CN101084065A - Synthesis of silicoaluminophosphate molecular sieves - Google Patents
Synthesis of silicoaluminophosphate molecular sieves Download PDFInfo
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Abstract
In a method of synthesizing a silicoaluminophosphate molecular sieve comprising a CHA framework type material, an AEI framework type material, or a material comprising at least one intergrown phase of an AEI framework type and a CHA framework type, the amount of alkali metal present in said synthesis mixture is controlled so as to reduce the crystal size of the molecular sieve and/or to increase the AEI character of the intergrown phase.
Description
Invention field
Synthetic and the gained molecular sieve that the present invention relates to silicoaluminophosphamolecular molecular sieve is used for oxygenatedchemicals especially methanol conversion is become the especially purposes of ethene and propylene of alkene as catalyst.
Background of invention
Light olefin, ethene for example, propylene, butylene and their mixture are as the raw material of many important chemical substances of preparation and polymer.Usually, C
2-C
4Light olefin passes through petroleum refining logistics, for example C
3+ paraffinic feedstock cracking preparation.Limited in view of the supply of emulative petroleum, prepare the influence of the supply that low-cost light olefin reduced by petroleum.Therefore, the effort of exploitation light olefin production technology is goed deep on the basis of alternative materials.
The important kind that is used to prepare the alternative materials of light olefin is an oxygenatedchemicals, for example C
1-C
4Alkanol, especially methyl alcohol and ethanol; C
2-C
4Dialkyl ether, especially dimethyl ether (DME), methyl ethyl ether and diethyl ether; Dimethyl carbonate and methyl formate and their mixture.Arranged in these oxygenatedchemicals many can the preparation by fermentation by the alternate source material, or by the synthesis gas preparation derived from natural gas, petroleum liquid, carbonaceous material (comprising coal), recycled plastic, municipal waste or any organic material.Because source material various in style, alcohol, 01 derivatives and other oxygenatedchemicals are promising as the non-petroleum source material of economy that is used to prepare light olefin.
Preferably be used for oxygen-containing compound material, for example methyl alcohol changes into one or more alkene, mainly is that the method for ethene and/or propylene comprises and allows described raw material contact with the crystalline molecular sieve catalyst composition.After deliberation as among the molecular sieve of oxygenate conversion catalyst, aperture silicoaluminophosphate (SAPO), for example SAPO-34 and SAPO-18 have demonstrated exclusive prospect.SAPO-34 belongs to the molecular sieve family with zeolite group mineral chabasie (CHA) framework types, and SAPO-18 belongs to the molecular sieve family with AEI framework types.Except regular silicoaluminophosphamolecular molecular sieve, disordered structure as not only comprising AEI but also comprising the plane homobium of CHA framework types material, also is known and has shown activity as oxygenate conversion catalyst.
It is also known that the silicoaluminophosphate with smaller particle size is especially effective methanol conversion being become aspect the alkene.Therefore, for example, people such as De Chen report that the SAPO-34 crystal of 0.4-0.5 μ m produces the maximum capacity (Microporous andMesoporous Materials, 29,191-203,1999) that alkene forms.In this research, from a collection of crystal, obtain crystal, with the crystal of described a collection of crystal classification with the different size that obtains to be estimated.
U.S. Patent number 5,126,308 disclose the ELAPO molecular sieve, wherein EL is the metal that is selected from silicon, magnesium, zinc, iron, cobalt, nickel, manganese, chromium and their mixture, described molecular sieve is made up of particle, at least 50% particle size that has less than 1.0 μ m in these particles, 10% particle size that has greater than 2.0 μ m at the most, described molecular sieve shows improved selectivity and catalyst life at methyl alcohol in the catalyzed conversion of alkene.
In on June 12nd, 2003 disclosed International Patent Publication No. WO 03/048084 disclose, at methyl alcohol in the catalyzed conversion of alkene, when catalyst comprises the ELAPO molecular sieve with laminar crystal habit, obtained selectivity to the raising of ethene and propylene, wherein EL is the metal that is selected from silicon, magnesium, zinc, iron, cobalt, nickel, manganese, chromium and their mixture, and the average minimum crystal dimension of wherein said crystal is that the length-width ratio of 0.1 micron and crystal is less than or equal to 5 at least.
Therefore, for synthetic have CHA and/or AEI framework types at oxygenatedchemicals to effective silicoaluminophosphamolecular molecular sieve aspect the catalyzed conversion of alkene, importantly can not only control the skeleton structure of molecular sieve but also control its crystalline size, especially can produce the lower material of change in size that has than between small average crystalline size and each crystallite reliably.
The synthetic of silicoaluminophosphamolecular molecular sieve with CHA and/or AEI framework types comprises: the reactive sources material with silicon, phosphorus and aluminium in the presence of water and organic directed agents (especially tetraethylammonium hydroxide (TEAOH)) mixes, then this mixture is heated to crystallization temperature (normally 150 ℃-250 ℃), after this under this crystallization temperature, kept mixture 150 hours at the most.Although various suitable silicon, phosphorus and aluminium source material are obtainable, most of commercial sources materials comprise the impurity of higher level, comprise metal.For example, some commercial sources material of TEAOH comprises nearly 1.6wt% potassium and 0.05wt% sodium, and comprises the alkali metal above 0.01wt% usually as the phosphoric acid of preferred phosphorus source material.
The synthetic research of silicoaluminophosphamolecular molecular sieve shows that alkali metal (especially sodium and the potassium) level of impurity in synthetic mixture contains the material of CHA and AEI to mensuration average crystalline size and crystal size distribution have material impact.Specifically, have now found that to have average (d less than 2.2 microns
50) crystalline size and low crystal size distribution [(d
90-d
10)/d
50=＜1.0] material can be obtained by the synthetic mixture that comprises the about 0.9g alkali metal of about 0.08-/mole aluminium oxide.On the contrary, when alkali metal concn was increased to greater than 0.9g/ mole aluminium oxide, crystalline size change to increase, and under alkali metal concn drops to about 0.0 8g/ mole aluminium oxide the time, had the loss of crystalline size repeatability.
In addition, in AEI/CHA homobium synthetic, find that the level of alkali metal impurity in synthetic mixture has material impact to the composition of measuring this homobium.Therefore, when alkali metal concn in this synthetic mixture during less than 1.0g/ mole aluminium oxide, the preparation of the material of rich CHA is favourable, and the material of rich AEI tends to be prepared under the concentration of 1.0g/ mole aluminium oxide at least.
Synthesizing of silicoaluminophosphamolecular molecular sieve (comprising SAPO-34), be described in 871 at U.S. Patent number 4,440.According to this patent, in synthetic these SAPO compositions, the preferred reaction mixture is gone up the alkali-free metal cation substantially and is had the composition of representing according to following mole oxide ratio:
aR
2O∶bM
2O∶(Si
xAl
vP
z)O
2∶cH
2O
Wherein " R " is organic formwork agent, and " a " has even as big as the value of the valid density that constitutes " R " and in＞0 to 3 scope; " b " has the value of 0-2.5; " c " has 0-500, the value of preferred 2-30; " x ", " y " and " z " represent (Si respectively
xAl
yP
z) O
2Silicon in the component part, the molar fraction of aluminium and phosphorus, and have at least 0.01 value separately.Except the control of pH value, U.S. Patent number 4,440,871 do not provide the concrete reason of preferred alkali-free reactant mixture.
