CN103447081A - Low-silicon ALPO-5/low-silicon ALPO-18 composite molecular sieve for preparing catalyst for preparing low-carbon alkene from organic oxygen-containing compound and preparation method of composite molecular sieve - Google Patents
Low-silicon ALPO-5/low-silicon ALPO-18 composite molecular sieve for preparing catalyst for preparing low-carbon alkene from organic oxygen-containing compound and preparation method of composite molecular sieve Download PDFInfo
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Abstract
The invention discloses a composite molecular sieve for preparing a catalyst for preparing low-carbon alkene from an organic oxygen-containing compound and a preparation method of the composite molecular sieve. The composite molecular sieve comprises a low-silicon ALPO-5 molecular sieve and a low-silicon ALPO-18 molecular sieve which are symbiotic. Raw materials used for preparing the composite molecular sieve are in the following proportion: the mole ratio of Al2O3:P2O5:SiO2=1:(0.7-1.3):(0.05-0.3). The catalyst prepared through the composite molecular sieve disclosed by the invention has the advantages of good catalytic activity, higher propylene and butylene selectivity and longer service life.
Description
Technical field
The present invention relates to composite molecular screen of a kind of catalyst for the preparation of the organic oxygen-containing compound producing light olefins and preparation method thereof, particularly, relate to a kind of composite molecular screen formed by low silicon ALPO-5 molecular sieve and the symbiosis of low silicon ALPO-18 molecular sieve and preparation method thereof.
Background technology
The petroleum 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 dimethyl ether producing light olefins day by day is subject to people and pays close attention to.This technique is used molecular sieve catalyst usually.The molecular sieve catalyst of organic oxygen-containing compound producing light olefins is the ZSM-5 molecular sieve that is proposed and adopted by U.S. Mobil company the earliest, but this molecular sieve pore passage is large, surface acidity is strong, ethene and/or propylene selective also lower (ethylene selectivity is 2% left and right, Propylene Selectivity is 35% left and right), simultaneously, also can generate the accessory substances 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 catalytic active component of the molecular sieve in various little ducts as organic oxygen-containing compound producing light olefins catalyst gradually, for example T zeolite molecular sieve, erionite molecular sieve, chabasie (CHA) molecular sieve, but these catalyst in use show easy coking and the fast feature of deactivation rate, these shortcomings cause their further promotion and application to be restricted.
The SAPO-34 non-zeolite molecular sieve is a kind of crystalline silico-alumino-phosphate of U.S. UCC company development in 1984, has the three dimensional intersection duct, and average pore size is about 0.38-0.43nm.With ZSM-5, compare, SAPO-34 has less aperture, is applicable to generating micromolecular ethene, propylene and n-alkane, and isohydrocarbon and aromatic hydrocarbons will be severely limited.Because SAPO-34 has the acid and pore passage structure of suitable proton, larger specific area, absorption property and heat endurance and hydrothermal stability preferably, SAPO-34 presents catalytic activity and selective preferably to methanol to olefins reaction, to selectively reaching more than 90% of low-carbon alkene, can be described as at present the optimal catalyst that promotes this course of reaction.
In the SAPO-n Series Molecules sieve of UCC company exploitation, the molecular sieve identical with chabasie (CHA) type SAPO-34 molecular sieve bore diameter comprises the catalytic active component of the SAPO-18 molecular sieve of AEI structure as organic oxygen-containing compound producing light olefins catalyst, and the SAPO-18 molecular sieve has the service life more superior than SAPO-34 molecular sieve.
It is the purpose product that traditional MTO technology mainly be take ethene and/or propylene, butylene and C
5the above component of+hydrocarbon is only accessory substance.But C
4hydrocarbon is petrochemical industry and organic chemical industry's important raw materials for production, and its purposes comes into one's own day by day.C4 alkene downstream derivative is wide in variety, and market potential is large.The 2-propyl enanthol of butylene production is the primary raw material of producing DPHP, China the coming years DPHP market prospects wide, and there is good economic benefit.Develop extraordinary polyolefin and specific rubber, as polybutene, polyisobutene, butadiene-styrene rubber; Take isobutene as development of raw materials MTBE, ETBE or through isobutene---MTBE---isooctene produce the isooctane alkylate oil all meet in country's 12 planning, propose " downstream product be take general synthetic material as main; the product differentiation journey is lower, and high added value, functional, the special product ratio is not high.Improve the ratio of alkene downstream high-end product, develop and produce the PP Pipe Compound such as extraordinary polyethylene and polypropylene, isoprene rubber, rare earth polybutadiene rubber ", accelerate to realize the industry development guilding policy of the alkene industrial product structure adjustment and escalation replacement.Now, C
4the hydrocarbon resource is mainly derived from the accessory substance of petroleum refining, preparing ethylene by steam cracking and methanol-to-olefins (MTO) technique, so, C
4the hydrocarbon resource is badly in need of further expanding.
In oil plant, C
4butane in hydrocarbon, especially iso-butane content is high, and alkene be take 2-butylene and isobutene as main, containing butadiene.And the C of cracking
4in hydrocarbon, olefin(e) centent accounts for 93%, take butadiene and isobutene as main, and butadiene content is high, and Determination of Alkane Content is very low.
Traditional methanol-to-olefins (MTO) technique of use SAPO-34 molecular sieve catalyst is the C of by-product 5.5% left and right (to methyl alcohol) only
4hydrocarbon mixture, this C
4in hydrocarbon mixture, 1,3-butadiene, isobutene content are lower, and key component is butene-1 and butene-2, and they account for 90%.(referring to " olefin hydrocarbon making by coal and the downstream product market demand and Analysis on Processing Technology ", Wu Xiuzhang).For realizing that carbon four utilizations reach scale and benefit, need to improve carbon four output, urgently exploitation has the catalyst that high C4 alkene is selected.
