CN1066431A - Stable aluminophosphate-based molecular sieve compositions - Google Patents

Abstract

Aluminophosphate-based molecular sieve compositions with APMS-54 crystalline structure by make its stabilization with boric acid or borate processing under hydration status, prevents that the branch of network from can or change into other crystalline structure.Stable product feature is, except must also containing 6ppm at least and add boron in APMS-54 structure.

Description

Stable aluminophosphate-based molecular sieve compositions

The present invention relates to have AlPO ₄The stabilization technology of the aluminophosphate-based molecular sieve compositions of-54 distinctive crystalline structure (being called APMS-54 here), and the composition of the stabilization that obtains therefrom.The present invention be more particularly directed to the processing of this crystal formation composition, having comprised: the aluminum phosphate raw material, be preferably under the hydration status, contact with the boric acid or the borate aqueous solution, formation has identical crystalline structure, adds the boron weight content stable composition of 6ppm at least.

In in the past 10 years, a variety of crystalline aluminophosphate based molecular sieve compositions have been synthesized.These mixtures may contain AlO ₂And PO ₂Tetrahedron element, or also contain any tetrahedral oxide units in the multiple metals such as beryllium, boron, chromium, cobalt, gallium, germanium, iron, lithium, magnesium, manganese, titanium, vanadium and zinc.Aluminium phosphate molecular sieve includes only AlO ₂And PO ₂Tetrahedron element generally is expressed as " AlPO ₄' S ", people such as Wilson have in (open day January 12 nineteen eighty-two) and mention at United States Patent (USP) 4,310,440.These molecular sieves have network structure, and its chemical constitution is expressed as by the mol ratio of oxide compound:

Al ₂O ₃∶1.0±0.2P ₂O ₅;

Each said network structure is the micropore shape, and hole wherein is uniformly, generally has and the nominal diameter of concrete molecular diameter in same range as promptly at least 3

Composition is by hydrothermal crystallization method synthetic by the aluminum phosphate mixture of the forming panel agent that contains an organic structure.This crystallization composition comprises water or organic formwork, in they intracrystalline gaps, removes the microporous crystal sorbent material of generation with the hole of homogeneous.General, preparation process comprises the following reaction mixture of representing by the mol ratio of oxide compound of formation:

Al ₂O ₃∶1±0.5P ₂O ₅∶7-100H ₂O

And every mole of Al ₂O ₃The template that comprises 0.2-2.0mol.Reaction mixture is placed in the reactor, rare gas element feeds reactive system, be heated at least 100 ℃, preferably 100～300 ℃, up to obtaining solid crystallized product, this process usually needs 2 hours to 2 weeks, and crystallized product can adopt any traditional method to reclaim then, as filtration, centrifugal settling, washing and in air by room temperature to 100 ℃ drying.

After the existing aluminium phosphate molecular sieve of secondary, people find again, by mix can form the tetrahedral oxide network structure element in reaction mixture, can produce another kind of aluminophosphate-based crystalline molecular sieve.Silicon is particularly suitable for being mixed in the aluminum phosphate network, by people such as LOK at U.S.P.4,440,871, related well-known in open day 3 days April in 1984 by this represented molecular sieve analog of abbreviation " SAPO ' S ".Similarly, at U.S.P4,567.029, spoken of " MeAPO " molecular sieve in open day 28 days January in 1986, wherein " Me " represents at least a in magnesium, manganese, cobalt, the zinc, and crystallization tertiary iron phosphate aluminium (FeAPO) is at U.S.P4, and 554,143, mention in open day 19 days November in 1985 that titanium phosphate aluminium (TAPO) is at U.S.P.4,500,651, mention in open day 19 days February in 1985.The molecular sieve of called after " ELAPO ' S " and " ELAPSO ' S " is well known in the art, and, publish a day 1985.10.13 at EPO number of patent application 85104386.9(notification number 0158976) and EPO publication number 0159624(publish a day 1985.10.30) in described respectively.

In a word, aluminophosphate-based molecular sieve, sometimes be called " none zeolite " molecular sieve or " NZMS " technically, can enough following molecular formula describe its experience chemical constitution under anhydrous state, comprised " EL " represented element in abbreviation " ELAPO " and " ELAPSO " at this Q.

