CN103833047A - SAPO-5/SAPO-18/SAPO-34 symbiotic composite molecular sieve and preparation method for same - Google Patents
SAPO-5/SAPO-18/SAPO-34 symbiotic composite molecular sieve and preparation method for same Download PDFInfo
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Abstract
The invention discloses a composite molecular sieve, which is obtained by the symbiosis of an SAPO-5 (silico-alumino-phosphate-5) molecular sieve, an SAPO-18 molecular sieve and an SAPO-34 molecular sieve. The composite molecular sieve is characterized in that the molar ratio of raw materials for preparing the composite molecular sieve, namely R:SiO2:Al2O3:P2O5:H2O is (1.2-1.8):(0.2-0.8):1:(0.9-1.25):(40-80), wherein R represents a triethylamine or N,N-diisopropylethylamine template agent. A catalyst which is prepared from the composite molecular sieve and is used for preparing light olefin from an organic oxygen-containing compound is high in catalytic activity and propene and butene selectivity and long in service life.
Description
Technical field
The present invention relates to a kind of composite molecular screen being formed by SAPO-5 molecular sieve, SAPO-18 molecular sieve and the symbiosis of SAPO-34 molecular sieve and preparation method thereof, this composite molecular screen is for the preparation of the catalyzer of organic oxygen-containing compound producing light olefins, and can significantly improve the productive rate of propylene and butylene.
Background technology
Petro-technology route is produced the method for low-carbon alkene as an alternative, and the technique of organic oxygen-containing compound, for example methyl alcohol and/or dme producing light olefins is day by day subject to people and pays close attention to.This technique is used molecular sieve catalyst conventionally.The molecular sieve catalyst of organic oxygen-containing compound producing light olefins is the ZSM-5 molecular sieve that is proposed and adopted by Mobil company of the U.S. the earliest, but this molecular sieve pore passage is large, surface acidity is strong, the selectivity of ethene and/or propylene is also lower, simultaneously, also can generate the by product such as aromatic hydrocarbons and paraffin, so people begin one's study and develop the more practical molecular sieve catalyst of other organic oxygen-containing compound producing light olefins.
Afterwards, people have developed again the molecular sieve in various little ducts gradually as the catalytic active component of organic oxygen-containing compound producing light olefins catalyzer, for example T zeolite molecular sieve, erionite molecular sieve, chabazite (CHA) molecular sieve, but these catalyzer in use show easy coking and the fast feature of deactivation rate, these shortcomings cause their further promotion and application to be restricted.
USP4499327 and US5095163 disclose the Catalysts and its preparation method of a kind of aluminosilicophosphate (SAPO) as methanol-to-olefins (MTO).,, also there are numerous documents to disclose multiple SAPO family molecular sieves, especially SAPO-34 molecular sieve as the active ingredient of the catalyzer of preparing light olefins from methanol thereafter.
For example, CN102557073A discloses a kind of preparation method of SAPO-34 molecular sieve, the method is by the order by merging of optimizing materials and the state of initial gel, take two sections of ways that heat up and control temperature rise rate, improve the degree of crystallinity of the SAPO-34 molecular sieve of synthesized, effectively control strength of acid and the sour density of SAPO-34 molecular sieve, made it when for methanol to olefins reaction, there is higher ethene and/or Propylene Selectivity.
CN101767800B also discloses a kind of preparation method of SAPO-34 molecular sieve, and by adopting fluorochemical, as auxiliary template, agent improves the relative crystallinity of SAPO-34 molecular sieve and the selectivity of light olefin in MTO reaction to the method.
Conventionally, silicon aluminium phosphate (SAPO) molecular sieve that can be used as the catalytic active component of organic oxygen-containing compound producing light olefins catalyzer has SAPO-5, SAPO-11, SAPO-17, SAPO-18 and/or SAPO-34 molecular sieve etc., and wherein general with SAPO-34 molecular sieve, although above-mentioned SAPO Series Molecules sieve is all by [SiO
4], [AlO
4] and [PO
4] tetrahedron element forms, but their microcosmic crystalline structure there are differences, and for example, the crystalline structure of SAPO-34 molecular sieve is chabazite (CHA) type; And the crystalline structure of SAPO-18 molecular sieve is AEI structure, although its AEI structure is and the microcosmic pore passage structure of CHA structure similar.
In fact, the AEI structure elementary cell of SAPO-18 molecular sieve is two six-rings and tetra-atomic ring, and its orifice diameter is 0.43 nanometer, and therefore, it belongs to pore zeolite structure.Experiment shows: as the catalytic active component of organic oxygen-containing compound producing light olefins catalyzer, SAPO-18 molecular sieve has the work-ing life more superior than SAPO-34 molecular sieve.
In reaction for preparing light olefins from methanol, though SAPO-34 show ethene and propylene than more excellent product selectivity, but in reaction process, easily form carbon distribution fast and make rapid catalyst deactivation.And SAPO-18 molecular sieve B acid acid position is less, medium tenacity acid site compared with SAPO-34 molecular sieve a little less than, therefore SAPO-34/SAPO-18 composite molecular screen can reduce carbon distribution speed, the life-span of extending catalyst.
CN102372291A discloses composite molecular screen of a kind of SAPO-18/SAPO-34 symbiosis and preparation method thereof, and it has solved the problem that existing molecular sieve bore diameter is single, catalytic activity is not high.The method is the template that is simultaneously applicable to SAPO-18 and SAPO-34 growth by adopting, control the proportioning raw materials in the crystallization liquid that is applicable to SAPO-18 and SAPO-34 growth, regulate the crystallization temperature of related SAPO-18 and SAPO-34 growth, the composite molecular screen of synthetic SAPO-18 and SAPO-34 symbiosis under hydrothermal condition.In the time that above-mentioned composite molecular screen is used for methanol to olefins reaction, ethene and propene yield can reach more than 80%, and the life-span can reach 120 minutes.
Conventionally, micro porous molecular sieve has regular microvoid structure, suitable acidity, good hydrothermal stability, but micro porous molecular sieve also can generate compared with macromole in reaction process, and narrow duct causes macromole product mass transfer diffusional resistance excessive, product is out comparatively difficult from duct internal divergence, thereby, aggravated the coking of molecular sieve catalyst duct, and caused catalyst deactivation.
For methanol to olefins reaction, molecular sieve inside diffusional resistance has affected the rate of diffusion of product; In the cage of molecular sieve, generate after target product-alkene, alkene is in the process to external diffusion, on acidic site that can be in molecular sieve, further there is oligomeric, condensation, hydrogen transfer reactions, cause catalyst carbon deposit or generate by product alkane, this has just reduced the selectivity of object product-alkene, and causes catalyzer coking and deactivation.
