CN85104941A - Synthesizing of Silicophosphoaluminaand - Google Patents

Abstract

Silicophosphoaluminaand is to crystallize out from the biphasic reaction mixture that comprises raw silicon oxide material, alumina raw material and phosphorous oxide raw material and a suitable directing agent composition.Prepared silicon phosphosilicate has ion-exchange performance, and changes active catalytic material into easily.

Description

Synthesizing of Silicophosphoaluminaand

Synthetic silicon metal aluminophosphates can be synthesized from the reaction medium of being made up of two liquid phases and contain organic or inorganic directing agent, specific reactant with a kind of new method.This method causes a Silicophosphoaluminaand crystallization skeleton that has ion-exchange performance and change active catalytic material easily into.

Aluminum phosphate can be consulted for example United States Patent (USP) 4310440 and 4385994.Aluminum phosphate material has the electroneutral lattice, thereby can not be used as ion-exchange or catalytic component, and micro porous aluminum phosphate has a following typical case and forms:

XR:Al ₂O ₃: (1.0 ± 0.2) P ₂O ₅: YH ₂O here, R be retained within the aluminum phosphate and play a kind of organic amine or quaternary amine as crystalline forming agent effect; X and Y represent R and need be full of the H of micro cellular voids ₂The number of O molecule.Because the aluminium of these materials/phosphorus atoms ratio is approximately 1, they do not show ion-exchange performance in fact, at the skeleton positive charge on the phosphorus by the corresponding negative electrical charge institute balance on aluminium:

The zeolite that phosphorus replaces in Canadian Patent 911,416,911,417 and 911,418 is called as " alumo-silicate " zeolite.Some phosphorus is seemingly contained interior rather than be on the structure.This material contains silicon, aluminium and phosphorus, is feature with following general formula:

Here, M is a monovalent cation; X is about 1-4; Y is 0.05-1.0; With Z be hydrone number in conjunction with water.Replace the material realization that structural silicon has been called the silica clathrate compound with phosphorus.(DRP 3,128,988).

United States Patent (USP) 4,363,748 have described the same aluminium-calcium of a kind of silica-phosphatic composition of cerium; The low acid activity catalyst that it is used as the oxygen supply fluidized dehydrogenation.BP 2,068,253 disclose the composition of the same aluminium-calcium of a kind of silica-tungsten phosphate, and it is the low acid activity catalyst used as the oxygen supply fluidized dehydrogenation.United States Patent (USP) 3,801,704 have described and have a kind ofly handled so that have acid aluminum phosphate through certain way.United States Patent (USP) 4,228,036 has delivered the aluminium oxide-aluminum phosphate-silica substrate that supplies the usefulness of catalytic cracking with the amorphous form of mixing with zeolite.United States Patent (USP) 3,213,035 discloses with the phosphoric acid processing to improve the hardness method of aluminosilicate catalyst.This catalyst is an amorphous state.

United States Patent (USP) 2,876,266 have described by preformed silicate or alumino-silicate activated silica phosphoric acid or its salt face by a kind of amorphous material of absorbing phosphoric acid and preparing.

Other report about aluminum phosphate and preparation thereof is seen U.S. Patent number 4,365,095; 4,361,705; 4,222,896; 4,210,560; 4,179,538; 4,158,621; 4,071,471; 4,014,945; 3,697,550; With 3,904,550.Lack ion-exchange performance because of their neutral backbone formula structure, so they are only as catalyst carrier or matrix.Synthetic silicon metal aluminophosphates is a molecular sieve, or shows other skeleton constructions ion-exchange performance and that be easy to and change into easily the catalytically-active materials with inherence.The known technology of synthetic zeolite or aluminum phosphate is not particularly useful for synthetic these silicon metal aluminophosphates.

The method of synthetic crystallization Silicophosphoaluminaand is provided, and they have some to have micropore and catalytic activity, and all silicon metal aluminophosphates show ion-exchange performance and are easy to be converted into the ability with catalytically-active materials.The synthetic method for preparing such Silicophosphoaluminaand material comprises the following steps: 1) one of preparation contain particular components and in a water liquid phase, respectively contain the organic biphasic reaction mixture of a kind of liquid phase; 2) with 5 ℃ to 200 ℃ speed per hour reactant mixture is heated to 80-300 ℃; 3) stir this reactant mixture in the mode that said liquid organic facies and water are mixed each other fully; 4) under 80 ℃ to 300 ℃ temperature and pH value be to keep this reactant mixture that stirred at 2 to 9 o'clock, up to the crystal that forms the Silicophosphoaluminaand material; With 5) recovery Silicophosphoaluminaand material from reactant mixture.

The raw material, a kind of organic directing agent A, inorganic cation M and the anion N that comprise water, aluminium oxide, silica and phosphorous oxide in the key component of this biphasic reaction mixture; And a kind of in fact with the immiscible organic solvent of water.Such component exists by following relation:

(A) a:(M ₂O) b:(Al ₂O ₃) c:(SiO ₂) d:(P ₂O ₅) the e:(solvent) the f:(negative ion source) g:(H ₂O) among the h, a, b, c, d, e, f, g and h are the numerals that satisfies following relationship:

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

A/(c+d+e) less than 2;

D/(c+e) less than 2;

F/(c+d+e) 0.1 to 15;

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

H/(c+d+e) 3 to 150.

When beginning preparation feedback mixture, one of aluminium oxide, silica or phosphorous oxide raw material are dispersed or dissolved in the organic facies.

With the prepared Silicophosphoaluminaand of this law, it is characterized in that the number of aluminium and phosphorus atoms is bigger than silicon atom number in this composition, that is A+P＞Si.

Consider that its crystallization is formed and its locational distribution of charges of skeleton tetragonal body T-, it is called " Silicophosphoaluminaand ".The characteristic component of the Silicophosphoaluminaand of synthetic attitude like this, under anhydrous state, have as shown in the formula:

A ¹ _v: M ^M+ _X/m: (AlO ₂) ^- _1-y: (PO ₂) ⁺ _1-x: (SiO ₂) _X+y: N ^N- _Y/nWherein, v is the molal quantity of A ', and A ' is by the organic matter of occlusion, it confess synthetic usefulness with fill organic directing agent A of using the Silicophosphoaluminaand micropore and (or) organic solvent, these organic matters can be removed when calcining; M is a kind of inorganic cation of m valency; N is a kind of anion of n valency, and x and y be satisfy following relationship greater than-1 to less than+1 number.

(1) be 0 as x, then y is not 0;

(2) be 0 as y, then x is not 0;

(3) if the Al/P atomic ratio greater than 1, then (x+y) greater than 0, for example 0.001, and y+0.6x less than 0.04 and

(4) if the atomic ratio of Al/P less than 1, then (x+y) greater than 0, for example 0.001,0.5 then than 0.5(x+y) big.

In said components, when x greater than y, then Silicophosphoaluminaand is possible as a kind of cation-exchanger of acidic catalyst.When x less than y, then Silicophosphoaluminaand be a kind of may be as the anionite of base catalyst.In any case Silicophosphoaluminaand will show the ion-exchange capacity of at least 0.002 milliequivalent/gram.

Silicophosphoaluminaand under anhydrous state, except the component after the organic matter as follows, wherein M, m, N, n, x and y explained.

M ^m+ _x/m∶（AlO ₂） ^- _1-y∶（PO ₂） ⁺ _1-x∶（SiO ₂） _x+y∶N ^n- _y/n

By the prepared synthetic crystallization Silicophosphoaluminaand of this law, when its aluminium/phosphorus than greater than 1 the time, be a kind of effective cationic ion-exchanger and acid catalyst.This catalyst has an acidity scope different with zeolite.This acidity scope is useful in some catalytic process.Because aluminium/phosphorus ratio is less than 1, the anion exchange performance is preponderated, and makes that reaction is active to this material for base catalysis.They also provide a kind of new catalyst carrier, and meaningful especially in this respect, because their macroion exchange capacity will make it keep quite high metal carrying.In back one situation, they will show the catalysis flexibility that other catalyst that metallic carrier is arranged are the same.Sorption property shows that this micro porous Silicophosphoaluminaand is to molecular shape selectively, and this performance is good in many catalytic process, and is known as the prior art at zeolite catalyst.

