CN102099117B

CN102099117B - Synthesis of chabazite-containing molecular sieves and their use in the conversion of oxygenates to olefins

Info

Publication number: CN102099117B
Application number: CN2009801283382A
Authority: CN
Inventors: M·M·默滕斯; S·N·沃恩; 曹光; L·R·M·马滕斯; M·阿费沃尔基
Original assignee: Exxon Chemical Patents Inc
Current assignee: ExxonMobil Chemical Patents Inc
Priority date: 2008-07-25
Filing date: 2009-06-03
Publication date: 2013-03-27
Anticipated expiration: 2029-06-03
Also published as: CN102099117A

Abstract

In a method of synthesizing a silicoaluminophosphate molecular sieve having 90%+ CHA framework type character, a reaction mixture is prepared comprising first combining a reactive source of aluminum with a reactive source of phosphorus to form a primary mixture that is aged. A reactive source of silicon and a template for directing the formation of the molecular sieve can then be added to form a synthesis mixture. Crystallization is then induced in the synthesis mixture. Advantageously, (i) the source of silicon comprises an organosilicate, (ii) the source of phosphorus optionally comprises an organophosphate, and (iii) the crystallized silicoaluminophosphate molecular sieve has a crystal size distribution such that its average crystal size is not greater than 5 [mu]m. The molecular sieve can then preferably be used in a hydrocarbon (oxygenates-to-olefins) conversion process.

Description

Contain molecular sieve synthetic of chabasie and they in the application of oxygenate to the conversion of olefines

Invention field

The present invention relates to contain the synthetic of Chabazite-type molecular sieve, and they are in oxygenate, particularly methanol conversion becomes alkene, particularly the application in ethene and/or the propylene.

Background of invention

Oxygenate to the conversion of alkene (OTO) is the theme of further investigation at present, because it has the potential that substitutes long-standing steam cracking technology (it is to produce now the ethene of world scale quantity and the industrial standard of propylene).The very large volume that relates to shows that there is significant economic motivation in the alternative technologies for the high-throughput of light olefin can be provided in the effective mode of cost.Although steam cracking depends on the non-selective induced reactions of the hydrocarbon of naphtha range under unusual high-temperature, OTO has utilized catalysis and the micro-structural performance of acidic molecular sieve under relatively mild temperature conditions, to be got ethene and the propylene of high yield by Methanol.

The existing understanding of OTO reaction has been hinted the sequence of a complexity, wherein can determine three main steps: the induction period that (1) causes activated carbon pond (alkyl-aromatic compounds) to form, (2) alkylation-removal of alkylation reaction of these reactive intermediates, obtain product, and the building up of (3) fused rings aromatic compounds.Therefore, OTO is that wherein catalyst is in the intrinsic temporary chemical transformation of continuous variable condition.Catalyst keeps the ability of high olefin productive rate to depend on fine equilibrium between the relative speed that said process carries out for a long time.The formation of coke shape molecule is very important, because gathering of they affects desirable reaction sequence in many ways.Especially, coke so that the carbon pond be inertia, reduce reactant and product diffusion rate, increase undesirable side reaction may with the limiting catalyst life-span.

Over the last couple of decades, many catalysis materials are determined and can be used for carrying out the OTO reaction.Crystalline molecular sieve is current preferred catalyst, because they have solved acidity and the form requirement of reaction simultaneously.Particularly preferred material is 8 yuan of ring aluminosilicates, for example has those of chabasie (CHA) framework type, and the aluminate or phosphate of CHA framework type (AlPO) and silicoaluminophosphate (SAPO), for example SAPO-34.

Chabasie is to have approximate expression Ca ₆Al ₁₂Si ₂₄O ₇₂Naturally occurring zeolite.The chabasie of three kinds of synthesized forms is described in " Zeolite Molecular Sieves ", D.W.Breck, and 1973 by John Wiley ﹠amp; Sons publishes.Described three kinds of synthesized forms by the Breck report are to be described in J.Chem.Soc., p.2822 (1956), the zeolite among the people such as Barrer " K-G "; Be described in the zeolite D in the British Patent No. 868,846 (1961); Be described in U.S. Patent number 3,030, the zeolite R in 181 (1962).Zeolite K-G has 2.3: 1-4.15: 1 silica: alumina molar ratio, and zeolite D and R have respectively 4.5: 1-4.9: 1 and 3.45: 1-3.65: 1 silica: alumina molar ratio.

At U.S. Patent number 4,440, in 871, a variety of SAPO materials synthetic of various framework types described with many specific embodiments.With some specific embodiments a large amount of possible organic formwork agents is disclosed also.In described specific embodiment, the material of many CHA framework types has been described.The mixture of having reported use tetraethylammonium hydroxide (TEAOH) or isopropylamine or TEAOH and di-n-propylamine (DPA) prepares SAPO-34 as template.Also disclose and used cyclohexylamine to prepare the specific embodiment of SAPO-44.Although described other template material, there is not other template to be specified the SAPO that is suitable for preparing the CHA framework type.

U.S. Patent number 6,162,415 disclose synthesizing silicoaluminophosphamolecular molecular sieves SAPO-44 in the presence of the indicator that comprises cyclohexylamine or hexamethylene ammonium salt such as chlorination cyclohexyl ammonium or brominated hexyl ammonium, and it has the CHA framework type.

The silicoaluminophosphate that special hope has the CHA framework type of low silicon content is used for methyl alcohol to olefin process.Therefore, the people such as Wilson, Microporous and MesoporousMaterials, 29,117-126,1999 reports, having lower Si content is useful for methyl alcohol to olefine reaction, particularly reduces the effect that propane formed and reduced catalysqt deactivation because low Si content has.

U.S. Patent number 6,620,983 disclose the preparation silicoaluminophosphamolecular molecular sieve, particularly has the method less than the silicoaluminophosphamolecular molecular sieve of the low silica of 0.5 Si/Al atomic ratio, the method comprises: formation comprises aluminium source, silicon source, phosphorus source, at least a organic formwork agent, at least a reactant mixture that comprises two or more fluoro substituents and the compound of fluorine ion can be provided, and makes silicoaluminophosphamolecular molecular sieve from described reactant mixture crystallization.Suitable organic formwork agent allegedly comprises one or more in the following material: tetraethylammonium hydroxide, phosphoric acid etamon, fluoridize etamon, teabrom, tetraethyl ammonium chloride(TEAC, acetic acid etamon, di-n-propylamine, isopropylamine, cyclohexylamine, morpholine, methyl butyl amine, morpholine, diethanol amine and triethylamine.In an embodiment, by with 18 hours reactant mixture being heated to 170 ℃ and then mixture is remained on this temperature 18 hours to carrying out crystallization over 4 days.

U.S. Patent number 6,793,901 disclose a kind of method for preparing the microporous silicon aluminophosphate molecular sieve with CHA framework type, the method comprises: (a) form and comprise aluminium source, silicon source, phosphorus source, optional at least a fluoride sources and at least aly to comprise one or more N, the reactant mixture of the template of N-dimethylamino base section, (b) make silicoaluminophosphamolecular molecular sieve from described reactant mixture crystallization, and (c) reclaim silicoaluminophosphamolecular molecular sieve from described reactant mixture.Suitable template allegedly comprises one or more in the following material: N, N-dimethylethanolamine, N, N-dimethyl butyrate hydramine, N, N-dimethyl-g hydramine, N, N-Exxal8 amine, N, N-dimethyl-ethylenediamine, N, N-dimethylated propyl diethylenetriamine, N, N-diamine dimethyl butyrate, N, N-dimethyl-g diamines, N, N-dimethyl hexamethylene diamine, or dimethylethyl amine, dimethyl propyl amine, dimethyl heptyl amine and dimethyl hexyl amine.When in the presence of fluorine ion, carrying out, the synthetic silicoaluminophosphamolecular molecular sieve that has effectively made the low silica of the Si/Al atomic ratio with 0.01-0.1.In an embodiment, carried out crystallization in 1-5 days by reactant mixture being heated to 170-180 ℃.

U.S. Patent number 6,835,363 disclose a kind of method of microporous crystalline silico-alumino-phosphate molecular sieve of the CHA of preparation framework type, the method comprises: the reactant mixture that comprises alumina source, phosphate source, silica source, hydrogen fluoride and organic formwork agent (a) is provided, and described organic formwork agent comprises the compound of one or more formulas (I):

(CH ₃) ₂N-R-N(CH ₃) ₂

Wherein R is the alkyl of 1-12 carbon atom; (b) make silicoaluminophosphate from the reactant mixture crystallization; (c) reclaim silicoaluminophosphamolecular molecular sieve.Suitable template allegedly comprises one or more in lower group: N, N, N ', N '-tetramethyl-1,3-propane diamine, N, N, N ', N '-tetramethyl-Putriscine, N, N, N ', N '-tetramethyl-1,3-butanediamine, N, N, N ', N '-tetramethyl-1, the 5-pentanediamine, N, N, N ', N '-tetramethyl-1, the 6-hexamethylene diamine, N, N, N ', N '-tetramethyl-1,7-heptamethylene diamine, N, N, N ', N '-tetramethyl-1,8-octamethylenediamine, N, N, N ', N '-tetramethyl-1,9-nonamethylene diamine, N, N, N ', N '-tetramethyl-1,10-decamethylene diamine, N, N, N ', N '-tetramethyl-1,11-hendecane diamines and N, N, N ', N '-tetramethyl-1,12-dodecane diamines.In an embodiment, carried out crystallization in 4-48 hour by reactant mixture being heated to 120-200 ℃.