Another kind of SAPO Series Molecules sieve is SAPO-5 molecular sieve, and it belongs to AFI type molecular sieve, the one-dimensional linear of the twelve-ring that its skeleton is alternately made up of two tetra-atomic rings and six-ring and not cross one another channel system, and it belongs to macroporous type micro porous molecular sieve.If introduce appropriate wide-aperture SAPO-5 molecular sieve in the SAPO-34 of small-bore molecular sieve, will likely improve the performance of SAPO-34 molecular sieve and catalyzer thereof, and overcome the shortcoming of above-mentioned SAPO-34 molecular sieve catalyst.
CN102372290A discloses the synthetic method of a kind of SAPO-5 and SAPO-34 coexisting molecular sieve, and described method, by optimizing material proportion, obtains SAPO-5 and SAPO-34 coexisting molecular sieve, and wherein, material proportion is: Al
2o
3: P
2o
5: SiO
2: R:H
2o mol ratio is 1.0:(0.2-2.0): (0.1-2.0): (0.5-2.5): (20-100), wherein, R represents template.
CN102049294B discloses molecular sieve of a kind of composite structure and its preparation method and application, in fact, it is a kind of AlPO-5/SAPO-34 composite molecular screen, in the preparation process of this composite molecular screen, SAPO-34 molecular sieve is incorporated in the raw material of preparing AlPO-5 molecular sieve and is gone, finally form by AlPO-5 and the synthetic composite molecular screen of SAPO-34.In the time that this composite molecular screen is used for organic oxygen-containing compound reaction for preparing light olefins, due to macropore and/or meso-hole structure that AlPO-5 has some amount, is extended the work-ing life of molecular sieve catalyst to some extent, and increased the selectivity of propylene.But in above-mentioned AlPO-5/SAPO-34 composite molecular screen, AlPO-5 and SAPO-34 are not obviously symbiosis.
Above patent documentation is introduced with for referencial use in full at this.
Traditional MTO technology is mainly take ethene and/or propylene as object product, butylene and C
5the above component of+hydrocarbon is only by product.But C
4hydrocarbon is petrochemical complex and organic chemical industry's important raw materials for production, and its purposes comes into one's own day by day.C
4alkene downstream derivative is wide in variety, and market potential is large.
The 2-propyl enanthol of being produced by butylene is to produce the main raw material of DPHP, China the coming years DPHP market outlook wide, and there is good economic benefit.Develop extraordinary polyolefine and specialty elastomer, produce as polybutene, polyisobutene, styrene-butadiene rubber(SBR) with take iso-butylene as development of raw materials MTBE, ETBE or through iso-butylene-MTBE-isooctene the requirement that octane-iso alkylate oil all meets " derived product is take general synthetic materials as main " that propose in country's 12 planning, products obtained therefrom differentiation degree is low, and added value is high, functional strong.
Improve the ratio of alkene downstream high-end product, develop and produce the PP Pipe Compound such as extraordinary polyethylene and polypropylene, it is industry development guilding policy that polyisoprene rubber, rare earth polybutadiene rubber, quickening realize the replacement of alkene industrial product structure adjustment and escalation.Now, C
4hydrocarbon resource is mainly derived from the by product of refining of petroleum, preparing ethylene by steam cracking and methanol-to-olefins (MTO) technique, so, C
4hydrocarbon resource need further expand.
Use the only C of by-product 5.5% left and right (to methyl alcohol) of traditional methanol-to-olefins (MTO) technique of SAPO-34 molecular sieve catalyst
4hydrocarbon mixture, this C
4in hydrocarbon mixture, 1,3-butadiene, iso-butylene content are lower, and main ingredient is butene-1 and butene-2, and they account for 90%.(referring to " olefin hydrocarbon making by coal and the derived product market requirement and Analysis on Processing Technology ", Wu Xiuzhang).For realizing C
4hydrocarbon utilization reaches scale and benefit, needs to improve C
4hydrocarbon output, like this, just urgently exploitation has high C
4the catalyzer of olefine selective.
The present invention is devoted to solve above-mentioned technical barrier, and strives developing a kind of SAPO-5/SAPO-18/SAPO-34 composite molecular screen for the preparation of organic oxygen-containing compound alkene catalyst processed simultaneously with good catalytic activity, higher propylene and/or butylene selectivity and excellent work-ing life.
Summary of the invention
According to a first aspect of the invention, provide a kind of composite molecular screen, formed by SAPO-5 molecular sieve, SAPO-18 molecular sieve and the symbiosis of SAPO-34 molecular sieve, it is characterized in that: prepare this composite molecular screen raw material used and meet following ratio: R:SiO
2: Al
2o
3: P
2o
5: H
2o mol ratio is (1.2-1.8): (0.2-0.8): 1:(0.9-1.25): (40-80), wherein, R represents triethylamine or N, N-diisopropyl ethyl amine template.
Preferably, prepare this composite molecular screen raw material used and further meet following ratio: Et
3n:SiO
2: Al
2o
3: P
2o
5: H
2o mol ratio is 1.5:(0.3,0.4 or 0.6): 1:1:50.
Conventionally, in the raw material of the above-mentioned composite molecular screen of preparation, SiO
2come from tetraethoxy, silicon sol, white carbon black, water glass, white carbon black or they mixture arbitrarily; Al
2o
3come from pseudo-boehmite, pseudobochmite, aluminium colloidal sol, aluminum isopropylate, aluminium salt, aluminate, activated alumina or they mixture arbitrarily; P
2o
5come from phosphoric acid, phosphorous acid, phosphoric acid salt and/or phosphorous oxides.
Preferably, by regulating triethylamine or the N in above-mentioned composite molecular screen raw material, N-diisopropyl ethyl amine template and SiO
2consumption, adjusts SAPO-5 molecular sieve, SAPO-18 molecular sieve and the relative content of SAPO-34 molecular sieve in composite molecular screen, and then adjusts pore passage structure distribution and the acidity of described composite molecular screen.
