CN1061903C - SAPO-34/metal or ceramic catalyzing composite material and preparation thereof - Google Patents
SAPO-34/metal or ceramic catalyzing composite material and preparation thereof Download PDFInfo
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- CN1061903C CN1061903C CN96106312A CN96106312A CN1061903C CN 1061903 C CN1061903 C CN 1061903C CN 96106312 A CN96106312 A CN 96106312A CN 96106312 A CN96106312 A CN 96106312A CN 1061903 C CN1061903 C CN 1061903C
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Abstract
The present invention relates to an SAPO-34 metal or a ceramic catalyzing composite material, which is composed of an SAPO-34 molecular sieve and a metallic or ceramic base material, wherein the metallic or ceramic base material is predesigned and loaded with the SAPO-34 molecular sieve, and is provided with the same or similar shape and size of a loose packed filler, a regular filler, a static mixer, a heterogeneous catalyst and a monolithic catalyst. The catalyzing property of the SAPO-34 molecular sieve is kept and requirement of different reactions are met by modifying the property; in the engineering property, the requirement of different process is met through changing the shape and size of the metallic or ceramic base material. The present invention can be used as a catalytic distilling element and a heterogeneous catalyst, and is used for the catalytic course of large amount of treatment and high speed of mass transfer and heat transfer.
Description
The invention relates to the catalytic composite materials and the preparation thereof that contain zeolite molecular sieve, specifically directly be compound in the catalytic composite materials and the preparation thereof on metal or ceramic base material surface about the SAPO-34 molecular sieve.
The development and application of catalytic distillation new technology is a kind of new trend, and it fills in solid catalyst in the destilling tower by rights, makes catalytic reaction separate two traditional technical process with product and also carries out continuously simultaneously in same tower.This suitable catalyst loading pattern, concrete version is arranged, and this version is called catalytic distillation structure, and it should guarantee that catalytic reaction carries out expeditiously, guarantee carrying out smoothly of separated process again, promptly it should have catalyst and two kinds of functions of filler.If in fixed bed fills in tower, then cause pressure drop very big traditional small catalyst particles, still-process is successfully carried out.Should prepare a kind of new catalytic composite materials for this reason, make it not only have advantages of high catalytic activity, and enough gas-liquid channels and enough gas-liquid contacts area can be provided after in filling in tower, to guarantee that pressure drop is low, mass-transfer efficiency is high.This shows,, just might be applied as catalytic distillation structure if this new catalytic material has the same with filler or similar shape and size.
Catalytic distillation is compared with traditional chemical process, advantage with many uniquenesses, one of them is exactly the combination that separates with product by catalytic reaction, reactant is in time separated apace with product, and product shifted out reaction zone, thereby the conversion ratio and the selectivity of reversible reaction and complex reaction (also, cascade reaction) are improved.If as fixed bed, product can not in time shift out reaction zone, then can not bring into play the superiority of catalytic distillation fully.Therefore the design of catalytic distillation structure should avoid being similar to the conversion zone existence of little fixed bed as much as possible, and the catalyst activity component is distributed on the catalytic distillation structure with higher separating power equably.
Present three common problems of catalytic distillation structure existence (USP 4232177,4443559, and 4215011,5057468,4847430,4624748, EP 428265A1): I) its shape and size differ bigger with filler, and the design and the operation of still-process brought inconvenience; II) existence can not separate product as the reaction zone of fixed bed effectively in tower; III) makes and the loading and unloading difficulty.Therefore, catalytic distillation needs a kind of new catalytic composite materials, and the separating power of existing filler has catalytic performance preferably again, and requires active component to be distributed on the composite equably.
Development from special-shaped catalyst.Now adopting maximum is pellet type catalyst, as cylindrical, trilobal etc., loads by the fixed bed mode.In order to improve the utilization rate of catalyst, can reduce the granularity of catalyst, but pressure drop is increased.So developed integral catalyzer, as honeycombed catalyst, provide parallel passage to material flow, pressure drop is reduced, geometrical surface increases (Chengdu Univ. of Science ﹠ Technology's journal 2,29～34 (1985)).But lacked the transmission of material between the parallel channels, the existence in passage inner laminar flow district simultaneously makes the even mass-transfer efficiency of material concentration skewness low.If can reduce laminar flow zone, strengthen radial diffusion, the product that catalyst surface is generated enters the main body phase apace, and reactant moves on to catalyst surface fast, then will improve catalytic reaction efficient.Therefore be necessary to change the flow regime of material, strengthen mass transfer and heat transfer by the geometry that changes catalyst.