Therefore, for following market demand, optionally molecular sieve and catalyst thereof just seem particularly important to find a kind of butylene that greatly increases in the reaction of organic oxygen-containing compound producing light olefins of the SAPO-34 of being different from molecular sieve catalyst.But single catalyst due to pore passage structure and catalytic active center more single, being difficult to can be as the catalyst of such function.
Some researchers sieve aspect the catalyst that compound mode increases the C4 hydrocarbon-selective in finding the organic oxygen-containing compound reaction for preparing light olefins and have done some effort by different molecular, for example, EP0609152B1 discloses a kind of catalyst be composited by two kinds of ALPO based molecular sieves that does not contain the unformed binding agent of significant amounts, wherein, the average grain diameter of the second molecular sieve crystal is less than the average grain diameter of the first molecular sieve crystal.First synthetic the first molecular sieve, by the first molecular sieve with cementing agent (aluminium colloidal sol), mix, spraying or kneading, extrusion, drying, roasting; Outer wrap prepared by second step has the aluminium source to mix with the shell molecular sieve pulp as the molecular sieve of binding agent, and hydrothermal crystallizing forms and hands over phase looks or nucleocapsid structure molecular sieve.The second molecular sieve crystal is grown in the first sub-sieve outside by being wrapped in the outer cementing agent of the first molecular sieve, cementing agent forms at least a portion coating on the first molecular sieve crystal, and the first molecular sieve crystal is cemented together, due to the second molecular sieve crystal length on the coating formed by cementing agent, therefore, in catalyst, in fact the first molecular sieve crystal and the second molecular sieve crystal have formed nucleocapsid structure, be that the first molecular sieve crystal is core, be that the second molecular sieve crystal is shell, as an example, the first molecular sieve crystal can be SAPO-34, SAPO-37, SAPO-40, SAPO-5, MAPO-36, SAPO-11, GaSAPO-11, ZnSAPO-11, SAPO-17 or NiSAPO-34, the second molecular sieve crystal can be ALPO-17, ALPO-18, ALPO-11, ALPO-5, ALPO-41, GaALPO-11 or ZnALPO-11.
The above-mentioned catalyst be composited by two kinds of ALPO based molecular sieves shows higher C in the reaction of organic oxygen-containing compound producing light olefins
4hydrocarbon-selective, but in above-mentioned catalyst, two kinds of nucleocapsid structure molecular sieves that the ALPO based molecular sieve adopts three-step approach to synthesize: the first step is first to synthesize the stratum nucleare molecular sieve; Second step be by the molecular sieve molecular sieve with aluminium colloidal sol, mix, spraying or kneading, extrusion, drying, roasting; Outer wrap prepared by second step has the aluminium source to mix with the shell molecular sieve pulp as the molecular sieve of binding agent, and hydrothermal crystallizing forms and hands over phase looks or nucleocapsid structure molecular sieve.This method step complexity, preparation cost is high, and in its product, methane content is higher, so its selectivity of product remains to be further improved.
Above patent documentation is introduced with for referencial use in full at this.
Chemically composited molecular sieve, for example two or more molecular sieve is combined with each other by synthetic method, formed composite molecular screen is by synergy, often show the performance more excellent than the composite molecular screen of single molecular sieve or simple and mechanical mixing, especially the different or discrepant different molecular sieve of microcosmic crystal structure is chemically composited together the time, and the catalytic performance shown is just more excellent.
The present invention is devoted to sieve chemically composited mode by different molecular, strives developing a kind of have in the organic oxygen-containing compound reaction for preparing light olefins good catalytic activity and higher propylene, butylene optionally low silicon ALPO-5/ALPO-18 composite molecular screen and catalyst thereof.
Summary of the invention
According to a first aspect of the invention, provide a kind of composite molecular screen, it is formed through symbiosis by low silicon ALPO-5 molecular sieve and low silicon ALPO-18 molecular sieve, prepares this composite molecular screen raw material used and meets following ratio: Al
2o
3: P
2o
5: SiO
2mol ratio is 1:(0.7-1.3): (0.05-0.3).
In the low silicon ALPO-18 composite molecular screen of above-mentioned low silicon ALPO-5/, preferably, described SiO
2come from ethyl orthosilicate, Ludox, white carbon, waterglass, white carbon or they mixture arbitrarily; Al
2o
3come from boehmite, pseudobochmite, aluminium colloidal sol, aluminium isopropoxide, aluminium salt, aluminate, activated alumina or they mixture arbitrarily; P
2o
5come from phosphoric acid, phosphorous acid, phosphate and/or phosphorous oxides.
Preferably, by adjusting above-mentioned Al
2o
3: P
2o
5: SiO
2mol ratio, adjust the relative scale of low silicon ALPO-5 molecular sieve and low silicon ALPO-18 molecular sieve, and then adjust pore passage structure and the acidity of the low silicon ALPO-18 composite molecular screen of described low silicon ALPO-5/.
According to a second aspect of the invention, provide a kind of above-mentioned low silicon ALPO-5/ preparation method of low silicon ALPO-18 composite molecular screen, it comprises the following steps successively:
(1) in proportion template, ,Lin source, ,Lv source, silicon source and water are mixed at the temperature of 20 ℃-90 ℃, obtain comprising the mixed solution of template, ,Lin source, ,Lv source, silicon source and water, template in above-mentioned mixed solution: SiO
2: Al
2o
3: P
2o
5: H
2the mol ratio of O is (1.0-1.6): (0.05-0.3): 1:(0.7-1.3): (30-80);
(2) stir described mixed solution until each component of mixed solution is uniformly dispersed, the standing mixed liquor 2-24 hour of ageing subsequently,, until form the colloid mixed liquor;
(3) the colloid mixed liquor of the standing rear formation of ageing is put into to 160 ℃ of-180 ℃ of reactors and carried out Hydrothermal Synthesis crystallization 3-8 days;
(4) separate the formed solid crystal thing of crystallization, then under 80 ℃-120 ℃ dry described solid crystal thing 2-12 hour;
(5) at the 450-650 ℃ of above-mentioned dried solid crystal thing 2-8 hour of lower roasting, to remove template wherein, thereby, obtain the composite molecular screen by low silicon ALPO-5 molecular sieve and the symbiosis of low silicon ALPO-18 molecular sieve.
