CN101076401A - Crystal symbiotic material and its synthetic and application in conversion of oxygen-containing compound to olefin - Google Patents
Crystal symbiotic material and its synthetic and application in conversion of oxygen-containing compound to olefin Download PDFInfo
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Abstract
A silicoaluminophosphate molecular sieve is disclosed that comprises first and second intergrown phases of a CHA framework type and an AEI framework type, wherein said first intergrown phase has an AEUCHA ratio of from 5/95 to 40/60 as determined by DIFFaX analysis, the second intergrown phase has an AEI/CHA ratio of 30/70 to 55/45 as determined by DIFFaX analysis and said molecular sieve has a silica to alumina molar ratio (Si/Al2) from 0.13 to 0.24.
Description
Invention field
The present invention relates to comprise crystalline material and synthetic and the purposes in oxygenatedchemicals (especially methyl alcohol)-alkene (especially ethene and propylene) method for transformation of the commensal of CHA framework types molecular sieve and AEI framework types molecular sieve.
Background of invention
Light olefin, for example ethene, propylene, butylene and their mixture are as the many important chemicals of preparation and the raw material of polymer.Usually, C
2-C
4Light olefin is by with oil plant materials flow C for example
3The cracking of+paraffinic feed prepares.Limited in view of the supply of competitive petroleum, prepare low-cost light olefin by petroleum and run into the problem that supply reduces.Therefore, people are increasing based on the technical effort of paying of the light-olefin production of alternative materials in exploitation.
A kind of important alternative materials type that is used to prepare light olefin is an oxygenatedchemicals, for example C
1-C
4Alcohols, especially methyl alcohol and ethanol; C
2-C
4Dialkyl ether, dimethyl ether (DME) especially, methyl ethyl ether and diethyl ether; Dimethyl carbonate and methyl formate and their mixture.These many oxygenatedchemicals can be prepared by the source that substitutes by fermentation, or by the synthesis gas preparation that comes from natural gas, petroleum liquid, carbonaceous material (comprising coal), regenerated plastics, municipal waste or other organic material.Because wide material sources, alcohol, 01 derivatives and other oxygenatedchemicals have the prospect as the non-petroleum sources of the economy that is used to prepare light olefin.
Preferably be used for oxygen-containing compound material for example methanol conversion allow described raw material contact for the method for one or more alkene (mainly being ethene and/or propylene) comprises with the crystalline molecular sieve catalyst composition.Crystalline molecular sieve has common angle [TO
4] skeleton structures that tetrahedral three-dimensional, four connects, wherein T is the cation of any tetrahedral coordination.What belong to known molecular sieve form is silicoaluminophosphate (SAPO) molecular sieve, and it contains [SiO
4], [AlO
4] and [PO
4] dimensional microporous crystal framework structure of angle tetrahedron element altogether.
SAPO-34 and SAPO-18 be as many important method (comprise by oxygenatedchemicals for example methyl alcohol prepare the method for light olefin) the crystalline silico-alumino-phosphate molecular screen material of suitable catalyst report.SAPO-34 belongs to the molecular sieve family of the framework types with zeolite group mineral chabasie (CHA).SAPO-18 belongs to the family of the molecular sieve with AEI framework types.Other molecular sieve with AEI framework types is ALPO-18 and RUW-18.
The preparation of SAPO-34 and be characterized in several pieces of publications report is arranged comprises US patent No.4,440,871; People such as J.Chen, " Studies in Surface Science andCatalysis ", the 84th volume, 1731-1738 page or leaf; US patent No.5,279,810; People such as J.Chen, " Journal of Physical Chemistry ", the 98th volume, 10216-10224 page or leaf (1994); People such as J.Chen, " Catalysis Letters ", the 28th volume, 241-248 page or leaf (1994); People such as A.M.Prakash, " Journal of theChemical Society, Faraday Transactions ", the 90th (15) volume, 2291-2296 page or leaf (1994); People such as Yan Xu, " Journal of the ChemicalSociety, Faraday Transactions ", the 86th (2) volume, 425-429 page or leaf (1990).
Have the AEI framework types molecular sieve preparation and be characterized in several pieces of publications report arranged, comprise US patent No.4,440,871; People such as J.Chen, " Studies in SurfaceScience and Catalysis ", the 84th volume, 1731-1738 page or leaf; US patent No.5,279,810; People such as J.Chen, " Journal of Physical Chemistry ", the 98th volume, 10216-10224 page or leaf (1994); People such as J.Chen, " CatalysisLetters ", the 28th volume, 241-248 page or leaf (1994); 2291-2296 page or leaf (1994); People such as Yan Xu, " Journal of the Chemical Society, FaradayTransactions ", the 86th (2) volume, 425-429 page or leaf (1990); With U.S. patent No.5,609,843.
In methanol-to-olefins transforms, SAPO-34 show high relatively to ethene and propylene selectivity of product and low to alkane with have 〉=selectivity of product of the alkene of 4 carbon.Therefore the catalyst that contains SAPO-34 is particularly suitable for the conversion of methanol-to-olefins.Though it has good performance, carbonaceous sediment (being referred to as coke usually) is very fast to be formed in the catalysis cage of SAPO-34.Finally, these cages have been stopped up in the existence of too many coke, and passivation catalyst.Also have, though SAPO-34 is low to the selectivity of alkane, it has still produced accessory substance.Separating by-products has increased the fringe cost of methanol-to-olefins method for transformation from required ethene and propylene.Therefore, constantly need to find to have the novel molecular sieve of good selectivity of product and generation accessory substance seldom.
US patent No.6,334,994 (being incorporated herein for reference) have disclosed a kind of silicoaluminophosphamolecular molecular sieve (being referred to as RUW-19), it is said that it is that AEI/CHA mixes combined thing.Especially, RUW-19 has the peak character of CHA and AEI framework types molecular sieve according to reports simultaneously, just the quant's sign that concentrates on about 16.9 (2 θ) in RUW-19 has substituted the paired reflection of concentrating on of AEI material about 17.0 (2 θ), RUW-19 do not have concentrate on 17.8 with the reflection relevant at 24.8 2 θ value places with the CHA material.As at US patent No.6,334, the DIFFaX of the X-ray diffractogram of prepared RUW-19 analyzes indication among 994 the embodiment 1,2 and 3, and these material characteristics are to have respectively the AEI of about 60/40,65/35 and 70/30 AEI/CHA ratio and the single coexisting phase (referring to accompanying drawing 2) of CHA framework types molecular sieve.