U.S. Patent number 7,247,287 disclose and have used the synthetic silicoaluminophosphamolecular molecular sieve with CHA framework type of the indicator with following formula:

R ¹R ²N-R ³

R wherein ¹And R ²Be independently selected from the alkyl with 1-3 carbon atom and the hydroxy alkyl with 1-3 carbon atom and R ³Be selected from optional by 1-3 the 4-8 unit cycloalkyl with alkyl replacement of 1-3 carbon atom, with have the heteroatomic 4-8 of 1-3 unit heterocyclic radical, described heterocyclic radical is optional to be replaced by 1-3 the alkyl with 1-3 carbon atom, and the hetero atom in the described heterocyclic radical is selected from O, N and S.Preferably, indicator is selected from N, N-dimethyl cyclohexyl amine, N, N-dimethyl-methyl cyclohexylamine, N, N-dimethyl cyclopentamine, N, N-dimethyl-methyl cyclopentamine, N, N-dimethyl cycloheptylamine, N, N-dimethyl-methyl cycloheptylamine, and most preferably be N, the N-dimethyl cyclohexyl amine.Carry out under the synthetic existence that can be in or be not in fluorine ion, and in an embodiment, carried out crystallization in 3-7 days by reactant mixture being heated to 180 ℃.

According to the present invention, find beyond expectationly, in the prescription of silicoaluminophosphamolecular molecular sieve, whether inorganic or organic the interpolation order of synthetic mixture component and relative homogeneity and some synthetic mixture component be, can improve the performance of some hope, for example reduce the crystalline size of product, still keep acceptable product yield simultaneously.Interesting ground, opposite with inorganic source, the organosilicon source and randomly the use of organic phosphorus sources can promote the synthetic mixture component more closely/reactive combination, and seemingly prepare the strong mode of synthetic mixture, preferably cause more desirable molecular sieve product.

Summary of the invention

In one aspect, the present invention relates to a kind of method for preparing the silicoaluminophosphamolecular molecular sieve of tool crystalline size likely, the method comprises: (a) phosphorus source and aluminium source are merged, randomly merge with the liquid mixture medium, to form the first mixture; (b) with described the first mixture aging one section ageing time under aging condition, described ageing time and aging condition are enough to allow the homogenizing of described the first mixture, and the physical-chemical between described phosphorus source and described aluminium source interacts, or both; (c) with silicon source, at least a organic formwork agent and randomly other liquid mixture medium add in described the first aging mixture, to form synthetic mixture; (d) under crystallization temperature, induce show 90% or the silicoaluminophosphamolecular molecular sieve of larger CHA framework type feature by described synthetic mixture crystallization, wherein said silicon source comprises organic esters of silicon acis and described phosphorus source randomly comprises organophosphorus ester, and the aluminophosphate molecular sieve of wherein said crystallization has so that its average crystalline size is not more than the crystal size distribution of 5 μ m.

On the other hand, the present invention relates to a kind of hydrocarbon be changed into the method for alkene, it comprises: (a) prepare silicoaluminophosphamolecular molecular sieve according on the one hand method before the present invention; (b) described silicoaluminophosphamolecular molecular sieve is mixed with the silicoaluminophosphamolecular molecular sieve carbon monoxide-olefin polymeric that comprises from least 10% to 50% molecular sieve with binding agent and optional host material; (c) described carbon monoxide-olefin polymeric and hydrocarbon charging are contacted being enough to make described hydrocarbon feedstock conversion to become mainly to comprise under the condition of product of one or more alkene.

On the other hand, the present invention relates to a kind of formation based on the method for the polymer product of alkene, it comprises: (a) method according to first aspect present invention prepares silicoaluminophosphamolecular molecular sieve; (b) described silicoaluminophosphamolecular molecular sieve is mixed with the silicoaluminophosphamolecular molecular sieve carbon monoxide-olefin polymeric that comprises from least 10% to 50% molecular sieve with binding agent and optional host material; (c) described carbon monoxide-olefin polymeric and hydrocarbon charging are contacted being enough to make described hydrocarbon feedstock conversion to become mainly to comprise under the condition of product of one or more alkene; (d) make at least a in described one or more alkene, randomly with one or more other comonomers with randomly in the presence of polymerization catalyst, polymerization under being enough to form based on the condition of (being total to) polymer of alkene.

Brief description of drawings

Fig. 1 has shown X-ray diffraction (XRD) analysis according to the molecular sieve of comparative example A's 1 preparation.

Fig. 2 has shown the SEM microphoto according to the molecular sieve of comparative example A's 1 preparation.

Fig. 3 has shown the XRD analysis according to the molecular sieve of comparative example A's 2 preparations.

Fig. 4 has shown the SEM microphoto according to the molecular sieve of comparative example A's 2 preparations.

Fig. 5 has shown the XRD analysis according to the molecular sieve of embodiment 1 preparation.

Fig. 6 has shown the SEM microphoto according to the molecular sieve of embodiment 1 preparation.

Fig. 7 has shown the XRD analysis according to the molecular sieve of embodiment 2 preparations.

Fig. 8 has shown the SEM microphoto according to the molecular sieve of embodiment 2 preparations.

Fig. 9 has shown the SEM microphoto according to the molecular sieve of embodiment 3 preparations.

Figure 10 has shown the SEM microphoto according to the molecular sieve of embodiment 4 preparations.

Figure 11 has shown the SEM microphoto according to the molecular sieve of Comparative Examples B1 preparation.

Figure 12 has shown the SEM microphoto according to the molecular sieve of embodiment 5 preparations.

Figure 13 has shown the SEM microphoto according to the molecular sieve of embodiment 6 preparations.

Figure 14 has shown the SEM microphoto according to the molecular sieve of embodiment 14 preparations.

Figure 15 has shown according to the present invention, has adopted Si/Al in different silica source and the different synthetic mixture ₂Productive rate chart than the product for preparing.

The detailed description of embodiment

Described herein is synthetic containing to have 90% or the crystalline aluminium phosphate of the molecular sieve of larger CHA framework type feature or the method for silicoaluminophosphate, react the especially application of oxygenate to the conversion of light olefin in organic transformation as catalyst with the molecular sieve of gained.

Especially, find, in Zeolite synthesis by adopting specific component interpolation order (namely at first merging phosphorus source and aluminium source) and by introducing some organic source (for example organosilicon acid esters and randomly organophosphorus ester in addition), can make the crystalline size that tool reduces hopefully (for example 5 microns or less, rather than above 10 microns), contain 90% or the molecular sieve of larger CHA framework type.

In a preferred embodiment, the interpolation of (namely in step (a)) component order may be important in the mixture, and can advantageously be conditioned, so that better uniformity for example to be provided.For example, step (a) can preferably include: (i) described phosphorus source and described aluminium source are merged, randomly merge with the liquid mixture medium, to form the first mixture; (ii) with described the first mixture in (for example under aging temperature) under the aging condition aging one section ageing time, described ageing time and aging condition preferably are enough to allow the homogenizing of described the first mixture, physical-chemical between described phosphorus source and described aluminium source interacts, or both; (iii) with described silicon source, described at least a organic formwork agent and randomly other liquid mixture medium add in described the first aging mixture, to form described synthetic mixture.In some situation of this embodiment, in step (iii), adding described at least a organic formwork agent (structure indicator or SDA) before, described silicon source and described the first mixture are merged.Advantageously, described the first mixture and described silicon source can merge a period of time to form the second mixture under certain condition (for example temperature), described condition and time preferably are enough to allow the homogenizing of described the second mixture, physical-chemical between described silicon source and described the first mixture interacts, or both; Afterwards with described at least a organic formwork agent and its merging.

When a kind of component is added in the mixture when allowing homogenizing and/or physical-chemical to interact, ageing time and temperature are two main conditions.Although can exist various conditions to allow enough contacts to be used for homogenizing and/or interaction, but in one embodiment, when aging temperature was somewhere between 0 ℃ and 50 ℃, ageing time can advantageously be at least 5 minutes, for example at least 10 minutes, at least 15 minutes, at least 20 minutes, at least 25 minutes, at least 30 minutes, at least 45 minutes, at least 1 hour or at least 2 hours.Again, when aging temperature was somewhere between 0 ℃ and 50 ℃, ageing time can not have maximum veritably, but can be 350 hours at the most, for example at the most 300 hours, 250 hours at the most, 200 hours at the most, 168 hours at the most, 96 hours at the most, 48 hours at the most, 24 hours at the most, 16 hours at the most, 12 hours at the most, 8 hours at the most, 6 hours at the most, or 4 hours at the most, depend on the actual consideration that relates to generated time, cost efficiency, manufacturing schedule etc.