The serious technical process of diffusion in some as hydrocarbon steam conversion, can not make full use of the activity of such catalysts component simultaneously, and the geometrical surface of catalyst granules is depended in the reinforcement of process at this moment.If adopt the method that reduces catalyst granules, then cause pressure drop to increase, therefore should under the condition that guarantees the catalyst mechanical strength, change the geometry of catalyst.At present existing wheel shape, inside and outside gear-like, many sieve plates of thin-walled steering wheel etc., but its wall thickness still differs big (3,1～8 pages of chemical fertilizer and catalysis, 1988) with the effecting reaction layer thickness.
The SAPO-34 molecular sieve was succeeded in developing (USP4,440,871) from 1984 by Union Carbide company and through updating afterwards, is expected to be applied in many chemical processes.If the SAPO-34 molecular sieve is prepared into a kind of catalytic composite materials that meets above-mentioned requirements, for example be prepared into a kind of catalytic distillation structure with shape and size of filler, the application of SAPO-34 is brought into play more fully, might be made some traditional chemical process bring revolutionary breakthrough and beneficial effect.
CA1235684 has described a kind of filter that directly forms one deck zeolite membrane on cellular glass, and the thickness of zeolite membrane is 1～500 μ m.A kind of membrane material of being made up of the zeolite membrane on the porous alumina carrier has been described among the JP-A-63291809.EP180200 has described a kind of membrane material that deposits particulate zeolite on porous substrate, and the aqueous slkali of milipore filter or cellular glass dipping being gone up the ultrafine zeolite particle prepares.
Described a kind of synthetic film that has zeolite crystal among the EP 0511739A1, its preparation process comprises: (1) preparation aperture is approximately the porous substrate of 0.1～3 μ m, Al wherein
2O
3Content is at least 90%; (2) at least one surface of this its material is immersed in the slurries of being formed by zeolite crystal and its precursor (making) by silicon source such as sodium metasilicate or waterglass; (3) at least once with base material and this slurry water thermal crystallisation.Forming high-density layer in this membrane material mesolite crystal duct He on the surface at base material, thus can be used for separating and refining mixture in useful component.
A kind of method for preparing molecular screen membrane from colloidal sol has been described among the WO 93/17781, this method comprises a kind of the water base of zeolite or alcohol radical sol composition of forming of formation, this sol composition is deposited on a kind of porous carrier, and this porous carrier and sol composition are exposed in the water vapour atmosphere under temperature is enough to make the condition of sol composition hydrothermal crystallizing and form zeolite membrane.
People such as Bratton in EP0481660A1, described a kind of on porous substrate load the film of zeolite type material is arranged, base material be shaped as flat plate, tubular or coiled, porous substrate can be porous metals, pottery, cermet, glass, mineral matter, charcoal or polymer, porous metals wherein can be that fiber screen shape, fibre metal combine or sintered metal fiber with sintered metal particle, and wherein available porous ceramics, glass, charcoal or mineral intermediate comprise poroid charcoal, carborundum, adobe or other silicate minerals.The preparation method of this film be with porous substrate (aperture can be 1～2000 μ m) but at least one surface be immersed in crystallization and become in the synthesized gel rubber of zeolite type material, make zeolite type material on the substrate surface crystallization, repeat these steps of one or many after the taking-up again and obtain the membrane material of zeolite type material direct crystallization on base material.Porous substrate is being immersed before synthesized gel rubber carries out crystallization, can be earlier at substrate surface in conjunction with last layer Ni, Co, Mo metal or its oxide (EP0481658A1), and/or, perhaps base material is carried out sour preliminary treatment (EP0481659A1) in conjunction with the oligomer (WO 93/19840) of last layer silicic acid.