According to a second aspect of the invention, provide a kind of preparation method of above-mentioned composite molecular screen, it comprises the following steps successively:
(1) in proportion by aluminium source, phosphorus source, silicon source, triethylamine or N, N-diisopropyl ethyl amine template and water mix at the temperature of 20 ℃-90 ℃, control the rate of addition of each step raw material, obtain comprising aluminium source, phosphorus source, silicon source, triethylamine template or N, the mixing solutions of N-diisopropyl ethyl amine and water, in above-mentioned mixing solutions, triethylamine or N, N-diisopropyl ethyl amine template: SiO
2: Al
2o
3: P
2o
5: H
2the mol ratio of O is (1.2-1.8): (0.2-0.8): 1:(0.9-1.25): (40-80); (2) stir described mixing solutions until the each component of mixing solutions is uniformly dispersed, mixing solutions described in ageing subsequently, until form gel mixture; (3) gel mixture is put into 170 ℃ of-210 ℃ of reactors and carried out Hydrothermal Synthesis crystallization 24-80 hour; (4) separate the solid crystal thing that crystallization forms, drier described solid crystal thing, the former powder of composite molecular screen obtained; (5) the former powder 2-8 hour of the above-mentioned composite molecular screen of roasting at 450-650 ℃, removes triethylamine or N wherein, and N-diisopropyl ethyl amine template obtains the composite molecular screen by SAPO-5 molecular sieve, SAPO-18 molecular sieve and the symbiosis of SAPO-34 molecular sieve.
In above-mentioned preparation method, preferably, described silicon source is tetraethoxy, silicon sol, white carbon black, water glass, white carbon black or they mixture arbitrarily; Described aluminium source is pseudo-boehmite, pseudobochmite, aluminium colloidal sol, aluminum isopropylate, aluminium salt, aluminate, activated alumina or they mixture arbitrarily; Described phosphorus source is phosphoric acid, phosphorous acid, phosphoric acid salt and/or phosphorous oxides.
Preferably, in above-mentioned preparation method, in step (4), the solid crystal thing that described separation crystallization forms refers to: the solid crystal thing that centrifuging forms, the crystallisate mother liquor being produced to remove Hydrothermal Synthesis crystallization, with solid crystal thing described in deionized water wash at least one times, then described in centrifuging solid crystal thing is at least one times.
Preferably, in above-mentioned preparation method, the described mixing solutions in step (1) is prepared by the following method: mix aluminium source, He Gui source, phosphorus source respectively (1) with water, forms aluminium source solution, phosphorus source solution and silicon source solution; (2) lentamente aluminium source solution is added drop-wise in the solution of phosphorus source, or phosphorus source solution is added drop-wise in the solution of aluminium source, form the mixing solutions in He Lin source, aluminium source; (3) lentamente silicon source solution is added drop-wise in the mixing solutions in He Lin source, aluminium source, or the mixing solutions in He Lin source, aluminium source is added drop-wise in the solution of silicon source, form the mixing solutions in aluminium source, He Gui source, phosphorus source; (4) in the mixing solutions in described aluminium source, He Gui source, phosphorus source, add triethylamine or N again, N-diisopropyl ethyl amine template, comprises aluminium source, phosphorus source, silicon source, triethylamine or N, the mixing solutions of N-diisopropyl ethyl amine template and water thereby form.
According to a third aspect of the invention we, provide a kind of catalyzer by organic oxygen-containing compound producing light olefins, the catalytic active component of described catalyzer is above-mentioned composite molecular screen or the composite molecular screen of being prepared by aforesaid method.
Preferably, above-mentioned organic oxygen-containing compound is methyl alcohol and/or dme; Described low-carbon alkene is ethene, propylene and/or butylene.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) photo of SAPO-5/SAPO-18/SAPO-34 composite molecular screen of the present invention.
Fig. 2 is the X-ray diffracting spectrum of SAPO-5/SAPO-18/SAPO-34 composite molecular screen in embodiment 1.
Fig. 3 is the X-ray diffracting spectrum of SAPO-5/SAPO-18/SAPO-34 composite molecular screen in embodiment 2.
The X-ray diffracting spectrum of SAPO-5/SAPO-18/SAPO-34 composite molecular screen in Fig. 4 embodiment 3.
Fig. 5 is each reaction product selectivity and the relation curve in reaction times when SAPO-5/SAPO-18/SAPO-34 symbiosis composite molecular screen is as catalyzer in embodiment 1.
Fig. 6 is each reaction product selectivity and the relation curve in reaction times when SAPO-5/SAPO-18/SAPO-34 symbiosis composite molecular screen C is as catalyzer in embodiment 3.
Fig. 7 is each reaction product selectivity and the relation curve in reaction times when SAPO-5/SAPO-18/SAPO-34 symbiosis composite molecular screen D is as catalyzer in embodiment 4.
Fig. 8 is each reaction product selectivity and the relation curve in reaction times when SAPO-5 molecular sieve is as catalyzer in comparative example 1-1.
Fig. 9 is each reaction product selectivity and the relation curve in reaction times when SAPO-34 molecular sieve is as catalyzer in comparative example 1-3.
Figure 10 is each reaction product selectivity and the relation curve in reaction times when SAPO-5/SAPO-34 composite molecular screen is as catalyzer in comparative example 1-2.
Embodiment
By being further explained in detail the present invention below with reference to the description of embodiment and accompanying drawing, but below describe only for making general technical staff of the technical field of the invention can more be expressly understood principle of the present invention and marrow, and do not mean that the present invention is carried out to any type of restriction.
SAPO-5/SAPO-18/SAPO-34 composite molecular screen of the present invention is formed by the cubes SAPO-34 symbiosis that has the SAPO-5 lamella molecular sieve of twelve-ring pore passage structure and have the SAPO-18 lamella molecular sieve of octatomic ring pore passage structure and have an octatomic ring pore passage structure of selecting by force shape, twelve-ring SAPO-5 molecular sieve has certain catalytic cracking reaction activity because being acidity, its macroporous structure has been eliminated the shape selectivity to the butylene product including iso-butylene, can make to react the rich butylene that produces; Octatomic ring SAPO-18 acidic zeolite is moderate, and it is in the time of catalysis organic oxygen-containing compound reaction for preparing light olefins, and catalytic activity is higher, and due to medium tenacity acid site acidity a little less than, stability is better, catalyst carbon deposit deactivation rate prepared therefrom is slow; The octatomic ring SAPO-34 molecular sieve of selecting by force shape has suitable proton acidity and pore passage structure, larger specific surface area, good absorption property and good hydrothermal stability, and it presents good catalytic activity and olefin product selectivity to organic oxygen-containing compound olefine reaction processed.