U.S. Patent number 5,741,751 disclose the method that is prepared silicoaluminophosphamolecular molecular sieve such as SAPO-11 by the reactant mixture of activated source material that comprises phosphorus and graininess hydrated alumina, and described graininess hydrated alumina has less than about 40 microns average particle size particle size, less than about 1.0g/cm
3Grain density and less than the alkali content of 0.12wt%.The material that does not openly prepare CHA and/or AEI framework types.
In on June 12nd, 2003 disclosed International Patent Publication No. WO 03/048042 disclose by synthetic mixture and carried out the method that hydrothermal treatment consists is made the SAPO-34 crystalline molecular sieve surfactant-free, the synthetic mixture of described surfactant-free comprises the source material of structure directing agent and silicon, aluminium and phosphorus, and wherein the source material of silicon is an orthosilicic acid tetraalkyl ester.Gained SAPO-34 crystalline molecular sieve has the average particle size particle size of 400nm at the most.
In on June 12nd, 2003 disclosed International Patent Publication No. WO 03/048043 disclose by the synthetic mixture crystallization that makes the source material that comprises aluminium, phosphorus and silicon and made average particle size particle size the silicoaluminophosphate crystalline molecular sieve of 400nm such as the method for SAPO-34 at the most, but wherein the source material of silicon in solution with water compatibility organic base.
The Application No. of submitting on April 28th, 2,003 10/425,587 disclose silicoaluminophosphamolecular molecular sieve, as the preparation methods of CHA framework types, wherein average particle size particle size is consistent is that 1 μ m or littler and particle size distribution satisfy up to 80% (on the number) particle in the scope of mean value ± 10%.This method comprises makes the source material that comprises aluminium, the source material of phosphorus, at least two kinds of organic formwork R
1And R
2, randomly the source material of silicon and the synthetic mixture crystallization of seed, wherein organic formwork (R in synthetic mixture
1+ R
2) with mol ratio≤1.25 of aluminium (Al).
U.S. Patent number 6,334,994 disclose the silicoaluminophosphamolecular molecular sieve that is called RUW-19, and it it is said that AEI/CHA mixes combined thing.U.S. Patent number 6,334, the DIFFaX of X-ray diffraction pattern of the RUW-19 of preparation the analysis showed that these materials are characterised in that the ratio of AEI/CHA is the single symbiotic form of the molecular sieve of about 60/40,65/35 and 70/30 AEI and CHA framework types among 994 the embodiment 1,2 and 3.RUW-19 is following synthetic: at first Al source material (especially isopropyl alcohol Al) is mixed with water and P source material (especially phosphoric acid), after this add especially cataloid and organic formwork material tetraethylammonium hydroxide especially of Si source material, with the preparation precursor gel.Then this gel is put into the steel autoclave, after a period of time of slaking at room temperature, this autoclave is heated to 180 ℃-260 ℃, and preferred at least 200 ℃ maximum temperature at least 1 hour is wherein shaken in the whole process of slaking and crystallization, stirring or rotary autoclave.The RUW-19 crystal of gained allegedly has the crystalline size of 0.001-10 micron.
In on September 12nd, 2002 disclosed International Patent Publication No. WO 02/70407 silicoaluminophosphamolecular molecular sieve (now being expressed as EMM-2) is disclosed, it comprises at least one symbiotic form with molecular sieve of AEI and CHA framework types, and wherein said symbiotic form has the AEI/CHA ratio of x-ray diffractogram of powder case by about 5/95-40/60 of DEFFaX assay determination of the sample of the calcination of using this molecular sieve.The synthetic of described coexisting material realized by in the presence of organic directed agents especially tetraethyl ammonium compount the reactive sources material of silicon, phosphorus and hydrated alumina being mixed.The mixture of gained is stirred and be heated to crystallization temperature, preferred 150 ℃-185 ℃, when stirring, under this temperature, kept 2-150 hour then.The crystal of gained allegedly has platy morphology, and wherein average minimum dimension is less than 0.1 micron, and maximum ratio with minimum dimension is 2-20.
Brief summary of the invention
In one aspect, the present invention relates to the synthetic method of silicoaluminophosphamolecular molecular sieve, described molecular sieve comprise the CHA framework types material, AEI framework types material or comprise the material of at least one AEI framework types and the material of the coexisting phase of the material of CHA framework types, this method comprises:
(a) preparation comprises the synthetic mixture of the source material of water, organic directed agents and phosphorus, aluminium oxide and silica, and the alkali-metal total amount that wherein is present in the described synthetic mixture is the about 0.90g/ mole of an about 0.08-aluminium oxide;
(b) described synthetic mixture is heated to about 100 ℃-about 300 ℃ crystallization temperature; With
Aptly, the alkali-metal total amount that is present in the described synthetic mixture is the about 0.80g/ mole of an about 0.08-aluminium oxide, as the about 0.50g/ mole of about 0.10-aluminium oxide.Usually, the alkali metal that is present in the described synthetic mixture is sodium and/or potassium.
In one embodiment, described silicoaluminophosphamolecular molecular sieve comprises the material of CHA framework types.
In another embodiment, described silicoaluminophosphamolecular molecular sieve comprises the material of AEl framework types.
In another embodiment, described silicoaluminophosphamolecular molecular sieve is the material of coexisting phase that comprises the material of the material of at least one AEI framework types and CHA framework types.Aptly, described at least one coexisting phase has by about 5/95-of DIFFaX assay determination about 40/60, and is about 30/70 as about 10/90-, such as the about AEI/CHA ratio of 15/95-about 20/80.
In another embodiment, described silicoaluminophosphamolecular molecular sieve comprises first and second symbiotic forms, and they have the material of AEI framework types and the material of CHA framework types separately.Aptly, described first symbiotic form has the AEI/CHA ratio by about 5/95-about 40/60 of DIFFaX assay determination, described second symbiotic form has the AEI/CHA ratio different with described first symbiotic form, for example by about 55/45, for example about 50/50 the AEI/CHA ratio of about 30/70-of DIFFaX assay determination.
In one aspect of the method, the present invention relates to the synthetic method of silicoaluminophosphamolecular molecular sieve, described molecular sieve comprises the coexisting phase of the material of the material of at least one CHA framework types and AEI framework types, wherein said at least one coexisting phase has the AEI/CHA ratio by about 5/95-about 40/60 of DIFFaX assay determination, and this method comprises:
(a) preparation comprises the synthetic mixture of the source material of water, organic directed agents and phosphorus, aluminium oxide and silica, and the alkali-metal total amount that wherein is present in the described synthetic mixture is that the mole that about 0.08-about 0.90g/ mole aluminium oxide and described mixture have in following scope is formed:
The P of about 0.6-about 1.2
2O
5: Al
2O
3,
The SiO of about 0.12-about 0.20
2: Al
2O
3,
About 25 to about 50 H
2O: Al
2O
3,
(b) under agitation described mixture is heated to about 100 ℃-about 300 ℃ crystallization temperature; With
(c) reclaim described molecular sieve.