MR∶（QwAlxPySiz）O ₂

Here Q represents the element that at least one presents netted oxide unit structure, " QO n ₂" have an index " n ", here " n " can be-3 ,-2 ,-1,0 or+1; " R " represents at least a organic formwork agent at the crystals microcellular system; The mole number of " m " representative " R " is with every mole of (QwAlxPySiz) O ₂Expression, it is worth by 0 to 0.3; " w " " x " " y " and " z " represent QO respectively n ₂, AlO - ₂, PO + ₂, SiO ₂The unitary molar fraction of network oxide, " Q " is a kind of specific element, has in tetrahedral structure said 1.51

To 2.06

Between " T-0 " distance, " Q " has positive charge, electronegativity is between 125 kcal/gm-atom to 310kcal/gm-atom." Q " can form stable Q-O-P, and Q-O-Al, or Q-O-Q key have " Q-O " key in crystalline three-dimensional oxide structure, and its association energy is when 298 ° of K, greater than 59kcal/gm-atom.Above-mentioned mol ratio drops in the combined value or point of qualification as described below:

(W+Z) equal the 0-98 molar percentage;

Y equals the 1-99 molar percentage;

X equals the 1-99 molar percentage;

By those prior arts, know that easily the formation scope of the aluminophosphate-based molecular sieve that each is surrounded by above-mentioned molecular formula depends on and existing TO to a great extent ₂The static charge that the unit is relevant.So crystalline A lPO ₄Molecular sieve must contain the AlO of same amount especially ₂And PO ₂The unit is so crystallization SAPO molecular sieve contains the SiO of mol ratio 98% ₂The unit, remaining is AlO ₂And PO ₂The unit.

In the situation of general aluminosilicate zeolite molecular sieve, can see that the heat of aluminophosphate-based molecular sieve is different with the structure kind of general class with hydrothermal stability.For example, the U.S.P4 that mentions in the above in 310,440 the example 51, has reported and has used different reaction mixtures, and different organic formwork agents prepares a kind of AlPO of being called with different reaction times, temperature ₄The process of-21 molecular sieve.In each example, all from reaction mixture, isolate AlPO ₄-21 products and 110 ℃ of following dry airs.When 500～600 ℃ of following calcination in air, find AlPO ₄-21 products have been transformed into the AlPO of crystalline structure ₄-25, relatively the X-ray powder diffraction pattern spot of two kinds of structures can be found its structure and AlPO ₄-21 obvious difference.AlPO ₄-23 can see similar conversion under calcination, formed AlPO under 600 ℃ ₄-28.In other words, AlPO ₄-31 had both made in air temperature up to 1000 ℃ of calcination, the crystalline structure when still keeping it synthetic.

One of considerable change that comprises generic aluminophosphate-based molecular sieve compositions crystalline structure is called APMS-54 hereinafter." APMS " is the abbreviation of aluminophosphate-based molecular sieve, data such as table 1 or the simpler and clearer crystal structure characteristic illustrated as the d value of table 2 that " 54 " expression provides by X-ray diffraction.It is conventionally believed that APMS-54 is similar to Smith and the imaginary network 81(1 of Dytrych on the geology), see " nature " magazine, be published in 1984, the 607th phase, 309 pages, though AlPO ₄-54 the X-ray diffraction spot and the pattern of this imaginary network structure are not to conform to fully.