In above-mentioned preparation method, preferably, described template is N, the N-diisopropyl ethyl amine; Described silicon source is ethyl orthosilicate, Ludox, white carbon, waterglass, white carbon or they mixture arbitrarily; Described aluminium source is boehmite, pseudobochmite, aluminium colloidal sol, aluminium isopropoxide, aluminium salt, aluminate, activated alumina or they mixture arbitrarily; Described phosphorus source is phosphoric acid, phosphorous acid, phosphate and/or phosphorous oxides.
Preferably, in above-mentioned preparation method's step (4), the formed solid crystal thing of described separation crystallization refers to the formed solid crystal thing of centrifugal filtration, the crystal mother liquor produced to remove the Hydrothermal Synthesis crystallization, wash described solid crystal thing at least one times by deionized water, the more described solid crystal thing of centrifugal filtration at least one times.
Usually, in the preparation method of the low silicon ALPO-18 composite molecular screen of above-mentioned low silicon ALPO-5/, relative consumption, hybrid mode and/or the feeding sequence of ,Lin source, ,Lv source, silicon source, template and water be can pass through to control, and then pore passage structure and the acidity of described composite molecular screen controlled.
For example, in the preparation method of the low silicon ALPO-18 composite molecular screen of above-mentioned low silicon ALPO-5/, can prepare by following process by described mixed solution:
(1) respectively He Lin source, ,Lv source, silicon source is mixed with water, form silicon source solution, aluminium source solution and phosphorus source solution;
(2) lentamente phosphorus source solution is added drop-wise to aluminium source solution, forms the mixed solution in He Lv source, phosphorus source;
(3) lentamente silicon source solution is added drop-wise in the mixed solution in He Lv source, phosphorus source, forms the mixed solution in He Gui source, ,Lv source, phosphorus source;
(4) again to the described template of mixed solution and dripping in He Gui source, ,Lv source, described phosphorus source, thereby, the mixed solution that comprises ,Gui source, ,Lv source, phosphorus source, water and template formed.
According to a third aspect of the invention we, a kind of catalyst of organic oxygen-containing compound producing light olefins is provided, the catalytic active component of described catalyst is the low silicon ALPO-18 composite molecular screen of the low silicon ALPO-5/ of the invention described above, and preferably, described organic oxygen-containing compound is methyl alcohol and/or dimethyl ether; Described low-carbon alkene is ethene, propylene and/or butylene.
According to a forth aspect of the invention, provide a kind of preparation method of catalyst of organic oxygen-containing compound producing light olefins, it comprises the following steps successively:
(1) respectively the low silicon ALPO-18 composite molecular screen of above-mentioned low silicon ALPO-5/, molding adhesive, additive, peptizing agent are mixed to each self-forming solution or slurries with water;
(2) above-mentioned each solution or slurries are mixed, form even mixed serum, and standing or ageing;
(3) the mixed slurries after standing or ageing are carried out to spray drying forming, obtain shaped granule, again through roasting, thereby, obtain the low silicon ALPO-18 composite molecular sieve catalyst of described low silicon ALPO-5/, wherein, the weight ratio of the low silicon ALPO-18 composite molecular screen of low silicon ALPO-5/, molding adhesive, additive, peptizing agent is 1:0.1-0.6:0.5-1.5:0.01-0.25.
Preferably, in above-mentioned steps (2), described composite molecular screen slurries are mixed with molding adhesive solution, additive slurries, peptizing agent solution successively, finally form even mixed serum, and standing or ageing.
In above-mentioned method for preparing catalyst, described molding adhesive is boehmite, aluminium colloidal sol, Ludox, silicon-aluminum sol, aluminum phosphate, zirconia, titanium oxide or they one of mixture arbitrarily; Described additive is diatomite, kaolin (stone), imvite (stone), talcum, bentonite or they one of mixture arbitrarily, and they are activated by acid treatment before use; Described peptizing agent is inorganic acid and/or organic acid, and preferably, described inorganic acid comprises nitric acid, hydrochloric acid and/or sulfuric acid; Described organic acid comprises formic acid, acetic acid, propionic acid and/or citric acid.
Generally, based on the slurries gross weight, the described mixed serum solid content formed in above-mentioned steps (2) is 15-40%.
The accompanying drawing explanation
Fig. 1 is the x-ray diffraction pattern of the low silicon ALPO-18 composite molecular screen of the low silicon ALPO-5/ of the present invention.
Fig. 2 is the Si-nuclear magnetic resonance figure of the low silicon ALPO-18 composite molecular screen of the low silicon ALPO-5/ of the present invention.
Fig. 3 is the N of the low silicon ALPO-18 composite molecular screen of the low silicon ALPO-5/ of the present invention
2adsorption isothermal curve.
Fig. 4 is the NH of the low silicon ALPO-18 composite molecular screen of the low silicon ALPO-5/ of the present invention
3-TPD curve.
Fig. 5 is ESEM (SEM) figure of the low silicon ALPO-18 composite molecular screen of the low silicon ALPO-5/ of the present invention.