Aptly, described synthetic mixture (a) has the mole composition in following scope:
The P of about 0.8-about 1.1
2O
5: Al
2O
3,
The SiO of about 0.12-about 0.15
2: Al
2O
3,
The H of about 3 5-about 45
2O: Al
2O
3
In yet another aspect, the present invention relates to comprise the synthetic method of silicoaluminophosphamolecular molecular sieve of coexisting phase of the material of the material of at least one CHA framework types and AEI framework types, wherein said at least one coexisting phase comprises the material by the described AEI framework types of 50wt% at least of DIFFaX assay determination, and this method comprises:
(a) preparation comprises the synthetic mixture of source material of water, organic directed agents and phosphorus, aluminium oxide and silica, and the alkali-metal total amount that wherein is present in the described synthetic mixture is formed for the mole that 1.00g/ mole aluminium oxide and described mixture at least have in following scope:
The P of about 0.6-about 1.2
2O
5: Al
2O
3,
The SiO of about 0.005-about 0.15
2: Al
2O
3,
About 10 to about 50 H
2O: Al
2O
3,
(b) under agitation described mixture is heated to about 100 ℃-about 300 ℃ crystallization temperature; With
(c) reclaim described molecular sieve.
In a further aspect, the present invention relates to by the synthetic silicoaluminophosphamolecular molecular sieve of method described here and oxygen-containing compound material is being changed into the purposes that contains in the olefin product.Aptly, described silicoaluminophosphamolecular molecular sieve has less than 2.2 microns, for example about 1.5 microns-about 1.9 microns average (d
50) crystalline size and less than 1.0 (d
90-d
10)/d
50Crystal size distribution.
The accompanying drawing summary
Fig. 1 a is the DIFFaX simulated diffraction figure with AEI/CHA coexisting phase of different AEI/CHA ratios with 1b.
The specific embodiment
The present invention relates to have AEI and/or CHA framework types silicoaluminophosphamolecular molecular sieve synthetic method and gained silicoaluminophosphamolecular molecular sieve with oxygen-containing compound material for example methanol conversion become to contain for example purposes in the product of ethene and propylene of alkene.
Molecular sieve
Crystalline molecular sieve has common angle [TO
4] tetrahedral 3 dimensions, four connection skeleton structures, wherein T is any tetrahedral coordination cation.Under the situation of silicoaluminophosphate (SAPO), skeleton structure is by [SiO
4], [AlO
4] and [PO
4] common angle tetrahedron element composition.
Molecular sieve is classified according to the IUPAC committee rule of relevant zeolite name by the International Zeolite Association structure committee.According to this classification, the zeolite of the framework types that structure has been established and the molecular sieve of zeolite type are specified three alphanumeric codes and are described in Atlas ofZeolite Framework Types, the 5th edition, Elsevier, London, among the England (2001), the document is introduced for reference at this fully.
A kind of known molecular sieve that structure has been established is the material of called after CHA, and it is the molecular sieve with the hole that is limited by two groups of vertical passages of cardinal principle, and each passage has the cross sectional dimensions of about 3.8 dusts.The material of CHA framework types comprises the mineral chabasie of natural generation, and many synthetic materials, comprises silicoaluminophosphamolecular molecular sieve, SAPO-34.The preparation of SAPO-34 and sign are reported in some publications, comprise U.S. Patent number 4,440,871; People such as J.Chen are at " Studies in Surface Science and Catalysis " the 84th volume, in the 1731-1738 page or leaf; U.S. Patent number 5,279,810; People such as J.Chen are at " Journal ofPhysical Chemistry " the 98th volume, in the 10216-10224 page or leaf (1994); People such as J.Chen are at " Catalysis Letters ", and the 28th rolls up 241-248 page or leaf (1994); People such as A.M.Prakash are at " Journal of the Chemical Society, FaradayTransactions " the 90th (15) volume, 2291-2296 page or leaf (1994); People such as Yan Xu are at " Journal of the Chemical Society, Faraday Transactions " the 86th (2) volume, in the 425-429 page or leaf (1990).CHA framework types material is known to have in that oxygenate is become and has activity and selectivity aspect the light alkene.
AEI framework types molecular sieve is similar to the CHA material, because their hole is that the passage of about 3.8 dusts defines by cross sectional dimensions.Although AEI framework types molecular sieve does not exist at occurring in nature, many aluminate or phosphate and silicoaluminophosphates with AEI framework types synthesize, and comprise SAPO-18, ALPO-18 and RUW-18.In addition, because their little pore-sizes, AEI type molecular sieve has been reported as the suitable catalyst that is used for various important chemical technologies, comprises conversion of oxygenates to olefins.For example, referring to U.S. Patent number 5,095,163, the document is hereby incorporated by.
The silicoaluminophosphamolecular molecular sieve (for example SAPO-18 and SAPO-34) of rule is made up by the constant structural unit of structure (being called the periodical configuration unit), and is that the cycle is orderly in three dimensions.Unordered structure is less than three-dimensional on the structure, promptly two, one or zero dimension on the display cycle prefaceization.It is unordered that this phenomenon is called piling up of the constant periodical configuration unit of structure.If in whole three dimensions performance period prefaceization, then the crystal structure by the periodical configuration cell formation is called the end member structure.Disordered structure be wherein periodical configuration element stack successive offset cycle prefaceization to adding up those of stacking order.
Symbiosis silicoaluminophosphamolecular molecular sieve described here is the unordered plane homobium of end member structure AEI and CHA.For AEI and CHA framework types, the periodical configuration unit is two hexa-atomic circular layers.Have two types layer " a " and " b ", they are identical on topological form except that " b " is the mirror image of " a ".When the layer of same type when piling up each other, promptly ... aaa... or ... bbb... produces framework types CHA.As layer " a " and " b " alternately the time, for example ... abab..., produce different framework types, i.e. AEI.Coexisting molecular sieve described here comprises the stacked body of layer " a " and " b ", and they comprise the zone of CHA framework types and the zone of AEI framework types.CHA is to pile up unordered or planar disfigurement to each change of AEI framework types.
Under the situation of the crystal with planar disfigurement, the explanation of X-ray diffraction pattern needs to simulate to pile up unordered influence.DIFFaX is based on the computer program that is used to calculate from the Mathematical Modeling of the intensity of the crystal that contains planar disfigurement (referring to people such as M.M.J.Tracey, Proceedings of the Royal Chemical Society, London, A[1991], the 433rd volume, the 499-520 page or leaf).DIFFaX be International Zeolite Association selected and can from its acquisition be used for simulate the simulation program of XRD powder diagram of zeolite coexisting phase (referring to " the Collection of Simulated XRD PowderPatterns for Zeolites " of M.M.J.Treacy and J.B.Higgins, 2001, the 4th edition, represent Structure Commissionof the International Zeolite Association to publish).It also is used for studying in theory the coexisting phase of AEI, CHA and KFI, and at " Studiesin Surface Science and Catalysis ", 1994, the 84 volumes are reported in the 543-550 page or leaf as people such as K.P.Lillerud.