If more synthetic with aluminium/phosphorus atoms than ratio greater than 1, then will be greater than 1.5 than the aluminium/phosphorus atoms ratio of silicon metal aluminophosphates, and usually in 1.6 to 600 scope.Aluminium when synthetic/phosphorus atoms is than less than 1 the time, and then the phosphorus of silicon metal aluminophosphates/silicon atom is than greater than 1, usually in 1.2 to 100 scopes.The atomic ratio of the phosphorus/aluminium of aluminum phosphate is 1 and does not have silicon that this is that everybody knows.

Have, the zeolite compositions that phosphorus replaces is called as " alumo-silicate " zeolite sometimes again, and its silicon/al atomic ratio is usually greater than 1, generally from 0.66 to 8.0, and its phosphorus/al atomic ratio is less than 1, generally than 0 greatly up to 1.

Use a two-phase synthesis reaction mixture system, remove solid, this makes one can remain liquid in the organic facies of one or more reactants mutually, and this reactant is generally insoluble or unstable at aqueous phase under synthesis condition.Such operation can prepare Silicophosphoaluminaand, uses other technologies then can not successfully synthesize.Two-phase synthetic method of the present invention also promotes the ability of crystallization control reaction.And in the presence of the organic or inorganic directing agent, owing to carry out inorganic synthesizing, the silicon metal aluminophosphates can obtain micropore character, and except its moulding effect, organic directing agent also can play the effect of surfactant.It can help to contain the common decentralized of the organic facies of reactant and water.

In synthetic method of the present invention, reactant mixture contains raw material, directing agent and the organic solvent of silica, phosphorous oxide and aluminium oxide according to the above-mentioned relation of having illustrated.

Organic directing agent can be selected from have following formula, include organically single two one or polyamine and compounds group:

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

Wherein, R or R ' are the alkyl that from 1 to 20 carbon atom is arranged, the assorted alkane of from 1 to 20 carbon atom, aryl, heteroaryl, the cycloalkyl of from 3 to 6 carbon atoms, the ring of from 3 to 6 carbon atoms mix alkyl, perhaps their combination; M is one four coordination valence element (as nitrogen, phosphorus, arsenic, antimony or bismuth) or alicyclic ring, the hetero atom (as N, O, S, Se, P, As etc.) in heterolipid ring or the heteroaromatic structure; With X be an anion (as fluoride, chloride, bromide, iodide, hydroxide, acetate, sulfate, carboxylate etc.).When M is in an alicyclic ring, the structure heterolipid ring or heteroaromatic during a hetero atom, this structure may be as non-limiting example.

Wherein, R ¹Be the alkyl of from 1 to 20 carbon atom, the assorted alkyl of from 1 to 20 carbon atom, aryl, heteroaryl, the ring of the cycloalkyl of from 3 to 6 carbon atoms or from 3 to 6 carbon atoms alkyl of mixing.

Comprise the alkanamine class for the particularly preferred organic directing agent of this method, wherein alkyl is to contain 1 to 3 carbon atom; And based compound (top explained), wherein R is the alkyl of 1 to 4 carbon atom, and R ' is the alkylene of 1 to 6 carbon atom, and M is that nitrogen and X are halide or hydroxide.Their non-limitative example includes di-n-propyl amine, tetrapropylammonium hydroxide, tetraethyl ammonium hydroxide, bromine hundred million tetrapropyl ammonium and hydroxide hexamethyl hexane two ammoniums or bromination hexamethyl hexane two ammoniums.A kind of inorganic hydroxide or salt as pH value conditioning agent also can be used as an additional directing agent.The non-limiting example of these compounds has: KOH, NaOH, Cs H, CsBr, NaCl, Ca(OH) ₂With and similar compound.

The useful raw material of aluminium oxide includes as non-limiting example: known any type of aluminium oxide or aluminium hydroxide, organic or inorganic salt or its compound.

The useful raw material of phosphorous oxide includes as non-limiting example: known any type of phosphoric acid class or oxide, phosphate and the phosphite of phosphorus and the organic derivative of phosphorus.

The useful raw material of silica includes as non-limiting example: known any type of silicic acid or silica, other compounds of the alkoxyl of silicon or silicon.

The organic solvent that is used to form the biphasic reaction mixture can be any organic liquid, and this organic liquid is under the crystallization condition of this method, in fact with the water unmixing.The non-limiting example of this solvent comprises: C ₅-C ₁₀Alcohols, phenols and aphthols and other not miscible organic solvents with water.Polar organic compound is preferentially as the organic facies solvent.

The main inorganic cation and the anion that exist in reactant mixture can not be provided by the component that adds respectively usually.Usually these cations and anion are on the contrary from the compound that joins in the reactant mixture, and these compounds are to be used to provide other main components, as silicon, aluminium and (or) raw material of phosphorus or for example directing agent or any pH value conditioning agent that may use.

One of raw material of silica, aluminium oxide or phosphorous oxide must be present in the organic facies of reactant mixture when beginning.Therefore water includes directing agent, cation and anion, and pH value conditioning agent and those do not join all the other key components in the organic facies.

The reactant mixture of the composition of having described above will having, under 5 ℃ to 200 ℃ speed per hour, be heated to 80 ℃-300 ℃ temperature carefully, and under this temperature, be incubated, crystal up to required Silicophosphoaluminaand forms, and needs 5 hours to 500 hours usually.When crystallization, the pH value of reactant mixture is controlled at 2 to 9 carefully.This can finish by regulating the concentration that adds bases.

In heating and crystallization stage, usually reactant mixture is stirred in the degree that is enough to make in fact immiscible organic facies and water to mix fully.Make organic facies and water disperse the technical staff of the technology of mixing to know mutually.Form the emulsion of an organic facies and water so that the interface between two liquid phases reaches maximum, this also is desirable.

After crystallization went out required Silicophosphoaluminaand, the reactant mixture that will contain this Silicophosphoaluminaand filtered, and with for example water flushing of crystal of reclaiming, dry then.For example under atmospheric pressure be heated to 25 ℃-150 ℃.

Be described more specifically this synthetic method: aqueous phase contains phosphorus and al reactant, for example phosphoric acid and aluminium oxide.Have pure organic facies and contain the silicon raw material, for example neighbours position alkyl silicate as solvent.Organic directing agent (as tetraalkylammonium hydroxide or a kind of amine) also can be used as surfactant and works, and makes water and organic facies emulsification and makes the interface reach maximum.The hydrolysis of the organic compound by silicon with by the interface the mode in the product transmission water inlet mutually, silicon is fed in the gel in building-up process continuously.

Must make the Silicophosphoaluminaand of crystallization produce nucleus effectively simultaneously as silicon, aluminium and phosphorus, the supply rate of all these three elements must be comparable.This meaning is meant neutralization reaction, for example at phosphoric acid and AI ₂O ₃Between neutralization reaction and the hydrolysis of organo-silicon compound must coordinate.Therefore, it may be important anticipating aluminium oxide-phosphate mixture.More critical is the supply rate of silicon, and this supply rate is decided according to following factors: as the interface size, and temperature, the pH of water, the character of concentration and organic solvent and pasc reaction thing.

Because the hydrolysis of silicon and transmission speed are subjected to the control of interface size, as discussing the front, the blending expection to silicon when strengthening mixing is favourable.

