ₅） ₄10.0 10.0 10.0 10.0

Hexanol-(1) 60.0 60.0 60.0 60.0

Organic base

TMAOH（25%）????…????…????…????31.0

TEAOH（40%）????37.0????…????37.0????…

Two-n-propylamine ... 10.1

Inorganic base

(milliliter, 5 * 10 ²Mole)

KOH????…????…????…????2.0

CsOH????0.04????…????2.0????…

Condition

The nucleation time, hours 24 24 24 24

The nucleation temperature, ℃ 130 130 130 130

Crystallization time, hours 144 24 144 144

Crystallization temperature, ℃ 180 200 180 180

Rotating speed, revolutions per 800 800 800 800

Initial PH 6.5 5.5 6.5 5.5

Stop PH 6.5 9 6.0 7

The component of product

(T-atomic percentage)

Si????19.7????12.7????19.8????15.3

P????39.9????41.7????39.6????46.3

Al????40.4????45.6????40.7????38.4

The product oxide component of product

(weight % is under synthetic state)

SiO ₂15.83 10.45 14.33 11.49

P ₂O ₅37.85 41.06 33.90 41.22

Al ₂O ₃27.63 32.29 25.10 24.60

Nitrogen content (weight %) 1.2 1.3 1.2 1.3

Carbon content (weight %) 5.46 5.95 6.32 8.13

Content of ashes (weight %) 85.9 87.2 85.2 87.6

Ion exchange capacity 0.56 1.16 0.80 0.29

(milliequivalent/every gram ash content)

Table 12(MCM-6)

The relative intensity of the observation between crystal face (plane)

D-spacing (A) 2x θ I/I _O

11.81457????7.476????93.1

6.83915????12.934????12.5

5.92518????14.939????32.4

4.48008????19.801????81.1

4.20412????21.115????78.7

3.95564????22.458????100.0

3.66765????24.847????5.0

3.42339????26.006????42.3

3.06571????29.104????18.8

2.96477????30.118????22.1

2.65646????33.712????6.8

2.58880????34.620????22.3

Table 13(MCM-7)

The relative intensity of the observation between crystal face (plane)

D-spacing (A) 2x θ I/I _O

10.85413????8.139????18.2

9.32129????9.480????29.9

6.69511????13.213????11.9

5.63770????15.706????25.9

4.36818????20.313????85.7

4.20785????21.096????100.0

4.00432????22.181????60.3

3.93218????22.594????64.8

3.90051????22.780????71.1

3.82889????23.211????76.6

3.10868????28.693????8.9

3.00339????29.721????10.4

2.71879????32.917????11.9

Table 14(MCM-2)

The relative intensity of the observation between crystal face (plane)

D-spacing (A) 2x θ I/I _O

9.2412????9.563????99.21

6.8600????12.894????24.93

6.4868????13.640????7.48

6.2515????14.155????14.65

5.5144????16.059????72.90

4.8868????18.138????21.38

4.8257????18.370????11.67

4.3030????20.624????100.00

4.2584????20.843????23.57

4.0000????22.205????5.00

3.8400????23.142????5.00

3.5075????25.373????21.42

3.4376????25.897????22.89

3.3947????26.230????7.27

3.1239????28.550????1.77

3.0495????29.262????14.07

3.0160????29.594????5.90

2.9190????30.601????33.97

2.8492????31.370????25.06

Table 15(MCM-8)

The relative intensity of the observation between crystal face (plane)

D-spacing (A) 2x θ I/I _O

6.3139????14.015????68.10

4.4698????19.847????48.03

3.6517????24.355????100.00

3.1578????28.237????15.37

2.8291????31.599????12.03

2.5869????34.647????13.37

3.9910????22.256????5.40

Table 16

Product 21 22 23 in the example

Constraint indices of crystallographic plane 0.5-0.7 1.0 100

（Constraint????Index）

The α value ... 3.5

Following example 25～39 has illustrated the preparation and the character of the oxide type product of the non--Silicophosphoaluminaand among the present invention.

Example 25

The two-phase synthesis reaction mixture is to use by 11 gram Ti(OC ₂H ₅) ₄With 60 restrain oneself organic facies that alcohol-(1) forms and by 23.1 gram H ₃PO ₄(85%), 10 gram Al ₂O ₃, 37 gram TEAOH(40%) and the waters preparation formed of 71 gram water.As a whole, the composition of reactant mixture is represented with atomic percentage, then is 10.8%Ti, 45%P and 44.2%Al.Directing agent in organic facies is etamon hydrogen-oxygen (tetraethylammonium hydroxide)

Reactant mixture to be per hour to increase by 50 ℃ firing rate, is heated to 130 ℃ and kept 24 hours in this this temperature.Be heated to 180 ℃ and kept 144 hours then.In the meantime, mixing is that the rotating speed by 800 revolutions per reaches, and it is 7 that initial sum stops pH value.