Fig. 1 a and 1b show the simulated diffraction figure that obtains from the homobium of CHA framework types molecular sieve with various AEI/CHA ratios and AEI framework types molecular sieve.It is the diffraction pattern 15-35 (2 θ) scope in of the coexisting phase of 0/100 (CHA end member), 10/90 (AEI/CHA=0.11), 20/80 (AEI/CHA=0.25), 30/70 (AEI/CHA=0.41), 40/60 (AEI/CHA=0.67), 50/50 (AEI/CHA=1.00) and 60/40 (AEI/CHA=1.50) by the DIFFaX simulation that Fig. 1 a shows the AEI/CHA ratio.It is 0/100 (CHA end member), 10/90 (AEI/CHA=0.11), 20/80 (AEI/CHA=0.25), 50/50 AEI/CHA=1.0 that Fig. 1 b shows the AEI/CHA ratio), the coexisting phase of 70/30 (AEI/CHA=2.33), 80/20 (AEI/CHA=4.0), 100/0 (AEI end member) diffraction pattern in 5-20 (2 θ) scope by the DIFFaX simulation.With of the top normalization of all XRD diffraction patterns, promptly at the about 9.5 corresponding pure CHA (the AEI/CHA ratio is 0/100) in peak that spend 2 θ places for whole group simulation pattern.The normalization of this kind intensity level allows the mixture of quantitative assay homobium.
In coexisting phase, along with AEI increases with respect to the ratio of CHA, the intensity that can observe some peak reduces, and for example, the peak at about 2 θ=25.0 places, and the intensity at other peak improves is such as at the peak at about 2 θ=17.0 5 places with at the shoulder at 2 θ=21.2 places.The AEI/CHA ratio is that 50/50 coexisting phase that reaches above (AEI/CHA 〉=1.0) shows with about 16.9 (2 θ) to be the quant's sign at center.
In one embodiment, symbiosis silicoaluminophosphamolecular molecular sieve by the inventive method preparation is the homobium of at least a AEI framework types and CHA framework types, wherein said at least a homobium has the about 5/95-about 40/60 by the DIFFaX assay determination, about 30/70 such as about 10/90-, as the AEI/CHA ratio of about 15/85-about 20/80.The homobium of the rich CHA of this kind be characterised in that powder X-ray RD diffraction pattern (by after roasting and do not have the sample of rehydration after the roasting to obtain) in 5-25 as shown in table 1 below (2 θ) scope, have reflection at least.
Table 1
| 2θ(CuKα) |
| 9.3-9.6 |
| 12.7-13.0 |
| 13.8-14.0 |
| 15.9-16.1 |
| 17.7-18.1 |
| 18.9-19.1 |
| 20.5-20.7 |
| 23.7-24.0 |
At this X ray diffracting data that relates to is that (Scintag Inc., USA) (use copper K-alpha radiation) collected with SCINTAG X2 x-ray powder diffraction instrument.By step scan record diffraction data under becoming at 0.02 of 2 θ, wherein θ is a Bragg angle, and the gate time in each step is 1 second.Before each experiment X-ray diffraction pattern of record, sample must be in anhydrous state and not contain any its synthetic template agent that is used for, and this is that outer material of the skeleton that do not have such as water or template agent are in cavity because only use skeletal atom to calculate the simulation pattern.If silicoaluminophosphamaterial material is to water sensitive under the record temperature, according to following program after preparation with the sieve sample roasting and to keep it be anhydrous.
In baking oven, under flow of nitrogen gas, every kind of sieve sample of about 2 grams is heated to 200 ℃ with 3 ℃/minute speed from room temperature, and when keeping this nitrogen stream, with sample remain on 200 ℃ following 30 minutes, with 2 ℃/minute speed oven temperature is elevated to 650 ℃ then.Then sample is remained on 650 ℃ following 8 hours, wherein at first last 3 hours under air under nitrogen in 5 hours.With 30 ℃/minute baking oven is cooled to 200 ℃ then, in the time will writing down the XRD figure case, with sample from baking oven directly transfer to the shuttle and with the covering of Mylar paper tinsel to prevent rehydration.After removing the Mylar paper tinsel, write down under the same conditions immediately also will provide and be suitable for the diffraction pattern that DIFFaX analyzes.
In another embodiment, the symbiotic form that comprises many CHA of having and AEI framework types by the symbiosis silicoaluminophosphamolecular molecular sieve of the inventive method preparation, common wherein first symbiotic form has the AEI/CHA ratio by about 5/95-about 40/60 of DIFFaX assay determination, and second symbiotic form has the AEI/CHA ratio different with described first symbiotic form.Second symbiotic form has the about 30/70-about 55/45 by the DIFFaX assay determination usually, for example about 50/50 AEI/CHA ratio, in this case, the reflection peak in being listed in table 1, the XRD diffraction pattern shows that also with about 16.9 (2 θ) be the quant's sign at center.
In another embodiment, comprise 50wt% at least by the AEI/CHA coexisting molecular sieve of the inventive method preparation, for example the material of 75wt%AEI framework types at least by the DIFFaX assay determination.The homobium of the rich AEI of this kind is characterised in that powder X-ray RD diffraction pattern (sample by rehydration after calcining and after calcining obtains) has reflection at least in 5-25 as shown in table 2 below (2 θ) scope.
Table 2
| 2θ(CuKα) |
| 9.3-9.6 |
| 12.7-13.0 |
| 13.8-14.0 |
| 15.9-16.1 |
| 16.7-16.9 |
| 18.9-19.1 |
| 20.5-20.7 |
| 23.7-24.0 |
Preferably, the CHA framework types molecular sieve in the above-mentioned AEI/CHA homobium is that SAPO-34 and AEI framework types molecular screening are from SAPO-18, ALPO-18 and their mixture.In addition, when the symbiosis silicoaluminophosphate was the material of rich CHA, this homobium preferably had greater than 0.16 and less than 0.19, and for example approximately 0.165-is about 0.185, the framework silica/alumina molar ratio (Si/Al such as about 0.18
2).Described framework silica/alumina molar ratio is aptly by the NMR assay determination.
Molecular sieve is synthetic
AEI of the present invention and/or CHA framework types silicoaluminophosphamolecular molecular sieve are synthetic by the source material of the source material of the source material that makes aluminium oxide, phosphorus, silica and at least a organic directed agents hydrothermal crystallization.Specifically, to comprise the source material of silica, aluminium oxide and phosphorus and water, one or more organic directed agents (R) and, randomly, from another kind of or add the pressure vessel of sealing with a kind of reactant mixture of seed of framework types molecular sieve, this pressure vessel is a lining with inert plastic such as polytetrafluoroethylene (PTFE) randomly, and heats under crystallization temperature and form up to crystalline material.Usually, reactant mixture has composition in following scope with the molar ratio computing of oxide:
| Reactant | Useful | Typically |
| P 2O 5/Al 2O 3 | 0.6-1.2 | 0.75-1.1 |
| SiO 2/Al 2O 3 | 0-0.3 | 0.1-0.2 |
| H 2O/Al 2O 3 | 25-50 | 30-45 |
| R/Al 2O 3 | 0.5-1.2 | 0.7-1.0 |
When silicoaluminophosphamolecular molecular sieve comprises at least one coexisting phase with CHA framework types and AEI framework types, wherein said at least one coexisting phase has the AEI/CHA ratio by about 5/95-about 40/60 of DIFFaX assay determination, and the mole that described reactant mixture preferably has in following scope is formed:
The P of about 0.6-about 1.2
2O
5: Al
2O
3,
The SiO of about 0.12-about 0.20
2: Al
2O
3,
About 25 to about 50 H
2O: Al
2O
3
More preferably, in following scope:
The P of about 0.8-about 1.1
2O
5: Al
2O
3,
The SiO of about 0.12-about 0.15
2: Al
2O
3,
The H of about 35-about 45
2O: Al
2O
3
When silicoaluminophosphamolecular molecular sieve comprises at least one AEI/CHA coexisting phase, when this coexisting phase comprised by the material of the framework types of 50wt%AEI at least of DIFFaX assay determination, the mole that described reactant mixture preferably has in following scope was formed:
The P of about 0.6-about 1.2
2O
5: Al
2O
3,
The SiO of about 0.005-about 0.15
2: Al
2O
3,
About 10 to about 50 H
2O: Al
2O
3
The limiting examples of the silica source material that is fit to comprises silicate, vapour phase processes silica, for example, can be from Degussa Inc., New York, the Aerosil-200 that New York obtains, with CAB-O-SEL M-5, organo-silicon compound such as orthosilicic acid tetraalkyl ester, for example, original quanmethyl silicate (TMOS) and tetraethyl orthosilicate (TEOS), silica gel or its water slurry, for example can be from E.I.du Pont de Nemours, Wilmington, Ludox HS-40 colloidal sol, silicic acid or their any combination that Delaware obtains.