Table 1

2 θ d dust relative intensities

5.3±0.2 16.07-17.32 VS

9.3±0.2 9.31-9.72 W

10.7±0.25 8.08-8.47 M

14.3±0.3 6.07-6.33 W

16.1±0.3 5.40-5.61 W

18.7±0.3 4.67-4.82 W

21.7±0.4 ^＊4.02-4.17 M

21.9±0.4 3.99-4.13 M

22.4±0.4 ^＊3.90-4.04 M

22.6±0.4 3.87-4.00 M

23.6±0.4 3.71-3.83 W

24.5±0.4 3.58-3.69 W

24.8±0.4 3.53-3.65 W

26.0±0.4 3.38-3.48 W

27.15±0.4 3.249-3.333 M

28.2±0.4 3.126-3.209 W

28.9±0.4 3.048-33.132 W

29.4±0.4 2.998-3.079 W

30.25±0.4 2.917-2.993 W

30.8±0.4 2.867-2.940 W

32.3±0.4 2.739-2.805 W

32.65±0.4 2.710-2.776 W

34.0±0.4 2.607-2.667 W

35.85±0.4 2.478-2.532 W

37.6±0.4 2.368-2.417 W

38.3±0.4 2.327-2.374 W

41.0±0.4 2.181-2.222 W

48.8±0.4 1.852-1.881 W

49.2±0.4 1.838-1.866 W

49.6±0.4 1.824-1.852 W

55.0±0.4 1.658-1.680 W

Table 2

2 θ d(dusts) relative intensity

5.1-5.5 16.07-17.32 VS

10.45-10.95 8.08-8.47 M

21.3-22.1 ^＊4.02-4.17 M

21.5-22.8 3.99-4.13 M

22.0-22.8 ^＊3.90-4.04 M

22.2-23.0 3.87-4.00 M

23.2-24.0 3.71-3.83 W

26.75-27.45 3.249-3.333 M

Other phenomenon after these x-ray diffraction patterns and this be by the x-ray powder diffraction technique that uses standard or by Applied Computer Techniques as from Siemens Company, the siemens D-500X ray powder diffraction instrument that Cherry Hill N.J obtains and.When adopting the Standard X-Ray technology, source of radiation is high-strength, and copper palladium, X-x ray tube are operated when 40KV and 49ma.From Cu K-α radiation that come with the diffractogram spot graphite homogeneous beam just by X-ray spectrometer scintillometer, pulsed height analyzer and the recorder trace of long strip shape recording paper.The sample of being pressed flatly is with the velocity sweeping of 2 ° of per minutes (2 θ), and 2 seconds constant.Can obtain spacing (d) from the position of diffraction peak, be expressed as 20, O is a Bragg angle here, as what seen on strip chart.Intensity is by the diffraction peak height decision of removing after the background, relative intensity value 100 * I/I ₀, available digital, also available symbols is represented, and: W(is weak), among the M(), S(is strong) and VS(extremely strong), during with numeral, general W=0-10; M=11-20; S=21-50; VS=51-100.

We know by these known technologies, determine parameter 2 θ, as the technology of not considering to be adopted, mainly are subjected to the influence of people and machine error, and the 2 θ values of taking all factors into consideration each report may influence about about 0.4 degree.This uncertainty shows that also this uncertainty is the out of true of whole technique on the d value that is calculated by 2 θ certainly, is not enough to hinder us to distinguish the present crystal and the compound of prior art.

Aluminophosphate-based molecular sieve analog, we are referred to as APMS-54 here, comprise that all have identical feature crystalline structure, but the different various molecular sieves of the network structure of structure oxide show and remove AlO ₂And PO ₂Outer other unit in addition.For example: AlPO ₄-54 only by AlO ₂And PO ₂The unit constitutes; SAPO-54 is by SiO ₂, AlO ₂And PO ₂The unit constitutes; CoAPO-54 is by CoO ₂, AlO ₂And PO ₂The unit constitutes or the like.

Related to zeolite and molecular sieve technology with present publication before the people such as M.E.Davis, obviously, the aluminophosphate-based molecular sieve of called after VPI-5 is identical with APMS-54 herein or perhaps similar.These publications comprise C﹠amp; EN, 1988.3.21, people such as P22-24 and Davis " nature " 331, P698(1988).

Effectively the data evidence shows: that report synthetic and preparation APMS-54 for the first time is U.S.P.4, and 310,440 example 29 is at its synthetic AlPO ₄In-54 the process, 115 ℃ of dried recovered, the washing solid gets major product.The X-ray powder diffraction pattern of dry compound shows, at 115 ℃ of dry AlPO ₄During-54 crystal, this crystal is very fast from changing into AlPO in essence fully ₄-8.Further be reported in (research notes; The zeolite outline, Ge Lujiya engineering college, 1988 autumns, Vol.2.No.2), and at U.S.P.4,673, disclosing its preparation method and MCM-9 in 559 is the mixture that contains VPI-5 and SAPO-11, as other APMS-54 class, this compound, when high temperature, be unsettled, tend to dehydration.

Invent a kind of AMPS-54 of making compound stabilization now, can prevent the method that its crystal formation transforms.This method comprises makes the APMS-54 crystal contact with a kind of solution, and preferably the boric acid or the boratory aqueous solution make to contain the 6ppm(weight ratio in the crystal at least), 15ppm preferably is more preferably the boron that adds of 150ppm.Boracic APMS-54 can withstand high-temperature calcination, in some cases even can reach 1000 ℃.At dewatering state, the APMS-54 compound of handling than boron useless has part still less to change into AlPO ₄-8 feature crystalline structure, and seldom be degraded into amorphous state, its reason is not understood fully as yet fully.In the calcination process, preferably gently rise to final calcination temperature by room temperature with 5 ℃/minute or slower speed, the present invention also comprises the APMS-54 product that novel boracic is stable.