As described above, pH is a critical synthetic parameter.When being formed on of Silicophosphoaluminaand carried out, should keep the pH value near or surpass neutral (as be about 6 or bigger, up to being up to 9) than 6.When the alkaline stability of wishing Silicophosphoaluminaand was between aluminum phosphate and zeolite, the pH value preferably was about or a little higher than 8.Because the important function that the hydrolysis of pasc reaction thing is risen and need to control it in the method, this just requires to have one near constant pH value (particularly will be avoided the rapid acid hydrolysis of silicon raw material) in crystallization process.This can just can reach by anticipated aluminium oxide in phosphoric acid before adding other reactants, anticipates to make the initial pH value of synthetic mixture be elevated to 5-7.In order to reach or to keep higher pH (PH=8 or surpass), even after organic hydroxide partly decomposes, can add inorganic base.These inorganic bases are directing agent and working as a supplement also.

For this reason, having silicon, phosphorus and aluminium can be molecular sieve or other skeleton structures as the Silicophosphoaluminaand of lattice framework component.When they are molecular sieve or dense material, they will have clear and definite and can debate other crystalline texture, and this crystalline texture presents with the characteristic X-ray powder diffraction pattern.When they are not molecular sieve, and be layered crystal structure for example, then their characteristic just can not be come out from X-ray data perfect representation simply.X-ray interval in extendible layer structure, the basis is unfixed, and can change in a broad range.Sharp-pointed diffraction maximum number is normally very limited, and big change is often arranged on the intensity at peak.Because the d-of layer structure changes with the content of water at interval, consider that the X-ray data of identifying this material dehydration sample suits.Below the prepared novel crystallization Silicophosphoaluminaand structure of the inventive method, just discuss, and identify by each MCM title.

MCM-1 is a densification or layer structure, and it shows a clear and definite and X-ray diffraction style that can be different from other crystalline materials.The X-ray diffraction style of the MCM-1 of this synthetic attitude has following characteristic value:

Table 1-A

Between face d-(A) relative intensity at interval

9.67±0.01????m

6.86±0.01????vs

6.49±0.01????s

4.86±0.05????s-vs

4.25±0.05????vs

3.61±0.03????w

3.39±0.03????m

3.06±0.02????vs

2.93±0.02????w

2.89±0.02????w

2.78±0.02????w

2.68±0.02????m

Table 1-B enumerates the feature diffracted ray of the calcined state (450 ℃ in nitrogen, under atmospheric pressure, 4 hours) of MCM-1.

Table 1-B

Between face d-(A) relative intensity at interval

6.83±0.1????vs

4.83±0.06????w

4.27±0.04????vs

4.14±0.04????m

3.62±0.03????w

3.42±0.02????w

3.08±0.02????w

3.04±0.02????w

MCM-3 also be a densification or layer structure, it shows a clear and definite and X-ray diffraction style that can be different from other crystalline materials.The X-ray diffraction style of synthetic attitude MCM-3 has following characteristic value:

Table 2-A

Crystal face d-is (A) relative intensity at interval

5.19±0.05????m

4.30±0.05????vs

3.93±0.04????m

3.85±0.03????w

3.58±0.04????s

3.04±0.03????w

2.91±0.02????w

2.63±0.02????w

Table 2-B enumerates MCM-3(450 ℃ of calcined state, calcining, in nitrogen, under atmospheric pressure, 4 hours) the feature diffracted ray

Table 2-B

Crystal face d-is (A) relative intensity at interval

5.18±0.05????m

4.30±0.05????vs

3.95±0.05????w

3.84±0.05????w

3.58±0.05????m-s

3.04±0.02????w

2.91±0.02????w

2.63±0.02????w

MCM-4 under synthetic attitude be a densification or layer structure, it has following X-ray diffraction style:

Table 3-A

Crystal face d-is (A) relative intensity at interval

4.46±0.05????w

4.35±0.05????m

4.27±0.05????vs

4.07±0.05????w

3.65±0.03????m

3.37±0.03????s

3.05±0.02????w

2.95±0.02????w

Table 3-B enumerates MCM-4(450 ℃ of calcined state, in nitrogen, under atmospheric pressure, 4 hours) the feature diffracted ray:

Table 3-B

Crystal face d-is (A) relative intensity at interval

4.45±0.05????w

4.35±0.04????m

4.27±0.04????vs

4.08±0.04????m

3.65±0.04????m

3.37±0.03????vs

3.05±0.03????w

2.95±0.02????w

2.89±0.02????w

MCM-5 under synthetic attitude be a densification or layer structure, its characteristic X-ray diffraction pattern is shown in table 4-A

Table 4-A

Crystal face d-is (A) relative intensity at interval

8.60±0.1????vs

6.78±0.1????w

4.75±0.05????w

4.64±0.05????w

4.35±0.03????w

3.71±0.03????w

3.66±0.03????w

3.39±0.03????w

3.22±0.03????w

3.16±0.02????w

3.02±0.02????w

2.70±0.02????w

Table 4-B enumerates MCM-5(450 ℃ of calcined state, in nitrogen, under atmospheric pressure, 4 hours) the feature diffracted ray.

Table 4-B

Crystal face d-is (A) relative intensity at interval

6.84±0.05????w

4.45±0.05????w

4.36±0.05????vs

4.12±0.05????vs

3.86±0.04????s

3.77±0.04????w

3.44±0.04????w

3.00±0.03????w

2.88±0.02????w

2.81±0.02????w

MCM-9 is a molecular screen material that has ordered micro-cellular structure, and this structure is only accepted certain molecule; And repulsion other molecule.MCM-9 show one clear and definite, with the distinguishing X-ray diffraction style of other crystalline materials.The X-ray diffraction style of synthetic attitude MCM-9 has following characteristic value:

Table 5-A

Crystal face d-is (A) relative intensity at interval

16.41±0.1????vs

10.84±0.1????w

9.33±0.1????w

8.20±0.1????m

6.68±0.05????w

6.17±0.05????w

5.65±0.05????w

5.46±0.05????w

4.74±0.05????w

4.34±0.05????w

4.21±0.05????s

4.10±0.03????m

4.05±0.03????m

4.00±0.03????w

3.94±0.03????m

3.83±0.03????m

3.77±0.03????w

3.64±0.03????w

3.59±0.02????w

3.39±0.02????w

3.28±0.02????m

3.16±0.02????w

3.09±0.02????w

3.03±0.02????w

2.95±0.02????w

2.90±0.02????w

2.74±0.02????w

2.63±0.02????w

Table 5-B enumerates the feature diffracted ray of the MCM-9 of calcined state (450 ℃, under atmospheric pressure, 4 hours).

Table 5-B

Crystal face d-is (A) relative intensity at interval

16.36±0.10????m

14.05±0.10????w

10.92±0.10????w

8.94±0.10????m

8.19±0.10????w

6.90±0.05????w

5.50±0.05????m

4.47±0.05????w

4.36±0.05????w

4.08±0.05????vs

3.94±0.05????s

3.79±0.05????m

3.54±0.03????w

3.45±0.03????w

3.33±0.03????w

3.28±0.02????w

3.22±0.02????w

3.01±0.02????m

2.95±0.02????w

2.82±0.02????w

2.74±0.02????w

MCM-10 also is a synthetic attitude molecular screen material, and it has following characteristic X-ray diffraction pattern:

Table 6-A

Crystal face d-is (A) relative intensity at interval

11.85±0.1????w

10.20±0.1????s-vs

7.65±0.05????vs

6.86±0.05????m

5.93±0.05????w

5.67±0.05????m

5.11±0.05????s

5.01±0.05????s

4.49±0.05????w

4.37±0.05????vs

4.09±0.05????vs

3.95±0.03????w

3.80±0.03????m

3.73±0.03????w

3.43±0.03????m

3.22±0.03????m

3.16±0.03????w

2.99±0.02????w

2.97±0.02????w

2.93±0.02????m

2.85±0.02????m

2.75±0.02????w

2.68±0.02????m

2.59±0.02????w

Table 6-B enumerates the feature diffracted ray of the MCM-10 of calcined state (450 ℃, under atmospheric pressure, 4 hours):