In the methods of the invention, preparation comprises the reactant mixture in aluminium source, phosphorus source, at least a organic indicator and optional silicon source.Can use any organic indicator that can indicate CHA framework type Zeolite synthesis, but common described indicator is the compound with formula (I):

R ¹R ²N-R ³ (I)

R wherein ¹And R ²Be independently selected from the alkyl with 1-3 carbon atom and the hydroxy alkyl with 1-3 carbon atom and R ³Be selected from optional by 1-3 the 4-8 unit cycloalkyl with alkyl replacement of 1-3 carbon atom, with have the heteroatomic 4-8 of 1-3 unit heterocyclic radical, described heterocyclic radical is optional to be replaced by 1-3 the alkyl with 1-3 carbon atom, and the described hetero atom in the described heterocyclic radical is selected from O, N and S.

More particularly, described organic indicator is the compound with formula (II):

(CH ₃) ₂N-R ³ (II)

R wherein ³Optional by 1-3 methyl substituted 4-8 first cycloalkyl, especially cyclohexyl.The object lesson of suitable organic indicator includes but not limited at least a in the following material: N, N-dimethyl cyclohexyl amine, N, N-dimethyl-methyl cyclohexylamine, N, N-dimethyl cyclopentamine, N, N-dimethyl-methyl cyclopentamine, N, N-dimethyl cycloheptylamine and N, N-dimethyl-methyl cycloheptylamine, especially N, the N-dimethyl cyclohexyl amine.

Be suitable for aluminium, phosphorus and the silicon source of synthetic method of the present invention normally as known in the art those, or about describing in the document of producing aluminate or phosphate and silicoaluminophosphate those.For example, the aluminium source can be the aluminum oxide (aluminium oxide) of optional hydration, aluminium salt, especially phosphate, aluminate, or their mixture.Other source can comprise aluminium colloidal sol or organic oxidation aluminium source, for example aluminium-alcohol salt such as aluminium isopropoxide.Preferred source is hydrated alumina, pseudobochmite most preferably, and it contains the Al of 75 % by weight ₂O ₃H with 25 % by weight ₂O.Typically, the phosphorus source is phosphoric acid, orthophosphoric acid especially, although can use other phosphorus source, and for example organophosphorus ester (for example tricresyl phosphate alkane ester such as triethyl phosphate) and aluminate or phosphate.When using organophosphorus ester and/or aluminate or phosphate, they exist with inorganic phosphorous sources (for example phosphoric acid) combination of in a small amount 50 % by weight of phosphorus source (namely less than) and main amount (namely at least 50 % by weight in phosphorus source) jointly usually.Suitable silicon source comprises silica, for example cataloid and pyrogenic silica, and organosilicon source such as orthosilicic acid tetraalkyl ester, preference such as tetraethyl orthosilicate (TEOS), original quanmethyl silicate (TMOS) etc. or their combination.

Although in most of embodiments, silicon, phosphorus and aluminium source be form burnt silicoaluminophosphamolecular molecular sieve of the present invention framework component only arranged, but for some embodiment; the silicon source of small scale (for example usually be no more than 10wt%, preferably be no more than 5wt%) can use one or more the source in magnesium, zinc, iron, cobalt, nickel, manganese and the chromium to replace.

In some embodiments, reactant mixture can have the mole composition in following scope:

P ₂O ₅∶Al ₂O ₃ 0.75-1.25，

SiO ₂∶Al ₂O ₃ 0.01-0.32，

H ₂O: Al ₂O ₃25-50, and

SDA∶Al ₂O ₃ 1-3，

Wherein SDA represents structure indicator (template), and wherein the mol ratio in aluminium, phosphorus and silicon source is calculated based on oxide form, no matter how (for example, no matter the phosphorus source is as phosphoric acid H for the form in the source of adding reactant mixture ₃PO ₄Or as triethyl phosphate adding reactant mixture, mol ratio is standardized into P ₂O ₅Molar equivalent).

Although reactant mixture can also comprise fluoride sources, find that the present invention does not synthesize having and can carry out in the presence of the fluorine ion yet, therefore the common preferred reactant mixture that is substantially free of fluorine ion that uses.

Typically, reactant mixture also comprises seed, to promote crystallization process.The consumption of seed can change in wide region, but reactant mixture comprises 0.01 ppm by weight-10,000 ppm by weight usually, for example the described seed of 100 ppm by weight-5,000 ppm by weight.Usually, described seed can be isostructural with desirable product, the material that namely belongs to the CHA framework type is although can use seed different structure, for example AEI, LEV, ERI, AFX or OFF framework type molecular sieve or their combination or symbiotic form.Described seed can be added by the form with the suspended substance in liquid medium such as water in the reactant mixture; In some cases, particularly have in the situation of relatively little size at seed, described suspended substance may be colloidal state.The preparation of the seed suspended substance of colloidal state and their application in Zeolite synthesis for example are disclosed on February 10th, 2000 disclosed international publication number WO 00/06493 and WO 00/06494.

The crystallization of reactant mixture under static state or stirring condition, suitable reactor vessel such as polypropylene tank or Teflon lining or stainless autoclave in carry out.In one embodiment, crystallization procedure can comprise with above 10 ℃/hour, expediently with at least 15 ℃/hours or at least 20 ℃/hours, for example with in 15 ℃ of/hour-150 ℃ of/hour scopes or the speed in 20 ℃ of/hour-100 ℃ of/hour scopes at a good pace add thermal reaction mixture to the crystallization temperature of wishing, they are usually between 50 ℃ and 250 ℃, for example in 150 ℃-225 ℃ or 150 ℃-200 ℃ scope, for example in 160 ℃-195 ℃ scope.Yet in some embodiments, the crystallization temperature of hope is at least 165 ℃ in addition, for example at least 170 ℃, and can randomly also be no more than 190 ℃, for example is no more than 185 ℃ or be no more than 180 ℃.In in these embodiments any one, when reaching desirable crystallization temperature, can stop crystallization immediately or after 5 minutes-350 hours, and can allow the reactant mixture cooling; Additionally or alternatively, crystallization can be carried out 12 hours at least before cooling, preferably at least 16 hours, for example at least 24 hours, at least 36 hours, at least 48 hours, at least 60 hours, at least 72 hours, at least 84 hours, at least 96 hours, at least 120 hours or at least 144 hours.In addition, in this embodiment, after cooling, can be by standard method such as centrifugal or filtered and recycled crystallized product, then washing and dry.

In an alternate embodiment, crystallization procedure can comprise with less than 8 ℃/hour, expediently with at least 1 ℃/hour, for example slowly add thermal reaction mixture to the crystallization temperature of wishing with the speed in 2 ℃ of/hour-6 ℃ of/hour scopes, they are usually between 50 ℃ and 250 ℃, for example in 150 ℃-225 ℃ or 150 ℃-200 ℃ scope, for example in 160 ℃-195 ℃ scope.Yet in some embodiments, the crystallization temperature of hope is at least 165 ℃ in addition, for example at least 170 ℃, and can randomly also be no more than 190 ℃, for example is no more than 185 ℃ or be no more than 180 ℃.In in these embodiments any one, when reaching desirable crystallization temperature, can be less than 10 hours immediately or at least, for example be less than in 5 hours and stop crystallization, and can allow the reactant mixture cooling.In addition, in this embodiment, after cooling, can be by standard method such as centrifugal or filtered and recycled crystallized product, then washing and dry.

Randomly, the step of described induced crystallization can under agitation be carried out.

In one embodiment, the silicoaluminophosphamolecular molecular sieve of described crystallization has so that its average crystalline size is no more than 5 μ m, preferably be no more than 3.0 μ m, for example be no more than 2.0 μ m, be no more than 1.5 μ m, be no more than 1.2 μ m, be no more than 1.1 μ m, be no more than 1.0 μ m, or be no more than the crystal size distribution of 0.9 μ m.

Term used herein " average crystalline size " about crystal size distribution should be understood to mean the measured value that obtains at representative sample or the mean value that forms together a plurality of samples of a representative sample.Average crystalline size can be measured by SEM, must measure in this case the crystalline size of at least 30 crystal, to obtain average crystalline size; And/or average crystalline size can pass through the laser light scattering particle size analyzer, the d of the sample of measuring in this case ₅₀Can represent average crystalline size.Should also be appreciated that, although many crystal that this paper relates to are quite uniformly (for example very near cube, therefore for example when in SEM, observing, almost there is not difference along between the diameter of length, height or width measure), but when by the SEM vision measurement, the longest distance of " average crystalline size " representative one of in the three-dimensional orthogonal axle (greatest length of length, width/diameter and height for example, but the diagonal in non-cube, rectangle, parallelogram, ellipse, cylindrical, truncated cone, plate shape, orbicule or the rhombus etc.).Yet, when in Particle Size Analyzer, passing through light scattering measurement, d ₅₀Be used as the report of spherical equivalent diameter, no matter the relative homogeneity of the shape of crystal and/or shape how in each sample.In some cases, the d by particle size analyzer ₅₀Value may not correspond to (not even not roughly corresponding to) by the average crystalline size of representative SEM microphoto vision measurement.Frequently, in these cases, described difference is relevant with the gathering (Particle Size Analyzer is interpreted as individual particle with it) of relatively little crystal.Derive from therein the d of Particle Size Analyzer ₅₀In the significantly different such situation of value and the average crystalline size that derives from representative SEM, described representative SEM microphoto should be the more accurately measurement of " average crystalline size ".