Can make former synthetic (promptly unsettled) aluminophosphate-based molecular sieve stable aptly according to the present invention, it comprises having AlPO ₄-54 feature crystalline structures also have corresponding X-ray powder diffraction pattern as shown in table 1 or comprise the d value that proposes in the table 2 at least, and all the APMS-54 molecular sieve analogs with following chemical constitution:

MR∶（QwAlxPySiz）O ₂

Here " Q " represents at least a element that exists with the network oxide unit, " QO n ₂" the index n here may be-3 ,-2 ,-1,0 or+1; The intrasystem at least a organic formwork agent of " R " expression crystal pores; The molar weight of " m " expression " R " is with every mole of (QwAlxPySiz) O ₂Expression, its value can be by 0 to 0.3; " w ", " x ", " Y " and " Z " represent QO in the network oxide unit respectively n ₂, AlO - ₂, PO + ₂And SiO ₂Molar fraction." Q " specific be molecular weight greater than 20, in the tetrahedral oxide structure effectively " T-Q " distance 1.51

-2.06

Between element.Q is a positive ion, and electronegativity is between 125kcal/gm-atom-310kcal/gm-atom, and in the crystal three-dimensional oxide structure of " Q-0 " key was arranged, " Q " can form stable Q-O-P; Q-O-Al or Q-O-Q key, its association energy is greater than 59kcal/gm-atom when 298 ° of K; Above-mentioned mol ratio drops in the combined value or point of qualification as described below:

(W+Z) equal 0～98%(mol ratio)

Y equals the 1-99%(mol ratio)

X equals the 1-99%(mol ratio)

When in the molecular formula Q being arranged, better be a kind of in arsenic, chromium, cobalt, gallium, germanium, iron, magnesium, manganese, titanium, vanadium or the zinc, preferably one of cobalt, magnesium, manganese or zinc.Good especially is that " W " value is 0, or " W " and " Z " value all is a class of 0, i.e. AlPO ₄-54 and SAPO-54.

The APMS-54 compound is according to known technological process synthetic, specially refers to these in a lot of publications of quoting in above-mentioned prior art.People such as R.J.Pellet disclose a kind of synthetic technology at United States Patent (USP) 4,740,650 among the open day 1988.4.26, and at this, this patent is introduced reference.N-Ethylbutylamine is the good template that forms the 54-structure, but also available other template comprises dipropyl amine, two n-pentyl amine, dibutylamine, tributylamine, TBuA ion, four n-pentyl ammonium ion and Neosupranols.

Phosphorus source in the reaction mixture is 85% water-soluble aqueous ortho-phosphoric acid (H ₃PO ₄).The aluminium source is false boehmite stone, as Pural(Condea).Synthetic, comprise in the stirred reaction mixture process, it is found that commodity in use " Versal 250 " general aluminum oxide (Kaiser) by name can obtain rarer easy stirred mixture.

When containing silicon in the 54-structure, the silicon source in the reaction mixture is four tetraethoxys, silicon sol and solid active amorphous silicon, as commodity Cab-O-Sil(Cabot by name) and the silicon of being fuming Hisil(PPG), outstanding after two kinds for well.

In the molecular formula of superincumbent compound, with the source of element of " Q " representative, the normally compound of reaction of element, particularly oxide compound, oxyhydroxide and salt, the nitrate of acetate, vitriol, halogen and these elements can.In some cases, when for example element is titanium, also available alkoxide and water soluble chelate compound.

At preparation AlPO ₄-54 o'clock, reaction mixture generally comprised: every mole of Al ₂O ₃About 0.5～1.5 mole P ₂O ₅, the water of the organic formwork agent of 0.2-2.0 mole and 7-100 mole, to ELAPO-54, the reaction mixture of representing with the form of mol ratio is:

aR∶（QwAlxPySiz）O ₂∶bH ₂O

O＜a＜6 wherein, the b value is 2-500, representative element Q, Al and P are the molar fraction value of " W ", " x " and " Y " respectively, divide other 0.01～0.98; 0.01～0.6; With 0.01～0.6." z " value is 0.For SAPO-54, reaction mixture is identical with above-mentioned ELAPO, but " W " value is 0, and " z " value is 0.01～0.98.