The zeolite type material that loads in the above-mentioned patent on the base material all is to be used for the material that film separates, promptly has the material that maximum surface/body is compared, base material wherein all must be a porous material, zeolitic material wherein all is to be filled in the duct of porous substrate to form compacted zone, should control the appearance of " pinprick " in order to avoid influence the effect that film separates as far as possible.At present also not with SAPO-34 zeolite type material load bibliographical information with preparation catalytic distillation structure and irregular shape catalyst on the given shape base material, if the zeolite type material can be made catalytic distillation structure or irregular shape catalyst, bring revolutionary breakthrough and beneficial effect will for catalysis engineering field.
Though there are many scholars that active component ZSM-5 molecular sieve is compound in asbestos (USP4511667, catalysis journal 11 (3) 204-209 (1990)), make composite on vermiculite (CN 1059673A), the silica gel (CN1084100A), but still have the problem of shaped catalyst, promptly do not solve the problem of catalyst geometry in the commercial Application process.
The purpose of this invention is to provide a kind of new catalytic composite materials, the SAPO-34 molecular sieve directly is compound on metal or the ceramic base material, it can be used as excellent catalytic distillation structure, catalytic reaction and product separation energy while continuous high-efficient ground in same tower is carried out, also can use to strengthen mass transfer, heat transfer and the reduction pressure drop of logistics as special-shaped catalyst, reduce the thickness of catalyst layer simultaneously, improve the utilization rate of catalyst.
Catalytic composite materials provided by the present invention directly is compound in SAPO-34 molecular sieve thin layer in advance equably, securely and designs as required, arbitrary shape, the arbitrarily metal of size or ceramic base material surface and the catalytic composite materials that forms.
SAPO-34 molecular sieve on the said composite can be various SAPO-34 molecular sieves included in the prior art, wherein SiO
2/ Al
2O
3Be 0.1～5, Al
2O
3/ P
2O
5Be 0.1～5, and can carry out various modifications to enlarge its range of application the molecular sieve on this composite.
The material of said metal base can be that simple metal comprises iron, nickel, copper, molybdenum, aluminium, magnesium, chromium, titanium, vanadium, manganese, zinc etc., also can be that the alloy that contains these metals comprises various stainless steels, various aluminium alloy, each Albatra metal-etc.; The crystalline phase of its ceramic base material can be an oxysalt, as silicate, titanate, zirconates etc., also can be oxide, nitride and carbide etc.Metal wherein or ceramic base material are dense materials, it also can be porous material, the design arbitrarily as required of its shape and big I, as be designed to dumped packings such as θ ring, rectangular saddle ring, cascade ring, Pall ring, regular filler such as corrugated plating, ripple silk net, and the shape of special-shaped catalysts such as static mixer, cellular integral catalyzer, wheel shape and size or shape similarly and size.
The thickness of SAPO-34 molecular sieve thin layer is 5～300 microns in the said composite.Because the molecules of active components of this composite sieve layer can be very thin, composite will keep the geometry and the size of metal or ceramic base material, can design the shape and the size of metal or ceramic base material according to the requirement of concrete application, that is to say that the Flow of Goods and Materials state can be determined by the design of metal or ceramic base material in the use.
The preparation method of said composite provided by the present invention is immersed in crystallization in the synthetic liquid that can synthesize the SAPO-34 molecular sieve with metal or ceramic base material, take out after washing, drying, perhaps repeat this submergence crystallization steps of one or many again, obtain catalytic composite materials of the present invention, it can carry out modification by ion-exchange or other method before use.
The said synthetic liquid that can synthesize the SAPO-34 molecular sieve can design its composition and prescription by prior art, but the amount of water is big when more synthetic than routine, wherein can contain silicon sources such as Ludox or waterglass, aluminium source such as sodium metaaluminate, aluminium salt or replace other hetero atom of aluminium such as boron, phosphorus, iron etc., inorganic base and/or organic base, water and the agent of organic ammonium template.Wherein preferable molar ratio scope is SiO
2/ Al
2O
3=0.1～5, P
2O
5/ Al
2O
3=0.1～5, R
+(agent of organic ammonium template)/P
2O
5=0.5～5, H
2O/Al
2O
3=40～400.