Fig. 6 is the selective graph of relation with reaction time of the low silicon ALPO-18 composite molecular screen of the low silicon ALPO-5/ of the present invention as the butylene isomer of catalyst.
The specific embodiment
Be further explained in detail the present invention by the description below with reference to embodiment and accompanying drawing, but following description is only for making the 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.
The low silicon ALPO-18 composite molecular screen of the low silicon ALPO-5/ of the present invention is formed by the ALPO-5 lamella molecular sieve with twelve-ring pore passage structure and the ALPO-18 lamella molecular sieve symbiosis with octatomic ring pore passage structure, the twelve-ring ALPO-5 molecular sieve that contains Trace Silicon is because being acid certain catalytic cracking reaction activity that has, its macroporous structure has been eliminated the shape selectivity of the butylene product to comprising isobutene, can make the rich butylene that produces of reaction.The ALPO-18 acidic zeolite that contains the Trace Silicon element a little less than, it is when catalysis methanol olefine reaction processed, catalytic activity is higher, and due to acidity a little less than, stability is better, catalyst carbon deposit deactivation rate prepared therefrom is slow.
Usually, micro porous molecular sieve has regular microcellular structure, suitable acidity, good heat endurance and hydrothermal stability, but micro porous molecular sieve generates larger molecule in reaction process, narrow duct very easily induce reaction thing and product mass transfer diffusional resistance excessive, inside, reactant crystal extremely difficult to get access duct is reacted, and product is out also comparatively difficult from the duct diffusion inside, thereby, aggravate the coking of catalyst duct, and caused catalysqt deactivation.For methanol to olefins reaction, the molecular sieve inside diffusional resistance has had a strong impact on the diffusion rate of raw material, has reduced the efficiency of catalyst; Generate target product-alkene in the cage of molecular sieve after, alkene is in the process to external diffusion, can on the acidic site in molecular sieve, hydrogen transfer reaction further occur, generating accessory substance alkane or polymerization reaction take place generates burnt, this has just reduced the selective of purpose product-alkene, and causes the catalyst coking and deactivation.
For above-mentioned technical problem, the present invention proposes a kind of new solution, i.e. synthetic a kind of AlPO-5 and ALPO-18 lamellar structure complex type molecular sieve containing micro-Si that simultaneously there is macropore and micropore.In this composite molecular screen, the ALPO-18 molecular sieve of the AlPO-5 molecular sieve of macropore, low silicon and micropore, low silicon is all chain carriers, the acid centre that contains the macropore AlPO-5 molecular sieve of micro-Si can make the alkene in the methanol to olefins reaction product not affected by micro porous molecular sieve cage aperture shape selectivity, for raw material and product provide unimpeded the evolving path, the low-carbon alkene generated is diffused into rapidly in the gas phase main body, thereby, reduced coking deactivation speed.The low-carbon alkene that the macroporous structure of the molecular sieve that this macropore and micropore are compound produces reaction is after leaving acid active sites, and inner diffusing rate is accelerated, and oligomeric, hydrogen migration, cyclisation, condensation reaction probability greatly reduce, and finally cause C
2alkene-C
4the selective raising of alkene.This composite molecular screen silicone content is low, the sour density of strong acid center is less, so its coking deactivation speed is slow.
The present invention strives that one of technical problem underlying of solution is to guarantee under the prerequisite of high Propylene Selectivity, in the raising methanol to olefins reaction, butylene is selective, and adopt the series of steps of controlling Si content, optimizing raw material proportioning and order by merging, regulation and control crystallization time in synthesized gel rubber, synthesize once the lamellar composite molecular sieves with acid micropore and macropore.The synthetic complex type molecular sieve of the inventive method has diffusion flux and suitable acidity preferably, while using it for methanol to olefins reaction, has higher propylene and a butylene selective, is conducive to realize Coal Chemical Industry C
4the derivative large-scale production of alkene resource downstream.
Above-mentioned low silicon ALPO-5/ is low, and silicon ALPO-18 composite molecular screen can be used as the catalyst of catalytic active component for the preparation of organic oxygen-containing compound, particularly reaction for preparing light olefins from methanol.When using the catalyst of so preparation, the reaction of preparing light olefins from methanol can richly be produced propylene and butylene, and in catalyst, silicone content is low, total acid density is little.Preferably, while using above-mentioned catalyst, in reaction for preparing light olefins from methanol, ethylene selectivity can be between 24-33%, and Propylene Selectivity can be between 38-46%, and butylene selectively can be between 18-27%; In the butylene product, the 1-butylene can account for 15-20%, and the 2-butylene can account for 46-56%, and isobutene can account for 21-37%.
Preferably, the present invention, by the preparation method of the composite molecular screen of ALPO-5 molecular sieve and the symbiosis of ALPO-18 molecular sieve, comprises the following steps successively:
(1) by ,Lin source, ,Lv source, proper amount of silicon source, template and water for example, in preference temperature, mix under 20 ℃-90 ℃, in the gained mixed solution, each component mol ratio is: aR:bSiO
2: Al
2o
3: cP
2o
5: dH
2o, wherein, R means template, the scope of a is: 1.0-1.4, the scope of b is: 0.05-0.3, the scope of c is: 0.7-1.3, the scope of d is: 30-80;
(2) stir described mixed solution until each component of mixed solution is uniformly dispersed, the standing mixed solution 2-24 hour of ageing subsequently, until form the colloid mixed liquor;
(3) the colloid mixed liquor of still aging rear formation is inserted in reactor, make it to carry out Hydrothermal Synthesis crystallization 3-8 days under 160 ℃-180 ℃;
(4) mixed liquor after crystallization is completed carries out centrifugation, thereby obtains the solid crystal thing, then under 80 ℃-120 ℃ dry above-mentioned solid crystal thing 2-12 hour, obtain dry solid crystal thing, be the former powder of composite molecular screen;
(5), at 450 ℃-650 ℃ former powder 2-8 hour of the above-mentioned composite molecular screen of lower roasting, after removing template, finally obtain the low silicon ALPO-18 composite molecular screen of low silicon ALPO-5/.