For ELAPSO-54, represent that with the form of mol ratio reaction mixture is as follows:

aR∶（QwAlxPySiz）Q ₂∶bH ₂O

" a " is identical with the situation of ELAPO-54 with " b " value, and the value of " x ", " Y " and " Z+W " is respectively: 0.1～0.55; 0.10-0.55; And 0.01-0.98.When synthetic APMS-54 compound, once observed and formed a lot of impure crystalline tendencies.Low shear-mixed also avoids occurring nucleation, stirs or the crystal seed mixture is arranged as hypervelocity, can suppress to form these impurities.Whether this material occurs.Also depend on reaction mixture to a great extent and be that stir or static digestion.As, during static digestion, Cab-O-Sil can generate pure SAPO-54, but when stirring digestion down, Hisil generates pure substantially SAPO-54.For reducing the generation of impurity, the digestion temperature should remain on 125～175 ℃.When synthetic 54-structure, low-temperature digestion easily forms the H3(Bulletin Soc.Chemical France with similar D ' Yvoire, and the 1762(1961) aluminum phosphate of) X-ray powder diffraction pattern, and during high temperature easily forms and has AlPO ₄-11 and AlPO ₄The compound of-41 structures; Sometimes the two can reach a balance.

Handling the APMS-54 compound, preferably contain the boric acid or the boratory aqueous solution of significant quantity so that its stabilization when preventing structural transformation, makes crystal contact with a solution.Stabilization treatment is preferably in building-up process finish after, the product crystal is separated from reaction mixture, carries out behind the residual reaction mixture of water flush away.In preparation APMS-54, can join boric acid or borate in the synthetic mixture, stabilization treatment can be carried out in reaction process and after forming the APMS-54 crystal like this.In this case, the product crystal can not be washed the content of unnecessary boron except that finishing needed amount to being lower than stabilization.Here employed " boric acid " means any tetraboric acid (H ₂B ₄O ₇), metaboric acid (HBO ₂) and orthoboric acid (H ₃BO ₃).When temperature was higher than 70 ℃, orthoboric acid changed into metaboric acid; Metaboric acid changes into tetraboric acid in the time of 140 ℃.Known available multiple boric acid and salt, comprised basic metal, alkaline-earth metal, thallium and magnesium, ammonium salt also is economical and practical.A variety of alkali metal borates have M ₂O _mB ₂O ₃Molecular formula, wherein can be up to 6 except that " m " of K salt value, general m value is 1～4, the m value of ammonium borate is 2 or 4.Except that forming the aqueous solution, borate also dissolves in the organic hydroxy compounds, particularly acid.

In treatment solution, boric acid or boratory concentration are not very harsh conditions, but preferably contain the 1%(weight ratio at least).The temperature of treatment solution should not surpass 90 ℃, is preferably between 30-80 ℃.Acid concentration is the 1-10%(weight ratio) the orthoboric acid aqueous solution be a good treatment liquid under the temperature between 60～75 ℃, the complete butt of the general every 100g APMS-54(of used effective treatment solution) boron compound of 2-3 mole can be provided at least.Effectively solution amount should be enough to make hydration APMS-54 stable, prevents to change into when being higher than 100 ℃ of calcination other structure.When using borate solution, if desired, the PH that preferably adjusts salts solution is between 3-5.When the APMS-54 of stabilization compound at high temperature uses, preferably use boric acid or alkali metal borate, with the crystal formation degraded of avoiding causing because of fusing.

The APMS-54 of final stabilization contains 6ppm at least, preferably the boron of 150ppm (weight) at least.In this case, in order to distinguish the network structure boron that may exist, the boron of this stabilization is called " adding " boron.As if intracrystalline definite mode it be unclear that although boron is mixed into APMS-54, may be form and the lattice dot matrix combination of boron or boracic part with chemical bond.

Following Example illustrates the effective ways of process of the present invention and product and synthetic initial APMS-54 raw material.In these examples, the boron-containing quantity of the product of being reported, its used analytic process can be determined the 3.07ppm(weight ratio) boron.Correspondingly, when the boron amount that is contacted during near " zero ", the content of boron is too low, can not accurately measure, even not show.When the measuring vol of boron is arranged, the accuracy of its numerical value is approximately ± and 2.5%.

Example 1. preparation AlPO ₄-54

(a) static preparation: in plastic beaker, add the 46.12g positive acid solution (H of 85% weight content ₃PO ₄) and 117.89g water.Stir and in phosphoric acid solution, slowly add pseudobochmite class aluminum oxide (70.6wt%Al down ₂O ₃).Trade(brand)name Pural(Cordea).Use magnetic agitation, make the mixture retrogradation, manually continue to add aluminum oxide and mixing under the stirring with spatula behind the thickness.Under manually stirring, in the gained mixture, add the N-Ethylbutylamine of 20.24g again.The gained mixture has following composition.