The agent of said organic ammonium template can be all organic ammonium template agent that can synthesize the SAPO-34 molecular sieve, as tetraethylammonium bromide etc.
Condition when the condition of said crystallization is synthesized the SAPO-34 molecular sieve with routine is identical, and wherein crystallization temperature is 150～230 ℃, and crystallization time is 0.5～10 day.
In recombination process, will need the metal or the ceramic base material of composite molecular screen to be immersed in the synthetic liquid, but the time of submergence can change, as metal or ceramic base material and synthetic liquid are put into synthesis reactor simultaneously, also can be earlier with synthesize liquid at a certain temperature crystallization put into base material after a period of time again, also can take out composite after compound at different crystallization times.
Catalytic composite materials provided by the present invention has following advantage as catalytic distillation structure or irregular shape catalyst:
I) its geometry and big I are flexible and changeable as required, to reduce pressure drop, improve mass transfer and heat transfer efficiency, the catalytic distillation process is efficiently successfully carried out, and make product in time shift out reaction zone, improve the conversion ratio and the selectivity of catalytic reaction;
II) the SAPO-34 active component is distributed in substrate surface equably, has improved the geometrical surface of catalyst;
III) the active component layer thickness is less and can regulate, and than custom catalysts higher utilization rate is arranged;
IV) can carry out modulation and modification to SAPO-34 active component layer and do not influence the intensity of active layer, make the range of application of SAPO-34 unrestricted.
Fig. 1,2,3,4 is respectively metal or the figure of the ESEM (SEM) before and after the ceramic base material surface recombination SAPO-34 molecular sieve among the embodiment 1,8,10,11.Wherein a represents the surface before the composite molecular screen, and b represents the surface after compound.
Fig. 5,6,7 is respectively metal or the figure of the X-ray diffraction (XRD) before and after the ceramic base material surface recombination SAPO-34 molecular sieve among the embodiment 1,8,11.Wherein a represents the sample before the composite molecular screen, and b represents the sample after compound.
The following examples will the present invention is further illustrated.
The thing on the catalytic composite materials surface of preparing in the example detects by X-ray diffraction (XRD) mutually; The pattern on surface is observed by ESEM (SEM); The body phase SiO of molecular sieve layer
2/ Al
2O
3Be to measure by plasma emission spectroscopy method (ICP) from the powder molecular sieve that composite scrapes off, the thickness of molecular sieve layer is measured by SEM on the composite cross-sections.
Example 1～3
Take by weighing 6.74g aluminium isopropoxide (The British Drug Houses Ltd), 24.3g tetraethyl ammonium hydroxide (10wt%TEAOH), phosphoric acid 3.805g (Red Star chemical plant, 85wt% Beijing), 2.4g Ludox (25%SiO2, state-run Wenzhou catalyst plant) put into three beakers respectively for each three parts, add deionized water 1 respectively) 11.4g, 2) 31.99g, 3) 74.99g gets three parts of synthetic liquid after stirring.These three parts of synthetic liquid are poured into respectively in three synthesis reactors that 3 * 3 * 0.1mm θ ring stainless steel helices (Iron and Steel Research Geueral Inst filler factory) has been housed, in 180 ℃ of following crystallization after three days, take out washing, found that three samples all have uniform, firm SAPO-34 molecular sieve layer to be compound in stainless steel surfaces, its thickness is respectively 1 after measured) 45 μ m; 2) 36 μ m; 3) 27 μ m, and along with water content increases and reduces.
Example 4
The method of pressing example 2 is synthetic, records the SAPO-34/ stainless steel composite material that molecular sieve layer thickness is 36 μ m after the washing drying; With this composite carry out the second time with the quadrat method crystallization after, its molecular sieve layer thickness is 69 μ m; This composite is carried out for the third time with after the quadrat method crystallization again, and its molecular sieve layer thickness is 103 μ m; This composite is carried out the 4th time again with after the quadrat method crystallization, and its molecular sieve layer thickness is 145 μ m, illustrates that molecular sieve layer thickness increases with the crystallization number of times.At last molecular sieve layer is drawn together the SiO that gets off to record crystal
2/ Al
2O
3Be 0.41, P
2O
5/ Al
2O
3Be 0.79.