In said method, described template is preferably N, the N-diisopropyl ethyl amine.
Usually, 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, sintering 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 catalyst that the low silicon ALPO-18 composite molecular screen of above-mentioned low silicon ALPO-5/ is catalytic active component is take in the present invention, comprises the following steps successively:
(1) above-mentioned ALPO-5/ALPO-18 composite molecular screen, molding adhesive, additive, peptizing agent are mixed to each self-forming solution or slurries with water.When each self-forming solution or slurries, can be auxiliary in heating or stir, mix promoting, but the water deionized water;
(2) ALPO-5/ALPO-18 composite molecular screen slurries are mixed with molding adhesive solution, additive slurries, peptizing agent solution successively, finally form even mixed serum, and standing or ageing;
(3) the mixed slurries after standing or ageing are carried out to spray drying forming, obtain shaped granule, then through roasting, thereby, obtain described ALPO-5/ALPO-18 composite molecular sieve catalyst,
Wherein, the weight ratio of described ALPO-5/ALPO-18 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: ALPO-5/ALPO-18 composite molecular screen: water=1:0.2-5.0 is preferably 1:0.5-3.0; Binding agent: water=1:0.5-5.0, be preferably 1:1.0-3.0; Additive: water=1:0.5-5.0, be preferably 1:1.0-3.0; Peptizing agent: water=1:0.2-5.0, be preferably 1:0.5-4.5.Preferably, the incorporation time of each solution, slurries or mixed liquor is 5-60 minute, more preferably 15-30 minute.
In a more preferred, described molding adhesive is boehmite; Described additive is kaolin (stone); Described peptizing agent is rare nitric acid, the gross weight based on acid solution, and acid concentration is 5-45%, preferably 10-40%.
In the invention described above method for preparing catalyst, the particle mean size of ALPO-5/ALPO-18 composite molecular screen, binding agent, additive (diameter) preferably is no more than 75 microns, more preferably the 0.1-20 micron.
In a preferred embodiment, the weight ratio of described ALPO-5/ALPO-18 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, at first described ALPO-5/ALPO-18 composite molecular screen slurries mix with molding adhesive solution, form the first mixed liquor; Then, this first mixed liquor mixes with the additive slurries, forms the second mixed liquor; This second mixed liquor mixes with peptizing agent solution again, forms the third mixed liquor, i.e. mixed serum, and based on the 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 liquor that forms of back, thereby form, contains more multi-component mixed liquor.
In above-mentioned steps (2), the incorporation time of each blend 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 ALPO-5/ALPO-18 composite molecular screen, molding adhesive, additive, peptizing agent and water is carried out to the strong stirring mixing, in order to form even mixed serum.Preferably, the strong stirring mixing is carried out with colloid 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, colloid mill and/or high shear boxshear apparatus rotating speed are 4000-12000 rev/min, and more preferably 4500-10000 rev/min, be particularly preferably 5000-8000 rev/min.
Usually, 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 the slurries gross weight, the solid content of the even mixed serum after standing or ageing is 8-35%, is preferably 10-30%, more preferably 15-25%.
Preferably, the operating condition of spray drying forming is as follows: spray dryer inlet temperature: 250-400 ℃, outlet temperature: 100-200 ℃.Shaped granule particle diameter: 40-100 micron, preferably 45-90 micron.
Usually, the sintering temperature of shaped granule is 450-650 ℃, more preferably 500-600 ℃; Roasting time is preferably 2-8 hour, more preferably 5-7 hour.Formed catalyst contains the material from components such as ALPO-5/ALPO-18 composite molecular screen, molding adhesive, additive and peptizing agents, in butt, each components by weight is: ALPO-5/ALPO-18 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 particle mean size of final ALPO-5/ALPO-18 composite molecular sieve catalyst is preferably the 60-80 micron.
Above-mentioned Optimization of preparation mixing or the dispersion order of preparation ALPO-5/ALPO-18 composite molecular screen of the present invention and required each active principle of catalyst, and the formed mixed slurries that comprise be necessary component are carried out to the strong stirring mixing, thereby, cause the combination property of molecular sieve of the present invention and catalyst to obtain General Promotion.
The low silicon ALPO-18 composite molecular screen of the low silicon ALPO-5/ of the present invention and the preferred condition of work of catalyst are as follows: reaction temperature: 300-500 ℃, preferably 400-500 ℃; Reaction pressure: 0-0.5MPa; Methanol quality air speed: 1.0-5.0/ hour; Under this condition of work, methanol conversion approaches 100%; Propylene+butylene yield between 62-70%, ethene+propylene+butylene yield>90%; ALPO-5/ALPO-18 composite molecular screen service life surpasses 200 minutes, and ALPO-5/ALPO-18 composite molecular sieve catalyst service life was over 2 hours.
Embodiment
Embodiment 1: the ALPO-5/ALPO-18 composite molecular screen of preparation symbiosis
By 17.6 gram boehmites and 20.0 gram deionized water mix and blends, form aluminium source solution, the phosphoric acid that is 85 % by weight by 20.0 gram concentration and 10.0 gram deionized water mix and blends, form phosphorus source solution, by 2.9 gram 40% Ludox and 4.5 gram deionized water mix and blends, form silicon source solution.