The present invention strives that one of technical problem underlying solving is under the prerequisite of guaranteeing high Propylene Selectivity, improve the selectivity of butylene in organic oxygen-containing compound olefine reaction processed, and triethylamine or N in synthesized gel rubber, N-diisopropyl ethyl amine template and SiO are controlled in employing
2content, optimizing materials proportioning and order by merging, the series of steps of regulation and control crystallization time, successfully synthetic once have the lamellar of acid micropore and macropore and a composite molecular sieves of cubic.The synthetic complex type molecular sieve of preparation method of the present invention has good diffusion flux and suitable acidity, while using it for organic oxygen-containing chemical combination olefine reaction processed, has higher propylene and butylene selectivity, is conducive to realize Coal Chemical Industry C
4the derivative large-scale production of alkene resource downstream.
Above-mentioned SAPO-5/SAPO-18/SAPO-34 composite molecular screen can be used as the catalyzer of catalytic active component for the preparation of organic oxygen-containing compound, particularly reaction for preparing light olefins from methanol.In the time using the catalyzer of so preparation, propylene and butylene can be richly produced in the reaction of preparing light olefins from methanol.Preferably, while using above-mentioned catalyzer, in reaction for preparing light olefins from methanol, ethylene selectivity can be in 10-15% left and right, and Propylene Selectivity can be in 35-40% left and right, and butylene selectivity can be in 20-30% left and right; In butylene product, 1-butylene can account for 15-20%, and 2-butylene can account for 46-56%, and iso-butylene can account for 21-37%.
The inventor is in the process of preparation SAPO-5 molecular sieve, SAPO-34 molecular sieve and SAPO-5/SAPO-34 composite molecular screen, find amazedly: in the time that each proportioning raw materials is in the specified range of a relative narrower, for example, as triethylamine or N, N-diisopropyl ethyl amine template: SiO
2: Al
2o
3: P
2o
5: H
2o mol ratio is (1.2-1.8): (0.2-0.8): 1:(0.9-1.25): (40-80) time, what obtain is not SAPO-5 molecular sieve, SAPO-34 molecular sieve or SAPO-5/SAPO-34 composite molecular screen, but SAPO-5/SAPO-18/SAPO-34 three-phase composite molecular sieve.The inventor, on this basis, has completed the present invention through performing creative labour and a large amount of screening operations.
Preferably, the present invention, by the preparation method of the composite molecular screen of SAPO-5/SAPO-18/SAPO-34 molecular sieve symbiosis, comprises the following steps successively:
(1) in proportion by aluminium source, phosphorus source, silicon source, triethylamine or N, N-diisopropyl ethyl amine template and water mix at the temperature of 20 ℃-90 ℃, control the rate of addition of each step raw material, obtain comprising aluminium source, phosphorus source, silicon source, triethylamine or N, the mixing solutions of N-diisopropyl ethyl amine template and water, in above-mentioned mixing solutions, triethylamine or N, N-diisopropyl ethyl amine template: SiO
2: Al
2o
3: P
2o
5: H
2the mol ratio of O is (1.2-1.8): (0.2-0.8): 1:(0.9-1.25): (40-80); (2) stir described mixing solutions until the each component of mixing solutions is uniformly dispersed, mixing solutions 2-24 hour described in ageing subsequently, until form gel mixture; (3) gel mixture is put into 170 ℃ of-210 ℃ of reactors and carried out Hydrothermal Synthesis crystallization 24-80 hour; (4) separate the solid crystal thing that crystallization forms, then at 80 ℃-120 ℃, be dried described solid crystal thing 2-12 hour, obtain the former powder of composite molecular screen; (5) the former powder 2-8 hour of the above-mentioned composite molecular screen of roasting at 450-650 ℃, removes triethylamine or N wherein, and N-diisopropyl ethyl amine template obtains the composite molecular screen by SAPO-5 molecular sieve, SAPO-18 molecular sieve and the symbiosis of SAPO-34 molecular sieve.
Conventionally, in above-mentioned steps (5), it is in order to remove template that the former powder of described composite molecular screen is carried out to roasting, and preferably, maturing temperature is 450-650 ℃, more preferably 500-600 ℃; Preferably, roasting time is 2-8 hour, more preferably 3-6 hour.
Preferably, the preparation method of the organic oxygen-containing compound producing light olefins catalyzer of the present invention take above-mentioned SAPO-5/SAPO-18/SAPO-34 composite molecular screen as catalytic active component, comprises the following steps successively:
(1) above-mentioned SAPO-5/SAPO-18/SAPO-34 composite molecular screen, molding adhesive, additive, peptizing agent are mixed to each self-forming solution or slurries with water.In the time of each self-forming solution or slurries, can be auxiliary in heating or stir, mix promoting, but water deionized water; (2) SAPO-5/SAPO-18/SAPO-34 composite molecular screen slurries are mixed with molding adhesive solution, additive slurries, peptizing agent solution successively, finally form even mixed serum, and leave standstill or ageing; (3) the mixed slurries after standing or ageing are carried out to spray drying forming, obtain shaped granule, then through roasting, thereby, described SAPO-5/SAPO-18/SAPO-34 composite molecular sieve catalyst obtained.
Wherein, the weight ratio of described SAPO-5/SAPO-18/SAPO-34 composite molecular screen, molding adhesive, additive, peptizing agent is preferably 1:0.1-0.6:0.5-1.5:0.01-0.25.
In above-mentioned steps (1), the weight ratio of each material and water can be respectively: SAPO-5/SAPO-18/SAPO-34 composite molecular screen: water=1:0.2-5.0, is preferably 1:0.5-3.0; Binding agent: water=1:0.5-5.0, is preferably 1:1.0-3.0; Additive: water=1:0.5-5.0, is preferably 1:1.0-3.0; Peptizing agent: water=1:0.2-5.0, is preferably 1:0.5-4.5.Preferably, the mixing time of each solution, slurries or mixed solution is 5-60 minute, more preferably 15-30 minute.
In a more preferred, described molding adhesive is pseudo-boehmite; Described additive is kaolin (stone); Described peptizing agent is rare nitric acid, and based on the gross weight of acid solution, acid concentration is 5-45%, preferably 10-40%.
In method for preparing catalyst of the present invention, the mean particle size (diameter) of above-mentioned SAPO-5/SAPO-18/SAPO-34 composite molecular screen, binding agent, additive is preferably no more than 75 microns, more preferably 0.1-20 micron.
In a preferred embodiment, the weight ratio of described SAPO-5/SAPO-18/SAPO-34 composite molecular screen, binding agent, additive, peptizing agent is 1:0.15-0.55:0.65-1.45:0.05-0.20.