The limiting examples of the alumina source material that is fit to includes machine aluminium compound such as aluminium alcoholates, for example aluminium isopropoxide and inorganic aluminium source material, and as aluminum phosphate, aluminium hydroxide, sodium aluminate, pseudobochmite, zirlite and alchlor, or their any combination.Preferred source material is no machine aluminium compound such as hydrated alumina, especially boehmite and pseudobochmite.
The limiting examples of the phosphorus source material (they also can comprise the phosphorus composition that contains aluminium) that is fit to comprises phosphoric acid, organophosphorus ester such as triethyl phosphate and crystallization or amorphous aluminate or phosphate such as AlPO
4, microcosmic salt, or their combination.The preferred source material of phosphorus is a phosphoric acid.
The organic directed agents that is used for synthetic method of the present invention will depend on wants the specific silicoaluminophosphamolecular molecular sieve that synthesizes.The organic directed agents that is fit to that is used to prepare CHA framework types silicoaluminophosphamolecular molecular sieve comprises tetraethylammonium hydroxide, fluoridize etamon, isopropylamine, di-n-propylamine, cyclohexylamine, triethylamine, triethanolamine, N-methylethanolamine, N methyldiethanol amine, N, N-dimethylethanolamine, N, N,-diethyl ethylene diamine, dimethyl propanol amine, 1-(N, N-dimethylamino)-2-propyl alcohol, morpholine and their mixture.The organic directed agents that is fit to that is used to prepare AEI framework types silicoaluminophosphamolecular molecular sieve comprises tetraethylammonium hydroxide, teabrom, tetraethyl ammonium chloride(TEAC, N, N-diisopropylethylamine and their mixture.The organic directed agents that is fit to that is used to prepare symbiosis AEI/CHA framework types silicoaluminophosphamolecular molecular sieve comprises etamon based compound, especially tetraethylammonium hydroxide.
The impurity that most of commercial sources materials of the silica of listing above, aluminium oxide and phosphorus and organic directed agents comprise the level of signifiance comprises alkali metal.For example, some commercial sources material of TEAOH comprises nearly 1.6wt% potassium and 0.05wt% sodium, and phosphoric acid (preferred phosphorus source material) comprises the alkali metal above 0.01wt% usually.According to the present invention, have now found that alkali metal (especially sodium and the potassium) content of impurity in synthetic mixture contains the material of CHA and AEI to mensuration average crystalline size and crystal size distribution have material impact.Specifically, it is found that to comprise about 0.08-about 0.90 when synthetic mixture, the about about 0.80ppm wt of 0.08-for example for example approximately during the about 0.50g alkali metal of 0.10-/mole aluminium oxide, has the average (d less than 2.2 microns
50) crystalline size and less than 1.0 low crystal size distribution (d
90-d
10)/d
50Synthetic the obtaining that contains CHA and AEI material promote.In addition, in AEI/CHA homobium synthetic, it is found that when alkali metal content is a 1.00g/ mole aluminium oxide at least, for example during 1.00-2.50g/ mole aluminium oxide, the CHA character of homobium reduces the AEI component and increases.
The all components of reactant mixture in conjunction with after, wish to make mixture about at the most 12 hours of slaking under about 10 ℃-about 30 ℃ temperature.Aptly, in this maturation stage, stirred reaction mixture.
After this optional maturation stage, be sealed in reactant mixture in the container and heating (preferably under self-generated pressure) to 100 ℃-about 350 ℃, for example about 125 ℃-about 250 ℃, for example about 150 ℃-about 200 ℃ temperature.Forming the required time of crystallized product depends on temperature and can be from once until several weeks usually.Usually, crystallization time is about about 30 minutes to 2 week, for example about 45 minutes to about 240 hours, and for example about 1 hour to about 120 hours.Can be not or have under the condition of stirring (more preferably stirring) to carry out hydrothermal crystallization.
In case formed crystallization molecular sieve product (being in slurry form usually), just can for example it have been reclaimed by the standard technique of knowing in any this area by centrifugation or filtration.For example water for example carries out drying then with the crystallized product washing of reclaiming in air then.
In the embodiment of a reality, in tubular reactor, synthesize by continuation method.In this method, can be with in two reaction logistics inlet tube formula reactors, a logistics comprises the alumina source material that is dispersed in the hypoergia medium, for example comprise the part of phosphoric acid and the neutral solution of organic directed agents, another logistics comprises remaining reactant in acid " reactivity " medium.After optional preliminary treatment, for example when being undertaken, can logistics be tied by the on-line mixing device and be incorporated in high temperature by the formation of precursor when synthetic, for example pump via this tubular reactor under the crystallization temperature.The different sections of reactor can be used for preliminary treatment and crystallization, and by controlling the length of flow velocity and section, can obtain the required time of staying in each section.
As the result of this synthesis technique, in its hole, comprise at least a portion of the organic directed agents that is used to synthesize from the crystallized product of reactant mixture recovery.In a preferred embodiment, activate by this way, make and from molecular sieve, to remove organic directed agents and in the microporosity passage of the molecular sieve opening that contacts with raw material, stay the active catalytic position.Described activation process is following finishing usually: roasting, or mainly heating at about 200 ℃ of molecular sieves that will comprise the template agent to about 800 ℃ temperature in the presence of the oxygen-containing gas.In some cases, the heating molecular sieve may be desirable in the environment with low or zero oxygen concentration.These class methods can be used for partially or completely removing organic directed agents from the intracrystalline pore system.
Molecular sieve catalyst composition
Silicoaluminophosphamolecular molecular sieve by synthetic method of the present invention preparation is especially for designing as the organic transformation catalyst.Before being used for catalysis, usually by making molecular sieve and other material, for example binding agent and/or matrix material in conjunction with and be mixed with carbon monoxide-olefin polymeric, described other material provides additional hardness or catalytic activity for final catalyst.
Can various inertia or catalytically-active materials with the material of molecular sieve blend.These materials comprise composition such as kaolin and other clay, various forms of rare earth metal, other non-zeolite catalysts component, zeolite catalyst components, aluminium oxide or alumina sol, titanium oxide, zirconia, quartz, silica or Ludox and their mixture.These components reduce the total catalyst cost, serve as hot natural pond heat insulation to help at regeneration period chien shih catalyst, make catalyst fine and close and to improve aspect the catalyst strength also be effective.When with these component blend, the amount that is included in the molecular sieve in the final catalyst prod is the 10-90wt% of total catalyst, is preferably the 20-80wt% of total catalyst composition.