1.0R∶Al ₂O ₃∶P ₂O ₅∶40H ₂O

Then, mixture digested 4 hours in 150 ℃ baking oven in a stainless steel polytetrafluoroethylene wire tube container.Final stage in digestion makes container be quenched to room temperature with cold water, filters with B, gets solid phase prod after the washing.The solid that recovery obtains environmental drying under the room temperature in stink cupboard.Obtain the pure AlPO of about 25g ₄-54, what its X-ray powder diffraction pattern and table 1 provided is identical.

(b) the identical operating process of using and (a) partly describing, same digestion temperature, 4 hours digestion time, the Al of same molar weight ₂O ₃, P ₂O ₅And organic formwork agent, every mole of Al ₂O ₃Add 40 mole of water, synthesize AlPO ₄Other seven experiments of-54.One of organic formwork agent below each compound experiment uses,

ⅰ) just-TBAH

ⅱ) just-amyl group ammonium hydroxide

ⅲ) just-dibutylamine

ⅳ) just-diamyl amine

ⅴ) Neosupranol

ⅵ) n-dipropylamine

ⅶ) n-tributylamine

In each example, in room temperature, when washing is reclaimed, AlPO ₄The yield of-54 products very high (proving) with x-ray diffraction pattern

(c) stir preparation

In a plastic beaker, add ortho-phosphoric acid (85%) 110.69g and water 228.68g respectively, under the magnetic agitation, add 57.87g aluminum oxide (versal 250brand; The 70.6%(weight ratio) Al ₂O ₃), add 20.2g N-Ethylbutylamine and mixing then, add the 111.2g tributylamine again.The pH=4.8 of final mixture, and have following composition:

0.5EtBuNH∶1.5Bu ₃N∶Al ₂O ₃∶P ₂O ₅∶40H ₂O

All mixtures are enclosed in one the 0.6 liter stainless steel reactor that has a whipping appts, are heated to 80 ℃ from 40 ℃ in 1 hour, again in 1 hour 80 ℃ be raised to 130 ℃, then 130 ℃ of digestion 1 hour.After reaching the digestion temperature, reaction mixture becomes sticky, and forms the solid viscous mass, can stop in the digestive process stirring several times.When digestion stopped, reaction mixture was quenched to 100 ℃ with flowing water.Products therefrom grinds into tractable fragment with pestle in large beaker, centrifugal settling also washes twice with water, and after handling like this, product becomes and can filter, and filters and washs product is isolated, dry air under the room temperature with several distilled water or de-ionates of rising.X-ray analysis shows, gets the pure AlPO of 165g ₄-54 dry products.Chemical analysis shows that product contains 0.87(wt) %C, 0.6%(wt) N, 32.2%(wt) Al ₂O ₃, 43.6%(wt) P ₂O ₅And 25.7%(wt) LOI.Mol ratio according to oxide compound provides the composed as follows of product:

1.0Al ₂O ₃∶1.0P ₂O ₅∶4.3H ₂O

(d) general technology of use (c), (b) six kinds of different template in Bu Fen front and tributylamine are used preparation AlPO with ₄-54.Every mole of Al ₂O ₃With the template of 0.5～1.0mol(b) part, surplus is a tributylamine, makes with respect to every mole of Al ₂O ₃, the mixed templates consumption is 2.0mol, during digestion, interior reaction temperature was added to 125-130 ℃ in 2 hours, added 1 hour digestion time at last more in addition.

Example 2.SAPO-54's is synthetic:

In beaker, add 92.24g85%H ₃PO ₄With 235.77g H ₂O gets reaction mixture, when mixing, slowly adds 57.87g vacation-boehmite, adds 7.2g SiO then ₂(Cab-O-Sil EH ₅) obtain the blended mixture, add the 50.0g N-Ethylbutylamine again, blend mixture is up to becoming homogeneous phase, and the chemical constitution of reaction mixture is as follows:

1.25R∶0.3SiO ₂∶Al ₂O ₃∶P ₂O ₅∶40H ₂O

In a polytetrafluorethyletubular tubular container, with mixture digestion 44 hours, cooling vessel then, centrifugation goes out product, with distillation washing back drying at room temperature.The chemical analysis of product show contain C 0.27%(wt), N 0.05%(wt), Al ₂O ₃33.6%(wt), P ₂O ₅34.7%(wt), SiO ₂7.36%(wt), LOI 23.6%(wt), providing product with the mol ratio of oxide compound consists of:

1.0Al ₂O ₃∶0.74P ₂O ₅∶0.18SiO ₂∶3.9H ₂O

The X-ray powder diffraction characteristic that the major ingredient of product has sees Table 3, and " I " is intensity here, and " d " is spacing.