Preferably, the Si/Al that adds synthetic mixture ₂Than can be as far as possible near the Si/Al of the silicoaluminophosphamolecular molecular sieve of crystallization ₂Than (for example, the Si/Al in the synthetic mixture ₂Si/Al in the silicoaluminophosphamolecular molecular sieve of ratio and crystallization ₂Difference between ratio can be no more than 0.10, preferably is no more than 0.08, for example is no more than 0.07), and/or the silicoaluminophosphamolecular molecular sieve of synthetic mixture and crystallization all can have relative low Si/Al ₂Than (for example, all can preferably less than 0.30, for example be no more than 0.25 less than 0.33, be no more than 0.20, be no more than 0.15 or be no more than 0.10).

In a preferred embodiment, one or more being satisfied in below requiring: described aluminium source comprises aluminium oxide; Described phosphorus source comprises phosphoric acid and organophosphorus ester, and this organophosphorus ester comprises trialkylphosphate; Described silicon source can comprise the organosilicon acid esters that comprises orthosilicic acid tetraalkyl ester; Comprise N, the N-dimethyl cyclohexyl amine with described at least a organic formwork agent.

The product of described crystallization is aluminate or phosphate or the silicoaluminophosphate that contains CHA framework type molecular sieve, and it has and comprises at least x-ray diffraction pattern of the d spacing shown in the following table 1:

Although the molecular sieve of the normally single-phase CHA framework type of described crystallized product, but in some cases, described product can contain CHA framework type molecular sieve and for example AEI framework type molecular sieve or a small amount of commensal of other crystalline phase such as APC and/or AFI framework type molecular sieve.In one embodiment, crystallized product preferably has high as far as possible CHA framework type amount, 95%CHA framework type feature at least for example, perhaps even 100%CHA framework type feature (perhaps as far as possible close at present detectable single-phase CHA framework type feature).Not bound by theory, it is believed that CHA framework type feature (and/or the uniformity that silicon distributes in the molecular sieve frame structure that increases with increase, the silicon that namely reduces becomes the island amount) silicoaluminophosphamolecular molecular sieve in the oxygenate-to-olefin conversion reaction, particularly in the methanol to olefins conversion reaction, can advantageously show better performance (POS that for example increases, it refers to less olefine selective (primeolefin selectivity) or to the two selective of ethene and propylene; The POR that randomly increases, it refers to that less alkene is than (prime olefin ratio) or ethene and propylene ratio).

As the result of crystallization process, the crystallized product of recovery contains the organic indicator that at least a portion is used in its hole in synthetic.In a preferred embodiment, so that organic indicator is removed from molecular sieve, the mode that the active catalytic site in the micro channel of molecular sieve is opened wide to be used for contacting with charging activates.Described activation process is usually by at the temperature lower calcination in 200 ℃ of-800 ℃ of scopes in the presence of the oxygen-containing gas or heat in fact the described molecular sieve that comprises template and finish.In some cases, the heating molecular sieve may be wished in the environment with low or zero oxygen concentration.These class methods can be used in the crystal pore system and partly or entirely remove organic indicator.

In case described crystallized product is activated, it can be formulated into carbon monoxide-olefin polymeric by merging with other material of other hardness or catalytic activity being provided for final catalyst such as binding agent and/or host material.

The material that can comprise with the material of molecular screen material blend of the present invention various inertia and catalytic activity.These materials comprise composition such as kaolin and other clay, various forms of rare earth metals, other non-zeolite catalysts component, zeolite catalyst components, aluminium oxide or aluminium colloidal sol, titanium dioxide, zirconia, quartz, silica or Ludox, and their mixture.These components also reduce total catalyst cost effectively, serve as hot pond to help the catalyst heat shielding at regeneration period, make the densified and increase catalyst strength of catalyst.When with such component blend, the amount that is contained in the CHA of the containing crystalline material of the present invention in the final catalyst prod is the 10-90 % by weight of total catalyst, is preferably the 20-80 % by weight of total catalyst.

The CHA framework type crystalline material of producing by the inventive method can be used to dry gas and liquid; Be used for the selective molecular separation based on size and polar behavior; As ion-exchanger; As chemistry carrier; Be used in the gas chromatography; With in organic transformation reaction, be used as catalyst.The example that the appropriate catalytic of the CHA framework type crystalline material of describing is herein used comprises: (a) hydrocracking of heavy crude residual raw materials, ring-type raw material and other isocrackate charging, usually in the presence of the hydrogenation component of the 6th and the 8-10 family that are selected from the periodic table of elements; (b) dewaxing comprises isomerization dewaxing, with from comprise raffinate and lube base stock, usually boiling point is higher than 177 ℃ the hydrocarbon feed and selectively removes the straight chain alkane; (c) catalytic cracking of hydrocarbon feed such as naphtha, gas oil and Residual oil is usually in the presence of macropore Cracking catalyst such as zeolite Y; (d) have 2-21, the straight chain of preferred 2-5 carbon atom and branched-chain alkene oligomeric, with production can be used for fuel such as gasoline or blended into gasoline raw material and chemicals in to weight alkene; (e) alkene particularly has the isomerization of alkene, the especially n-butene of 4-6 carbon atom, to produce isoalkene; (f) lower alkane such as methane quality escalate into more higher hydrocarbon, for example ethene and benzene; (g) disproportionation of alkylaromatic hydrocarbons such as toluene is to produce dialkyl group aromatic hydrocarbon such as dimethylbenzene; (h) with the alkylation to aromatic hydrocarbon such as benzene of alkene such as ethene and propylene, to produce alkylating aromatic compounds, for example ethylbenzene and isopropylbenzene; (i) isomerization of dialkyl group aromatic hydrocarbon such as dimethylbenzene; (j) catalytic reduction of nitrogen oxide; (k) monoalkylamine and dialkylamine is synthetic.

The crystalline material of the described CHA framework type of producing by the inventive method especially, can be used as catalyst in oxygenate to the conversion of one or more alkene, particularly ethene and propylene.Term used herein " oxygenate " is defined as including but not necessarily limited to aliphatic alcohol, ether, carbonyls (aldehyde, ketone, carboxylic acid, carbonic ester etc.), and contain heteroatomic compound, for example halide, mercaptan, sulfide, amine, and their mixture.The aliphatic series part contains 1-10 carbon atom, for example 1-4 carbon atom usually.

Representational oxygenate comprises the aliphatic alcohol of lower straight or branching, their unsaturated homologue, and their nitrogen, halogen and sulfur analogs.The example of suitable oxygenate compound can be including but not necessarily limited to methyl alcohol; Ethanol; Normal propyl alcohol; Isopropyl alcohol; C ₄-C ₁₀Alcohol; Ethyl methyl ether; Dimethyl ether; Diethyl ether; Diisopropyl ether; Methyl mercaptan; Methyl sulfide; Methylamine; Ethyl mercaptan; The diethyl thioether; Diethylamine; Chloric ethane; Formaldehyde; Dimethyl carbonate; Dimethyl ketone; Acetic acid; Alkyl amine; Positive alkyl halide; Alkyl sulfide with the alkyl that comprises 3-10 carbon atom; Etc.; With their mixture.Specially suitable oxygenate compound is methyl alcohol, dimethyl ether and their mixture, and most preferably comprises methyl alcohol.Term used herein " oxygenate " only indicates the organic material as charging.The combined feed that is fed to reaction zone can comprise other compound, for example diluent.

In an embodiment of oxygenate method for transformation, make be raw material vapour phase, that comprise organic oxygenate and optional one or more diluents in reaction zone effectively contacting with the catalyst that comprises molecular sieve of the present invention under the process conditions, to produce desirable alkene.Perhaps, described method can be carried out in the vapour/liquid phase of liquid phase or mixing.When described method is carried out in the vapour/liquid phase of liquid phase or mixing, can obtain selective to product of different conversion rates and raw material, depend on catalyst and reaction condition.

When existing, diluent is normally non-reacted for raw material or molecular sieve catalyst composition, and is generally used for reducing the concentration of oxygenate in the raw material.The non-limitative example of suitable diluent comprises helium, argon gas, nitrogen, carbon monoxide, carbon dioxide, water, non-reacted alkane (alkane especially basically, for example methane, ethane and propane), basically non-reacted aromatic compounds, and their mixture.Most preferred diluent comprises water and nitrogen, and water is particularly preferred.Diluent can account for the 1mol%-99mol% of combined feed mixture.

The temperature that adopts in the oxygenate method for transformation can change in wide scope, for example is 200 ℃-1000 ℃, for example is 250 ℃-800 ℃, comprises 250 ℃-750 ℃, is 300 ℃-650 ℃ expediently, is generally 350 ℃-600 ℃, particularly 400 ℃-600 ℃.

Light olefin product will at the pressure of wide region, include but not limited to form under the pressure in self-generated pressure and the 0.1kPa-10MPa scope, although not necessarily form with optimised quantity.Expediently, described pressure can be in the scope of 7kPa-5MPa, for example in the scope of 50kPa-1MPa.If any diluent exists, aforementioned pressure does not comprise diluent, and refers to the dividing potential drop of raw material, because raw material relates to oxygenate and/or their mixture.The pressure of lower end and upper end may adversely affect selectively, conversion ratio, coking rate and/or reaction rate; Yet light olefin such as ethene and/or propylene still can form.