Then, phosphorus source solution slowly is added drop-wise in the solution of aluminium source, forms the mixed solution in He Lin source, aluminium source, then silicon source solution is joined in the mixed solution in He Lin source, aluminium source.Uniform stirring 1 hour, the mixed solution in formation He Lin source, ,Lv source, silicon source afterwards, then adds 18.8 gram N in mixed solution, N-diisopropyl ethyl amine template, under stirring, ageing is 3 hours, thereby, form gel.
In said process, template in mixed solution: SiO
2: Al
2o
3: P
2o
5: H
2the mol ratio of O is 1.6:0.2:1:0.95:50.
The gel formed after above-mentioned ageing is packed in the stainless steel crystallization still that inner bag is polytetrafluoroethylene (PTFE) (teflon), carry out the Hydrothermal Synthesis crystallization 3 days under 170 ℃.After the cooling of crystallization still, solid crystallized product through the deionized water centrifuge washing with after being filtered to clear liquid pH value and being 7, drying 8 hours under 120 ℃ again, weigh, subsequently, in air atmosphere and 600 ℃ of lower roastings 5 hours, must hang down the low silicon ALPO-18 composite molecular screen of silicon ALPO-5/, this composite molecular screen is marked as molecular sieve-4 A.
Comparative example 1-1: the low silicon ALPO-18 molecular sieve of preparation
Except the Hydrothermal Synthesis crystallization time was become to 2 beyond the highest heavens by 3 days, repeat the process of embodiment 1, obtain low silicon ALPO-18 molecular sieve, this molecular sieve is marked as molecular sieve-4 A-1.
Comparative example 1-2: the low silicon ALPO-5 molecular sieve of preparation
By 17.6 gram boehmites and 20.0 gram deionized water mix and blends, form aluminium source solution, the phosphoric acid that is 85 % by weight by 20.0 gram concentration and 10.0 gram deionized water mix and blends, form phosphorus source solution, by 2.9 gram Ludox and 4.5 gram deionized water mix and blends, form silicon source solution.
Then, phosphorus source solution slowly is added drop-wise in the solution of aluminium source, forms the mixed solution in He Lin source, aluminium source, then silicon source solution is joined in the mixed solution in He Lin source, aluminium source.Uniform stirring 1 hour, the mixed solution in formation He Lin source, ,Lv source, silicon source afterwards, more dropwise adds 9.2 gram triethylamine templates in mixed solution, fully stirs still aging 24 hours 2 hours.
In said process, template in mixed solution: SiO
2: Al
2o
3: P
2o
5: H
2the mol ratio of O is 1.0:0.2:1:0.95:50.
Mixed solution after above-mentioned ageing is packed in the stainless steel crystallization still that inner bag is polytetrafluoroethylene (PTFE) (teflon), carry out the Hydrothermal Synthesis crystallization 1 day under 180 ℃.After the cooling of crystallization still, solid crystallized product through the deionized water centrifuge washing with after being filtered to clear liquid pH value and being 7, drying 5 hours under 120 ℃ again, subsequently, in air atmosphere and 600 ℃ of lower roastings 8 hours, must hang down silicon ALPO-5 molecular sieve, this molecular sieve is marked as molecular sieve-4 A-2.
Comparative example 1-3: the low silicon ALPO-18 composite molecular screen of the low silicon ALPO-5/ that processing machinery mixes
Low silicon ALPO-18 molecular sieve synthetic in comparative example 1-1 and low silicon ALPO-5 molecular sieve synthetic in comparative example 1-2 are carried out to physical mixed, after mixing, obtain the low silicon ALPO-18 composite molecular screen of low silicon ALPO-5/ of mechanical mixture, this composite molecular screen is marked as molecular sieve-4 A-3.
Embodiment 2: the low silicon ALPO-18 composite molecular screen of the low silicon ALPO-5/ of preparation symbiosis
Except the Ludox consumption is become 1.45 grams by 2.9 grams, repeat to implement the process of profit 1, obtain the low silicon ALPO-18 composite molecular screen of low silicon ALPO-5/, this composite molecular screen is marked as molecular sieve B.
In above-mentioned preparation process, template in mixed solution: SiO
2: Al
2o
3: P
2o
5: H
2the mol ratio of O is 1.6:0.1:1:0.95:50.
Embodiment 3: the low silicon ALPO-18 composite molecular screen of the low silicon ALPO-5/ of preparation symbiosis
By 17.6 gram boehmites and 20.0 gram deionized water mix and blends, form aluminium source solution, the phosphoric acid that is 85 % by weight by 26.7 gram concentration and 10.0 gram deionized water mix and blends, form phosphorus source solution, by 2.9 gram Ludox and 4.5 gram deionized water mix and blends, form silicon source solution.
Then, phosphorus source solution slowly is added drop-wise in the solution of aluminium source, forms the mixed solution in He Lin source, aluminium source, then silicon source solution is joined in the mixed solution in He Lin source, aluminium source.Uniform stirring 1 hour, the mixed solution in formation He Lin source, ,Lv source, silicon source afterwards, then adds 14.1 gram N in mixed solution, N-diisopropyl ethyl amine template, under stirring, ageing is 3 hours, thereby, form gel.
In said process, template in mixed solution: SiO
2: Al
2o
3: P
2o
5: H
2the mol ratio of O is 1.2:0.2:1:1.27:50.
The gel formed after above-mentioned ageing is packed in the stainless steel crystallization still that inner bag is polytetrafluoroethylene (PTFE) (teflon), carry out the Hydrothermal Synthesis crystallization 7 days under 160 ℃.After the cooling of crystallization still, solid crystallized product through the deionized water centrifuge washing with after being filtered to clear liquid pH value and being 7, drying 8 hours under 120 ℃ again, weigh, subsequently, in air atmosphere and 600 ℃ of lower roastings 5 hours, must hang down the low silicon ALPO-18 composite molecular screen of silicon ALPO-5/, this composite molecular screen is marked as molecular sieve C.