The purposes of molecular sieve
Silicoaluminophosphamolecular molecular sieve by the inventive method preparation is useful as catalyst in various technologies, and comprising: for example feed naphtha is cracked into light olefin or higher molecular weight (MW) hydrocarbon is cracked into low MW hydrocarbon; With for example heavy crude and/or the hydrocracking of ring-type raw material; With for example aromatic compounds such as xylene isomerization; Make for example one or more olefinic polymerizations with the preparation polymer product; Reform; Hydrogenation; Dehydrogenation; For example the hydrocarbon dewaxing is to remove linear paraffin; For example absorb Alkylaromatics to isolate their isomers; With for example aromatic hydrocarbon such as benzene and alkylbenzene alkylation, choose wantonly with the propylene alkylation to prepare isopropylbenzene or to use long chain olefin alkylation; Make for example bond transalkylation of aromatics and many alkylaromatic hydrocarbons; Dealkylation; Dehydrocyclization; For example make toluene disproportionation with preparation benzene and paraxylene; Make that for example straight chain and branched-chain alkene are oligomeric; With a synthetic alkylamine and dialkylamine.
Silicoaluminophosphamolecular molecular sieve by the inventive method preparation especially is suitable as catalyst and is used for conversion of oxygenates to olefins.Term as used herein " oxygenatedchemicals " is defined as comprising, but be not necessarily limited to aliphatic alcohol, ether, carbonyls (aldehyde, ketone, carboxylic acid, carbonic ester etc.), contain heteroatomic compound in addition in addition, as halide, mercaptan, sulfide, amine and their mixture.Aliphatic structure partly will comprise about 10 carbon atoms of about 1-usually, as about 4 carbon atoms of about 1-.
Representational oxygenatedchemicals comprises lower straight or branched aliphatic alcohols, their unsaturated homologue and their nitrogen, halogen and sulfur analogs.The example of the oxygenatedchemicals that is fit to comprises methyl alcohol; Ethanol; Normal propyl alcohol; Isopropyl alcohol; C
4-C
10Alcohol; Methyl ethyl ether; Dimethyl ether; Diethyl ether; Diisopropyl ether; Methyl mercaptan; Methyl sulfide; Methylamine; Ethyl mercaptan; The diethyl thioether; Diethylamine; Ethyl chloride; Formaldehyde; Dimethyl carbonate; Dimethyl ketone; Acetate; Have the positive alkylamine of the positive alkyl that comprises about 10 carbon atoms of about 3-, positive alkyl halide, positive alkyl sulfide; With their mixture.Especially the oxygenatedchemicals of Shi Heing is methyl alcohol, dimethyl ether or their mixture, very preferably methyl alcohol.Term as used herein " oxygenatedchemicals " is only represented the organic material as raw material.The combined feed in supply response district can comprise additional compound, as diluent.
In oxygenate technology of the present invention, under effective process conditions, in reaction zone, make to comprise organic oxygen-containing compound, randomly, thus contact with the catalyst that comprises molecular sieve of the present invention in gas phase with the raw material of one or more diluents and to prepare required alkene.Perhaps, can carry out this technology in liquid phase or in the mixed gaseous/liquid phase.When carrying out this technology in liquid phase or in the mixed gaseous/liquid phase, may produce differentiated yields and the selectivity of raw material to product, this depends on catalyst and reaction condition.
When existing, diluent is reactive and be commonly used to reduce the concentration of oxygenatedchemicals in the raw material to raw material or molecular sieve catalyst composition right and wrong generally.The limiting examples of the diluent that is fit to comprises helium, argon gas, nitrogen, carbon monoxide, carbon dioxide, water, non-reacted alkane (especially alkane such as methane, ethane and propane), non-reacted aromatic compounds and their mixture basically basically.Most preferred diluent is water and nitrogen, and water is especially preferred.Diluent can account for the about 99mol% of about 1mol%-of total raw material mixture.
The temperature that is used for oxygenate technology can change in wide region, as about 200 ℃-about 1000 ℃, for example about 250 ℃-about 800 ℃, comprise about 250 ℃-about 750 ℃, aptly, about 300 ℃-about 650 ℃, about 350 ℃-about 600 ℃ usually, especially about 400 ℃-about 600 ℃.
Although needn't form with optimised quantity, light olefin product will form in wide pressure limit, include but not limited to the pressure of self-generated pressure and about about 10MPa of 0.1kPa-.Aptly, pressure is the about 5MPa of about 7kPa-, for example about about 1MPa of 50kPa-.Above-mentioned pressure will not counted diluent in interior (if diluent existence), and above-mentioned pressure is meant the dividing potential drop of the raw material relevant with oxygenatedchemicals and/or its mixture.Upper and lower bound pressure may influence selectivity, conversion ratio, coking rate and/or reaction speed unfriendly; Yet light olefin such as ethene still can form.
Should make this technology continue one period that is enough to produce required olefin product.Reaction time may be tens seconds to some hours.Reaction time is determined according to reaction temperature, pressure, selected catalyst, weight hourly space velocity, phase (liquid or steam) and selected technological design feature to a great extent.
The weight hourly space velocity of the wide region of raw material (WHSV) will be effective in the methods of the invention.WHSV be defined as the weight of raw material (eliminating diluent)/hour/weight of the total reaction volume of molecular sieve catalyst (not comprising inert substance and/or filler).WHSV should be about 0.01hr usually
-1To about 500hr
-1, for example about 0.5hr
-1To about 300hr
-1, for example about 0.1hr
-1To about 200hr
-1
The actual embodiment that is used for the reactor assembly of oxygenate technology is the circulating fluid bed reactor of cyclic regeneration, and is similar to the fluidized catalytic cracker in modern times.For this technology, fixed bed is normally not preferred, and reason is that oxygenatedchemicals to conversion of olefines is the process of height heat release, and it need have several stages of intercooler or other cooling device.Because the generation of low pressure, low density gas, reaction also causes high pressure drop.
Because catalyst must be regenerated continually, so reactor should allow easily the part of catalyst is moved on to regenerator, wherein catalyst stands regenerating medium, the gas that for example comprises oxygen, for example air-treatment burnouting from the coke of catalyst, thereby recovers catalyst activity.Temperature conditions in the regenerator, oxygen partial pressure and the time of staying should be through selecting to reach coke content on the regenerated catalyst less than about 0.5wt%.At least a portion of regenerated catalyst should turn back to reactor.
Use various oxygen-containing compound material discussed above, especially contain the raw material of methyl alcohol, it is effective that carbon monoxide-olefin polymeric of the present invention mainly changes into one or more alkene with described raw material.The alkene that is produced has 2-30 carbon atom usually, preferred 2-8 carbon atom, and more preferably 2-6 carbon atom, still more preferably 2-4 carbon atom most preferably is ethene and/or propylene.The alkene of gained can be separated with oxygenate conversion product and sell maybe can supply with and be used for alkene is changed into for example subsequent technique of polymer.
Now the present invention is more specifically described with reference to following examples.