On November 7th, 2002 published and be incorporated herein US patent No.6 for reference, 812,372 have disclosed a kind of silicoaluminophosphamolecular molecular sieve (being accredited as EMM-2 now), the coexisting phase that comprises the molecular sieve of at least a AEI of having and CHA framework types, wherein said coexisting phase has about 5/95 to 40/60 AEI/CHA ratio, and described ratio uses the DIFFaX of x-ray diffractogram of powder of the calcining sample of described silicoaluminophosphamolecular molecular sieve to analyze determine.
Main olefine selective (POS) (its equal ethene in the product and the overall selectivity of propylene) and main olefin ratio (POR) (it equals ethene amount in the product divided by the propylene amount) are two main economic driving factors in any oxygenate conversion process.In fact, even the change of little POS and/or POR also can produce huge effect to the economy of commercial run.According to the present invention, have now found that for some AEI/CHA coexisting material to have best silica/alumina ratio ranges, in this scope, when these materials were used for oxygenatedchemicals-alkene and transform, it is maximum that POS and POR all reach.In addition, have been found that these AEI/CHA coexisting materials have showed excellent hydrothermal stability.
General introduction
In one aspect, the present invention relates to comprise at least the silicoaluminophosphamolecular molecular sieve of first and second coexisting phases of CHA framework types and AEI framework types, wherein said first coexisting phase has 5/95 to 40/60 AEI/CHA ratio by the DIFFaX assay determination, second coexisting phase has 30/70 to 55/45 AEI/CHA ratio by the DIFFaX assay determination, and described molecular sieve has the silica/alumina mol ratio (Si/Al of 0.13-0.24
2).
Suitably, silicoaluminophosphamolecular molecular sieve has 0.15-0.22, more preferably 0.17-0.21, for example silica of 0.18-0.19 and alumina molar ratio.
Suitably, described first coexisting phase has by 5/95 to 30/70 of DIFFaX assay determination, for example 5/95 to 20/80 AEI/CHA ratio.
In one embodiment, second coexisting phase has 35/65 to 54/46, preferred 40/60 to 53/47 and more preferably 45/55 to 50/50 AEI/CHA ratio.
Total AEI/CHA ratio (it is the weighted average of all coexisting phases) is preferably 20: 80 to 40: 60, more preferably 25: 75 to 35: 65.
Suitably, the AEI/CHA ratio weighted average of first coexisting phase and second coexisting phase is 10: 90 to 90: 10, preferred 25: 75 to 75: 25.Preferably, the molecular sieve of calcinated form has the XRD figure that shows two quant's signs (broad feature) in 16-18.5 2 θ scopes.
Suitably, in comprising the nitrogen atmosphere of steam, depress after 700 ℃ are down handled 30 days at the branch of 13psi (90kPa), silicoaluminophosphamolecular molecular sieve keep its with methanol conversion be ethene and propylene activity at least 40%, for example at least 45%.
In yet another aspect, the present invention relates to the method for the silicoaluminophosphamolecular molecular sieve of synthetic first and second coexisting phases that comprise CHA framework types and AEI framework types at least, wherein said first coexisting phase has 5/95 to 40/60 AEI/CHA ratio by the DIFFaX assay determination, second coexisting phase has 30/70 to 55/45 AEI/CHA ratio by the DIFFaX assay determination, and described molecular sieve has the silica/alumina mol ratio (Si/Al of 0.13-0.24
2), this method comprises:
(a) prepare the mixture that comprises water source, reactive silicon source, reactive aluminum source, reactive phosphorus source and be used to guide organic directed agents of described molecular sieve formation, the mole that makes described mixture have in following scope is formed:
P
2O
5∶Al
2O
3 0.6-1.2，
SiO
2∶Al
2O
3 0.10-0.20，
H
2O∶Al
2O
3 25-50，
(b) described mixture is mixed continuously and be heated to crystallization temperature, 150-200 ℃ usually, preferred 155-180 ℃;
(c) described mixture is kept time of 2-50 hour under described crystallization temperature; With
(d) reclaim described molecular sieve.
Suitably, (b) heating in should make with at least 8 ℃/hours, for example 10 ℃/hour to 40 ℃/hour the speed temperature of described mixture that raises.
Preferably, organic directed agents (also being called template sometimes) is 0.6-1.2 with the mol ratio of aluminium oxide, more preferably 0.7-1.1.Suitably, described organic directed agents comprises the tetraethyl ammonium compound.
In yet another aspect, the present invention relates to be prepared by oxygen-containing compound material the method for olefin product, described method comprises allows described oxygen-containing compound material contact with the catalyst that comprises silicoaluminophosphamolecular molecular sieve of the present invention.
Brief Description Of Drawings
Fig. 1 a is the DIFFaX simulated diffraction figure with symbiosis AEI/CHA phase of different AEI/CHA ratios with 1b, uses disclosed analog parameter in US patent application No.2002/0165089, but has 0.04 spectral line broadening parameter, but not 0.009.
Fig. 2 shows US patent No.6, the DIFFaX simulation drawing of the amplifier section of Fig. 1 of 334,994 and the single symbiosis AEI/CHA phase with different AEI/CHA ratios superimposed.
Fig. 3 a and 3b are the methanol conversion activity (Kmax) of the silicoaluminophosphamolecular molecular sieve for preparing in embodiment 2-11 of comparison and their silica/alumina ratio (Si/Al
2) and their POS and the figure of POR.
Fig. 4 is have the XRD figure of single coexisting phase material of about 15/85 AEI/CHA ratio and DIFFaX simulation drawing superimposed.
Fig. 5 is have the XRD figure of single coexisting phase material of about 45/55 AEI/CHA ratio and DIFFaX simulation drawing superimposed.
Fig. 6 is the XRD figure of the material of preparation in embodiment 9, and this material is the material with different two kinds of AEI/CHA phases forming; This material contain about 50% have about 10/90 AEI/CHA ratio first mutually and about 50% second phase with AEI/CHA ratio of 45/55.Fig. 6 is also superimposed DIFFaX simulation drawing.
The detailed description of embodiment
The present invention relates to comprise at least the silicoaluminophosphamolecular molecular sieve of first and second coexisting phases of CHA framework types material and AEI framework types material, wherein said first coexisting phase has 5/95 to 40/60 AEI/CHA ratio by the DIFFaX assay determination, second coexisting phase has 30/70 to 55/45 AEI/CHA ratio by the DIFFaX assay determination, and described molecular sieve has the silica/alumina mol ratio (Si/Al of 0.13-0.24
2).In addition, the present invention relates to the synthetic of this novel commensal and be converted into purposes in the method for alkene (especially ethene and propylene) at oxygenatedchemicals (especially methyl alcohol).