Table 3

2 θ d, (dust) 100 * I/I ₀

5.3 16.5 100

10.75 8.23 14

14.3 6.19 6

16.15 5.49 2

18.7 4.75 6

21.7 4.10 10

21.9 4.06 17

22.4 3.97 10

22.55 3.94 11

23.6 3.77 8

24.5 3.64 3

24.8 3.59 3

27.2 3.28 12

28.2 3.17 5

30.3 2.953 7

32.7 2.740 7

34.0 2.636 2

Example 3.CoAPO-54's is synthetic

The phosphoric acid and the 97.5g water that mix 46.1g85% make reaction mixture.In another container, the 2.5g cobalt acetate tetrahydrate is dissolved in 20g water.27.5g pseudobochmite (Pural) joins in the phosphoric acid solution, mixes up to forming homogeneous phase, then, stirs adding cobaltous acetate solution down.Then, the 20.24g N-Ethylbutylamine is added in the mixture, stirs, obtain the reaction mixture of following composition up to becoming homogeneous phase:

1.0R∶0.05CoO∶0.95Al ₂O ₃∶P ₂O ₅∶40H ₂O

The partial confounding compound digested 4 hours under 150 ℃ in tetrafluoroethylene line style container.Isolate product and use distilled water wash with centrifugal settling, drying under the room temperature, the X-ray powder diffraction pattern of product major ingredient and example 2 identical.Be included in small amount of impurities among CoAPO-5 and the CoAPO-11 respectively at United States Patent (USP) 4,567, the existing description in 029 the example 89 and 93.

Example 4

(a), use the N-Ethylbutylamine as template, the Al of identical mol ratio for the instability of synthetic APMS-54 structure before proving ₂O ₃(Pural) and P ₂O ₅(ortho-phosphoric acid) synthesizes AlPO ₄-54 samples.In the reaction mixture, every mole of aluminum oxide adds 40 mole of water, by routine 1(a) in the process preparation.150 ℃ of digestion temperature, digestion time 4 hours.Filter and use distilled water wash at ambient temperature, reclaim the AlPO of substantially pure ₄-54(is according to the data decision of X-ray).Just under the filter cake state of humidity, sample placed 350 ℃ air oven 0.5 hour.After shifting out, the X-ray diffraction analysis is found, is not contained AlPO in the sample ₄-54, contain AlPO basically fully ₄-8(describes in 310,440 the example 27 as at U.S.P.4), compare with laboratory standard, account for 91% of whole crystal amounts.

(b) second sample gets AlPO boracic, purity 92% according to top (a) process preparation partly ₄-54.Filter cake is dry under room temperature (22 ℃) and the room temp under air.This sample uses 1 normal atmosphere, 100% water vapour under hydration status, 600 ℃ were steamed 4 hours down.X-ray analysis shows, the AlPO during beginning ₄-54 are transformed into AlPO fully ₄-8.

(c) general process according to aforementioned (a) prepares not high-purity AlPO of boracic ₄-54 samples.Filter cake is dry under air themperature humidity, to remove the water attached to the crystal outside surface.Place air furnace with still keeping the dry-eye disease that absorbs water of hydration, kept 2 hours at 440-450 ℃, x-ray analysis finds that sample has converted AlPO to ₄-8.

(d) use the 0.5mole N-Ethylbutylamine, 1.5 moles of tributylamines, 1.0 moles of H ₃PO ₄, 1.0 moles of Al ₂O ₃(Pural) and 40 mole of water be mixed with AlPO ₄-54 samples.Under in autoclave pressure, stirring in 150 ℃ of digestion and crystallizations that carry out 1 hour.X-ray analysis shows, contains 71% AlPO in the product of recovery ₄-54.

(e) repeat above-mentioned (d) preparation process partly, but digestion and crystallized temperature are 125 ℃.The AlPO of gained ₄-54 products are 100% pure basically, compare degree of crystallinity 104%, not boracic with laboratory standard.