In an embodiment, DIFFaX analyzes the AEI/CHA ratio that is used for measuring molecular sieve.Use can generate the simulation powder X-ray RD diffraction pattern of different AEI/CHA ratios (also referring to people such as M.M.J.Tracey from the DIFFaX program that International Zeolite Association obtains, Proceedings of the RoyalChemical Society, London, A (1991), the 433rd volume, " the Collection of Simulated XRD PowderPatterns for Zeolites " 2001 of 499-520 page or leaf M.M.J.Treacy and J.B.Higgins, the 4th edition, represent Structure Commissionof the International Zeolite Association to publish).The table 2 of U.S. Patent Application Publication No. 2002/0165089 has provided the DIFFaX input file that is used for simulating the XRD diffraction pattern, and the document is hereby incorporated by.In order to obtain the optimal fitting between DIFFaX simulation pattern and the experiment pattern, the spectral line broadening (as described in Application No. 2002/0165089) of use 0.009 and 0.04 spectral line broadening (Fig. 1 a and 1b) generate two groups of simulation XRD figure cases.Then simulated diffraction figure and experimental powder XRD diffraction pattern are compared.At this on the one hand, tetchy scope is the 2 θ scopes of 15-19.5.
Adopt 2000 (d value is by volume represented) of Malvern Mastersizer to carry out crystalline size measurement among the embodiment.
Embodiment 1 (contrast)
Preparation 385.65g phosphoric acid (85% the aqueous solution in 2 liters of polyethylene bottles, Acros, contain 122ppm Na and 4ppm K), the mixture of 369.53g demineralized water and 701.49g tetraethylammonium hydroxide solution (35% the aqueous solution, Sachem contain 2ppm Na and 26ppm K).Then the gained mixture is transferred in the glass beaker, this glass beaker is placed on during Neslab under 30 ℃ bathes, after the stirring that starts with laboratory blender this mixture, with 37.27g Ludox AS 40 (40% silica, contain 815ppm Na and 39ppm K) add in this beaker, then add 227.01g aluminium oxide (Condea Pural SB-1 contains 18ppm Na and 26ppm K).Under continue stirring, produce slurry and be allowed to condition at 30 ℃ Neslab bathe in slaking 2 hours.Mixture is composed as follows with molar ratio computing:
0.15SiO
2/Al
2O
3/P
2O
5/TEAOH/35H
2O
The Na of total synthetic mixture and K content (from there being these elements in the raw material) are respectively 0.035g/ mole aluminium oxide and 0.007g/ mole aluminium oxide.Mixture is transferred in 2 liters of PARRPARR stainless steel autoclaves and with 20 ℃/hour is heated to 165 ℃.During whole hydrothermal treatment consists, under 200rpm (tip speed of 1.3m/s), stir the mixture with laboratory blender.165 ℃ of following maintenance autoclaves 60 hours.
After cool to room temperature, washing is dry slurry also, takes the X-ray diffraction pattern of crystallized product after above-mentioned calcination procedure.Use this diffraction pattern, carry out the DIFFaX analysis and show that this crystallized product comprises the AEI/CHA homobium, the latter comprises 28wt%AEI framework types molecular sieve and 72wt%CHA framework types molecular sieve.Framework silica/alumina molar ratio (Si/Al of crystallized product
2) find it is 0.19.In addition, product has the d of 2.0 μ m
50Particle size and 0.8 span [(d
90-d
10)/d
50].
Embodiment 2-4 (contrast)
Prepare several samples as in Example 1 and the result is summarised in the following table.
| Embodiment | D50 (micron) | Span | DIFFaX AEI/CHA ratio |
| 1 | 2.0 | 0.8 | 28/72 |
| 2 | 1.7 | 0.8 | n/a |
| 3 | 1.5 | 0.8 | n/a |
| 4 | 1.5 | 0.8 | 29/71 |
Embodiment 5-12
With preparing several mixtures, still add the Na and/or the K of variable with the form of its chloride salt with embodiment 1 the same method.The result is summarised in the following table.
| Embodiment | GNa/ mole aluminium oxide | GK/ mole aluminium oxide | D50 (micron) | Span | DIFFaX AEI/CHA ratio |
| 5 | 0.087 | 0.007 | 1.6 | 0.8 | 28/72 |
| 6 | 0.340 | 0.007 | 1.8 | 0.7 | 28/72 |
| 7 | 0.550 | 0.007 | 1.6 | 0.8 | 25/75 |
| 8 | 0.035 | 0.059 | 1.6 | 0.8 | 29/71 |
| 9 | 0.035 | 0.213 | 1.6 | 0.7 | 28/72 |
| 10 | 0.035 | 0.522 | 1.6 | 0.8 | 28/72 |
| 11 | 1.064 | 0.007 | 0.6 | 4.1 | 75/25 |
| 12 | 2.094 | 0.007 | 3.3 | 2.2 | 85/15 |
Though invention has been described and explanation with reference to specific embodiment, those skilled in the art will appreciate that the present invention is applicable to the variation that needn't illustrate in this article.Therefore, should only determine true scope of the present invention according to appended claims.
Claims (25)
1. the synthetic method of silicoaluminophosphamolecular molecular sieve, described molecular sieve comprise the CHA framework types material, AEI framework types material or comprise the AEI framework types and the material of at least a coexisting phase of CHA framework types, this method comprises:
(a) preparation comprises the synthetic mixture of the source material of water, organic directed agents and phosphorus, aluminium and silicon, and the alkali-metal total amount that wherein is present in the described synthetic mixture is the about 0.90g/ mole of an about 0.08-aluminium oxide;
(b) described synthetic mixture is heated to about 100 ℃-about 300 ℃ crystallization temperature; With
(c) reclaim described molecular sieve.
2. the process of claim 1 wherein that described silicoaluminophosphamolecular molecular sieve comprises the material of CHA framework types.
3. the process of claim 1 wherein that described silicoaluminophosphamolecular molecular sieve comprises the material of AEI framework types.
4. the process of claim 1 wherein that described silicoaluminophosphamolecular molecular sieve is the material that comprises at least a coexisting phase of AEI framework types and CHA framework types.
5. the method for claim 4, wherein said at least a coexisting phase have by about 5/95-of DIFFaX assay determination about 40/60, and be about 30/70 such as about 10/90-, for example the about AEI/CHA ratio of 15/95-about 20/80.
6. the method for claim 5, the X-ray diffraction pattern of wherein said silicoaluminophosphamolecular molecular sieve in 5-25 (2 θ) scope all has at least one reflection peak in following each scope:
2θ(CuKα)
9.3-9.6
12.7-13.0
13.8-14.0
15.9-16.1
17.7-18.1
18.9-19.1
20.5-20.7
23.7-24.0。
7. the method for claim 4, wherein said silicoaluminophosphamolecular molecular sieve comprise first and second symbiotic forms of the material of the material that has the AEI framework types separately and CHA framework types.
8. the method for claim 7, wherein said first symbiotic form has the AEI/CHA ratio by about 5/95-about 40/60 of DIFFaX assay determination, and described second symbiotic form has the AEI/CHA ratio different with described first symbiotic form.
9. the method for claim 8, wherein said second symbiotic form has about AEI/CHA ratio of 55/45, for example about 50/50 by about 30/70-of DIFFaX assay determination.