In above-mentioned steps (2), preferably, first described SAPO-5/SAPO-18/SAPO-34 composite molecular screen slurries mix with molding adhesive solution, form the first mixed solution; Then, this first mixed solution mixes with additive slurries, forms the second mixed solution; This second mixed solution mixes with peptizing agent solution again, forms the third mixed solution, i.e. mixed serum, and based on slurries gross weight, its solid content is 8-35%, is preferably 10-30%, more preferably 15-25%.Therefore, should be understood that: " successively " mixes is to add follow-up blending ingredients in the mixed solution that forms of back, contains more multi-component mixed solution thereby form.
In above-mentioned steps (2), the mixing time of each mixing step is approximately 5-80 minute, is preferably 7-60 minute, more preferably 10-45 minute.
Preferably, in above-mentioned steps (2), the mixed serum that comprises SAPO-5/SAPO-18/SAPO-34 composite molecular screen, molding adhesive, additive, peptizing agent and water is carried out to strong stirring mixing, to form even mixed serum.Preferably, strong stirring mixing is carried out with colloidal mill and/or high-shear boxshear apparatus.
For example, the time that above-mentioned strong stirring mixes is 10-80 minute, is particularly preferably 30-70 minute, most preferably is 35-60 minute; Preferably, colloidal mill and/or high-shear boxshear apparatus rotating speed are 4000-12000 rev/min, and more preferably 4500-10000 rev/min, is particularly preferably 5000-8000 rev/min.
Conventionally, the standing or Aging Temperature of above-mentioned even mixed serum is 10-80 ℃, is preferably 15-45 ℃, most preferably is 20-40 ℃.Preferably, standing or digestion time is 1-48 hour, more preferably 12-24 hour.
Based on slurries gross weight, leave standstill or ageing after the solid content of even mixed serum be 8-35%, be preferably 10-30%, more preferably 15-25%.
Preferably, the operational condition of above-mentioned even mixed serum spray drying forming is as follows: spray-dryer temperature in: 250-400 ℃, temperature out: 100-200 ℃.Shaped granule particle diameter: 40-100 micron, preferably 45-90 micron.
Conventionally, the maturing temperature of shaped granule is 450-650 ℃, more preferably 500-600 ℃; Roasting time is preferably 2-8 hour, more preferably 5-hour.The catalyzer forming contains the material from components such as SAPO-5/SAPO-18/SAPO-34 composite molecular screen, molding adhesive, additive and peptizing agents, in butt, each components by weight is: SAPO-5/SAPO-18/SAPO-34 composite molecular screen: molding adhesive: additive: peptizing agent=1:0.1-0.6:0.5-1.5:0.01-0.25, is preferably 1:0.15-0.55:0.65-1.45:0.05-0.20.The mean particle size of final SAPO-5/SAPO-18/SAPO-34 composite molecular sieve catalyst is preferably 60-80 micron.
The present invention's low silicon SAPO-5/SAPO-18/SAPO-34 composite molecular screen and the preferred working conditions of catalyzer thereof are as follows: temperature of reaction: 300-500 ℃, preferably 400-500 ℃; Reaction pressure: 0-0.5MPa; Methanol quality air speed: 1.0-5.0/ hour; Under this working conditions, methanol conversion approaches 100%; Propylene+butylene yield is between 60-70%; SAPO-5/SAPO-18/SAPO-34 composite molecular screen exceedes 200 minutes work-ing life, and the catalyzer of SAPO-5/SAPO-18/SAPO-34 composite molecular screen exceedes 2 hours work-ing life.
Embodiment
Embodiment 1: the SAPO-5/SAPO-18/SAPO-34 composite molecular screen of preparation symbiosis
By 12 grams of pseudo-boehmites and 20.0 grams of deionized water mix and blends, form aluminium source solution, the phosphoric acid that is 85 % by weight by 11.89 grams of concentration and 20.0 grams of deionized water mix and blends, form phosphorus source solution, be 40 % by weight silicon sol and 4.5 grams of deionized water mix and blends by 4.86 grams of concentration, form silicon source solution.
Then, phosphorus source solution is slowly added drop-wise in the solution of aluminium source, forms the mixing solutions in He Lin source, aluminium source, uniform stirring 1 hour, again silicon source solution is joined in the mixing solutions in He Lin source, aluminium source to uniform stirring 1 hour, the mixing solutions in formation silicon source, He Lin source, aluminium source.Afterwards, in above-mentioned mixing solutions, add 7.8 grams of triethylamine template, then add 7 grams of deionized waters, ageing 2 hours under whipped state, thereby, form gel.
In said process, triethylamine template: SiO in mixing solutions
2: Al
2o
3: P
2o
5: H
2the mol ratio of O is 1.5:0.6:1:1:50.
The gel forming after above-mentioned ageing is packed in the stainless steel crystallization still that inner bag is tetrafluoroethylene (teflon), under 200oC, carry out Hydrothermal Synthesis crystallization 48 hours.After the cooling of crystallization still, solid crystallized product is through deionized water centrifuge washing and filtration, to scavenging solution specific conductivity be 200 μ S/cm following after, again at 120 ℃ by dry 8 hours of solid crystallized product, weigh, obtain the former powder of SAPO-5/SAPO-18/SAPO-34 composite molecular screen.
Finally, in air atmosphere and under 600oC, the former powder of the above-mentioned composite molecular screen of roasting 5 hours, obtains SAPO-5/SAPO-18/SAPO-34 composite molecular screen, and this composite molecular screen is marked as molecular sieve-4 A.
Comparative example 1-1: preparation SAPO-5 molecular sieve
Except the consumption of triethylamine template is become 2.6 grams from 7.8 grams, repeat the process of embodiment 1, obtain SAPO-5 molecular sieve, this molecular sieve is marked as molecular sieve-4 A-1.
Comparative example 1-2: preparation SAPO-5/SAPO-34 composite molecular screen
Except the consumption of triethylamine template is become 5.2 grams from 7.8 grams, repeat the process of embodiment 1, obtain SAPO-5/SAPO-34 composite molecular screen, this composite molecular screen is marked as molecular sieve-4 A-2.
Comparative example 1-3: preparation SAPO-34 molecular sieve
Except the consumption of triethylamine template is become 10.4 grams from 7.8 grams, repeat the process of embodiment 1, obtain SAPO-34 molecular sieve, this molecular sieve is marked as molecular sieve-4 A-3.
Embodiment 2: the SAPO-5/SAPO-18/SAPO-34 composite molecular screen of preparation symbiosis
Except being that the silicon sol consumption of 40 % by weight becomes 3.24 grams from 4.86 grams by concentration, repeat the process of embodiment 1.
In said process, triethylamine template: SiO in mixing solutions
2: Al
2o
3: P
2o
5: H
2the mol ratio of O is 1.5:0.4:1:1:50.