Embodiment 4: the low silicon ALPO-18 composite molecular screen of the low silicon ALPO-5/ of preparation symbiosis
Except the template consumption is become 9.4 grams by 18.8 grams, repeat to implement the process of profit 1, obtain the low silicon ALPO-18 composite molecular screen of low silicon ALPO-5/, this composite molecular screen is marked as molecular sieve D.
In above-mentioned preparation process, template in mixed solution: SiO
2: Al
2o
3: P
2o
5: H
2the mol ratio of O is 0.8:0.2:1:1.27:50.
Embodiment 5: the low silicon ALPO-18 composite molecular sieve catalyst of the low silicon ALPO-5/ of preparation symbiosis
The low silicon ALPO-5/ that 300 grams are obtained by method in embodiment 1 hangs down silicon ALPO-18 composite molecular screen (particle mean size is 5 microns) to be mixed with 300 ml deionized water, forms slurries (1), and incorporation time is 20 minutes; 150 gram boehmites (20 microns of particle mean sizes) are mixed with 300 ml deionized water, form molding adhesive slurries (2), incorporation time is 30 minutes; By the 300 gram kaolin (place of production: Kaolin of Suzhou company, particle mean size is 20 microns) with 400 ml deionized water, mix, form additive slurries (3), incorporation time is 20 minutes, the rare nitric acid that is 37 % by weight by 150 ml concns and 200 ml deionized water are mixed, form peptizing agent solution (4), incorporation time is 15 minutes.
Composite molecular screen slurries (1) are mixed with molding adhesive slurries (2), additive slurries (3) and peptizing agent solution (4) successively, obtain successively mixed liquor a, mixed liquor b and mixed liquor c, mixed liquor a incorporation time is 20 minutes, mixed liquor b incorporation time is 30 minutes, mixed liquor c incorporation time is 20 minutes, then adds 800 ml deionized water in mixed liquor c, is mixed, form mixed liquor d(mixed serum), incorporation time is 20 minutes.
Then, mixed liquor d is carried out to the strong stirring mixing, wherein, colloid mill (purchased from Wenzhou person of outstanding talent dragon,, model JML-120A), motor speed is 2900 rev/mins; The strong stirring incorporation time is 50 minutes, and slurries finally are uniformly mixed.
Under the following conditions above-mentioned even mixed serum is carried out to standing or ageing: temperature: 25 ℃, the time: 24 hours; Under the following conditions the even mixed serum after standing or ageing is carried out to spray drying forming: inlet temperature: 360 ℃, outlet temperature: 170 ℃, shaped granule particle diameter: 50-70 micron; Under the following conditions shaped granule is carried out to roasting, roaster: Muffle furnace, temperature: 600 ℃, the time: 5 hours.
Through above-mentioned mixing, spray drying forming and roasting process, finally, the catalyst that the low silicon ALPO-18 composite molecular screen of low silicon ALPO-5/ that obtains take symbiosis of the present invention is catalytic active component, this catalyst is marked as catalyst A, and its service life and selectivity of product mean in the following Table 4.
Comparative example 5-1: the low silicon ALPO-18 molecular sieve catalyst of preparation
Except the low silicon ALPO-18 composite molecular screen of low silicon ALPO-5/ that will obtain by method in embodiment 1 becomes the low silicon ALPO-18 molecular sieve obtained by method in comparative example 1-1, repeat the process of embodiment 5.
Obtain hanging down the catalyst that silicon ALPO-18 molecular sieve is catalytic active component, this catalyst is marked as catalyst A-1, and its service life and selectivity of product mean in the following Table 4.
Comparative example 5-2: the low silicon ALPO-5/ALPO-18 composite molecular sieve catalyst that processing machinery mixes
Except the low silicon ALPO-18 composite molecular screen of low silicon ALPO-5/ that will obtain by method in embodiment 1 becomes the low silicon ALPO-18 composite molecular screen of low silicon ALPO-5/ by the mechanical mixture that in comparative example 1-3, method obtains, repeat the process of embodiment 5.
The catalyst that the low silicon ALPO-18 composite molecular screen of low silicon ALPO-5/ that obtains take mechanical mixture is catalytic active component, this catalyst is marked as catalyst A-3, and its service life and selectivity of product mean in the following Table 4.
Test case
Test case 1: to the physical property measurement of the low silicon ALPO-18 composite molecular screen of the low silicon ALPO-5/ of the present invention
(1) X-ray diffraction (XRD) is analyzed
The low silicon ALPO-18 composite molecular screen of low silicon ALPO-5/ to the symbiosis of the present invention that obtains in embodiment 1 carries out X-ray diffraction (XRD) analysis, obtain Fig. 1, from Fig. 1, can find: occurred the XRD characteristic diffraction peak of ALPO-5 molecular sieve and ALPO-18 molecular sieve in the XRD spectra of the low silicon ALPO-18 composite molecular screen of the low silicon ALPO-5/ obtained in embodiment 1, this explanation has formed the chemically composited structure of two kinds of molecular sieves simultaneously.
(2) Si-nuclear magnetic resonance (NMR) is analyzed
The low silicon ALPO-18 composite molecular screen of low silicon ALPO-5/ to the symbiosis of the present invention that obtains in embodiment 1 carries out Si-nuclear magnetic resonance (NMR) analysis, obtain Fig. 2, from Fig. 2, can find: at-89.9ppm, formant occurred, this formant has represented Si (4Al) tetrahedral coordination structure, illustrates in the composite molecular screen skeleton and has contained a small amount of silicon atom.