By reactant mixture is filtered, washes, isolate crystalline product 80 ℃ of dryings then.The composition of crystalline product titanium aluminophosphates is represented with atomic percentage, then is 0.8%Ti, 50.0%P, and 49.2%Al.Then this synthetic titanium aluminophosphates sample is carried out the x-ray analysis.Show it is a kind of crystalline molecular sieve that feature diffraction (spectral line) figure is arranged that presents shown in table 17.

Table 17

The relative intensity of the observation between crystal face (plane)

D-spacing (A) 2x θ I/I _O

11.7888????7.493????84.33

6.8098????12.990????12.26

5.8972????15.011????32.94

4.4601????19.890????72.79

4.2233????21.018????81.28

3.9476????22.504????100.00

3.5901????24.779????6.46

3.4113????26.100????22.94

3.0664????29.097????17.82

2.9540????30.231????24.44

2.6548????33.734????8.08

2.5788????34.759????21.55

Example 26

The crystallization titanium aluminophosphates of a certain amount of example 25 in air, 450 ℃ of calcinings 4 hours, carries out the x-ray analysis then.The results are shown in the table 18.

Table 18

The relative intensity of the observation between crystal face (plane)

D-spacing (A) 2x θ I/I _O

11.9513????7.391????100.00

6.8851????12.847????20.38

5.9644????14.841????8.00

4.5079????19.677????33.90

4.1992????21.140????41.54

3.9702????22.374????58.93

3.5845????24.818????2.48

3.4427????25.858????20.72

3.0772????28.993????12.35

2.9839????29.920????13.41

2.6639????33.615????3.96

2.6038????34.414????12.27

Example 27

The crystalloid titanium aluminophosphates of a certain amount of example 25, according to calcining in the condition described in the example 26, and with 1 mole NH ₄NO ₃The aqueous solution carries out ammonium-exchange.Determining ion exchange capacity according to the ammonia of emitting is 0.361 milliequivalent/gram.

Example 28

The product of example 27 carries out the α test and detects, and shows that the α value is 0.5.

Example 29

For the further absorption property of the property of the molecular sieve of product that confirms has been measured the sample of burnt product titanium aluminophosphates in the example 27, the result of mensuration, % is expressed as follows with weight:

Hexane (90 ℃): 3.35

Water (60 ℃): 0.84%

Example 30

A kind of two-phase synthesis reaction mixture is to use by 11 gram Ti(OC ₂H ₅) ₄With 60 restrain oneself organic facies that alcohol-(1) forms and by 23.1 gram H ₃PO ₄(85%), 10 gram Al ₂O ₃, 31 gram TMAOH(25%) and the waters preparation formed of 70 gram water.As a whole, the composition of reactant mixture is represented with atomic percentage, then is: 10.8%Ti, 45%P and 44.2%Al.Directing agent is tetramethylammonium hydrogen-oxygen (tetramethylammonium hydroxide).

Reactant mixture to be per hour to increase by 50 ℃ speed, is heated to 130 ℃ and remained on this temperature 24 hours.Be heated to 180 ℃ and kept 144 hours then.In the meantime, mixing is that rotating speed by 800 revolutions per reaches.It is 7.5 that initial sum stops pH value.

From reactant mixture,, 80 ℃ of dryings, isolate crystalline product then by filtering, washing.The composition of this titanium aluminophosphates crystalline product is represented with atomic percentage then to be: 12.3%Ti, 50.2%P, and 37.5%Al.Then this synthetic titanium aluminophosphates sample is carried out the x-ray analysis.Show it is a kind of crystalline molecular sieve that presents diffraction shown in table 19 (spectral line) figure.

Table 19

The relative intensity of the observation between crystal face (plane)

D-spacing (A) 2x θ I/I _O

6.3130????14.017????50.11

4.4639????19.873????40.22

3.9923????22.249????9.21

3.6437????24.409????100.00

3.3697????26.428????27.06

3.1570????28.244????18.28

2.8253????31.642????12.71

2.5792????34.753????21.29

Example 31

The crystallization titanium aluminophosphates of a certain amount of example 30 in air, 450 ℃ of calcinings 4 hours, carries out the x-ray analysis then.It the results are shown in the table 20.