Obtain SAPO-5/SAPO-18/SAPO-34 composite molecular screen, this composite molecular screen is marked as molecular sieve B.
Comparative example 2-1: preparation SAPO-5 molecular sieve
Except the consumption of triethylamine template is become 2.6 grams from 7.8 grams, repeat the process of embodiment 2, obtain SAPO-5 molecular sieve, this molecular sieve is marked as molecular sieve B-1.
Comparative example 2-2: preparation SAPO-5/SAPO-34 composite molecular screen
Except the consumption of triethylamine template is become 5.2 grams from 7.8 grams, repeat the process of embodiment 2, obtain SAPO-5/SAPO-34 composite molecular screen, this composite molecular screen is marked as molecular sieve B-2.
Comparative example 2-3: preparation SAPO-34 molecular sieve
Except the consumption of triethylamine template is become 10.4 grams from 7.8 grams, repeat the process of embodiment 2, obtain SAPO-34 molecular sieve, this molecular sieve is marked as molecular sieve B-3.
Embodiment 3: the SAPO-5/SAPO-18/SAPO-34 composite molecular screen of preparation symbiosis
Except being that the silicon sol consumption of 40 % by weight becomes 2.43 grams from 4.86 grams by concentration, repeat the process of embodiment 1.
In said process, triethylamine template: SiO in mixing solutions
2: Al
2o
3: P
2o
5: H
2the mol ratio of O is 1.5:0.3:1:1:50.
Obtain SAPO-5/SAPO-18/SAPO-34 composite molecular screen, this composite molecular screen is marked as molecular sieve C.
Comparative example 3-1: preparation SAPO-5 molecular sieve
Except the consumption of triethylamine template is become 2.6 grams from 7.8 grams, repeat the process of embodiment 3, obtain SAPO-5 molecular sieve, this molecular sieve is marked as molecular sieve C-1.
Comparative example 3-2: preparation SAPO-5/SAPO-34 composite molecular screen
Except the consumption of triethylamine template is become 5.2 grams from 7.8 grams, repeat the process of embodiment 3, obtain SAPO-5/SAPO-34 composite molecular screen, this composite molecular screen is marked as molecular sieve C-2.
Comparative example 3-3: preparation SAPO-34 molecular sieve
Except the consumption of triethylamine template is become 10.4 grams from 7.8 grams, repeat the process of embodiment 3, obtain SAPO-34 molecular sieve, this molecular sieve is marked as molecular sieve C-3.
Embodiment 4: the chemically composited molecular sieve of preparation SAPO-5/SAPO-18/SAPO-34
By 17.6 grams of pseudo-boehmites and 35.0 grams of deionized water mix and blends, form aluminium source solution, the phosphoric acid that is 85 % by weight by 20.0 grams of concentration and 35.0 grams of deionized water mix and blends, form phosphorus source solution, the silicon sol that is 40 % by weight by 2.9 grams of concentration and 2.5 grams of deionized water mix and blends, form silicon source solution.
Then, phosphorus source solution is slowly added drop-wise in the solution of aluminium source, forms the mixing solutions in He Lin source, aluminium source, uniform stirring 1 hour, again silicon source solution is joined in the mixing solutions in He Lin source, aluminium source to uniform stirring 1 hour, the mixing solutions in formation silicon source, He Lin source, aluminium source.Afterwards, in above-mentioned mixing solutions, add 14.1 grams of N, N-diisopropyl ethyl amine template, then add 2.6 grams of deionized waters, ageing 2 hours under whipped state, thereby, form gel.
In said process, N in above-mentioned mixing solutions, N-diisopropyl ethyl amine template: SiO
2: Al
2o
3: P
2o
5: H
2the mol ratio of O is 1.2:0.2:1:0.95:50.
The gel forming after above-mentioned ageing is packed in the stainless steel crystallization still that inner bag is tetrafluoroethylene (teflon), under 140oC, carry out Hydrothermal Synthesis crystallization 8 hours, then under 175oC, carry out Hydrothermal Synthesis crystallization 72 hours.After the cooling of crystallization still, solid crystallized product is through deionized water centrifuge washing and filtration, to scavenging solution specific conductivity be 200 μ S/cm following after, again at 120 ℃ by dry 8 hours of solid crystallized product, weigh, obtain the former powder of SAPO-5/SAPO-18/SAPO-34 composite molecular screen.
Finally, in air atmosphere and under 600oC, the former powder of the above-mentioned composite molecular screen of roasting 5 hours, obtains SAPO-5/SAPO-18/SAPO-34 composite molecular screen, and this composite molecular screen is marked as molecular sieve D.
Test case
Test case 1: to the physical property measurement of SAPO-5/SAPO-18/SAPO-34 composite molecular screen of the present invention
(1) X-ray diffraction (XRD) is analyzed
The SAPO-5/SAPO-18/SAPO-34 symbiosis composite molecular screen of the present invention obtaining in embodiment 1-3 is carried out to X-ray diffraction (XRD) analysis, obtain Fig. 2-4, from Fig. 2-4, can find: in the XRD spectra of the SAPO-5/SAPO-18/SAPO-34 symbiosis composite molecular screen obtaining in embodiment 1-3, occurred simultaneously SAPO-5 molecular sieve, SAPO-18 molecular sieve and the characteristic diffraction peak of SAPO-34 molecular sieve, this explanation has formed the chemically composited structure of above-mentioned three kinds of molecular sieves.
(5) scanning electron microscope (SEM) is analyzed
Fig. 1 is SAPO-5/SAPO-18/SAPO-34 symbiosis composite molecular screen scanning electron microscope of the present invention (SEM) photo synthetic in embodiment 1, can be found out by stereoscan photograph: the synthetic SAPO-5/SAPO-18/SAPO-34 symbiosis composite molecular screen grain-size of the present invention is between 3-10 micron, and it has the laminated structure of typical SAPO-5 molecular sieve and SAPO-18 molecular sieve and the cube structure of SAPO-34 molecular sieve.This also illustrates that SAPO-5/SAPO-18/SAPO-34 symbiosis composite molecular screen of the present invention has formed chemically composited structure.
Test case 2: molecular sieve catalytic active assessment
Adopt fixed bed catalyst evaluating apparatus, the molecular sieve obtaining in embodiment 1-4, comparative example 1-1,1-2,1-3 is carried out to catalytic activity and test in work-ing life.
Above-mentioned molecular sieve is carried out after compressing tablet and fragmentation, and it is that 20-40 object part is stand-by as sieve sample that sieve is got granularity.