Table 6-B

Crystal face d-is (A) relative intensity at interval

11.75±0.1????w

10.11±0.1????vs

7.56±0.05????vs

6.81±0.05????s

5.65±0.05????m

5.08±0.05????m

4.94±0.05????vs-s

4.46±0.05????w

4.35±0.05????vs

4.28±0.05????m

4.08±0.05????vs

3.85±0.03????w

3.75±0.03????w

3.41±0.03????m

3.18±0.03????s

2.96±0.02????m

2.92±0.02????m

2.88±0.02????w

2.83±0.02????m

2.66±0.02????m

2.58±0.02????w

All X-ray diffraction data all are to be collected by the X-ray system that Japan company of science produces, and it uses the K width of cloth of copper target to penetrate.The position (θ is Bragg angle (Bragg angle) here) at the peak of representing with 2 °, θ is by being one grade and each grade in the stepping scanning method decision in a second with at interval per 0.02 ° of 2 θ, interplanar every d with unit ⁰A measures, the relative intensity (1/1 of line ₀), here: I ₀Be 1/100 of the strongest line (comprising the background that deducts) intensity, derive by curve fitting procedure.The relative intensity symbolically, vs=very strong (75-100%); S=strong (50-74%); Among the m=(25-49%) and w=(0-24).The X-ray diffraction style that should understand any certified concrete MCM material is the feature of all kinds material that synthesizes of the present invention.By the ion-exchange of cation with other ions, resulting Silicophosphoaluminaand shows to be actually same X-ray diffraction style, only have interplanar every some small variations and the variation of relative intensity.Other variations may take place, and this is entirely according to the Si/Al and the P/Al ratio of particular sample, with and heat treatment degree and deciding.

Some Silicophosphoaluminaand classes are porous materials, and this material contains (passing through oxygen) Si, the P of four body coordinations and the skeleton of Al atom.They demonstrate and ion-exchange like the zeolite facies, acid and performance catalysis.Because the acidity scope that they are different, they have a potential significance as the catalyst of the conversion of acid-catalysis, and acidity too high or too low in this conversion may cause undesirable secondary response.Because of replacing phosphorus with silicon, produce the acidity that combines with framework aluminum, otherwise, when framework aluminum is replaced by silicon, produce the basicity that combines with skeleton phosphorus.With the Silicophosphoaluminaand class of the present invention's two phase synthesis preparation, with regard to the distribution of whole crystal structure, be more uniform with regard to silicon atom.

Thus He Cheng Silicophosphoaluminaand class with following a kind of metal component fully in conjunction with the time also useful as catalysts as silver, tungsten, vanadium, molybdenum, rhenium, chromium, manganese; Or VIII family such as platinum and palladium, they play the function of hydrogenization-dehydrogenation effect or oxidation therein.Such component can be entered composition by ion-exchange, and infiltration is entered or mixed fully each other therein.For example resemble following such class component can be infiltrated in it or dipping thereon, for example, come to this when handling crystal with the platinum solution that contains metal ion with under the situation of platinum.Therefore, suitable platinum compounds comprises chloroplatinic acid, platinous chloride and the various compound that contains platinum and amine complex compound.

The parent ion of the Silicophosphoaluminaand of synthetic attitude, promptly the technology that can know according to the technical staff of cation and anion by with other cations or anionic ion-exchange, is replaced at least in part.Replacing cation preferably comprises: the precursor of metal ion, hydrogen ion, hydrogen (for example ammonium) ion and composition thereof.Good especially cation comprises the metal of II A, III A, IV A, I B, II B, III B, IV B, VI B and VIII family on hydrogen, rare earth metal and the periodic table of elements.

Typical ion-exchange process should contact the Silicophosphoaluminaand of synthetic crystallization with the salt of the ion of desired displacement, comprises halide in the example of such cationic salts, for example chloride, nitrate and sulfate.

According to the prepared Silicophosphoaluminaand of this method, can advantageously change into other forms with heat treatment.This heat treatment generally is that one of these forms were heated at least one minute under at least 300 ℃, and generally is no more than 20 hours.Though can use to be lower than an atmospheric pressure and to heat-treat, under atmospheric pressure, meet the requirements usually, because its is convenient.Heat treatment can carried out under 1000 ℃ of temperature.The heat treatment product is particularly useful in some hydrocarbon conversion reaction.According to the prepared Silicophosphoaluminaand of two-phase synthetic method of the present invention, under some occasions, than bigger heat endurance being arranged with the prepared similar material of additive method.

In addition, when as the adsorbent ion-exchanger or as the catalyst in the organic compound conversion process, Silicophosphoaluminaand should be dehydrated, at least in part dehydration.This dehydrating operations is: in air, or in inert gas as nitrogen etc., under atmospheric pressure or be lower than 1 atmospheric pressure.Or under high pressure heated 30 minutes to 48 hours.Dehydration also can at room temperature be carried out, and just Silicophosphoaluminaand is put into vacuum, needs to want the Long time just can obtain enough dehydrating amounts.Therefore, depend on degree of dehydration and heat treatment that Silicophosphoaluminaand is desired, it can heat under the temperature from 200 ℃ to 1000 ℃, and the time was from 1 minute to 48 hours.

The prepared Silicophosphoaluminaand crystal energy of the present invention has the various granularity that haves a wide reach.In general, this particle can be a powdery, psephitic or mold pressing product, as have can be fully by 2 orders (Taylor) sieve aperture and stay the extrudate of the granularity on 400 orders (Taylor) sieve aperture.Under constituent is molded situation, for example use pressing method, this crystallization can before dry, push or partly drying push then.

For many catalyst, often wish that Silicophosphoaluminaand combines with the other material, this material ability temperature and stand the condition that other are used to the organic transformation process, these materials comprise active and inactive material, with zeolite and inorganic material synthetic or nature, for example clay, silica sand and (or) metal oxide, the latter both can be spontaneous also can be the form that contains the gelatinous precipitate or the gelinite of silica and metal oxide.A kind of material uses (promptly being combined into active with it) together with new Silicophosphoaluminaand, then help to improve in certain organic transformation process catalyst transformation and (or) selectivity.Non-active material is suitable for doing diluent being controlled at the inversion quantity in certain process, so that can obtain product economically and can need not to control with other means the speed of reaction.These materials can be incorporated in the clay of nature and go, and for example bentonite and kaolin are in order to improve the crushing strength of the catalyst under the industrial operation condition.Said material such as clay, oxide etc. can play the effect of the binding agent of making catalyst.It is gratifying that a kind of catalyst with good crushing strength is provided, because when commercial Application, normal hope prevents that catalyst is broken into the thing as powder.These clay bonds only are being used routinely for the crushing strength of improving catalysis.

Natural clay sometimes with comprise that to take off the new crystallization of covering stone and kaolin group compound, this kaolin group includes sub-Ben and common known Di Kexi (Dixie), Mike receives U.S. (Mc-Namee), and it is kaolinite, kaolin, dickite, nacrite or halloysite clay that George Ya (Georgia) and Florida (Florida) clay or other contain principal component.Such clay can be at the state in original ore deposit or is tentatively calcined, and the state of acid treatment or chemical modification uses down.Be used for also comprising inorganic oxide, famous alumina and silica with the compound adhesive of crystallization of the present invention.

Except above-mentioned material, Silicophosphoaluminaand also can be compound with porous matrix material, resembles aluminum phosphate, silica-alumina, silica-magnesia, silica-zirconium dioxide.Silica-thorium oxide, silica-beryllia, silica-titania, and ternary composition such as silica-alumina-thorium oxide, silica-alumina-zirconium dioxide, silica-alumina-magnesia and silica-magnesia-zirconium dioxide.Silicophosphoaluminaand crystalline material in small, broken bits alters a great deal with the relevant ratio of inorganic oxide gel matrix, and the scope of crystallization content is from 1 to 90(weight) %, particularly when constituent was prepared to pearl, crystallization content accounted for 2 of constituent and arrives about 80(weight) %.