In a preferred embodiment, the method that hydrocarbon is changed into alkene of the present invention comprises: (a) prepare silicoaluminophosphamolecular molecular sieve according to disclosed method above; (b) described silicoaluminophosphamolecular molecular sieve is mixed with the silicoaluminophosphamolecular molecular sieve carbon monoxide-olefin polymeric with binding agent and optional host material, it typically comprises from least 10% to 50% molecular sieve; (c) described carbon monoxide-olefin polymeric and hydrocarbon charging are contacted being enough to make described hydrocarbon feedstock conversion to become mainly to comprise under the condition of product of one or more alkene, preferably to obtain at least less olefine selective of 70wt% (500 ℃ of measurements).Preferably, described hydrocarbon charging is the charging that contains oxygenate, and it comprises methyl alcohol, dimethyl ether or their combination, and described one or more alkene generally include ethene, propylene or their combination.

The raw material weight (hourly) space velocity (WHSV) (WHSV) of wide region can be used in the described oxygenate method for transformation.WHSV be defined as the charging weight of (not comprising diluent)/hour/weight of the molecular sieve catalyst (not comprising inert substance and/or filler) of total reaction volume.WHSV usually should be at 0.01hr ^-1-500hr ^-1Scope in, for example at 0.5hr ^-1-300hr ^-1Scope in, for example at 0.1hr ^-1-200hr ^-1Scope in.

The embodiment of a reality that is used for the reactor assembly of described oxygenate method for transformation is the circulating fluid bed reactor with cyclic regeneration system.For described method, fixed bed is not preferred usually, because the conversion of oxygenate-to-olefin is the process of height heat release, its requirement has several stages of intercooler or other cooling device.Because produce the low-density gas of low pressure, described reaction also causes high Pressure Drop.

Because described catalyst need to be regenerated usually continually, described reactor preferably should allow easily to take out at least a portion catalyst to regenerator, described catalyst can stand regenerating medium there, for example wrap the processing of oxygen containing gas such as air, to burn coke from catalyst, this will recover at least some catalyst activities.Usually can select the condition of temperature, oxygen partial pressure and the time of staying in the regenerator, to realize being less than 1wt%, for example be less than the coke content on the regenerated catalyst of 0.5wt%.The catalyst of at least a portion regeneration will be returned in the reactor.

In a preferred embodiment, described formation comprises based on the method for the polymer product of alkene: (a) prepare silicoaluminophosphamolecular molecular sieve according to disclosed method above; (b) described silicoaluminophosphamolecular molecular sieve is mixed with the silicoaluminophosphamolecular molecular sieve carbon monoxide-olefin polymeric with binding agent and optional host material, it comprises from least 10% to 50% molecular sieve; (c) described carbon monoxide-olefin polymeric and hydrocarbon charging are contacted being enough to make described hydrocarbon feedstock conversion to become mainly to comprise under the condition of product of one or more alkene, preferably to obtain at least less olefine selective of 70wt% (500 ℃ of measurements); (d) make at least a in described one or more alkene, randomly with one or more other comonomers and randomly (but preferably) in the presence of polymerization catalyst, polymerization under being enough to form based on the condition of (being total to) polymer of alkene.Preferably, in this preferred embodiment, described hydrocarbon charging is the charging that contains oxygenate, it comprises methyl alcohol, dimethyl ether or their combination, described one or more alkene comprise ethene, propylene or their combination usually, and described (being total to) polymer based on alkene is (being total to) polymer that contains ethene, contains (being total to) polymer of propylene, or their copolymer, mixture or blend.

Additionally or alternatively, the present invention can describe by following embodiment.

1. 1 kinds of methods that prepare the silicoaluminophosphamolecular molecular sieve of tool crystalline size likely of embodiment, the method comprises: (a) phosphorus source and aluminium source are merged, randomly merge with the liquid mixture medium, to form the first mixture; (b) with described the first mixture aging one section ageing time under aging condition, described ageing time and aging condition are enough to allow the homogenizing of described the first mixture, and the physical-chemical between described phosphorus source and described aluminium source interacts, or both; (c) with silicon source, at least a organic formwork agent and randomly other liquid mixture medium add in described the first aging mixture, to form synthetic mixture; (d) under crystallization temperature, induce show 90% or the silicoaluminophosphamolecular molecular sieve of larger CHA framework type feature by described synthetic mixture crystallization, wherein said silicon source comprises organic esters of silicon acis and described phosphorus source randomly comprises organophosphorus ester, and the aluminophosphate molecular sieve of wherein said crystallization has so that average crystalline size is not more than the crystal size distribution of 5 μ m.

The method of embodiment 2. embodiments 1, it is optional by 1-3 4 to 8 yuan of cycloalkyl with alkyl replacement of 1-3 carbon atom that wherein said at least a organic formwork agent contains (i), or (ii) have 1-3 heteroatomic 4 to 8 yuan of heterocyclic radicals, described heterocyclic radical is optional to be replaced by 1-3 the alkyl with 1-3 carbon atom, and the described hetero atom in the described heterocyclic radical is selected from O, N and S.

The method of embodiment 3. embodiments 1 or embodiment 2, wherein said at least a organic formwork agent comprises N, the N-dimethyl cyclohexyl amine.

Each method in embodiment 4. previous embodiments, the Si/Al of the silicoaluminophosphamolecular molecular sieve of wherein said crystallization ₂Compare the Si/Al of described synthetic mixture ₂Than being no more than 0.10 greatly.

Each method in embodiment 5. previous embodiments, wherein said crystallization temperature is between 150 ℃ and 200 ℃.

Each method in embodiment 6. previous embodiments, the silicoaluminophosphamolecular molecular sieve of wherein said crystallization have so that average crystalline size less than the crystal size distribution of 2.0 μ m.

Each method in embodiment 7. previous embodiments, the silicoaluminophosphamolecular molecular sieve of wherein said crystallization have so that average crystalline size less than the crystal size distribution of 1.2 μ m.

Each method in embodiment 8. previous embodiments, the wherein said step of inducing is under agitation carried out.

Each method in embodiment 9. previous embodiments wherein in step (c), before adding described at least a organic formwork agent, merges described silicon source and described the first mixture.

The method of embodiment 10. embodiments 9, wherein said the first mixture and described silicon source merge a period of time under certain condition to form the second mixture, described condition and time are enough to allow the homogenizing of described the second mixture, physical-chemical between described silicon source and described the first mixture interacts, or both; Afterwards with described at least a organic formwork agent and its merging.

Each method in embodiment 11. previous embodiments, the silicoaluminophosphamolecular molecular sieve of wherein said synthetic mixture and described crystallization all has the Si/Al less than 0.33 ₂Ratio.

Each method among embodiment 12. embodiment 1-2 and the 4-11, wherein one or more being satisfied in following the requirement: described aluminium source comprises aluminium oxide; Described phosphorus source comprises phosphoric acid and organophosphorus ester, and this organophosphorus ester comprises trialkylphosphate; Described organosilicon acid esters comprises orthosilicic acid tetraalkyl ester; Comprise N, the N-dimethyl cyclohexyl amine with described at least a organic formwork agent.

Each method in embodiment 13. previous embodiments, wherein said organosilicon acid esters comprises original quanmethyl silicate, tetraethyl orthosilicate or their combination.

Each method in embodiment 14. previous embodiments, wherein use have CHA, AEI, AFX, LEV, their commensal or the seed completing steps (b) of the framework type of their combination.

15. 1 kinds of embodiments change into the method for alkene with hydrocarbon, and it comprises: (a) prepare silicoaluminophosphamolecular molecular sieve according to each method in the previous embodiments; (b) described silicoaluminophosphamolecular molecular sieve is mixed with the silicoaluminophosphamolecular molecular sieve carbon monoxide-olefin polymeric that comprises from least 10% to 50% molecular sieve with binding agent and optional host material; (c) described carbon monoxide-olefin polymeric and hydrocarbon charging are contacted being enough to make described hydrocarbon feedstock conversion to become mainly to comprise under the condition of product of one or more alkene.

The method of embodiment 16. embodiments 15, wherein said hydrocarbon charging is the charging that contains oxygenate, it comprises methyl alcohol, dimethyl ether or their combination, and wherein said one or more alkene comprise ethene, propylene or their combination.

17. 1 kinds of formation of embodiment are based on the method for the polymer product of alkene, and it comprises: (a) prepare silicoaluminophosphamolecular molecular sieve according to each method among the embodiment 1-14; (b) described silicoaluminophosphamolecular molecular sieve is mixed with the silicoaluminophosphamolecular molecular sieve carbon monoxide-olefin polymeric that comprises from least 10% to 50% molecular sieve with binding agent and optional host material; (c) described carbon monoxide-olefin polymeric and hydrocarbon charging are contacted being enough to make described hydrocarbon feedstock conversion to become mainly to comprise under the condition of product of one or more alkene; (d) make at least a in described one or more alkene, randomly with one or more other comonomers with randomly in the presence of polymerization catalyst, polymerization under being enough to form based on the condition of (being total to) polymer of alkene.