Coexisting molecular sieve is the unordered plane coexisting phase of framework of molecular sieve mutually.About the detailed description of coexisting molecular sieve phase, referring to " Catalog of Disordered Zeolite Structures ", 2000 editions, by the structure committee publication of International Zeolite Association; And " Collection ofSimulated XRD Powder Patterns for Zeolites ", M.M.J.Treacy and J.B.Higgins, publish with the name of the structure committee of International Zeolite Association by 2001 editions.
The crystalline solid of rule is made up of construction unit constant on the structure, is called the periodic structure unit, and periodically arranges on three-dimensional.Disordered structure has shown on the dimension that is being lower than three-dimensional, i.e. cycle ordering on two dimension, one dimension or zero dimension.It is unordered that this phenomenon is called as piling up of periodic structure unit constant on the structure.If reached on all three-dimensionals periodically in order, it is that the stacking order of wherein periodic structure unit departs from periodicity and reaches those of statistics stacking order in order that the crystal structure of being made up of the periodic structure unit is called as end member (end-member) structural disorder structure.
Silicoaluminophosphamolecular molecular sieve as herein described is the unordered plane commensal of end member's structure AEI and CHA.For AEI and CHA framework types, the periodic structure unit is two six circular layers.Layer " a " and " b " with two types, they are identical on topological structure, just " b " is the mirror image of " a ".When the layer of same type was stacked on each other top, promptly aaa or bbb had produced the CHA framework types.As layer " a " and " b " alternately the time, promptly abab has produced the AEI framework types.Molecular sieve as herein described comprises the layer " a " in zone of the zone of containing the CHA framework types and AEI framework types and the stacking material of " b ".CHA is to pile up unordered or planar fault (planar fault) to each variation of AEI framework types.
Under the situation of the crystal with planar fault, the explanation of X-ray diffractogram need be simulated the ability of piling up unordered effect.DIFFaX is based on the computer program that is used for from the Mathematical Modeling of the crystal calculating strength that contains planar fault (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 is selected and being used to of obtaining simulated the simulation program of XRD coatings of coexisting phase of zeolite (referring to " Collectionof Simulated XRD Powder Patterns for Zeolites " by International Zeolite Association, M.M.J.Treacy and J.B.Higgins, 2001, the 4th edition, publish) with the name of the structure committee of International Zeolite Association.It also is used for studying in theory the coexisting phase of AEI, CHA and KFI, and at " Studies in Surface Science andCatalysis ", 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 single coexisting phase with different AEI/CHA ratios obtains.These figures use at US patent No.6, and disclosed model parameter is calculated in 812,372, only are to use 0.04 spectral line broadening parameter but not 0.009.All XRD diffraction patterns are turned to the top of whole mimic diagram group by nominal, that is, and and the peak at about 9.6 degree 2 θ places.The nominalization of intensity level makes can carry out contrast between the diffraction pattern of the intensity at the X-ray diffraction peak under certain 2 θ values.
When the ratio of the AEI in the single coexisting phase increases with respect to CHA, can find that the intensity reduction at some peak and the intensity at other peak increase.Have 〉=coexisting phase of 50/50 AEI/CHA ratio (AEI/CHA 〉=1.0) shown the quant's sign that concentrates on about 16.9 (2 θ).Have≤coexisting phase of 40/60 AEI/CHA ratio (AEI/CHA≤0.67) shown the quant's sign that concentrates on about 18 (2 θ).
Fig. 2 shows US patent No.6, the amplification of three the XRD figure shapes in top of Fig. 1 of 334,994, and it is corresponding to US patent No.6, the material of preparation among 334,994 the embodiment 1,2 and 3.With as mentioned above the XRD figure shape by the DIFFaX simulation is superimposed for these XRD figure shapes.DIFFaX analyzes demonstration, and embodiment 1,2 and 3 material have 60/40,65/35 and 70/30 AEI/CHA ratio respectively, has considered that the material of embodiment 2 and 3 it is said by the fact of contaminating impurity.US patent No.6,334,994 embodiment 1,2 and 3 material all have the quant's sign that concentrates on about 16.9 (2 θ).
Silicoaluminophosphate of the present invention is characterised in that, powder X-ray RD diffraction pattern (by after the calcining and do not having the sample of rehydration to obtain after the calcining) have as in the reflection in 5-25 (2 θ) scope at least as shown in the following table.
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 |
Here (Scintag Inc. USA), uses copper K-α radiation to collect to the X ray diffracting data of mentioning with SCINTAG X2 x-ray powder diffraction instrument.Diffraction data comes record by step scan (wherein θ is a Bragg angle) and 1 second the gate time of each step under 2 θ of 0.02 degree.Before each experiment X-ray diffractogram of record, sample must be in anhydrous state, and is not contained in its synthetic middle any template of using, because the figure of simulation only uses skeletal atom to calculate, and does not make water and template.Suppose silicoaluminophosphamaterial material sensitiveness to water under the record temperature, sieve sample is calcined after preparation, and keeps moisture-free according to following operation.
Flow down at nitrogen, in baking oven, each sieve sample of about 2g is heated to 200 ℃ with 3 ℃/minute speed from room temperature, when keeping nitrogen stream, this sample was kept 30 minutes down at 200 ℃, then temperature of oven is elevated to 650 ℃ with 2 ℃/minute speed.Then this sample was kept 8 hours down at 650 ℃, be under the nitrogen in preceding 5 hours and be under the air in last 3 hours.With 30 ℃/minute baking oven is cooled to 200 ℃ then, in the time will writing down XRD figure shape, sample is directly transferred in the shuttle from baking oven, cover to prevent rehydration with the Mylar paper tinsel.Can also be after cool to room temperature, fast recording XRD figure shape (for example by using total scanning time) immediately after removing the Mylar paper tinsel less than 5 minutes.
As can be seen from Table 1, be characterised in that in 9.8-12.0 (2 θ) scope according to the XRD diffraction pattern of the coexisting phase of AEI/CHA of the present invention and do not have the peak, more specifically in 10.0-11.0 (2 θ) scope, there is not the peak, particularly in 10.4-10.6 (2 θ) scope, do not have the peak.Another characteristic is to have the peak in 17.7-18.1 (2 θ) scope.Reflection peak in 17.7-18.1 (2 θ) scope has 0.09-0.4, and the relative intensity of preferred 0.1-0.35 is with respect to the reflection peak of locating at 17.9 (2 θ) in the diffraction pattern of SAPO-34.