Crystalline material of the present invention is easy to be converted into catalytically-active materials, be suitable for many organically, as the compound conversion process of hydroxyl.This conversion process comprises: as having of non-limiting example: cracking hydroxyl class, its reaction condition has: temperature is from 300 ℃ to 700 ℃, and pressure is that from 0.1 to 30 atmospheric pressure (crust) and weight hourly space velocity are 0.1hr ⁺To 20hr ⁺; The dehydrogenation of hydroxy compound, its reaction condition comprises: temperature is 300 ℃ to 700 ℃, pressure is from 0.1 atmospheric pressure to 10 atmospheric pressure, the weight hourly space velocity is 0.1 to 20, is paraffin conversion aromatics, and its reaction condition comprises: temperature is from 100 ℃ to 700 ℃, and pressure is 0.1 to 60 atmospheric pressure, the weight hourly space velocity is 0.5 to 400, hydrogen/hydroxyl mol ratio from 0 to 20; Alkene is converted into aromatics, benzene,toluene,xylene for example, reaction condition comprises: temperature is from 100 ℃ to 700 ℃, from 0.1 to 60 atmospheric pressure of pressure, weight hourly space velocity from 0.5 to 400, hydrogen/hydroxyl mol ratio from 0 to 20; Alcohols, for example methyl alcohol or ether, for example dimethyl ether, or their mixture is converted into the hydroxyl class, and comprising aromatics, its reaction condition comprises: temperature is from 275 ℃ to 600 ℃, from 0.5 to 50 atmospheric pressure of pressure, liquid hourly space velocity from 0.5 to 100; Make the isomerization of dimethylbenzene starting compound, its reaction condition comprises: temperature is from 230 ℃ to 510 ℃, from 3 to 35 atmospheric pressures of pressure, and weight hourly space velocity from 0.1 to 200, and hydrogen/hydroxyl mol ratio is from 0-100; Make toluene disproportionation, its reaction condition comprises: temperature is from 200 ℃ to 760 ℃, from 1 to 60 atmospheric pressure of pressure and weight hourly space velocity from 0.08 to 20; Make the hydroxyl class alkylation of aromatics, for example benzene and alkyl benzene, having in the presence of a kind of alkylating agent, for example chain alkene, formaldehyde, alkyl halide and alkylol, its reaction condition comprises: temperature is from 340 ℃ to 500 ℃, from 1 to 200 atmospheric pressure of pressure, weight hourly space velocity from 2 to 2000 and fragrant hydroxyl/alkylating agent mol ratio from 1/1 to 20/1; In the presence of the fragrant hydroxyl of polyoxyethylene alkyl aryl, make fragrant hydroxyalkyl transferization, its reaction condition comprises: temperature is from 1 to 200 atmospheric pressure of pressure from 340 ℃ to 500 ℃, weight hourly space velocity from 10 to 1000, the fragrant hydroxyl mol ratio from 1/1 to 16/1 of fragrant hydroxyl/polyoxyethylene alkyl aryl.

Therefore, in general, aspect catalyst, comprising the activity form of Silicophosphoaluminaand, its catalyticing conversioning condition comprises: temperature is from 100 ℃ to 760 ℃, from 0.1 to 200 atmospheric pressure of pressure (crust), and the weight hourly space velocity is from 0.08hr ^-1To 200hr ^-1, and hydrogen/organic matter, for example the compound of hydroxyl from 0 to about 100.

In order further to illustrate essence of the present invention and embodiment thereof, provide the following example.In an embodiment, no matter when, absorption data is in order to illustrate the comparison to the absorbability of various different absorbates, and these data are determined as follows:

Calcining absorbent sample through weighing, the equilibrium vapor flow direction contact at 25 ℃ of same absorbates mixes with the nitrogen of drying.Absorbate is steam, n-hexane, 2-methylpentane, dimethylbenzene or cyclohexane vapor.Specimen temperature remains on 90 ℃ for the absorbate except adjacent hexane and water, and adjacent hexane is remained on 120 ℃, and water is remained on 60 ℃.The weightening finish of measuring with gravimetric method changes that to calculate be the absorbability of sample, and unit is the burnt absorbent of gram/100 grams (550 ℃, in air, 20 ℃ of calcinings of per minute).

When the tested timing of α value, notice the approximate index that catalytic cracking activity that this α value is a catalyst is compared with standard catalyst, he provides relative velocity constant (catalyst of every volume, the conversion rate of time per unit n-hexane).This relative velocity constant is based on the activity of the silica-alumina Cracking catalyst of high activity, and its is got does α=1(velocity constant=0.016 second ^-1).In the occasion of zeolite HZSM-5, only need the tetragonal body coordination Al of 174PPm ₂O ₃It is 1 that the α value just is provided.This test is stated from United States Patent (USP) 33,543, and 078 and in the 4th of catalysis magazine (The Journal of Catalysis), 522 to 529 pages (1965,8).

When calibrating during ion-exchange capacity, with the titration of sulfamic acid solution, the gaseous ammonia of in the silicon phosphorus ammonium aluminate attitude decomposition temperature process of drafting, being emitted and determined.The method is stated from:

Thermochmiea Acta, the Vol. III, PP.113-124,1971 authors are G.T.Kerr, A.W.Chester.

Embodiment 1

With 1-hexanol that contains 60 grams and 10 gram Si(OC ₂H ₅) ₄Organic facies; With include 13.7 the gram Al ₂O ₃, 23.1 gram H ₃PO ₄(85%), the water of 25% tetrapropylammonium hydroxide (TPAOH) of 84 grams and 30 gram water makes a kind of two-phase synthesis reaction mixture.The component of this reactant mixture is 9.3%Si as a whole, 38.8%P and 51.9%Al(atomic percentage).Directing agent is a tetrapropylammonium hydroxide.

This reactant mixture is heated to 150 ℃ and kept 65 hours with 50 ℃ firing rate per hour under this temperature, in forming the present invention till the Silicophosphoaluminaand crystallization of called after MCM-1.Initial PH is between 5 to 7.

By filtering crystallized product is separated from reactant mixture, washing, then in 80 ℃ of dryings, analyze this product crystallization and contain 15.7%Si, 34.8%P and 49.5%Al(atomic percentage) carry out x-ray analysis with a synthetic attitude MCM-1 Silicophosphoaluminaand sample then, and be determined as a kind of crystalline texture with diffracted ray shown in the table 7.

Table 7(MCM-1)

Interplanar d-interval (

) observe 2 * 0 promptly to intensity 1/1

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 2

Example 1 more described MCM-1 Silicophosphoaluminaand crystallizations were calcined 4 hours in nitrogen in 450 ℃, carry out x-ray analysis then.The result shows as table 8.

Table 8

Interplanar d-interval (

) observe 2 * θ relative intensity 1/1

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 3

With containing 60 gram 1-hexanols and 10 gram Si(OC ₂H ₅) ₄Organic facies and contain 23.1 the gram H ₃PO ₄(85%), 10 gram Al ₂O ₃, 84 gram TPAOH(tetrapropylammonium hydroxides) and (25%) and 30 gram H ₂The water of O makes a kind of two-phase synthesis reaction mixture.As a whole, this reactant mixture consists of 10.8%Si, 45.0%P and 44.2%Al(atomic percentage).Directing agent is a tetrapropylammonium hydroxide.

This reactant mixture is heated to 150 ℃ and kept 168 hours with 50 ℃/hour firing rate under this temperature, in forming the present invention till the Silicophosphoaluminaand crystallization of called after MCM-2.Initial PH is between 5-7.