10. the synthetic method of silicoaluminophosphamolecular molecular sieve that comprises the coexisting phase of at least a CHA framework types and AEI framework types, wherein said at least a coexisting phase has the AEI/CHA ratio by about 5/95-about 40/60 of DIFFaX assay determination, and this method comprises:
(a) preparation comprises the synthetic mixture of the source material of water, organic directed agents and phosphorus, aluminium and silicon, and the alkali-metal total amount that wherein is present in the described synthetic mixture is that the mole that about 0.08-about 0.90g/ mole aluminium oxide and described mixture have in following scope is formed:
The P of about 0.6-about 1.2
2O
5: Al
2O
3,
The SiO of about 0.12-about 0.20
2: Al
2O
3,
The H of about 25-about 50
2O: Al
2O
3,
(b) under agitation described mixture is heated to about 100 ℃-about 300 ℃ crystallization temperature; With
(c) reclaim described molecular sieve.
11. aforesaid right requires each method, the alkali-metal total amount that wherein is present in the described synthetic mixture is the about 0.80g/ mole of an about 0.08-aluminium oxide, such as the about about 0.50g/ mole of 0.10-aluminium oxide.
12. aforesaid right requires each method, the alkali metal that wherein is present in the described synthetic mixture is sodium and/or potassium.
13. the mole that each method among the claim 10-12, wherein said synthetic mixture (a) have in following scope is formed:
The P of about 0.8-about 1.1
2O
5: Al
2O
3,
The SiO of about 0.12-about 0.15
2: Al
2O
3,
The H of about 35-about 45
2O: Al
2O
3
14. comprise the synthetic method of silicoaluminophosphamolecular molecular sieve of coexisting phase of the material of the material of at least a CHA framework types and AEI framework types, wherein said at least a coexisting phase comprises the material by the described AEI framework types of 50wt% at least of DIFFaX assay determination, and this method comprises:
(a) preparation comprises the synthetic mixture of source material of water, organic directed agents and phosphorus, aluminium oxide and silica, and the alkali-metal total amount that wherein is present in the described synthetic mixture is formed for the mole that 1.00g/ mole aluminium oxide and described mixture at least have in following scope:
The P of about 0.6-about 1.2
2O
5: Al
2O
3,
The SiO of about 0.005-about 0.15
2: Al
2O
3,
The H of about 10-about 50
2O: Al
2O
3,
(b) under agitation described mixture is heated to about 100 ℃-about 300 ℃ crystallization temperature; With
(c) reclaim described molecular sieve.
15. the method for claim 14, the alkali-metal total amount that wherein is present in the described synthetic mixture is the about 2.50g/ mole of an about 1.00-aluminium oxide.
16. each method among the claim 10-15, wherein said organic directed agents comprises tetraethyl ammonium compount.
17. each method among the claim 10-16 is wherein carried out heating in (b) and is made the temperature of described mixture with at least 8 ℃/hours, raises such as about 10 ℃/hour-about 40 ℃/hour speed.
18. each method among the claim 10-17 is wherein carried out described stirring to prevent the precipitation of synthetic mixture component.
19. aforesaid right requires each method, wherein said crystallization temperature is about 150 ℃-about 200 ℃.
20. aforesaid right requires each method, wherein heats (b) in having the continuous synthesizer of import and outlet, by this import described synthetic mixture is introduced, and reclaims described molecular sieve by this outlet.
21. require the silicoaluminophosphamolecular molecular sieve of each method preparation by aforesaid right.
22. (d claim 21 and average
50) crystalline size is less than 2.2 microns, such as about 1.5 microns-about 1.9 microns silicoaluminophosphamolecular molecular sieve.
23. claim 21 or claim 22 and (d
90-d
10)/d
50Crystal size distribution is less than 1.0 silicoaluminophosphamolecular molecular sieve.
24. prepare the method for olefin product by oxygen-containing compound material, comprise that the catalyst of each silicoaluminophosphamolecular molecular sieve in making described oxygen-containing compound material and comprising claim 21-23 contacts.
25. the method for claim 24, wherein said oxygen-containing compound material comprise methyl alcohol, dimethyl ether or its mixture, described olefin product comprises ethene and propylene.
26. claim 24 or claim 25 and comprise that at least a portion with olefin product changes into the method for polymer.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US63871204P | 2004-12-22 | 2004-12-22 | |
| US60/638,712 | 2004-12-22 | ||
| US11/048,072 | 2005-01-31 | ||
| US11/048,072 US7528201B2 (en) | 2004-12-22 | 2005-01-31 | Synthesis of silicoaluminophosphate molecular sieves |
| PCT/US2005/043524 WO2006068801A2 (en) | 2004-12-22 | 2005-12-02 | Synthesis of silicoaluminophosphate molecular sieves |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014089738A1 (en) * | 2012-12-10 | 2014-06-19 | 中国科学院大连化学物理研究所 | Sapo-34 zeolite having n-methyldiethanolamine as templating agent and synthesis method for the zeolite |
| CN105358483A (en) * | 2013-07-09 | 2016-02-24 | 三菱化学株式会社 | Zeolite production method |
| CN110023242A (en) * | 2016-09-30 | 2019-07-16 | 庄信万丰股份有限公司 | The synthesis of AEI and Cu-AEI zeolite |
| CN110785379A (en) * | 2017-06-19 | 2020-02-11 | 赛成公司 | Morpholine-based quaternary ammonium cations and AEI-type zeolites prepared therefrom |
| CN112469666A (en) * | 2018-08-02 | 2021-03-09 | 巴斯夫欧洲公司 | Method for continuous synthesis of zeolitic materials using seeds loaded with organic template |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6812372B2 (en) * | 2001-03-01 | 2004-11-02 | Exxonmobil Chemical Patents Inc. | Silicoaluminophosphate molecular sieve |
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2005
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2014089738A1 (en) * | 2012-12-10 | 2014-06-19 | 中国科学院大连化学物理研究所 | Sapo-34 zeolite having n-methyldiethanolamine as templating agent and synthesis method for the zeolite |
| CN105358483A (en) * | 2013-07-09 | 2016-02-24 | 三菱化学株式会社 | Zeolite production method |
| CN105358483B (en) * | 2013-07-09 | 2019-06-04 | 三菱化学株式会社 | The manufacturing method of zeolite |
| US10308516B2 (en) | 2013-07-09 | 2019-06-04 | Mitsubishi Chemical Corporation | Zeolite production method |
| CN110023242A (en) * | 2016-09-30 | 2019-07-16 | 庄信万丰股份有限公司 | The synthesis of AEI and Cu-AEI zeolite |
| CN110785379A (en) * | 2017-06-19 | 2020-02-11 | 赛成公司 | Morpholine-based quaternary ammonium cations and AEI-type zeolites prepared therefrom |
| CN110785379B (en) * | 2017-06-19 | 2022-12-27 | 赛成公司 | Morpholine-based quaternary ammonium cations and AEI-type zeolites prepared therefrom |
| CN112469666A (en) * | 2018-08-02 | 2021-03-09 | 巴斯夫欧洲公司 | Method for continuous synthesis of zeolitic materials using seeds loaded with organic template |
| CN112469666B (en) * | 2018-08-02 | 2023-12-01 | 巴斯夫欧洲公司 | Method for continuous synthesis of zeolite materials using seed crystals loaded with an organic template |
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