The method of embodiment 18. embodiments 17, wherein said hydrocarbon charging is the charging that contains oxygenate, it comprises methyl alcohol, dimethyl ether or their combination, wherein said one or more alkene comprise ethene, propylene or their combination, and wherein said (being total to) polymer based on alkene is (being total to) polymer that contains ethene, (being total to) polymer that contains propylene, or their copolymer, mixture or blend.

Referring now to following examples and accompanying drawing the present invention is described more specifically.

Embodiment

Following analytical technology belongs to the technology that derives from each sample of embodiment for sign.

ICP-OES

Use ICP-OES (inductively coupled plasma-optical emission spectroscopy determination method) to carry out elementary analysis.Sample is dissolved in the acid blend and in deionized water dilutes.Use reference material (usually at least 3 reference materials and a blank) calibration instrument (deriving from the Simultaneous VISTA-MPX of Varian) of commercially available acquisition.The power that uses is 1.2kW, and plasma flow is 13.5L/min, and sprayer pressure is 200kPa for all circuits.The result represents with wt% or ppm by weight (wppm), and described numerical value is recalculated into Si/Al ₂Mol ratio.

XRD

Use in two X-ray diffraction meters: STOE Stadi-P CombiTransmission XRD and the Scintag X2 ReflectionXRD with optional rotary sample.Use Cu-K _αRay.Usually use the step-length of 0.2 ° of 2 Θ and 1 hour Measuring Time.

SEM

Use JEOL JSM-6340F field emission rifle SEM (SEM), under 2kV and 12 μ A, operate.Before the measurement, sample dispersion in ethanol, is carried out ultrasonic processing 5-30 minute, be deposited on the SEM sample holder, and lower dry in environment temperature and pressure (20-25 ℃ and 101kPa).If measure average particle size particle size based on the SEM microphoto, usually at least 30 crystal measured.Under the situation of approximate cube crystal, mean value is based on the size on a limit of each crystal.

PSA

The Mastersizer APA2000 that derives from Malvern Instruments Limited of 4mW laser beam is equipped with in use, carries out grain size analysis based on the laser light scattering of the particle of random movement in liquid medium.Sample to be measured under processing, continuous ultrasound is dispersed in water, to guarantee suitable dispersion.The pump speed that adopts is 2000RPM, and agitator speed is 800RPM.The parameter that is used for operation sequence is: refractive index=1.544, absorptivity=0.1.Use " susceptibility (general purpose-enhanced sensitivity) that general purpose strengthens " the model calculation.The result is with d ₅₀Expression this means that the particle of 50vol% is worth less than this.The mean value of at least 2 measurements of at least 10 seconds of report delay.

The comparative example A 1

Has 0.15SiO according to following program preparation ₂: P ₂O ₅: Al ₂O ₃: 1.5DMCHA: 40H ₂The mole composition of O and the synthetic mixture of 100wt ppm (wppm) seed.By with phosphoric acid [Acros, 85%] and hydration and prepare phosphoric acid solution.The Condea Pural SB[Sasol that adds appropriate amount in this solution, 74.2wt%Al ₂O ₃], and described slurries were stirred 10 minutes at 10 ℃.The Ludox AS40[that adds appropriate amount in this mixture contains 40 % by weight SiO ₂, with the Ludox of ammonium stabilisation, derive from Grace NV], and described slurries were stirred 10 minutes at 10 ℃ again.Then add the dimethyl cyclohexyl amine [deriving from the DMCHA of Purum Fluka, 99%] of appropriate amount.This mixture was stirred 10 minutes, then add seed (SAPO-34 seed).Final mixture is transferred in the autoclave, it was stirred 2 hours in that approximately room temperature (20-25 ℃) is lower, then under agitation be heated to 170 ℃ with the rate of heat addition of 40 ℃/hr.After this temperature keeps 72 hours, autoclave is cooled to about room temperature, and with solids with the demineralized water washing with 120 ℃ of dryings.Determine productive rate by the solids of the drying of weighing and with this weight divided by the weight of initial synthetic mixture.The productive rate that so calculates is 12.5wt%.The phase purity of sample is determined by X-ray diffraction.Owing to be presented at peak listed in the table 1, this sample contains the CHA framework, but also contains the peak of the indication AFI framework of significant quantity.XRD figure is presented among Fig. 1.Record SEM microphoto (Fig. 2), and crystalline size is estimated as 10 μ m.

The comparative example A 2

Has 0.15SiO according to following program preparation ₂: 0.75P ₂O ₅: Al ₂O ₃: 1.5DMCHA: 40H ₂The mole composition of O and the synthetic mixture of 100wt ppm seed.By with phosphoric acid [Acros, 85%] and hydration and prepare phosphoric acid solution.The Condea Pural SB[Sasol that adds appropriate amount in this solution, 74.2wt%Al ₂O ₃], and described slurries were stirred 10 minutes at 10 ℃.The Ludox AS40[that adds appropriate amount in this mixture contains 40 % by weight SiO ₂, with the Ludox of ammonium stabilisation, derive from Grace NV], and described slurries were stirred 10 minutes at 10 ℃ again.Then add the dimethyl cyclohexyl amine [deriving from the DMCHA of Purum Fluka, 99%] of appropriate amount.This mixture was stirred 10 minutes, then add seed (SAPO-34 seed).Final mixture is transferred in the autoclave, it was approximately being stirred 2 hours under the room temperature, then under agitation be heated to 170 ℃ with the rate of heat addition of 40 ℃/hr.After this temperature keeps 72 hours, autoclave is cooled to about room temperature, and with solids with the demineralized water washing with 120 ℃ of dryings.Determine productive rate by the solids of the drying of weighing and with this weight divided by the weight of initial synthetic mixture.The productive rate that so calculates is 14.9wt%.The phase purity of sample is determined by X-ray diffraction, and feature is the d spacing shown in the table 1 basically.XRD figure is presented among Fig. 3.Record SEM microphoto (Fig. 4), and crystalline size is estimated as 10 μ m or less.

Embodiment 1

Has 0.15SiO according to following program preparation ₂: P ₂O ₅: Al ₂O ₃: 1.5DMCHA: 40H ₂The mole composition of O and the synthetic mixture of 100wt ppm seed.By with phosphoric acid [Acros, 85%] and hydration and prepare phosphoric acid solution.25% of this phosphoric acid solution is taken out, and add triethyl phosphate [TEP, 99.8+% the derive from Aldrich] replacement of corresponding mole.The Condea Pural SB[Sasol that adds appropriate amount in this solution, 74.2wt%Al ₂O ₃], and described slurries were stirred 10 minutes at 10 ℃.The Ludox AS40[that adds appropriate amount in this mixture contains 40 % by weight SiO ₂, with the Ludox of ammonium stabilisation, derive from Grace NV], and described slurries were stirred 10 minutes at 10 ℃ again.Then add the dimethyl cyclohexyl amine [deriving from the DMCHA of Purum Fluka, 99%] of appropriate amount.This mixture was stirred 10 minutes, then add seed (SAPO-34 seed).Final mixture is transferred in the autoclave, it was approximately being stirred 2 hours under the room temperature, then under agitation be heated to 170 ℃ with the rate of heat addition of 40 ℃/hr.After this temperature keeps 72 hours, autoclave is cooled to about room temperature, and with solids with the demineralized water washing with 120 ℃ of dryings.Determine productive rate by the solids of the drying of weighing and with this weight divided by the weight of initial synthetic mixture.The productive rate that so calculates is 15.5wt%.The phase purity of sample is determined by X-ray diffraction, and feature is the d spacing shown in the table 1 basically.XRD figure is presented among Fig. 5.Record SEM microphoto (Fig. 6), and crystalline size is confirmed as 5 μ m or less.

Embodiment 2

Has 0.15SiO according to following program preparation ₂: P ₂O ₅: Al ₂O ₃: 1.5DMCHA: 35H ₂The mole composition of O and the synthetic mixture of 100wt ppm seed.By with phosphoric acid [Acros, 85%] and hydration and prepare phosphoric acid solution.The 25mol% of this phosphoric acid solution is taken out.The Condea Pural SB[Sasol that adds appropriate amount in this solution, 74.2wt%Al ₂O ₃], and described slurries were stirred 10 minutes at 10 ℃.The Ludox AS40[40 % by weight SiO that adds appropriate amount in this mixture ₂, derive from Grace NV], and described slurries were stirred 10 minutes at 10 ℃ again.Then add the dimethyl cyclohexyl amine [deriving from the DMCHA of Purum Fluka, 99%] of appropriate amount.Add triethyl phosphate [TEP, 99.8+% derive from Aldrich] in this mixture, its mole is corresponding to the phosphoric acid of described taking-up.This mixture was stirred 10 minutes, then add seed (SAPO-34 seed).Final mixture is transferred in the autoclave, it was approximately being stirred 2 hours under the room temperature, then under agitation be heated to 170 ℃ with the rate of heat addition of 40 ℃/hr.After this temperature keeps 72 hours, autoclave is cooled to about room temperature, and with solids with the demineralized water washing with 120 ℃ of dryings.Determine productive rate by the solids of the drying of weighing and with this weight divided by the weight of initial synthetic mixture.The productive rate that so calculates is 13.8wt%.The phase purity of sample is determined by X-ray diffraction, and feature is the d spacing shown in the table 1 basically.XRD figure is presented among Fig. 7.Record SEM microphoto (Fig. 8), and crystalline size is confirmed as 5 μ m or less.