Example 5～7
Take by weighing 10.6g aluminium isopropoxide (The British Drug Houses Ltd), 115g tetraethyl ammonium hydroxide (10wt%TEAOH), phosphoric acid 5.5g (85wt%, Red Star chemical plant, Beijing), add 5.6g sodium metaaluminate (Beijing Chemical Plant) after the mixing again, add 16g Ludox (25%SiO at last
2, state-run Wenzhou catalyst plant) mix synthetic liquid.This synthetic liquid is divided into three parts, pour three respectively into and be equipped with 5) stainless steel strip, 6) pure nickel bar, 7) in the synthesis reactor of pure iron bar, after three days, take out the lath washing in 190 ℃ of following crystallization, found that three samples all have uniform, firm SAPO-34 molecular sieve layer to be compound in the lath surface.The SiO of stainless steel lath surface molecular sieve after measured
2/ Al
2O
3Be 2.31, P
2O
5/ Al
2O
3Be 0.32.
Example 8～9
Take by weighing 6.74g aluminium isopropoxide (The British Drug Houses Ltd), 3.805g phosphoric acid (85wt%, Red Star chemical plant, Beijing), 2.4g Ludox (25%SiO
2, state-run Wenzhou catalyst plant) each two parts put into two beakers, add TEAOH (10wt%) 8 respectively) 24.3g, 9) 48.6g and deionized water 8) 11.4g, 9) 0.0g, after stirring two parts of synthetic liquid.These two parts of synthetic liquid are poured into respectively in the synthesis reactor that φ 14 * 32mm ceramic honey comb (Chinese Academy of Sciences ecological institute) has been housed, 200 ℃ of following crystallization find two days later two samples all equably, compound securely on the SAPO-34 molecular sieve layer.
Example 10～11
By the example 2 synthetic liquid of preparation that feeds intake, but base material adopts 10 respectively) pure alundum (Al potsherd (big Chemical Physics research institute), 11) pure iron sheet metal (non-ferrous metal is studied total institute).To synthesize liquid and after ten days, find all compound even, firm SAPO-34 molecular sieve layer on two kinds of substrate surfaces 160 ℃ of crystallization.
Example 12～15
By the example 1 synthetic liquid of preparation that feeds intake, but base material adopts 12 respectively) industrial Dg25 metal cascade ring filler, 13) industrial Dg25 pottery intalox saddle (Pingxiang City petrochemical industry porcelain structured packing factory), 14) φ 14 * 32mm ceramic honey comb (Chinese Academy of Sciences ecological institute), 15) φ 3 * 3 * 0.1mm θ encircles (Iron and Steel Research Geueral Inst filler factory).Same method crystallization finds that two days later four kinds of difform metals or ceramic base material are all covered equably by the SAPO-34 molecular sieve layer.
Example 16
20ml φ 3 * 3 * 0.1mm θ ring composite that example 15 is synthesized carry out again the second time with the quadrat method crystallization after the molecular sieve compound quantity be 1.2234g.This sample is carried out temperature-programmed calcination, and its programming rate is 1 ℃/min, respectively 120 ℃, 300 ℃, 450 ℃ C, 500 ℃, and constant temperature 1hr, 2hr, 24hr, cooling naturally then.Sample after the roasting is put into 1MNH
4In the Cl solution, under 90 ℃, stir and carry out ion-exchange 2hr, spend deionised water again to there not being Cl
-(AgNO
3Detect), at this moment the SAPO-34 molecular sieve has been finished NH
4 +Exchange.At last this SAPO-34 composite is made a strength test, be about to this composite and put into the glass destilling tower of φ 25.4 * 600mm, with benzene-carbon tetrachloride is that system is returned entirely and heated up in a steamer, each 8hr that continues, repeated experiments is 20 times like this, then composite is taken out washing, dry, weighing, its molecular sieve reservation amount is 0.9843g, and its retention is 80.5%.