By filtering crystallized product is separated from reactant mixture, washing is then in 80 ℃ of dryings.Analyze, the product crystallization contains 17.5%Si, 37.2%P and 45.4%Al(atomic percentage) and volume big.Carry out x-ray analysis and be determined as a kind of Chabazite-type crystalline molecular sieve with a synthetic attitude MCM-2 Silicophosphoaluminaand sample then with diffracted ray shown in Figure 9.

Table 9(MCM-2)

Interplanar d-interval (

) observe 2 * θ relative intensity 1/1

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????25.893????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

Example 4

It is described synthetic to repeat example 3, and different is that water contains 17.0 gram Ai ₂O ₃The product Silicophosphoaluminaand crystallization that generates is for having 13.2%Si, 36.3%P and 50.5%Ai(atomic percentage) little crystal grain.

Example 5

Example 3 more described MCM-2 Silicophosphoaluminaand crystallizations were calcined 4 hours in nitrogen in 450 ℃, carry out x-ray analysis then.The result shows as table 10.

Table 10

Interplanar d-interval (

) observe 2 * θ relative intensity I/I

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 6

With containing 60 gram 1-hexanols and 10 gram Si(OC ₂H ₅) ₄Organic facies and contain 7 the gram Al ₂O ₃, 23.1 gram H ₃PO ₄(85%), 84 restrain TPAOH(25) and 30 gram H ₂The water of O makes a kind of two-phase synthesis reaction mixture.As a whole, this reactant mixture consists of 12.4%Si, 52.0%P and 35.6%Al(atomic percentage).Directing agent is a tetrapropylammonium hydroxide.Initial PH is between 5-7.

This reactant mixture is heated to 150 ℃ and till the Silicophosphoaluminaand crystallization that keeps 65 hours called after MCM-3 in forming the present invention under this temperature with 50 ℃/hour firing rate.PH during the reaction beginning is between 5-7.

By filtering crystallized product is separated from reactant mixture, washing is then in 80 ℃ of dryings.Carry out x-ray analysis and be determined as crystal structure with a synthetic attitude MCM-3 Silicophosphoaluminaand sample then with diffracted ray shown in the table 11.

Table 11(MCM-3)

Interplanar d-interval (

) observe 2 * θ relative intensity I/I

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????22.432????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 7

With containing 60 gram 1-hexanols and 10 gram Si(OC ₂H ₅) ₄Organic facies and contain 15.8 the gram Al ₂O ₃, 42.3 gram H ₃PO ₄(85%), 84 restrain TPAOH(25%) and 30 gram H ₂The water of O makes a kind of two-phase synthesis reaction mixture.As a whole, this reactant mixture consists of 6.6%Si, 50.6%P and 42.8%Al(atomic percentage).Directing agent is a tetrapropylammonium hydroxide.This reactant mixture is heated to 150 ℃ and kept 168 hours with 50 ℃/hour firing rate under this temperature, till the Silicophosphoaluminaand crystallization with the MCM-4 name in forming the present invention.Initial PH is between 5-7.

By filtering this crystallized product is separated from reactant mixture, washing is then in 80 ℃ of dryings.Carry out x-ray analysis and be determined as crystalline material with a synthetic attitude MCM-4 Silicophosphoaluminaand sample then with diffracted ray shown in the table 12.

Table 12(MCM-4)

Interplanar d-interval ( ⁰A) observe 2 * θ relative intensity I/I ₀

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 8

With containing 60 gram 1-hexanols and 10 gram Si(OC ₂H ₅) ₄Organic facies and contain 13.8 the gram Al ₂O ₃, 23.1 gram H ₃PO ₄(85%), 4.0 gram NaOH, 26.0 gram TPABr(bromination tetrapropyl ammonium) and 100 gram H ₂The water of O makes a kind of two-phase synthesis reaction mixture.As a whole, this reactant mixture consists of 9.3%Si, 38.6%P and 52.1%Al(atomic percentage).Directing agent is the bromination tetrapropyl ammonium.Initial PH is between 5-7.

Reactant mixture is heated to 150 ℃ and keeping 168 hours under this temperature in forming the present invention till the Silicophosphoaluminaand crystallization with the MCM-5 name with 50 ℃/hour firing rate.

By filtering this crystallized product is separated from reactant mixture, washing is then in 80 ℃ of dryings.By analysis, the product crystallization contains 9.6%Si, 45.9%P and 44.5%Al(atomic percentage).Carry out x-ray analysis and be determined as crystalline material with a synthetic attitude MCM-5 Silicophosphoaluminaand sample then with diffracted ray shown in the table 13.

Table 13(MCM-5)

Interplanar d-(A) at interval observes 2 * θ relative intensity 1/1 ₀

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 9

A example 5 described calcining Silicophosphoaluminaand product crystallized sample are carried out the absorption property evaluation, to confirm its molecular sieve performance.Result (in weight %) is as follows:

Water (60 ℃) 10.3

N-hexane (90 ℃) 9.3

Paraxylene (90 ℃) 2.7

2-methylpentane (90 ℃) 1.1

Cyclohexane (90 ℃) 0.8

Ortho-xylene (120 ℃) 0.9

Example 10

Example 3 more described Silicophosphoaluminaand crystalline products 900 ℃ of absorption property evaluations that heat treatment is forward and backward have been carried out.The proof absorption property is not changed by such heat treatment, and this has shown that example 3 described Silicophosphoaluminaand crystalline molecular sieves have superior heat endurance.

Example 11

The method that discharges gaseous ammonia during with from 25 to 600 ℃ of heating of titration ammonium attitude has been evaluated the acidity of example 3 and 4 products.The result of this test shows that the eduction rate of ammonia in the time of 360 ℃ ion-exchange capacity the highest and each product is 0.7-0.8 milliequivalent/gram.

Example 12

By in nitrogen, the ammonium attitude is heated to 450～550 ℃ change into the hydrogen attitude after, with an experimental test product of example 3.Its α one value proves 8.6.Same product is proved to be has the methanol conversion activity in the time of 350 ℃, the alkyl that has toluene and methyl alcohol in the time of 538 ℃ replaces active, and the hydrocarbonylation action activity that has toluene and ethene between 450 ℃ and 500 ℃ the time.

Example 13-16

For synthetic four kinds different respectively with MCM-6, MCM-7, the Silicophosphoaluminaand crystalline material of MCM-2 and MCM-8 name has prepared four kinds of independently biphasic reaction mixtures.The composition of this reactant mixture and reaction condition are listed in the table 14 of back.Resulting four kinds of products respectively have silicon, phosphorus and the aluminium of tetrahedral coordination by the composition shown in the table 14.

The table 15 of difference typical example 13,14,15 and 16 described products below the X-ray diffraction analysis of every kind of Silicophosphoaluminaand is listed in, 16,17 and 18.

Restricted index that example 13,14 and 15 produces materials (United States Patent (USP) 4,385,195 in illustrated) and α value have been evaluated.The results are shown in table 19.