Material of the present invention has two quant's signs in the scope of 16.6-18.5 degree 2 θ usually, and each quant's sign is the characteristic of the first or the 2nd AEI/CHA coexisting phase.Fig. 6 for example understands this material, and it has two this quant's signs.Do not wish to be subjected to the restriction of any theory, it is believed that concentrate on about 16.9 the degree 2 θ first quant's signs be have 30/70 to 55/45 (in Fig. 6, the indication of the AEI/CHA phase of AEI/CHA ratio about 45/55), and second quant's signs that concentrate on about 18 degree, 2 θ are the indications of AEI/CHA phase with the AEI/CHA ratio of 5/95 to 40/60 (in Fig. 6, about 10/90).The best-fitting of the curve of the different ratios of the ratio of first and second coexisting phases by being used for first and second coexisting phase is determined.The ratio of first and second coexisting phase can change in the tolerance, comprises 10: 90 to 90: 10, and preferred 30: 70 to 70: 30, more preferably 40: 60 to 60: 40.For the material of Fig. 6, this ratio is defined as 50: 50.Preferably, the CHA molecular sieve is SAPO-34, and the AEI molecular screening is from SAPO-18, ALPO-18 and their mixture.
Material of the present invention has the total AEI/CHA ratio that is obtained by the contribution weighting with each coexisting phase.Total AEI/CHA ratio of Ji Suaning is 20: 80 to 40: 60 by this way, for example 25: 75 to 35: 65.For the material of Fig. 6, this weighted average AEI/CHA ratio is 28/72.
Silicoaluminophosphate of the present invention has 0.13-0.24, for example 0.15-0.22, for example 0.17-0.21, for example 0.18 or 0.19 silica and alumina molar ratio (Si/Al
2).The silica/alumina mol ratio is suitably measured by chemical analysis.
Silicoaluminophosphamolecular molecular sieve of the present invention can suitably prepare by the method that comprises the following steps:
(a) in the presence of organic structure directed agents (template), reactive silicon source, reactive phosphorus source and reactive aluminum source are merged, have the mixture that the mole in following scope is formed thereby form:
P
2O
5∶Al
2O
3 0.6-1.2，
SiO
2∶Al
2O
3 0.10-0.20，
H
2O∶Al
2O
3 25-50；
(b) described mixture (a) is mixed continuously and be heated to crystallization temperature, for example 150-220 ℃, 155-200 ℃ usually, preferred 165-190 ℃;
(c) described mixture is kept time of 2-150 hour under described crystallization temperature; And
(d) reclaim described molecular sieve.
Crystallization time in the step c) will change according to crystallization temperature, but crystallization time should be enough to obtain crystallization completely basically.For 155-175 ℃ temperature, 30-150 hour crystallization time is normally enough.
Preferably, the mixture for preparing in step a) has the mole composition in following scope:
P
2O
5∶Al
2O
3 0.8-1.1，
SiO
2∶Al
2O
3 0.12-0.15，
H
2O∶Al
2O
3 35-45。
Though the silica content that it should be understood that molecular sieve as a rule is more than the silica content in the reactant mixture, the silica in the reactant mixture and the mol ratio of aluminium oxide have determined the silica and the alumina ratio of formed molecular sieve.
The reactive silicon source of using in above mixture can be a silicate, fumed silica for example, Aerosil (available from Degussa) for example, orthosilicic acid tetraalkyl ester, or the aqueous colloidal suspension liquid of silica, for example those that sell by E.I.du Pont de Nemours with the trade name of Ludox.
The reactive phosphorus source of using in above mixture is suitably phosphoric acid.
The example in the reactive aluminum source that is fit to comprises hydrated alumina, for example boehmite and pseudobochmite.The preferred pseudobochmite that uses.
The organic structure directed agents comprises the tetraethyl ammonium compound aptly, tetraethyl ammonium hydroxide (TEAOH) for example, and the phosphoric acid tetraethyl ammonium is fluoridized tetraethyl ammonium, tetraethylammonium bromide, etamon chloride or acetic acid tetraethyl ammonium.Typically, directed agents comprises tetraethyl ammonium hydroxide.In some cases, can use more than one organic structure directed agents, for example the combination of tetraethyl ammonium compound and di-n-propylamine.
The amount of organic structure directed agents should make that usually the mol ratio of directed agents and aluminium oxide is 0.6-1.2, for example 0.7-1.1.
It is believed that the method for crystallising that is used to prepare molecular sieve of the present invention is included in during the described mixture of heating, form to have AlPO-H
3(silicon) aluminate or phosphate precursor (peganite or metavariscite) of structure, dissolve this precursor subsequently, with it molecular sieve nucleation of the present invention simultaneously.The factor that influence is used to prepare the method for crystallising of molecular sieve of the present invention has the mixture rate of heat addition and the mixture stir speed (S.S.) during precursor forms at least.Especially, if the rate of heat addition is at least 8 ℃/hours, for example at least 10 ℃/hours, the crystallization of desired molecule sieve increases.Usually, the rate of heat addition is 10 ℃/hour to 40 ℃/hour, for example 15 ℃/hour to 40 ℃/hour.
Preferably, synthetic mixture is mixed (promptly mix and stir, stir, drum changes, vibration, swing or any other hybrid mode), simultaneously reactant mixture is heated to crystallization temperature.Apply mixing with the intensity of avoiding synthetic mixture component precipitation.Here, the intensity of mixing can change according to the physics and the chemical property of each component.Randomly, can also during all or part of crystallization, mix.
In an actual embodiment, method for crystallising of the present invention comprises at least two stages: promptly, form the phase I of (silicon) aluminate or phosphate precursor material and this precursor material is converted into the second stage of required symbiosis AEI/CHA framework types molecular sieve.In the phase I, under agitation heat synthetic mixture, so that its temperature is elevated to 99-150 ℃ with described at least 8 ℃/hours speed, 115-125 ℃ first temperature for example.Then synthetic mixture is remained under described first temperature, preferred continue to stir certain hour, 0.5-120 hour usually, be used to form the intermediate product mixture of the slurry that contains precursor material.With this intermediate product mixture heating, so that with at least 8 ℃/hours, for example 10 ℃/hour to 40 ℃/hour speed is elevated to its temperature and is generally 150-220 ℃, for example 165-190 ℃ second temperature then.This second heating steps can carry out under quiescent conditions, or uses the stirring that reduces than the first heating steps degree to carry out.This second synthetic mixture remains under described second temperature then, crystallizes out from this mixture until coexisting molecular sieve, and this generally needs 2-150 hour; For example 5-100 hour, for example 10-50 hour.