Take respectively 1.0 grams of above-mentioned sieve samples, evenly mix with 4 grams of 20-40 object quartz sands, and respectively they are put into reactor, in 500 ℃ of downhill reaction devices, pass into nitrogen, activate above-mentioned molecular sieve 1 hour, then, temperature of reactor is down to 450 ℃, reaction pressure is normal pressure, methanol solution as raw material after flow metering pump, mix with carrier gas, and under carrying, nitrogen-carrier gas enters in preheating oven, methyl alcohol is gasificated into gas in preheating oven, then, enter in reactor, methyl alcohol carries out the reaction of producing light olefins under the katalysis of above-mentioned molecular sieve.
In said process, nitrogen flow rate: 150 ml/min, methyl alcohol weight space velocity: 3.0/ hour, reaction product adopts off-line gas-chromatography to carry out composition analysis, wherein, and in the time there is alcohol and ether in gas chromatogram, illustrate that methanol conversion has not been 100%, now, stop test, start to time now as molecular sieve work-ing life to react.
Using in the reaction of composite molecular screen of the present invention (embodiment) and existing molecular sieve (comparative example), measure the each product composition corresponding to the differential responses time, by experimental result drafting pattern 5-Figure 10.
Fig. 5 is each reaction product selectivity and the relation curve in reaction times when SAPO-5/SAPO-18/SAPO-34 symbiosis composite molecular screen A is as catalyzer in embodiment 1.As calculated, SAPO-5 molecular sieve in this composite molecular screen/(SAPO-18+SAPO-34) mol ratio of molecular sieve is 60:40.As can be seen from Figure 5: Propylene Selectivity is very stable, conventionally maintain 40% left and right; Ethylene selectivity extended gradually and reduces with the reaction times, last, was reduced to 18% by 40%; And butylene selectivity extends increase gradually with the reaction times, last, be increased to 30% left and right by 14%.
State in the use in the reaction of composite molecular screen A of the present invention, measure butylene product and comprise Trans-2-butene, cis-2-butene, 1-butylene and iso-butylene etc.
The invention described above composite molecular screen A(embodiment 1) be suitable as rich catalyzer or catalyst activity component of producing propylene and butylene.
Fig. 6 is each reaction product selectivity and the relation curve in reaction times when SAPO-5/SAPO-18/SAPO-34 symbiosis composite molecular screen C is as catalyzer in embodiment 3.As can be seen from Figure 6: Propylene Selectivity is also more stable, conventionally maintain 35-38% left and right; Ethylene selectivity extended and first increases gradually rear micro-decline that has with the reaction times, last, became to 38% left and right from 33%; And butylene selectivity extends decline gradually with the reaction times, last, drop to 13% left and right by 14%.
The invention described above composite molecular screen C(embodiment 3) be suitable as rich catalyzer or catalyst activity component of producing ethene and propylene.
Fig. 7 is each reaction product selectivity and the relation curve in reaction times when SAPO-5/SAPO-18/SAPO-34 symbiosis composite molecular screen D is as catalyzer in embodiment 4.As can be seen from Figure 7: Propylene Selectivity is relatively stable, conventionally maintain 37-35% left and right; Ethylene selectivity extended gradually and reduces with the reaction times, last, was reduced to 11% by 24%; And butylene selectivity extends increase gradually with the reaction times, last, be increased to 30% left and right by 19%.These change with Fig. 5 closely similar.
State in the use composite molecular screen D(embodiment 4 of the present invention) reaction in, measure equally butylene product and comprise Trans-2-butene, cis-2-butene, 1-butylene and iso-butylene etc.
The invention described above composite molecular screen D(embodiment 4) be equally also suitable as rich catalyzer or catalyst activity component of producing propylene and butylene.
Fig. 8 is each reaction product selectivity and the relation curve in reaction times when SAPO-5 molecular sieve-4 A-1 is as catalyzer in comparative example 1-1.As can be seen from Figure 8: Propylene Selectivity is micro-after first increasing gradually with reaction times prolongation decline, but conventionally maintains between 41-43%; Butylene selectivity is more stable, conventionally maintains between 18-19%; And ethylene selectivity minimum, it extends fluctuation to some extent with the reaction times, but also conventionally maintains between 11-13% left and right.Generally speaking, in comparative example 1-1 when synthetic SAPO-5 molecular sieve catalytic methanol to olefins reaction, selectivity of light olefin order is from high to low followed successively by: propylene > butylene > ethene, propylene, butylene, ethylene selectivity are respectively 40%, 20% and 10% left and right.
Above-mentioned SAPO-5 molecular sieve-4 A-1(comparative example 1-1) be suitable as rich catalyzer or catalyst activity component of producing propylene and butylene, but its butylene selectivity is starkly lower than SAPO-5/SAPO-18/SAPO-34 symbiosis composite molecular screen of the present invention (composite molecular screen A and D).
Fig. 9 is each reaction product selectivity and the relation curve in reaction times when SAPO-34 molecular sieve-4 A-3 are as catalyzer in comparative example 1-3.As can be seen from Figure 9: the products distribution rule of synthetic SAPO-34 molecular sieve catalytic methanol to olefins reaction in comparative example 1-3, propylene and butylene selectivity extended and reduce with the reaction times, wherein, Propylene Selectivity is reduced to 33% by 40%, butylene selectivity drops to 8.7% by 15%, ethylene selectivity extended and increases with the reaction times, was increased to 48% by 36%.
Above-mentioned SAPO-34 molecular sieve-4 A-3(comparative example 1-3) be suitable as rich catalyzer or catalyst activity component of producing ethene and propylene.
Figure 10 is each reaction product selectivity and the relation curve in reaction times when SAPO-5/SAPO-34 composite molecular screen A-2 is as catalyzer in comparative example 1-2.As calculated, in this composite molecular screen, the mol ratio of SAPO-5 molecular sieve/SAPO-34 molecular sieve is 80:20.As can be seen from Figure 10: in comparative example 1-2 when synthetic SAPO-5/SAPO-34 plyability molecular sieve catalytic methanol to olefins reaction, distribution of reaction products is: Propylene Selectivity is more stable, conventionally maintain between 35%-40%, ethylene selectivity extended gradually and reduces with the reaction times, be reduced to 13% by 29%, butylene selectivity extended gradually and increases with the reaction times, was increased to 22% by 14%.
Above-mentioned SAPO-5/SAPO-34 composite molecular screen A-2(comparative example 1-2) be suitable as rich catalyzer or catalyst activity component of producing propylene and butylene, but its butylene selectivity is starkly lower than SAPO-5/SAPO-18/SAPO-34 symbiosis composite molecular screen of the present invention (composite molecular screen A and D).