Table 20

The relative intensity of the observation between crystal face (plane)

D-spacing (A) 2x θ I/I _O

6.2896????14.069????88.77

4.4518????19.928????36.91

3.9821????22.307????6.65

3.6336????24.478????100.00

3.1496????28.312????24.27

2.8197????31.707????17.55

2.5728????34.842????21.41

Example 32

The crystalloid titanium aluminophosphates of a certain amount of example 30 is calcined according to the condition of being narrated in example 31, and with 1 mole of NH ₄NO ₃The aqueous solution carries out ammonium-exchange.The ion exchange capacity of measuring according to the ammonia of emitting is 0.472 milliequivalent/gram.

Example 33

Repeat the synthetic method of example 25, just with 12 gram Ge(OC ₂H ₅) ₄The reagent that replaces titanium.Initial PH is 6.5 and to stop PH be about 7.The composition of the crystalloid germanium aluminophosphates product that obtains is represented with atomic percentage, then is 0.01%Ge, 49.35%P and 50.64%Al, and show X-ray diffraction figure shown in table 21.

Example 34

Crystalloid germanium aluminophosphates in a certain amount of example 33 in air, 450 ℃ of calcinings 4 hours, and carries out the x-ray analysis then.It the results are shown in the table 22.

Table 21

The relative intensity of the observation between crystal face (plane)

D-spacing (A) 2x θ I/I _O

11.7908????7.491????77.43

6.8111????12.987????11.72

5.8997????15.004????32.03

4.4617????19.883????73.68

4.2249????21.010????77.79

3.9501????22.490????100.00

3.5911????24.772????6.07

3.4177????26.050????52.92

3.0678????29.084????18.00

2.9554????30.216????24.28

2.6563????33.714????7.71

2.5804????34.737????21.87

Table 22

The relative intensity of the observation between crystal face (plane)

D-spacing (A) 2x θ I/I _O

11.6198????7.602????94.26

6.7252????13.154????25.20

5.8292????15.187????10.87

4.4056????20.139????29.82

4.0399????21.984????15.05

3.9276????22.621????100.00

3.6255????24.533????5.17

3.3707????26.420????35.81

3.0865????28.904????18.65

3.0349????29.406????12.04

2.9222????30.567????22.28

2.6595????33.672????6.65

Example 35

The crystalloid germanium aluminophosphates of a certain amount of example 33 is calcined according to the condition of being narrated in example 33, and with 1 mole NH ₄NO ₃The aqueous solution carries out ammonium-exchange.The ion exchange capacity of measuring according to the ammonia of emitting is 1.25 milliequivalent/grams.

Example 36

Product to example 35 carries out α test detection, shows that the α value is 0.6.

Example 37

For further confirming the absorption property of the property of the molecular sieve of product, measured the sample of burnt product germanium aluminophosphates in the example 35, the result of mensuration, % is expressed as follows with weight:

Hexane (90 ℃): 2.87%

Water (60 ℃): 0.59%

Example 38

Repeat the synthetic method of example 30, just with 12 gram Ge(OC ₂H ₅) ₄Replace tiron.It is 7.5 that initial sum stops pH value.The composition of the crystalloid germanium aluminophosphates product that obtains is represented with atomic percentage, then is: 4.4%Ge, and 50.0%P, and 45.6%Al, and show feature X-ray diffraction figure shown in table 23.

Example 39

The crystalloid germanium aluminophosphates of a certain amount of example 38 450 ℃ of calcinings 4 hours, carries out the x-ray analysis then in air, it the results are shown in the table 24.

Table 23

The relative intensity of the observation between crystal face (plane)

D-spacing (A) 2x θ I/I _O

6.3046????14.036????48.14

4.4609????19.887????43.85

3.9898????22.263????7.52

3.6431????24.413????100.00

3.4258????25.988????68.73

3.3699????26.427????10.94

3.1550????28.262????17.00

2.8242????31.655????15.51

2.5780????34.769????22.07

Table 24

The relative intensity of the observation between crystal face (plane)

D-spacing (A) 2x θ I/I _O

6.3051????14.034????71.43

4.4604????19.889????43.55

3.9902????22.261????6.60

2.6431????24.413????100.00

3.4255????25.990????57.80

3.1556????28.257????18.11

2.8241????31.656????17.76

2.5784????34.765????24.57

Example 40

The crystalloid germanium aluminophosphates of a certain amount of example 37 is calcined according to the condition of being narrated in example 39, and with 1 mole NH ₄NO ₃The aqueous solution carries out ammonium-exchange.The ion exchange capacity of measuring according to the ammonia of emitting is 0.405 milliequivalent/gram.