(f) method by top (e) part prepares eight AlPO ₄-54 samples before dehydration, in different temperature, in the different time, respectively with amine acetate solution, ethanol, distilled water and boric acid solution washing, then, with each sample filtering, washing, again after the dry air, are put into 440-450 ℃ air furnace 2 hours.The analysis revealed of the similar sample of handling with boric acid solution wherein contains 918-1250ppm(wt) boron.These products are listed in the table 4 by the order of f-1-f-8.Wherein also have two sample compounds, handle with acetate and boric acid respectively again by the process preparation of top (d) part.These two samples are called as f-9 and f-10, are listed in respectively in the table 4, give the details and the product for the treatment of processes in the table.

From table 4, particularly when with routine 4(a) and routine 4(b) when comparing, can be easy to find out: the process with boric acid washing causes AlPO ₄-54 when the dewatering state calcination, and high stability is arranged.Absorbing is sample f-3, the AlPO that promptly uses ammonium acetate to handle ₄-54, boric acid still can play stabilization, thereby proof: ammonium acetate does not have what harm-only be the unable to get up function of stabilizer to crystalline structure.Handle the obvious AlPO that can suppress to form with distilled water ₄-8, but allow many AlPO ₄-54 become amorphous state.

(g) use the AlPO that synthesizes with quadrat method for two parts ₄-54 samples use acetic acid solution (pH=5.4) 80 ℃ of following processing 1.5 hours respectively, and the envrionment temperature drying is filtered, washs and used to boric acid solution (4%) then 80 ℃ of following processing 1.5 hours.With acetic acid treatment

Product is lower than the whole degree of crystallinity of the product of handling with boric acid, and only contains 54% AlPO ₄-54.The product of handling with boric acid contains 78% AlPO ₄-54.Based on degree of crystallinity, the product of acetic acid treatment contains 61% AlPO ₄-8, the product that boric acid is handled contains 43%AlPO ₄-8, illustrate in the time of 80 ℃ and handle optimum stable with boric acid, act on too high.

Claims (9)

1, stable APMS-54 crystalline molecular sieve has the X-ray powder diffraction pattern of the d-spacing that table 2 proposes at least, and contains the boron that adds of 6ppm (wt) at least.

2, by the said stable APMS-54 crystalline molecular sieve of claim 1, the content that adds boron is at least 150ppm(wt).

3, by the stable APMS-54 composition of claim 1 or 2, at anhydrous state, the chemical constitution of representing by the mol ratio of oxide compound is:

Al ₂O ₃∶1±0.2P ₂O ₅

4, have chemical constitution by claim 1,2 or 3 stable APMS-54 composition:

mR∶（QwAlxPySiz）O ₂

Here " Q " represents a kind of element " QO that at least one exists with the network oxide unit ⁿ ₂",

Index " n " value-3 ,-2 ,-1,0 or+1; At least a organic formwork agent in " R " expression crystal microcellular system; " m " expression is to every mole of (QwAlxPySiz) O ₂, the molar weight of " R ", it is worth by 0-0.3; " w ", " x ", " y " and " z " represent network oxide structural unit QO respectively n ₂, AlO ₂, PO ₂And SiO ₂Molar fraction, said molar fraction limits by following formula:

(w+z)=the 0-98%(mol ratio)

The y=0-99%(mol ratio)

The x=0-99%(mol ratio)

" Q " is further specific for having molecular weight greater than 20 element, and " T-O " distance of indication is 1.51 in the tetrahedral oxide structure

-2.06

5, by the stable APMS-54 of claim 4, when when being higher than 1000 ℃ of calcination, compound loses " R " part at least.

6, by claim 4 or 5 stable APMS-54 composition, " Q " represents at least a in this group element of Mg, Mn, Fe, Co and Zn.

7, by the stable APMS-54 aluminophosphate composition of claim 4 or 5, wherein " w " value is 0.

8, stablize APMS-54 crystal phosphoric acid aluminum compound, prevent the method for the thermal induction conversion of network structure, the X-ray powder diffraction pattern that said composition has, at least contain the d value that has in the table 2, at 20-90 ℃ composition is contacted with boric acid or borate, make 6ppm(wt at least) boron enter the APMS-54 composition, the boron-containing compositions that reclaims stablely.

9, by the method for claim 8, APMS-54 is AlPO here ₄-54 or MeAPO-54, " Me " represents at least a in Mg, Mn, Zn, Co or one group of metal of Fe.