Embodiment 3

Has 0.15SiO according to following program preparation ₂: P ₂O ₅: Al ₂O ₃: 1.5DMCHA: 40H ₂The mole composition of O and the synthetic mixture of 100wt ppm seed.By with phosphoric acid [Acros, 85%] and hydration and prepare phosphoric acid solution.The 25mol% of this phosphoric acid solution is taken out.The Condea Pural SB[Sasol that adds appropriate amount in this solution, 74.2wt%Al ₂O ₃], and described slurries were stirred 10 minutes at 10 ℃.The tetraethyl orthosilicate [TEOS, 98%, derive from Aldrich] that adds appropriate amount in this mixture, and described slurries were stirred 10 minutes at 10 ℃ again.Then add the dimethyl cyclohexyl amine [DMCHA, 99%, derive from PurumFluka] of appropriate amount.Add triethyl phosphate [TEP, 99.8+% derive from Aldrich] in this mixture, its mole is corresponding to the phosphoric acid of described taking-up.This mixture was stirred 10 minutes, then add seed (SAPO-34 seed).Final mixture is transferred in the autoclave, it was approximately being stirred 2 hours under the room temperature, then under agitation be heated to 170 ℃ with the rate of heat addition of 40 ℃/hr.After this temperature keeps 72 hours, autoclave is cooled to about room temperature, and with solids with the demineralized water washing with 120 ℃ of dryings.The phase purity of sample is determined by X-ray diffraction, and feature is the d spacing shown in the table 1 basically.Record SEM microphoto (Fig. 9), and crystalline size is confirmed as less than 1 μ m.

Embodiment 4

Has 0.15SiO according to following program preparation ₂: P ₂O ₅: Al ₂O ₃: 1.5DMCHA: 35H ₂The mole composition of O and the synthetic mixture of 100wt ppm seed.By with phosphoric acid [Acros, 85%] and hydration and prepare phosphoric acid solution.The 25mol% of this phosphoric acid solution is taken out.The Condea Pural SB[Sasol that adds appropriate amount in this solution, 74.2wt%Al ₂O ₃], and described slurries were stirred 10 minutes at 10 ℃.The tetraethyl orthosilicate [TEOS, 98%, derive from Aldrich] that adds appropriate amount in this mixture, and described slurries were stirred 10 minutes at 10 ℃ again.Then add the dimethyl cyclohexyl amine [DMCHA, 99%, derive from PurumFluka] of appropriate amount.Add triethyl phosphate [TEP, 99.8+% derive from Aldrich] in this mixture, its mole is corresponding to the phosphoric acid of described taking-up.This mixture was stirred 10 minutes, then add seed (SAPO-34 seed).Final mixture is transferred in the autoclave, it was approximately being stirred 2 hours under the room temperature, then under agitation be heated to 170 ℃ with the rate of heat addition of 40 ℃/hr.After this temperature keeps 72 hours, autoclave is cooled to about room temperature, and with solids with the demineralized water washing with 120 ℃ of dryings.The phase purity of sample is determined by X-ray diffraction, and feature is the d spacing shown in the table 1 basically.Record SEM microphoto (Figure 10), as if the size of crystal relatively even, and less than 1 μ m.

Comparative Examples B1

Has 0.15SiO according to following program preparation ₂: P ₂O ₅: Al ₂O ₃: 2DMCHA: 40H ₂The mole composition of O and the synthetic mixture of 100wt ppm seed.By with phosphoric acid [Acros, 85%] and hydration and prepare phosphoric acid solution.The Condea PuralSB[Sasol that adds appropriate amount in this solution, 75.6wt%Al ₂O ₃], and described slurries were stirred 1 hour at 10 ℃.The Ludox AS40[that adds appropriate amount in this mixture contains 40 % by weight SiO ₂, with the Ludox of ammonium stabilisation, derive from Grace NV].Then add the dimethyl cyclohexyl amine [deriving from the DMCHA of Purum Fluka, 99%] of appropriate amount.This mixture was stirred 10 minutes, then add seed (SAPO-34 seed).Final mixture is transferred in the autoclave, it under agitation is heated to 170 ℃ with the rate of heat addition of 20 ℃/hr.After this temperature keeps 24 hours, autoclave is cooled to about room temperature, and with solids with the demineralized water washing with 120 ℃ of dryings.Determine productive rate by the solids of the drying of weighing and with this weight divided by the weight of initial synthetic mixture.The productive rate that so calculates is 17.2wt%.The phase purity of sample is determined by X-ray diffraction, and feature is the d spacing shown in the table 1 basically.Record SEM microphoto (Figure 11), and crystalline size is measured as average about 2.5 μ m.

Embodiment 5

Has 0.15SiO according to following program preparation ₂: P ₂O ₅: Al ₂O ₃: 2DMCHA: 40H ₂The mole composition of O and the synthetic mixture of 100wt ppm seed.By with phosphoric acid [Acros, 85%] and hydration and prepare phosphoric acid solution.The Condea PuralSB[Sasol that adds appropriate amount in this solution, 75.6wt%Al ₂O ₃], and described slurries were stirred 1 hour at 10 ℃.The tetraethyl orthosilicate [TEOS, 98%, derive from Aldrich] that adds appropriate amount in this mixture.Then add the dimethyl cyclohexyl amine [deriving from the DMCHA of Purum Fluka, 99%] of appropriate amount.This mixture was stirred 10 minutes, then add seed (SAPO-34 seed).Final mixture is transferred in the autoclave, it under agitation is heated to 170 ℃ with the rate of heat addition of 20 ℃/hr.After this temperature keeps 24 hours, autoclave is cooled to about room temperature, and with solids with the demineralized water washing with 120 ℃ of dryings.Determine productive rate by the solids of the drying of weighing and with this weight divided by the weight of initial synthetic mixture.The productive rate that so calculates is 10.5wt%.The phase purity of sample is determined by X-ray diffraction, and feature is the d spacing shown in the table 1 basically.Record SEM microphoto (Figure 12), and crystalline size is measured as average 0.4 μ m or less.

Embodiment 6

Has 0.11SiO according to following program preparation ₂: P ₂O ₅: Al ₂O ₃: 2DMCHA: 40H ₂The mole composition of O and the synthetic mixture of 400wt ppm seed.By with phosphoric acid [Acros, 85%] and hydration and prepare phosphoric acid solution.The Condea PuralSB[Sasol that adds appropriate amount in this solution, 75.6wt%Al ₂O ₃], and described slurries were stirred 1 hour at 10 ℃.The tetraethyl orthosilicate [TEOS, 98%, derive from Aldrich] that adds appropriate amount in this mixture.Then this mixture was under agitation worn out 1 hour at 10 ℃ again.Then add the dimethyl cyclohexyl amine [deriving from the DMCHA of Purum Fluka, 99%] of appropriate amount.This mixture was stirred 10 minutes, then add seed (SAPO-34 seed).Final mixture is transferred in the autoclave, it under agitation is heated to 160 ℃ with the rate of heat addition of 40 ℃/hr.After this temperature keeps 144 hours, autoclave is cooled to about room temperature, and with solids with the demineralized water washing with 120 ℃ of dryings.Determine productive rate by the solids of the drying of weighing and with this weight divided by the weight of initial synthetic mixture.The productive rate that so calculates is 6.9wt%.The phase purity of sample is determined by X-ray diffraction, and feature is the d spacing shown in the table 1 basically.Record SEM microphoto (Figure 13), and crystalline size is measured as average 0.3 μ m or less.

Embodiment 7-13

Except changing the Si/Al of synthetic mixture ₂Than outside, prepare series of samples according to the program identical with embodiment 6.All products cause feature basically to be the material of the d-spacing shown in the table 1, have 0.4 micron average crystalline size.Yield results is summarized in the table 2.

Table 2. is according to different Si/Al in the rate of heat addition that adopts 40 ℃/hr and the mixture ₂The embodiment 6-13 of ratio uses the productive rate of the product of TEOS preparation

Embodiment	Si/Al ₂	Productive rate %
			6	0.11	6.9
7	0.12	8.0
			8	0.13	8.2
9	0.14	9.2
			10	0.15	9.8
11	0.16	10.3
			12	0.17	10.6
13	0.18	10.1

Embodiment 14

Has 0.11SiO according to following program preparation ₂: P ₂O ₅: Al ₂O ₃: 2DMCHA: 40H ₂The mole composition of O and the synthetic mixture of 400wt ppm seed.By with phosphoric acid [Acros, 85%] and hydration and prepare phosphoric acid solution.The Condea PuralSB[Sasol that adds appropriate amount in this solution, 75.6wt%Al ₂O ₃], and described slurries were stirred 1 hour at 10 ℃.The tetraethyl orthosilicate [TMOS, 99%, derive from Fluka] that adds appropriate amount in this mixture.Then this mixture was under agitation worn out 1 hour at 10 ℃ again.Then add the dimethyl cyclohexyl amine [deriving from the DMCHA of Purum Fluka, 99%] of appropriate amount.This mixture was stirred 10 minutes, then add seed (SAPO-34 seed).Final mixture is transferred in the autoclave, it under agitation is heated to 160 ℃ with the rate of heat addition of 40 ℃/hr.After this temperature keeps 144 hours, autoclave is cooled to about room temperature, and with solids with the demineralized water washing with 120 ℃ of dryings.Determine productive rate by the solids of the drying of weighing and with this weight divided by the weight of initial synthetic mixture.The productive rate that so calculates is 8.6wt%.The phase purity of sample is determined by X-ray diffraction, and feature is the d spacing shown in the table 1 basically.Record SEM microphoto (Figure 14), and average crystalline size is measured as 0.3 μ m or less.