Claims (14)

1, the anhydrous crystal oxide that has composition as follows:

$M^{\mathrm{m+}}{}_{\mathrm{\pi /m}}\mathrm{:［XO}{}_2］{}^{－}{}_{\mathrm{1－y}}\mathrm{:［ZO}{}_2］{}_{\mathrm{X＋y}}\mathrm{:N}{}^{\mathrm{n－}}{}_{\mathrm{y／n}}$

Wherein X represents the element of one or more positive trivalent, wherein Y represents the element of one or more positive pentavalent, wherein Z represents the element of one or more positive tetravalence, wherein the atomicity with Z representative is the atomicity sum that is less than with X and Y representative, wherein or X be not aluminium, Y is not that phosphorus or Z are not silicon or titanium, wherein M is the cation of m valency, N is the anion of n valency, and x and y are the numbers that arrives greater than+1 greater than-1, and satisfies following relation:

(1) if x is 0, then y is not 0,

(2) if y is 0, then x is not 0,

(3) if the atomic ratio of x/y greater than 1, then (x+y) is that y+0.6x is less than 0.4 greater than 0,

(4) if the atomic ratio of x/y less than 1, then (x+y) is that 0.5y+x is less than 0.5 greater than 0,

Said oxide has the ion exchange capacity at least about 0.002 milliequivalent/gram.

2, according to the oxide of claim 1, this oxide comprises following component in the anhydride state that is synthesized:

A _v∶M ^m+ _x/m∶〔XO ₂〕 ^- _1-y∶〔YO ₂〕 ⁺ _1-x∶〔ZO ₂〕 _x+y∶N ^n- _y/n

Wherein A is a kind of organic directing agent and v is the molal quantity of A.

3, according to the oxide of claim 2, wherein organic directing agent A is a kind of amine or a kind of compound with following chemical formula:

R ₄M ⁺X ^-Or (R ₃M ⁺R ' M ⁺R ₃) X ^- ₂

Wherein R and R ' respectively are the alkyl by 1 to 20 carbon atom, and by the assorted alkyl of 1 to 20 carbon atom, aryl, heteroaryl, by the cycloalkyl of 3 to 6 carbon atoms, or it is in conjunction with base; M is a four-coordination element cation that is selected from nitrogen, phosphorus, arsenic, antimony or bismuth, or a hetero atom that is selected from N, O, S, SeO, P or As with alicyclic ring, the heterolipid ring or heteroaryl structure; And X is an anion.

4, according to each oxide of claim 1 to 3, wherein X is selected from aluminium, iron, chromium, vanadium, molybdenum, arsenic, calcium halophosphate activated by antimony andmanganese, gallium or boron; Y is selected from phosphorus, arsenic, antimony or vanadium; And Z's is to be selected from silicon, germanium or titanium.

5, according to each oxide of claim 1 to 4, wherein X has percent 30 to 44 molar fraction, and Y has percent 43 to 50 molar fraction, and Z has percent 6 to 20 molar fraction.

6, contain adhesive and according to the carbon monoxide-olefin polymeric of the oxide of claim 1.

7, the method for synthetic crystallization oxide, this method comprises:

(a) a kind of reactant mixture that contains liquid organic facies and liquid water of preparation, said reactant mixture comprises water, one or more X element source with positive trivalent, one or more Y element source with positive pentavalent, have the one or more Z element source of positive tetravalence, a kind of organic directing agent A, inorganic cation M and anion N; A kind of in fact with the immiscible organic solvent of water, said reaction mixture components has following relation:

(A) _a: (M ₂O) _b: (X ₂O ₃) _c: (ZO ₂) _d: (Y ₂O ₅) _e: (solvent) _f: (negative ion source) _g: (H ₂O) _h

Wherein a, b, c, d, e, f, g and h are the numerical value that satisfies following relation:

A/(c+d+e) be to be less than 4,

B/(c+d+e) be to be less than 2,

C/(c+e) be to be less than 2,

F/(c+d+e) be by 0.1 to 15,

G/(c+d+e) be to be less than 2,

H/(c+d+e) be from 3 to 150,

Wherein when the reactant mixture initial preparation, one of them source in X, Y or the Z oxide is to be dispersed or dissolved in the said organic facies;

(b) said reactant mixture is heated to 80 ℃～300 ℃ temperature with the speed that per hour increases by 5 ℃～200 ℃.

(c) stir above-mentioned reactant mixture till liquid organic facies and water are finally fully mixed each other.

(d) reactant mixture with above-mentioned stirring remains on 80 ℃～300 ℃ of temperature, and PH is under 2～9 condition, up to the crystal generation of oxide.