The synthetic of described novel commensal can be owing to the 0.1ppm at least that exists based on the reactant mixture gross weight, 10ppm at least for example, 100ppm at least for example, the suitable seed crystal of 500ppm at least and obtain promoting.Seed crystal can be and crystalline material of the present invention, and for example front synthetic product homostyructure perhaps can be the crystalline material of heterojunction structure, for example AEI, LEV, CHA or ERI framework types molecular sieve.
Usually, crystallized product forms in solution, and can pass through standard mode, for example reclaims by centrifugal or filtration.Typically, the fractional crystallization product has stayed mother liquor from crystalline mixture, and its at least a portion can be recycled in the step (b), thereby has improved the commensal yield of every gram template.Under the situation that method for crystallising was undertaken by two stages, preferably mother liquor is recycled to second stage, promptly by this mother liquor is joined in the intermediate product mixture that contains this precursor material.The product that separates can also wash, reclaims by centrifugal or filtration, and dry.Crystallized product is generally plate, small pieces, stack chips or cubical shape.Usually, crystal has 0.1-3 μ m, for example 0.5-2.0 μ m, for example d of 1.3-1.9 μ m
50(50 volume % of crystal are less than d
50Value) granularity.
As the result of method for crystallising, the crystallized product of recovery contains organic directed agents of using of at least a portion in synthetic at its hole.In a preferred embodiment, activation is carried out by this way, and organic directed agents is removed from molecular sieve, and having stayed in the micro channel of molecular sieve can be for the active catalytic position of the opening that contacts with raw material.Activation method is finished by calcining usually, or heats at the molecular sieve that will comprise template under 200-800 ℃ the temperature in the presence of oxygen-containing gas in fact and finish.In some cases, may in the environment of hypoxemia or zero oxygen concentration, heat molecular sieve.These class methods can be used in and partially or completely remove organic directed agents from the intracrystalline pore system.In other cases, especially under the less situation of organic directed agents, from molecular sieve, remove organic directed agents wholly or in part and finish by conventional desorption method.
In case synthesized symbiosis crystalline material of the present invention, can by with other material for example binding agent and/or host material combine and it be formulated as carbon monoxide-olefin polymeric, these other materials provide additional hardness or catalytic activity for finished catalyst.
Can various inertia or catalytically-active materials with the material of symbiosis crystalline material of the present invention blend.These materials comprise the composition such as kaolin and other clay, various forms of rare earth metals, other non-zeolite catalysts component, zeolite catalyst components, aluminium oxide or alumina sol, titanium dioxide, zirconia, quartz, silica or Ludox and their mixture.These components can also effectively reduce the total catalyst cost, are the hot cave of catalyst shielding heat as helping in regenerative process, make the densified and increase catalyst strength of catalyst.When with this type of component blend, the amount of the symbiosis crystalline material that contains in final catalyst product is the 10-90wt% of total catalyst, the 20-80wt% of preferred total catalyst.
Symbiosis crystalline material as herein described can be used for dry gas and liquid; Be used for selectivity molecular separation based on size and polarity; As ion-exchanger; Urge through agent the oxidation of for example cracking, hydrocracking, disproportionation, alkylation, isomerization, monoalkylamine and dialkylamine and synthetic catalyst as what organic transformation was reacted; As chemistry carrier; Be used for gas chromatography; Remove the petroleum industry of normal paraffin hydrocarbons from distillate with being used for.
Especially, symbiosis crystalline material as herein described can be used for the catalyzed conversion of oxygenatedchemicals to one or more alkene, especially ethene and propylene.Therefore, have now found that with the silicoaluminophosphamolecular molecular sieve that comprises first and second coexisting phases of CHA framework types material and AEI framework types material at least according to the present invention, wherein said first coexisting phase has 5/95 to 40/60 AEI/CHA ratio by the DIFFaX assay determination, second coexisting phase has 30/70 to 55/45 AEI/CHA ratio by the DIFFaX assay determination, the silica/alumina ratio of described molecular sieve is chosen as 0.13-0.24, preferred 0.15-0.22, more preferably 0.17-0.21, for example 0.18 or 0.19, POS and POR when this material is used in oxygenatedchemicals-alkene transforms all reach maximum.
In addition, find that the of the present invention material list of silica/alumina ratio in this optimum range reveals excellent hydrothermal stability, as what discuss in detail among the open No.2004/0260140 of US patent application that publishes the 23 days December in 2004 of introducing comprehensively at this paper.Especially, find that molecular sieve of the present invention depresses after 700 ℃ are down handled 30 days at the branch of 13psi (90kPa) in comprising the nitrogen atmosphere of steam, kept its with oxygenatedchemicals for example methanol conversion be ethene and propylene activity at least 40%, for example at least 45%.
As used herein term " oxygenatedchemicals " is defined as including but not necessarily limited to aliphatic alcohol, ether, carbonyls (aldehyde, ketone, carboxylic acid, carbonic ester etc.) and contain heteroatomic compound in addition, halide for example, mercaptan, sulfide, amine, and their mixture.The aliphatic structure part contains 1-10 carbon atom, for example 1-4 carbon atom usually.
Representative 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; Di Iso Propyl Ether; Methyl mercaptan; Methyl sulfide; Methylamine; Ethanethio; Diethyl sulfide; Diethylamine; Ethyl chloride; Formaldehyde; Dimethyl carbonate; Dimethyl ketone; Acetate; Positive alkylamine, positive alkyl halide, positive alkyl sulfide, wherein positive alkyl has 3-10 carbon atom; With their mixture.Especially the oxygenatedchemicals of Shi Heing is a methyl alcohol, dimethyl ether or their mixture, most preferably methyl alcohol.The organic material as raw material only represented in as used herein term " oxygenatedchemicals ".The whole reinforced of reaction zone can contain other compound, for example diluent.