In sum, the present invention has found a kind of SAPO-5/SAPO-18/SAPO-34 symbiosis composite molecular screen and preparation method thereof, this composite molecular screen is catalytic performance excellence in the reaction of organic oxygen-containing compound producing light olefins, and can richly produce propylene and butylene, particularly with respect to existing congeneric elements sieve and catalyzer, butylene selectivity increases greatly, and butylene selectivity can reach 30%, and the overall selectivity of propylene and butylene can reach 70%.This novel three-phase composite molecular sieve can be used in the large-scale commercial production of propylene and butylene.
The term that this specification sheets is used and form of presentation are only used as descriptive and nonrestrictive term and form of presentation, in the time using these terms and form of presentation, are not intended to any equivalent exclusion of the feature representing and describe or its integral part.
Although represented and described several embodiment of the present invention, the present invention is not restricted to described embodiment.On the contrary; those skilled in the art should recognize in the situation that not departing from principle of the present invention and spirit can carry out any accommodation and improvement to these embodiments, and protection scope of the present invention is determined by appended claim and equivalent thereof.
Claims (10)
1. a composite molecular screen, is formed by SAPO-5 molecular sieve, SAPO-18 molecular sieve and the symbiosis of SAPO-34 molecular sieve, it is characterized in that: prepare this composite molecular screen raw material used and meet following ratio:
R:SiO
2: Al
2o
3: P
2o
5: H
2o mol ratio is (1.2-1.8): (0.2-0.8): 1:(0.9-1.25): (40-80), wherein, R represents triethylamine or N, N-diisopropyl ethyl amine template.
2. composite molecular screen according to claim 1, wherein, prepare this composite molecular screen raw material used and meet following ratio:
R:SiO
2: Al
2o
3: P
2o
5: H
2o mol ratio is 1.5:(0.3,0.4 or 0.6): 1:1:50.
3. composite molecular screen according to claim 1 and 2, wherein, SiO
2come from tetraethoxy, silicon sol, white carbon black, water glass, white carbon black or they mixture arbitrarily; Al
2o
3come from pseudo-boehmite, pseudobochmite, aluminium colloidal sol, aluminum isopropylate, aluminium salt, aluminate, activated alumina or they mixture arbitrarily; P
2o
5come from phosphoric acid, phosphorous acid, phosphoric acid salt and/or phosphorous oxides.
4. composite molecular screen according to claim 1 and 2, wherein, by regulating triethylamine or N, N-diisopropyl ethyl amine template and SiO
2consumption, adjusts SAPO-5 molecular sieve, SAPO-18 molecular sieve and the relative content of SAPO-34 molecular sieve in composite molecular screen, and then adjusts pore passage structure distribution and the acidity of described composite molecular screen.
5. according to a preparation method for one of any described composite molecular screen of claim 1-4, it comprises the following steps successively:
(1) in proportion by aluminium source, phosphorus source, silicon source, triethylamine or N, N-diisopropyl ethyl amine template and water mix at the temperature of 20 ℃-90 ℃, control the rate of addition of each step raw material, obtain comprising aluminium source, phosphorus source, silicon source, triethylamine or N, the mixing solutions of N-diisopropyl ethyl amine template and water, in above-mentioned mixing solutions, triethylamine or N, N-diisopropyl ethyl amine template: SiO
2: Al
2o
3: P
2o
5: H
2the mol ratio of O is (1.2-1.8): (0.2-0.8): 1:(0.9-1.25): (40-80);
(2) stir described mixing solutions until the each component of mixing solutions is uniformly dispersed, mixing solutions described in ageing subsequently, until form gel mixture;
(3) gel mixture is put into 170 ℃ of-210 ℃ of reactors and carried out Hydrothermal Synthesis crystallization 24-80 hour;
(4) separate the solid crystal thing that crystallization forms, drier described solid crystal thing, the former powder of composite molecular screen obtained;
(5) the former powder 2-8 hour of the above-mentioned composite molecular screen of roasting at 450-650 ℃, removes triethylamine or N wherein, and N-diisopropyl ethyl amine template obtains the composite molecular screen by SAPO-5 molecular sieve, SAPO-18 molecular sieve and the symbiosis of SAPO-34 molecular sieve.
6. preparation method according to claim 5, wherein, described silicon source is tetraethoxy, silicon sol, white carbon black, water glass, white carbon black or they mixture arbitrarily; Described aluminium source is pseudo-boehmite, pseudobochmite, aluminium colloidal sol, aluminum isopropylate, aluminium salt, aluminate, activated alumina or they mixture arbitrarily; Described phosphorus source is phosphoric acid, phosphorous acid, phosphoric acid salt and/or phosphorous oxides.
7. preparation method according to claim 5, wherein, in step (4), the solid crystal thing that described separation crystallization forms refers to: the solid crystal thing that centrifuging forms, the crystallisate mother liquor being produced to remove Hydrothermal Synthesis crystallization, with solid crystal thing described in deionized water wash at least one times, then described in centrifuging solid crystal thing is at least one times.
8. preparation method according to claim 5, wherein, the described mixing solutions in step (1) is prepared by the following method:
(1) respectively aluminium source, He Gui source, phosphorus source are mixed with water, form aluminium source solution, phosphorus source solution and silicon source solution;
(2) lentamente aluminium source solution is added drop-wise in the solution of phosphorus source, or phosphorus source solution is added drop-wise in the solution of aluminium source, form the mixing solutions in He Lin source, aluminium source;
(3) lentamente silicon source solution is added drop-wise in the mixing solutions in He Lin source, aluminium source, or the mixing solutions in He Lin source, aluminium source is added drop-wise in the solution of silicon source, form the mixing solutions in aluminium source, He Gui source, phosphorus source;
(4) in the mixing solutions in described aluminium source, He Gui source, phosphorus source, add triethylamine or N again, N-diisopropyl ethyl amine template, comprises aluminium source, phosphorus source, silicon source, triethylamine or N, the mixing solutions of N-diisopropyl ethyl amine template and water thereby form.
9. by the catalyzer of organic oxygen-containing compound producing light olefins, the catalytic active component of described catalyzer is one of any described composite molecular screen of claim 1-4 or the composite molecular screen of being prepared by one of any described method of claim 5-8.
10. catalyzer according to claim 9, wherein, described organic oxygen-containing compound is methyl alcohol and/or dme; Described low-carbon alkene is ethene, propylene and/or butylene.
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