Claims (9)
1.SAPO-34 molecular sieve directly is compounded in the catalytic composite materials as catalytic distillation structure or irregular shape catalyst on metal or the ceramic base material, it is characterized in that this composite is made up of the pre-designed shape with dumped packing, structured packing, static mixer, special-shaped catalyst and integral catalyzer of SAPO-34 molecular sieve and this molecular sieve of load and the metal or the ceramic base material of size or shape similarly and size, SAPO-34 molecular sieve wherein directly synthesizes on said base material by hydrothermal synthesis method.
2. according to the catalytic composite materials of claim 1, it is characterized in that said SAPO-34 molecular sieve is the molecular sieve of sial phosphorus, its SiO
2/ Al
2O
3Be 0.1～5, P
2O
5/ Al
2O
3Be 0.1～5.
3. according to the catalytic composite materials of claim 1, it is characterized in that wherein the thickness of SAPO-34 molecular sieve layer is 5～300 microns.
4. according to the catalytic composite materials of claim 1, the material that it is characterized in that said metal base is the simple metal of chosen from Fe, nickel, copper, molybdenum, aluminium, magnesium, chromium, titanium, vanadium, manganese, zinc, or is selected from the metal alloy of stainless steel, aluminium alloy, copper alloy; The crystalline phase of its ceramic base material is the oxysalt that is selected from silicate, titanate, zirconates, or their oxide, nitride or carbide.
5. the preparation method of the said catalytic composite materials of claim 1 is characterized in that this method comprises metal or ceramic base material are immersed in the H that can synthesize the SAPO-34 molecular sieve
2O/Al
2O
3Mol ratio is that hydrothermal crystallizing is at least once in 40～400 the synthetic liquid.
6. according to the preparation method of claim 5, it is characterized in that containing silicon source, aluminium source and phosphoric acid, inorganic base or organic base, water and the agent of organic ammonium template in the said synthetic liquid that can synthesize the SAPO-34 molecular sieve.
7. according to the preparation method of claim 6, it is characterized in that the molar ratio scope is SiO in the said synthetic liquid
2/ Al
2O
3=0.1～5, Al
2O
3/ P
2O
5=0.1～8, R
+/ P
2O
5=0.5～8, H
2O/Al
2O
3=40～400.
8. according to the preparation method of claim 5, the condition that it is characterized in that said crystallization is that crystallization temperature is 150～230 ℃, and the time is 0.5～10 day.
9. the described catalytic composite materials of claim 1 is as the application of catalytic distillation structure or special-shaped catalyst.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96106312A CN1061903C (en) | 1996-06-05 | 1996-06-05 | SAPO-34/metal or ceramic catalyzing composite material and preparation thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96106312A CN1061903C (en) | 1996-06-05 | 1996-06-05 | SAPO-34/metal or ceramic catalyzing composite material and preparation thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1167006A CN1167006A (en) | 1997-12-10 |
| CN1061903C true CN1061903C (en) | 2001-02-14 |
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ID=5119061
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96106312A Expired - Fee Related CN1061903C (en) | 1996-06-05 | 1996-06-05 | SAPO-34/metal or ceramic catalyzing composite material and preparation thereof |
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|---|---|---|---|---|
| CN1332761C (en) * | 2005-07-13 | 2007-08-22 | 清华大学 | Process for preparing load type silicon phoshporus aluminium molecular sieve |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| CN1077658A (en) * | 1992-04-20 | 1993-10-27 | 太原工业大学 | The method of preparation of molecular sieve membrane on porous silicate material surface |
| US5413975A (en) * | 1992-05-21 | 1995-05-09 | Basf Aktiengesellschaft | Fixing large zeolite and zeolite-like molecular sieve crystals on moldings |
-
1996
- 1996-06-05 CN CN96106312A patent/CN1061903C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4440871A (en) * | 1982-07-26 | 1984-04-03 | Union Carbide Corporation | Crystalline silicoaluminophosphates |
| CN1077658A (en) * | 1992-04-20 | 1993-10-27 | 太原工业大学 | The method of preparation of molecular sieve membrane on porous silicate material surface |
| US5413975A (en) * | 1992-05-21 | 1995-05-09 | Basf Aktiengesellschaft | Fixing large zeolite and zeolite-like molecular sieve crystals on moldings |
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| Publication number | Publication date |
|---|---|
| CN1167006A (en) | 1997-12-10 |
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