In oxygenate conversion process of the present invention, the raw material that comprises organic oxygen-containing compound and one or more diluents of choosing wantonly is effectively contacting under the process conditions with the catalyst that comprises molecular sieve of the present invention in the vapour phase of reaction zone, thereby forms required alkene.Alternatively, this method can be carried out in liquid phase or mixed steam/liquid phase.When this method is carried out in liquid phase or mixed steam/liquid phase, depend on catalyst and reaction condition, can obtain the conversion ratio and the selectivity of different raw material-products.
When existing, diluent does not react with raw material or molecular sieve catalyst composition usually, and is generally used for reducing the concentration of the oxygenatedchemicals in the raw material.The limiting examples of the diluent that is fit to comprises helium, argon gas, nitrogen, carbon monoxide, carbon dioxide, water, basically non-reacted alkane (the especially alkane such as methane, ethane and propane), non-reacted basically aromatic compounds, and their mixture.Most preferred diluent is water and nitrogen, and wherein water is particularly preferred.Diluent can account for the 1-99mol% of total raw material mixture.
The temperature of using in oxygenate conversion process can change in wide region, and for example 200-1000 ℃, for example 250-800 ℃, comprise 250-750 ℃, be suitably 300-650 ℃, typically 350-600 ℃, particularly 400-600 ℃.
Light olefins product can form in wide pressure limit, though may not be to form with optimised quantity, this pressure includes but not limited to self-generated pressure and the 0.1kPa pressure to 10MPa.Aptly, this pressure be 7kPa to 5MPa, for example 50kPa is to 1MPa.If above-mentioned pressure does not comprise the diluent that exists, be meant the dividing potential drop of the raw material relevant with oxygenatedchemicals and/or their mixture.The lower limit of pressure and the upper limit may influence selectivity, conversion ratio, coking rate and/or reaction rate unfriendly; Yet, still can form for example ethene of light olefin.
Described method should continue enough to form the time of required olefin product.Reaction time can be for tens of second to a few hours.Reaction time is largely decided by reaction temperature, pressure, selected catalyst, weight hourly space velocity, phase (liquid or steam) and selected technological design characteristic.
In the methods of the invention, the weight hourly space velocity of raw material wide region (WHSV) is effective.WHSV per hour is defined as the weight of raw material (not comprising diluent) of Unit Weight of the molecular sieve catalyst (not comprising inert substance and/or filler) of total reaction volume.WHSV generally should be 0.01hr
-1To 500hr
-1, 0.5hr for example
-1To 300hr
-1, 0.1hr for example
-1To 200hr
-1
An actual embodiment that is used for the reactor assembly of oxygenate conversion process is the circulating fluid bed reactor with cyclic regeneration, is similar to modern fluid catalytic cracking device.Fixed bed is not preferred for this method usually, is high heat release method because oxygenatedchemicals-alkene transforms, and this method need be equipped with the several stages of intercooler or other cooling device.This reaction has also caused high pressure drop, owing to formed low pressure, low density gas.
Because the necessary frequent regeneration of catalyst, so reactor should allow easily a part of catalyst to be moved out in the regenerator, catalyst contacts regenerating medium, for example oxygen containing gas (as air) there, be used for from the catalyst coke that burnouts, this has recovered catalyst activity.Should select the condition of the time of staying in temperature, partial pressure of oxygen and the regenerator, so that obtain to be lower than the coke content on regenerated catalyst of about 0.5wt%.The regenerated catalyst of at least a portion should turn back in the reactor.
With reference now to following examples, be described more specifically the present invention.
In an embodiment, use DIFFaX to analyze the AEI/CHA ratio of measuring molecular sieve.The DIFFaX program that use obtains from International Zeolite Association produces the simulation powder X-ray RD diffraction pattern of AEI/CHA of different ratios (also referring to people such as M.M.J.Tracey, " Proceedings ofthe Royal Chemical Society ", London, A (1991), the 433rd volume, the 499-520 page or leaf; " Collection of Simulated XRD Powder Patterns forZeolites ", M.M.J.Treacy and J.B.Higgins, publish with the name of the structure committee of International Zeolite Association by 2001, the four editions).The DIFFaX input data that is used to simulate the XRD diffraction pattern provides in 812,372 the table 2 at US patent No.6, and this patent is incorporated herein for reference.In order to obtain the best fit between DIFFaX simulation drawing and lab diagram, the spectral line broadening (as described in the US patent application No.2002/0165089) of use 0.009 and 0.04 spectral line broadening (Fig. 1 a and Fig. 1 b) produce two groups of simulation XRD figures.Diffraction pattern and experimental powder XRD diffraction pattern with simulation compares then.In this respect, sensitive range is 15-19.5 2 θ scopes.
The phosphoric acid of preparation 382.39g in the 2L polyethylene bottle (85% aqueous solution, Acros), demineralized water and 706.79g tetraethyl ammonium hydroxide solution (35% aqueous solution, mixture Sachem) of 371.99g.Then, formed mixture is transferred in the glass flask of the Neslab bath that places 30 ℃, after stirring this mixture with laboratory blender, 29.83gLudox AS 40 (40% silica) is joined in the flask, add the aluminium oxide (Condea Pural SB-1) of 227.01g subsequently.Form slurry, then this slurry was worn out 2 hours in 30 ℃ Neslab bath in continuous stirring.This mixture in molar ratio the meter composed as follows shown in:
0.12SiO
2/Al
2O
3/P
2O
5/TEAOH/35H
2O
This mixture is transferred in the 2L PARR stainless steel autoclave, and be heated to 165 ℃ with 20 ℃/hour speed.This mixture stirs down at 200rpm (the blade end speed of 1.3m/s) with laboratory blender in whole hydrothermal treatment consists process.Autoclave was kept 60 hours down at 165 ℃.After cool to room temperature, slurry is washed.This washed slurry has the d of 1.8 μ m
50Granularity is with Malvern Mastersizer 2000 (d
50Expression by volume) measures.Then should washed slurry drying, after above-mentioned calcination procedure, obtain the X-ray diffractogram of crystallized product.Use this diffraction pattern, carrying out DIFFaX analyzes, show that crystallized product contains two kinds of AEI/CHA commensals: 52% coexisting phase with AEI/CHA ratio of 10/90 and 48% the coexisting phase with AEI/CHA ratio of 45/55, overall A weighting EI/CHA ratio is 27/73.Silica/alumina mol ratio (the Si/Al of crystallized product
2) be found to be 0.16.