Embodiment 15-21

Except changing the Si/Al of synthetic mixture ₂Than outside, prepare series of samples according to the program identical with embodiment 14.All products cause feature basically to be the material of the d-spacing shown in the table 1, have 0.3 micron average crystalline size.Yield results is summarized in the table 2.

Table 3. is according to different Si/Al in the rate of heat addition that adopts 40 ℃/hr and the mixture ₂The embodiment 14-21 of ratio uses the productive rate of the product of TMOS preparation

Embodiment	Si/Al ₂	Productive rate %
			14	0.11	8.6
15	0.12	9.0
			16	0.13	9.1
17	0.14	10.0
			18	0.15	10.6
19	0.16	11.3
			20	0.17	11.9
21	0.18	12.5

Embodiment 22

Has 0.15SiO according to following program preparation ₂: P ₂O ₅: Al ₂O ₃: 2DMCHA: 40H ₂The mole composition of O and the synthetic mixture of 400wt ppm seed.By with phosphoric acid [Acros, 85%] and hydration and prepare phosphoric acid solution.The Condea PuralSB[Sasol that adds appropriate amount in this solution, 75.6wt%Al ₂O ₃], and described slurries were stirred 1 hour at 10 ℃.The tetraethyl orthosilicate [TEOS, 98%, derive from Aldrich] that adds appropriate amount in this mixture.Then this mixture was under agitation worn out 1 hour at 10 ℃ again.Then add the dimethyl cyclohexyl amine [deriving from the DMCHA of Purum Fluka, 99%] of appropriate amount.This mixture was stirred 10 minutes, then add seed (SAPO-34 seed).Final mixture is transferred in the autoclave, it under agitation is heated to 170 ℃ with the rate of heat addition of 40 ℃/hr.After this temperature keeps 24 hours, autoclave is cooled to about room temperature, and with solids with the demineralized water washing with 120 ℃ of dryings.Determine productive rate by the solids of the drying of weighing and with this weight divided by the weight of initial synthetic mixture.The productive rate that so calculates is 11.8wt%.Record SEM microphoto, and crystalline size is measured as average 0.5 μ m or less.Si/Al in the product that reclaims ₂Than being measured as 0.23.With the product molecular sieve granulation of embodiment 22 and 600 ℃ of calcinings 4 hours in air, and then test under the following conditions its methyl alcohol to alkene (MTO) conversion performance: 500 ℃ reaction temperature; 100 gram MeOH/ gram molecules sieves/hour WHSV; And the stagnation pressure of 25psig (273kPag).On average less olefine selective (POS) is measured as 77.8wt%.

Comparative Examples C1

Has 0.15SiO according to following program preparation ₂: P ₂O ₅: Al ₂O ₃: 2DMCHA: 40H ₂The mole composition of O and the synthetic mixture of 100wt ppm seed.By with phosphoric acid [Acros, 85%] and hydration and prepare phosphoric acid solution.The Condea PuralSB[Sasol that adds appropriate amount in this solution, 75.6wt%Al ₂O ₃], and described slurries were stirred 1 hour at 10 ℃.The Ludox AS40[that adds appropriate amount in this mixture contains 40 % by weight SiO ₂, with the Ludox of ammonium stabilisation, derive from Grace NV].After 10 minutes, add the dimethyl cyclohexyl amine [deriving from the DMCHA of Purum Fluka, 99%] of appropriate amount.This mixture was stirred 10 minutes, then add seed (SAPO-34 seed).Final mixture is transferred in the autoclave, it under agitation is heated to 170 ℃ with the rate of heat addition of 20 ℃/hr.After this temperature keeps 48 hours, autoclave is cooled to about room temperature, and with solids with the demineralized water washing with 120 ℃ of dryings.Determine productive rate by the solids of the drying of weighing and with this weight divided by the weight of initial synthetic mixture.The productive rate that so calculates is 16.5wt%.Record SEM microphoto, crystalline size typically is 2 μ m or larger.Si/Al in the product that reclaims ₂Than being measured as 0.15.With the product molecular sieve granulation of Comparative Examples C1 and 600 ℃ of calcinings 4 hours in air, and then test under the following conditions its methyl alcohol to alkene (MTO) conversion performance: 500 ℃ reaction temperature; 100 gram MeOH/ gram molecules sieves/hour WHSV; And the stagnation pressure of 25psig (273kPag).On average less olefine selective (POS) is measured as 76.5wt%.

As seeing from above embodiment and Comparative Examples, aspect crystalline size and POS (for methyl alcohol to olefine reaction) two, organosilicon source (for example esters of silicon acis of alkoxy-functional) has shown obvious advantage than inorganic silicon source (for example colloidal silica), is not so high although molecular sieve forms productive rate.And in the organosilicon source, TMOS has shown that advantageously slightly higher molecular sieve forms the crystalline size of productive rate and quite similar (or slightly less).Take from the productive rate of table 2-3 to Si/Al in the synthetic mixture ₂The chart of ratio relatively is presented among Fig. 5.

Although described with reference to particular and for example clear the present invention, it will be appreciated by the skilled addressee that the present invention is applicable to the modification that needn't illustrate in this article.Therefore, should only determine true scope of the present invention with reference to the appended claims.

Claims

1. method for preparing the silicoaluminophosphamolecular molecular sieve of tool crystalline size likely, the method comprises:

(a) with phosphorus source and aluminium source and the merging of liquid mixture medium, to form the first mixture;

(b) with described the first mixture aging one section ageing time under aging condition, described ageing time and aging condition are enough to allow the homogenizing of described the first mixture, and the physical-chemical between described phosphorus source and described aluminium source interacts, or both;

(c) with silicon source, N, N-dimethyl cyclohexyl amine organic formwork agent and randomly other liquid mixture medium add in described the first aging mixture, to form synthetic mixture; With

(d) under crystallization temperature, induce show 90% or the silicoaluminophosphamolecular molecular sieve of larger CHA framework type feature by described synthetic mixture crystallization,

Wherein said silicon source comprises organic esters of silicon acis and described phosphorus source comprises organophosphorus ester, and the silicoaluminophosphamolecular molecular sieve of wherein said crystallization has so that average crystalline size is not more than the crystal size distribution of 5 μ m.

2. the process of claim 1 wherein the Si/Al of silicoaluminophosphamolecular molecular sieve of described crystallization ₂Compare the Si/Al of described synthetic mixture ₂Than being no more than 0.10 greatly.

3. the process of claim 1 wherein that described crystallization temperature is between 150 ℃ and 200 ℃.

4. the process of claim 1 wherein that the silicoaluminophosphamolecular molecular sieve of described crystallization has so that average crystalline size less than the crystal size distribution of 2.0 μ m.

5. the process of claim 1 wherein that the silicoaluminophosphamolecular molecular sieve of described crystallization has so that average crystalline size less than the crystal size distribution of 1.2 μ m.

6. the process of claim 1 wherein that the described step of inducing under agitation carries out.

7. the process of claim 1 wherein in step (c), adding described N, before the N-dimethyl cyclohexyl amine organic formwork agent, described silicon source and described the first mixture are merged.

8. the method for claim 7, wherein said the first mixture and described silicon source merge a period of time under certain condition to form the second mixture, described condition and time are enough to allow the homogenizing of described the second mixture, physical-chemical between described silicon source and described the first mixture interacts, or both; Afterwards with described N, N-dimethyl cyclohexyl amine organic formwork agent and its merging.

9. the process of claim 1 wherein that the silicoaluminophosphamolecular molecular sieve of described synthetic mixture and described crystallization all has the Si/Al less than 0.33 ₂Ratio.

10. the process of claim 1 wherein one or more being satisfied in the following requirement: described aluminium source comprises aluminium oxide; Described phosphorus source comprises phosphoric acid and organophosphorus ester, and this organophosphorus ester comprises trialkylphosphate; Comprise orthosilicic acid tetraalkyl ester with described organosilicon acid esters.

11. the process of claim 1 wherein that described organosilicon acid esters comprises original quanmethyl silicate, tetraethyl orthosilicate or their combination.

12. the process of claim 1 wherein use have CHA, AEI, AFX, LEV, their commensal or the seed completing steps (d) of the framework type of their combination.

13. one kind changes into the method for alkene with hydrocarbon, it comprises:

(a) method according to claim 1 prepares silicoaluminophosphamolecular molecular sieve;

(b) described silicoaluminophosphamolecular molecular sieve is mixed with the silicoaluminophosphamolecular molecular sieve carbon monoxide-olefin polymeric that comprises from least 10% to 50% molecular sieve with binding agent and optional host material; With

(c) described carbon monoxide-olefin polymeric and hydrocarbon charging are contacted being enough to make described hydrocarbon feedstock conversion to become mainly to comprise under the condition of product of one or more alkene.