Table 14

Embodiment product 13 14 15 16

The component of synthetic mixture (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

1-hexanol 60.0 60.0 60.0 60.0

Organic base

Hydroxide trimethyl ammonium---31.0

TMAOH（25%）

The hydroxide triethyl ammonium

TEAOH（40%）????37.0????-????37.0????-

Di-n-propylamine-10.1--

Inorganic base

(milli is opened; 5x10 ^-2Mole)

KOH????-????-????-????2.0

CsOH????0.04????-????2.0????-

Condition

Nucleation time, hours 24 24 24 24

Nucleation temperature, ℃ 130 130 130 130

Crystallization time, hours 144 24 144 144

Crystallization temperature, ℃ 180 200 180 180

Trip's rotary speed, revolutions per 800 800 800 800

Initial PH 6.5 6.5 6.5 5.5

Final PH 6.5 9 6.0 7

Product is formed

(T-atomic component)

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 is formed

(weight %, synthetic attitude)

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/gram ash)

Table 15(MCM-6)

Interplanar d-interval ( ) observe 2x θ relative intensity I/I ₀

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 16(MCM-7)

Interplanar d-interval (

) observe 2x θ relative intensity I/I ₀

10.85413????8.139????18.2

9.32129????9.480????29.9

6.69511????13.213????11.9

5.69511????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 17(MCM-2)

Interplanar d-interval (

) observe 2x θ relative intensity I/I ₀

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 18(MCM-18)

Interplanar d-interval (

) observe 2x θ relative intensity I/I ₀

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 19

Embodiment product 13 14 15

Restricted index 0.5-0.7 1.0 100

α-value-3.5-

Example 17

With containing 10 gram Si(OC ₂H ₅) ₄With the organic facies of 60 gram 1-hexanols and contain 23.1 gram H ₃PO ₄(85%), 13.7 gram Al ₂O ₃, 10.1 gram di-n-propylamines and 59.6 gram H ₂The water of O makes a kind of two-phase synthesis reaction mixture.As a whole, consisting of of this reactant mixture contains 9.3%Si, 38.8%P and 51.9%Al(atomic percentage).Directing agent is a di-n-propylamine.Initial PH is between 5-7.

This reactant mixture is heated to 130 ℃ and kept 24 hours with 50 ℃/hour firing rate under this temperature.Be heated to 200 ℃ and under this temperature, kept 24 hours then, till the Silicophosphoaluminaand crystallization with the MCM-9 name in forming the present invention.

By filtering crystallized product is separated from reactant mixture, washing is then in 80 ℃ of dryings.By analysis, this product crystal contains 13%Si, 42.7%P and 44.2%Al(atomic percentage).Sample with a synthetic attitude MCM-9 Silicophosphoaluminaand carries out x-ray analysis and is determined as a kind of molecular sieve structure with diffracted ray shown in the table 20 then.

Table 20(MCM-9)

Interplanar d-(A) at interval observes 2x θ relative intensity I/I ₀

16.4111????5.381????62.39

10.8526????8.140????17.66

9.6576????9.149????32.12

9.3204????9.481????27.26

8.2047????10.774????20.52

6.8566????12.901????76.05

6.7054????13.193????12.08

6.4892????13.634????54.07

6.1653????14.354????10.73

5.6353????15.712????26.80

5.4550????16.235????4.23

4.8496????18.278????59.79

4.7388????18.710????14.59

4.6681????18.996????5.63

4.3551????20.375????49.35

4.2273????20.998????92.67

4.1353????21.471????37.27

4.0810????21.759????100.00

4.0106????22.146????20.79

3.9298????22.607????47.48

3.8322????23.191????40.95

3.7598????23.644????14.34

3.6060????24.668????14.55

3.3878????26.285????31.22

3.3439????26.636????9.32

3.2759????27.199????24.92

3.1640????28.180????13.98

3.0649????29.112????65.46

2.9449????30.325????18.46

2.8926????30.887????20.58

2.8367????31.512????7.14

2.7792????32.181????9.79

2.7311????32.764????15.65

2.6815????33.388????32.91

2.6183????34.218????8.19

Example 18

Repeat the synthetic of embodiment 17, different is that reactant mixture kept 48 hours at 200 ℃.By analysis, this Silicophosphoaluminaand crystallization contains 14.5%Si, 42.4%P and 43.1%Al(atomic percentage).The synthetic attitude MCM-9 Silicophosphoaluminaand sample of portion is carried out x-ray analysis and is determined as the crystallization of molecular sieves with diffracted ray shown in the table 21.

Table 21(MCM-9)

Interplanar d-interval ( ) observe 2x θ relative intensity I/I ₀

16.4079????5.382????100.00

10.8449????8.146????7.49

9.3382????9.463????14.69

8.2045????10.774????30.68

6.6779????13.247????7.67

6.1687????14.346????14.01

5.6460????15.683????12.66

5.4639????16.209????5.08

4.8358????18.331????3.08

4.7403????18.704????14.29

4.3370????20.461????14.88

4.2142????21.064????54.04

4.0922????21.699????28.93

4.0529????21.912????33.05

4.0066????22.169????16.42

3.9361????22.571????42.98

3.8330????23.186????25.28

3.7675????23.595????20.32

3.6367????24.457????7.76

3.5884????25.791????8.64

3.3881????26.282????5.67

3.3420????26.651????3.81

3.2787????27.176????32.35

3.1646????28.175????9.66

3.0888????28.881????13.52

3.0304????29.451????9.22

2.9527????30.244????19.34

2.8974????30.835????9.66

2.8383????31.494????3.59

2.7410????32.642????15.87

2.6273????34.097????6.96

Example 19

With example 18 more described Silicophosphoaluminaand crystallizations in 450 ℃ in nitrogen calcining carried out x-ray analysis in 4 hours then.The results are shown in table 22.

Table 22

Interplanar d-interval ( ) observe 2x θ relative intensity I/I ₀

16.3622????5.397????47.46

14.0545????6.284????21.20

10.9231????8.088????6.38

8.9443????9.881????41.09

8.1901????10.793????9.93

6.9002????12.819????13.13

5.4998????16.102????29.83

4.4683????19.853????22.63

3.3595????20.354????7.28

4.0790????21.770????100.00

3.9420????22.537????59.93

3.7815????23.507????34.47

3.5387????25.145????18.20

3.4518????25.788????10.08

3.3277????26.768????7.78

3.2785????27.177????13.51

3.2215????27.668????7.00

3.0139????29.615????33.24

2.9487????30.286????11.29

2.8231????31.668????7.73

2.7398????32.657????18.29

Example 20

With containing 60 gram n-hexyl alcohols and 10 gram Si(OC ₂H ₅) ₄Organic facies and contain 23.1 the gram H ₃PO ₄(85%), 10 gram Al ₂O ₃, 154.4 gram 3.6N two season-7(OH) ₂(i.e. (OH) (CH ₃) ₃N(CH ₃) ₃(OH)) water makes a kind of two-phase synthesis reaction mixture.As a whole, this reactant mixture consists of 10.8%Si, 45%P and 44.2%Al(atomic percentage).Directing agent be two the season-7(OH) ₂₀Initial PH is a little more than 6.

This reactant mixture is heated to 130 ℃ and kept 24 hours with 50 ℃/hour firing rate under this temperature.Be heated to 180 ℃ and under this temperature, kept 144 hours then.During this period, mix with 800 rev/mins rotating speed.

By filtering crystallized product is separated from reactant mixture, washing is then in 80 ℃ of dryings.The crystallization of Silicophosphoaluminaand product consist of 19.9%Si, 37.1%P and 43.0%Al(atomic percentage).Then a synthetic attitude Silicophosphoaluminaand sample that this sentences the MCM-10 name is carried out x-ray analysis.Be determined as molecular sieve with diffracted ray shown in the table 23.

Table 23(MCM-10)

Intergranular face d-interval (

) observe 2x θ relative intensity I/I ₀

11.8446????7.457????17.04

10.1960????8.665????78.40

7.6489????11.559????84.85

6.8567????12.900????24.39

5.9273????14.934????13.31

5.6856????15.573????35.97

5.1059????17.354????57.48

5.0091????17.692????64.21

4.4885????19.763????10.91

4.3742????20.285????85.60

4.0918????21.701????100.00

3.9534????22.471????11.66

3.7982????23.402????42.70

3.7262????23.861????13.62

3.4249????25.995????26.69

3.2165????27.711????81.46

3.1626????28.193????8.65

2.9904????29.854????20.84

2.9657????30.108????21.06

2.9347????30.433????32.19

2.8448????31.420????36.84

2.7846????32.118????7.41

2.6813????33.390????42.38

2.5893????34.614????19.50

Example 21

It is described synthetic to repeat example 20, and different is only to add 30 gram water.The X-ray diffraction style of the MCM-10 Silicophosphoaluminaand crystallized product that generates shows that it has and lines similar shown in the table 23.This product has 50% to be crystallization.