Embodiment 2-11
Repeat the operation of embodiment 1, but regulate the raw material of initiation material, have the silica/alumina mol ratio (Si/Al shown in the following table 2 with formation
2) reactant mixture.Crystallization is according to carrying out with embodiment 1 described identical mode, but as shown in table 2, in some cases, crystallization time is increased to 72 hours.Table 2 gives silica and alumina molar ratio, the d of washed slurry
50The AEI/CHA ratio of granularity and end product.
Table 2
| Embodiment | Mixture (Si/Al 2) | Crystallization time (hr) | Product (Si/Al 2) | AEI/CHA | d 50μm | ||
| | | Totally | |||||
| 1 | 0.12 | 60 | 0.16 | 10/90 52％ | 45/55 48％ | 27/73 | 1.8 |
| 2 | 0.10 | 60 | 0.13 | 10/90 50％ | 45/55 50％ | 27/73 | 1.9 |
| 3 | 0.11 | 60 | 0.14 | n/a* | n/a | n/a | 1.8 |
| 4 | 0.12 | 72 | 0.16 | 10/90 55％ | 45/55 45％ | 26/74 | 1.7 |
| 5 | 0.13 | 60 | 0.18 | 10/90 47％ | 45/55 53％ | 28/72 | 1.8 |
| 6 | 0.14 | 60 | 0.18 | 10/90 46％ | 45/55 54％ | 27/73 | 1.7 |
| 7 | 0.15 | 60 | 0.19 | n/a | n/a | n/a | 1.5 |
| 8 | 0.15 | 72 | 0.19 | n/a | n/a | n/a | 1.7 |
| 9 | 0.15 | 72 | 0.19 | 10/90 50％ | 45/55 50％ | 28/72 | 2.0 |
| 10 | 0.20 | 60 | 0.23 | 10/90 48％ | 45/55 52％ | 28/72 | 1.4 |
| 11 | 0.20 | 72 | 0.22 | 10/90 55％ | 45/55 45％ | 26/74 | 1.4 |
* n/a-can not obtain
The sample of each crystalline material of embodiment 2-11 is loaded in the fixed bed reactors that on-line gas chromatography is housed, is used for temperature at 450 ℃; 800-1000hr
-1WHSV and the methyl alcohol branch of 40psia (276kPa) depress and transform the raw material that contains methyl alcohol.The methanol conversion activity of each material, the first order rate constant K when reaching average methanol conversion
Max, calculate according to following equation:
K
max(Hz)＝-1n(1-Xm)/τ
Wherein Xm be methyl alcohol maximum conversion rate and
τ is space time (second).
Fig. 3 a has drawn the K that calculates
MaxThe Si/Al of value and each molecular sieve
2Relation curve.
Other sample of each crystalline material of embodiment 2-11 is loaded in the fixed bed reactors that on-line gas chromatography is housed, is used for temperature at 475 ℃; 100hr
-1WHSV and the pressure of 40psia (276kPa) transform the raw material that contains methyl alcohol down.Measure the mean P OS and the POR value of products therefrom, in Fig. 3 b, drawn the Si/Al of this result and each molecular sieve
2Relation curve.
Comparison diagram 3a and 3b as can be seen, at the about K of 400-650Hz
MaxDuring value, best POS and POR value have been obtained.
As follows, with embodiment 4 and 10 molecular sieve with have the Si/Al identical with the material of embodiment 3
2The AEI/CHA commensal form catalyst.
Preparation comprises the aqueous slurry of 45wt% solid, wherein said solid comprises the molecular sieve of 40wt%, the alumina binder that obtains by the aluminium chlorohydrate of the Reheis Inc. supply of N.J. Berkeley Heights with the trade name of Microdry of 12wt% and 48wt% with the trade name of Hydrite Ultrafine Imerys, the kaolin of Roswell supply by Georgia State, USA.With this slurry drying, then 650 ℃ of calcinings down, to form finished catalyst.
Determine the hydrothermal stability of each catalyst by the methanol conversion activity of quickening before the steam passivation test at catalyst and measure this catalyst afterwards.
Quicken steam passivation test and be loaded between the quartz fibre felt that piles up in 0.375 inch (0.95cm) internal diameter tubulose alloy reactor, use the remainder of silicon-carbide particle filling reactor then by catalyst with 2.0g.Allow the admixture of gas of nitrogen and steam flow through 30 days under with the speed of 300cc/min vapor partial pressure on this catalyst then at 700 ℃ and 13psi (90kPa).
In the microreactor of laboratory, measure the methanol conversion activity of each catalyst.The mixture of the carborundum of the catalyst granules of 10-30mg and 50-150mg is loaded in the stainless steel tube of external diameter 1/4 inch (0.63cm).This catalyst is placed between the two-layer quartz fibre frit, and allow methyl alcohol and this catalyst in reactor at 450 ℃, 25psi (172kPa) and 400hr
-1WHSV under (WHSV is based on the amount of the molecular sieve in the catalyst) contact.By online Agilent 6890 gas chromatographs of quick module LTM A58 have been installed, use the RVM Scientific that comes from Canadian Santa Barbara, the LOWOX DI-C300 10M of Inc. * 0.53mm pillar assay products materials flow.Following table 3 shows before the steam passivation and each activity of such catalysts K afterwards
Max(such as embodiment 12 definition).
Table 3
| Embodiment | Si/Al 2 | Initial K max | K after the steam treatment max | Loss of activity (%) |
| 3 | 0.14 | 113.4 | 44.4 | 60.8 |
| 4 | 0.16 | 296.9 | 194.1 | 34.6 |
| 10 | 0.23 | 306 | 237.4 | 22.4 |
Though with reference to particular the present invention has been described, has those skilled in the art will recognize that the present invention itself provides the modification that need not illustrate here.For this reason, should only determine true scope of the present invention so with reference to appended claims.
Claims (21)
1, the silicoaluminophosphamolecular molecular sieve that comprises first and second coexisting phases of CHA framework types and AEI framework types, wherein said first coexisting phase has 5/95 to 40/60 AEI/CHA ratio by the DIFFaX assay determination, second coexisting phase has 30/70 to 55/45 AEI/CHA ratio by the DIFFaX assay determination, and described molecular sieve has the silica/alumina mol ratio (Si/Al of 0.13-0.24
2).
2, silicoaluminophosphamolecular molecular sieve as claimed in claim 1, it has 0.15-0.22, the silica/alumina mol ratio of preferred 0.17-0.21.
3, silicoaluminophosphamolecular molecular sieve as claimed in claim 1 or 2, wherein said first coexisting phase has 5/95 to 20/80 AEI/CHA ratio.