(e) have the feature of following composition by obtaining the anhyrous crystalline oxide in the above-mentioned reactant mixture:

A _v∶M ^m+ _x/m∶〔XO ₂〕 ^- _1-y∶〔YO ₂〕 ^- _1-x∶〔ZO ₂〕 _x+y∶N ^n- _y-n

Wherein v is the molal quantity of A, and m is the valence mumber of cation M, and n is the anionic valence mumber of N, and x and y satisfy the numerical value of following relation from greater than-1 to less than+1:

(1) if x is 0, y is not 0,

(2) if y is 0, then x is not 0,

(3) if the atomic ratio of X/Y greater than 1, then (x+y) is that y+0.6x is less than 0.4 greater than 0,

(4) if the atomic ratio of X/Y less than 1, then (x+y) is that 0.5y+x is less than 0.5 greater than 0,

Above-mentioned crystalline oxides has the ion exchange capacity at least about 0.002 milliequivalent/gram.

8, according to the method for claim 7, wherein organic directing agent A is a kind of amine or a kind of compound with following chemical formula:

R ₄M ⁺X ^-Or (R ₃M ⁺R ' M ⁺R ₃) X ^- ₂

Wherein R and R ' respectively be by the alkyl of 1 to 20 carbon atom, by 1 to 20 carbon atom assorted alkyl, aryl, heteroaryl, by the cycloalkyl of 3 to 6 carbon atoms, or it is in conjunction with base; M is a four-coordination element cation that is selected from nitrogen, phosphorus, arsenic, antimony or bismuth, or one is selected from and has alicyclic ring, the hetero atom of N, O, S, Se, P or As the heterolipid ring or the heteroaryl structure; And X is an anion.

9, method according to Claim 8, wherein organic directing agent A is selected from the C with following chemical formula ₁-C ₃Alkylamine and alkyl compound.

R ₄M ⁺X ^-Or (R ₃M ⁺R ' M ⁺R ₃) X ^- ₂

Wherein R is C, arrives C more ₄Alkyl, R ' is C ₁-C ₆Alkene, M is a nitrogen and X is the halogen in the hydroxide, wherein organic solvent is C ₅-C ₁₀Alcohol.

10, according to each method of claim 7 to 9, wherein Z oxide source is to be present in the organic facies of reactant mixture at first, and wherein the pH value of the reactant mixture of Jiao Baning remains between 6 to 9.

11, according to each method of claim 7 to 9, comprising the additional step of the crystalline oxide to 300 of heating gained ℃-1000 ℃, thereby form the calcination crystalline oxides of anhydrous state, have following composition:

M ^m+ _x/m∶〔XO ₂〕 ^- _1-y∶〔YO ₂〕 ⁺ _1-x∶〔ZO ₂〕 _x+y∶N ^n- _y/n

Wherein M is the cation of m valency, and N is the anion of n valency, and X and Y be by greater than-1 to less than+1 the following numerical value that concerns that satisfies:

(1) if x is 0, then y is not 0,

(2) if y is 0, then x is not 0,

(3) if the atomic ratio of X/Y greater than 1, then (x+y) is greater than 0, and y+0.6x is less than 0.4,

(4) if the atomic ratio of X/Y less than 1, then (x+y) greater than 0, and 0.5y+x is less than 0.5,

The crystalline oxides of above-mentioned calcination just has the ion exchange capacity at least about 0.002 milliequivalent/gram.

12, method according to claim 10 comprising the additional step of the crystalline oxide to 300 ℃ of heating gained～1000 ℃, thereby forms the calcination crystalline oxides of anhydrous state, has following composition:

M ^m+ _x/m∶〔XO ₂〕 ^- _1-y∶〔YO ₂〕 ⁺ _1-x∶〔ZO ₂〕 _x+y∶N ^n- _y/n

Wherein M is the cation of m valency, and N is the anion of n valency, and x and y be by greater than-1 to less than+1 the following numerical value that concerns that satisfies:

(1) if x is 0, then y is not 0,

(2) if y is 0, then x is not 0,

(3) if the atomic ratio of X/Y greater than 1, then (x+y) be greater than 0 y+0.6x less than 0.4,

(4) if the atomic ratio of X/Y less than 1, then (x+y) be greater than 0 0.5y+x less than 0.5,

The crystallization chloride of above-mentioned calcination has the ion exchange capacity at least about 0.002 milliequivalent/gram.

13, according to the purposes of the crystalline oxides of the described preparation of claim 11, be in the conversion that organises as compound, to be used as catalyst.

14, according to the purposes of the prepared crystalline oxides of claim 12, in the conversion of organic compound, be used as catalyst.