Example 22

Example 20 more described MCM-10 Silicophosphoaluminaand crystallizations were calcined 4 hours in nitrogen in 450 ℃, carry out x-ray analysis then.The results are shown in table 24.

Table 24

Interplanar d-interval (

) observe 2x θ relative intensity I/I ₀

11.7521????7.516????20.81

10.1070????8.742????85.44

7.5640????11.690????100.00

6.8057????12.997????71.80

5.6522????15.665????25.38

5.0770????17.453????29.02

4.9416????17.935????78.18

4.4564????19.907????16.58

4.3515????20.392????99.63

4.2756????20.758????25.68

4.0759????21.787????83.25

3.8546????23.055????15.88

3.7499????23.707????21.15

3.4089????26.119????42.38

3.1778????28.056????68.19

2.9616????30.151????29.91

2.9230????30.558????51.09

2.8835????30.988????10.99

2.8321????31.564????36.78

2.6565????33.711????43.09

2.5795????34.749????19.66

Claims (18)

1, the method for a kind of synthesis silicon phosphorus aluminate crystallization, this method comprises:

A. prepare a kind of reactant mixture, this mixture contains a liquid organic facies and a liquid water, and described reactant mixture contains water, alumina source, silica source, phosphorous oxide source, a kind of organic directing agent A, inorganic cation M and anion N; And a kind of not miscible with water basically organic solvent, the composition of described reactant mixture has following relation:

(A) a: (M ₂O) b: (Al ₂O ₃) c: (SiO ₂) d: (P ₂O ₅) e: (solvent) f:(negative ion source g: (H ₂O) h

A wherein, b, c, d, e, f, g and h are the number that satisfies following relationship:

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

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

D/ (c+e) is less than 2,

F/ (c+d+e) from 0.1 to 15

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

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

Wherein when beginning to prepare described reactant mixture, with a kind of aluminium, silicon or phosphorous oxides source are dispersed or dissolved in the described organic facies;

B. with 5 ℃-200 ℃/hour firing rate described reactant mixture is heated to 80 ℃-300 ℃;

C. stir described reactant mixture in the mode that is enough to described liquid organic facies and water are mixed each other fully;

D. the reactant mixture that keeps described stirring under 80 ℃ of-300 ℃ of temperature and during PH2-9 is till forming the crystallization of Silicophosphoaluminaand material; And

E. reclaim the Silicophosphoaluminaand material from described reactant mixture, this material is a feature in following composition (with anhydrous state):

A _V＇:M _X/m ^m+:(AlO ₂) l-y:(PO ₂) _l-X ⁺:(SiO ₂) _X+y:N ^n- _y-n

The summation of organic directing agent A of A ' representative and organic solvent wherein, V is the molal quantity of A ', and m is the valence mumber of cation M, and n is the valence mumber of anion N, and x and y be＞-1 to＜+1 number, this number 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 Al/P greater than 1, then (x+y) greater than 0 y+0.6x less than 0.4, and

(4) if the atomic ratio of Al/P less than 1, then (x+y) greater than 0 and 0.5y+x less than 0.5.

Described Silicophosphoaluminaand has at least 0.002 milliequivalent/gram-ion exchange capacity.

2, method according to claim 1 is characterized in that organic directing agent wherein 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 or the alkylene 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 carbon atom mix alkyl or their combination; M is for being selected from nitrogen, phosphorus, arsenic, antimony, a tetravalence coordination element atom of bismuth or be selected from alicyclic ring, the N of heterolipid ring or heteroaromatic structure, O, S, Se, the hetero atom of P or As; And X is an anion.

3, method according to claim 2 is characterized in that organic directing agent A wherein is selected from C ₁-C ₃Alkylamine and father-in-law's compound with following chemical formula:

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

Wherein R is C ₁-C ₄Alkyl, R ' is C ₁-C ₆Alkylene, M is a nitrogen, X is halide or hydroxide; And organic solvent wherein is C ₅-C ₁₀Alcohol.

4, according to each described method among the claim 1-3, it is characterized in that wherein originally silica source is present in the organic facies of reactant mixture, the PH of the reactant mixture that wherein stirred maintains between the 6-9.

5, according to each described method of claim 1-3, this method is included in 300 ℃-1000 ℃ additional steps that heat the aluminium silicate salt that is reclaimed of temperature to form a kind of calcining Silicophosphoaluminaand, and this Silicophosphoaluminaand is a feature in following composition (with anhydrous state):

M ^m+ _x/m∶（AlO ₂） ^- _l-y∶（PO ₂） ⁺ _l-x∶（SiO ₂） _x+y∶N ^n- _y/n

Wherein M is a kind of cation of m valency, and N is a kind of anion of n valency, x and y for satisfy following relation from＞-1 to＜+1 number:

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

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

(3) if the Al/P atomic ratio greater than 1, then (x+y) greater than 0 y+0.6x less than 0.4, and

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

6,, it is characterized in that the Silicophosphoaluminaand material that is wherein reclaimed by reactant mixture is named as MCM-1, and before heating, have the X-ray diffraction style of listing in specification table 1-A substantially according to each described method of claim 1-3.

7,, it is characterized in that the Silicophosphoaluminaand material that is wherein reclaimed by reactant mixture is named as MCM-1, and before heating, have the X-ray diffraction style of listing in specification table 1-A substantially according to the described method of claim 5.

8,, it is characterized in that the Silicophosphoaluminaand material that is wherein reclaimed by reactant mixture is named as MCM-3, and before heating, have the X-ray diffraction style of listing in specification table 2-A substantially according to each described method of claim 1-3.

9,, it is characterized in that the Silicophosphoaluminaand material that is wherein reclaimed by reactant mixture is named as MCM-3, and before heating, have the X-ray diffraction style of listing in specification table 2-A substantially according to the described method of claim 5.

10,, it is characterized in that the Silicophosphoaluminaand material that is wherein reclaimed by reactant mixture is named as MCM-4, and before heating, have the X-ray diffraction style of listing in specification table 3-A substantially according to each described method of claim 1-3.

11,, it is characterized in that the Silicophosphoaluminaand material that is wherein reclaimed by reactant mixture is named as MCM-4, and before heating, have the X-ray diffraction pattern of listing in specification table 3-A substantially according to the described method of claim 5.

12,, it is characterized in that the Silicophosphoaluminaand material that is wherein reclaimed by reactant mixture is named as MCM-5 according to each described method of claim 1-3; And before heating, has an X-ray diffraction style of listing in specification table 4-A substantially.

13,, it is characterized in that the Silicophosphoaluminaand material that is wherein reclaimed by reactant mixture is named as MCM-5, and before heating, have the X-ray diffraction style of listing in specification table 4-A substantially according to the described method of claim 5.

14,, it is characterized in that the Silicophosphoaluminaand material that is wherein reclaimed by reactant mixture is named as MCM-9, and before heating, have the X-ray diffraction style of listing in specification table 5-A substantially according to each described method of claim 1-3.

15,, it is characterized in that the Silicophosphoaluminaand material that is wherein reclaimed by reactant mixture is named as MCM-9, and before heating, have the X-ray diffraction style of listing in specification table 5-A substantially according to the described method of claim 5.

16, according to any one described method of claim 1-3, wherein the Silicophosphoaluminaand material that is reclaimed by reactant mixture is named as MCM-10, and has the X-ray diffraction style of listing in specification table 6-A substantially before heating.

17,, it is characterized in that the Silicophosphoaluminaand material that is wherein reclaimed by reactant mixture is named as MCM-10, and before heating, have the X-ray diffraction style of listing in specification table 6-A substantially according to the described method of claim 5.

18, require the synthetic Silicophosphoaluminaand crystallization of described method with each aforesaid right.