4, as the described silicoaluminophosphamolecular molecular sieve of any one aforementioned claim, wherein said second coexisting phase has 40/60 to 50/50 AEI/CHA ratio.
5, as the described silicoaluminophosphamolecular molecular sieve of any one aforementioned claim, the ratio of wherein said first coexisting phase and second coexisting phase is 10: 90 to 90: 10, preferred 40: 60 to 60: 40.
6, as the described silicoaluminophosphamolecular molecular sieve of any one aforementioned claim, at least one reflection peak below its X-ray diffractogram has in 5-25 (2 θ) scope in 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, silicoaluminophosphamolecular molecular sieve as claimed in claim 6, wherein said X-ray diffractogram does not have reflection peak in 9.8-12.0 (2 θ) scope.
8, as the described silicoaluminophosphamolecular molecular sieve of any one aforementioned claim, its XRD figure shows two quant's signs in the scope of 16.6-18.5 (2 θ).
9, silicoaluminophosphamolecular molecular sieve as claimed in claim 8, wherein said first quant's sign concentrate on about 17 (2 θ) and described second quant's sign concentrates on about 18 (2 θ).
10, as the silicoaluminophosphamolecular molecular sieve of any one aforementioned claim, it has the d of 0.1-3 μ m
50Granularity.
11, the method for the silicoaluminophosphamolecular molecular sieve of synthetic any one aforementioned claim, described method comprises:
(a) prepare the mixture that comprises water source, reactive silicon source, reactive aluminum source, reactive phosphorus source and be used to guide organic directed agents of described molecular sieve formation, the mole that makes described mixture have in following scope is formed:
P
2O
5∶Al
2O
3 0.6-1.2，
SiO
2∶Al
2O
3 0.12-0.20，
H
2O∶Al
2O
3 25-50；
(b) described mixture is stirred and is heated to crystallization temperature;
(c) described mixture is kept time of 2-150 hour under described crystallization temperature; And
(d) reclaim described molecular sieve.
12, the mole that method as claimed in claim 11, wherein said mixture (a) have in following scope is formed:
P
2O
5∶Al
2O
3 0.8-1.1，
SiO
2∶Al
2O
3 0.12-0.15，
H
2O∶Al
2O
3 35-45。
13, as claim 11 or 12 described methods, the mol ratio of wherein organic directed agents and aluminium oxide is 0.6-1.2.
14, as each described method of claim 11-13, wherein said organic directed agents comprises the tetraethyl ammonium compound.
15, method as claimed in claim 14, wherein said organic directed agents also comprises dipropylamine.
16, as each described method of claim 11-15, wherein the heating in (b) should make with at least 8 ℃/hours speed, for example 10 ℃/hour to 40 ℃/hour the speed temperature of described mixture that raises.
17, as each described method of claim 11-16, wherein said crystallization temperature is 150-220 ℃.
18, as each described method of claim 11-17, wherein recycling step (d) is isolated described molecular sieve from mother liquor, and the mother liquor of at least a portion is recycled to step (b).
19, by the synthetic silicoaluminophosphamolecular molecular sieve of any one described method of claim 11-18.
20, the method that is prepared olefin product by oxygen-containing compound material, described method comprise allows described oxygen-containing compound material contact with each the catalyst of silicoaluminophosphamolecular molecular sieve that comprises claim 1-10 or claim 19.
21, method as claimed in claim 20, wherein said oxygen-containing compound material comprise methyl alcohol, dimethyl ether or their mixture.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US55961904P | 2004-04-05 | 2004-04-05 | |
| US60/559,619 | 2004-04-05 | ||
| US60/634,655 | 2004-12-09 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101935050A (en) * | 2010-09-10 | 2011-01-05 | 西北化工研究院 | Method for synthesizing silicoaluminophosphate molecular sieve by utilizing crystallization mother liquor |
| CN102099116A (en) * | 2008-07-25 | 2011-06-15 | 埃克森美孚化学专利公司 | Synthesis of chabazite-containing molecular sieves and their use in the conversion of oxygenates to olefins |
| JP2020529964A (en) * | 2017-08-10 | 2020-10-15 | 中触媒新材料股▲ふん▼有限公司 | AEI structure molecular sieve and its manufacturing method and use |
| CN112969662A (en) * | 2018-11-06 | 2021-06-15 | 巴斯夫公司 | Aluminosilicate zeolite intergrowth |
| WO2023130745A1 (en) * | 2022-01-05 | 2023-07-13 | 中汽研汽车检验中心（天津）有限公司 | Aei-cha symbiotic molecular sieve and catalyst thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO304108B1 (en) * | 1996-10-09 | 1998-10-26 | Polymers Holding As | A microporous silicoaluminophosphate composition, catalytic material comprising this composition and process for its preparation, and the use thereof to prepare olefins from methanol |
-
2005
- 2005-03-04 CN CNB2005800102771A patent/CN100503042C/en active Active
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102099116A (en) * | 2008-07-25 | 2011-06-15 | 埃克森美孚化学专利公司 | Synthesis of chabazite-containing molecular sieves and their use in the conversion of oxygenates to olefins |
| CN102099116B (en) * | 2008-07-25 | 2013-07-17 | 埃克森美孚化学专利公司 | Synthesis of chabazite-containing molecular sieves and their use in the conversion of oxygenates to olefins |
| CN101935050A (en) * | 2010-09-10 | 2011-01-05 | 西北化工研究院 | Method for synthesizing silicoaluminophosphate molecular sieve by utilizing crystallization mother liquor |
| CN101935050B (en) * | 2010-09-10 | 2012-06-20 | 西北化工研究院 | Method for synthesizing silicoaluminophosphate molecular sieve by utilizing crystallization mother liquor |
| JP2020529964A (en) * | 2017-08-10 | 2020-10-15 | 中触媒新材料股▲ふん▼有限公司 | AEI structure molecular sieve and its manufacturing method and use |
| JP7090158B2 (en) | 2017-08-10 | 2022-06-23 | 中触媒新材料股▲ふん▼有限公司 | Manufacturing method of AEI structural molecular sieve |
| CN112969662A (en) * | 2018-11-06 | 2021-06-15 | 巴斯夫公司 | Aluminosilicate zeolite intergrowth |
| WO2023130745A1 (en) * | 2022-01-05 | 2023-07-13 | 中汽研汽车检验中心（天津）有限公司 | Aei-cha symbiotic molecular sieve and catalyst thereof |
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| ZA200607123B (en) | 2008-08-27 |
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