(3) N
2isothermal adsorption is analyzed
Adopt N
2isothermal adsorption method carries out pore size distribution, specific area and pore volume analysis to the low silicon ALPO-18 composite molecular screen of low silicon ALPO-5/ of the symbiosis of the present invention that obtains in embodiment 1, obtain Fig. 3, it is 0.32cm that the single-point of the low silicon ALPO-18 composite molecular screen of the low silicon ALPO-5/ of symbiosis of the present invention adsorbs total pore volume
3/ g, t-plot Micropore volume are 0.17cm
3/ g.The pore size distribution figure that Fig. 3 is composite molecular screen of the present invention.From Fig. 3, can find: this composite molecular screen contains significantly mesoporous and macroporous structure.(4) NH
3-TPD analyzes
NH
3-TPD (Temperature-Programmed Desorption) technology is the effective means that characterizes solid catalyst surface acidity.The low silicon ALPO-18 composite molecular screen of low silicon ALPO-5/ to the symbiosis of the present invention that obtains in embodiment 1 carries out NH
3-TPD analyzes, and analysis result means in the following Table 1.
Table 1
| Desorption temperature, ℃ | Acid density, mmol/g | Ratio, % |
| 159.75 | 0.40 | 62 |
| 336.97 | 0.24 | 38 |
The result of table 1 shows: the low silicon ALPO-5/ of the symbiosis of the present invention obtained in embodiment 1 hangs down silicon ALPO-18 composite molecular screen total acid density lower (0.64mmol/g), and take weak acid as main.
Adopt NH
3-TPD technology is analyzed the acidity of the low silicon ALPO-18 composite molecular screen of low silicon ALPO-5/ of the symbiosis of the present invention that obtains in embodiment 1, and the corresponding curve map of drawing out relation between TCD and temperature, as shown in Figure 4.
(5) ESEM (SEM) is analyzed
Fig. 5 is low silicon ALPO-18 composite molecular screen ESEM (SEM) photo of the low silicon ALPO-5/ of the present invention synthetic in embodiment 1, by stereoscan photograph, can be found out: the low silicon ALPO-18 composite molecular screen crystallite dimension of the low silicon ALPO-5/ that the present invention synthesizes is between 1-3 μ m, and it has the lamellar structure of typical ALPO-5 molecular sieve and ALPO-18 molecular sieve.This also illustrates: the low silicon ALPO-18 composite molecular screen of the low silicon ALPO-5/ of the present invention has formed chemically composited structure.
(6) relation in the selective and reaction time of butylene isomer
The selective relation with the reaction time of butylene isomer when Fig. 6 means the low silicon ALPO-18 composite molecular screen of the low silicon ALPO-5/ of the present invention synthetic in embodiment 1 as the preparing light olefins from methanol catalyst.As seen from Figure 6: while using above-mentioned catalyst, butylene selectively can be between 18-27%; In the butylene product, the 1-butylene can account for 15-20%, and the 2-butylene can account for 46-56%, and isobutene can account for 21-37%.
Test case 2: molecular sieve catalytic active assessment
Adopt the fixed bed catalyst evaluating apparatus, the molecular sieve obtained in embodiment 1-4, comparative example 1-1 and 1-4 is carried out to catalytic activity and test in service life.
After above-mentioned molecular sieve is carried out to compressing tablet and fragmentation, it is that 20-40 purpose part is stand-by as sieve sample that sieve is got granularity.
Take respectively the above-mentioned sieve sample of 1.0 gram, with 4 gram 20-40 purpose quartz sands, evenly mix, and respectively they are put into to reactor, pass into nitrogen in 500 ℃ of downhill reaction devices, 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 the flow measurement pump, with carrier gas, mix, and enter preheating furnace under nitrogen-carrier gas is carried in, methyl alcohol is vaporized into gas in preheating furnace, then, enter in reactor, carry out reaction for preparing light olefins from methanol under the catalytic action of above-mentioned molecular sieve.
In said process, nitrogen flow rate: 150 ml/min, methyl alcohol weight space velocity: 3.0/ hour, product adopts the off-line gas-chromatography to carry out constituent analysis, wherein, and while in gas chromatogram, alcohol and ether occurring, illustrate that methanol conversion has not been 100%, now, stop test, the reaction of usining started to time now as molecular sieve service life.
Using composite molecular screen A(embodiment 1 of the present invention) and existing molecular sieve-4 A-1(comparative example 1-1) reaction in, measurement is corresponding to the product composition of differential responses time, its result means in the following Table 2.
Table 2
Result in comparison sheet 4 and table 5, can find out, composite molecular screen A(embodiment 1 of the present invention) to C
4alkene selectively far away higher than existing molecular sieve-4 A-1(comparative example 1-1) to C
4alkene selective; Simultaneously, composite molecular screen A(embodiment 1 of the present invention) to C
2-4selective and the existing molecular sieve-4 A-1(comparative example 1-1 of alkene) to C
2-4alkene selective quite.
Using composite molecular screen A(embodiment 1 of the present invention) reaction in, measure the C corresponding to the differential responses time
4the product composition of alkene distributes, C
4alkene comprises Trans-2-butene, cis-2-butene, 1-butylene and isobutene, and acquired results is illustrated in Fig. 6.
The result of Fig. 6 shows: composite molecular screen A(embodiment 1 of the present invention) to selectively substantially the approaching of Trans-2-butene, cis-2-butene, 1-butylene and isobutene, but along with the carrying out of reaction, to selectively increasing gradually of isobutene.
Existing molecular sieve-4 A-1(comparative example 1-1) to C
4alkene selectively well below composite molecular screen A(embodiment 1 of the present invention) to C
4alkene selective, and it is selectively very low to isobutene.Embodiment 1-1 is except remarkable increase C
4outside olefine selective, also can significantly improve selective isobutene.
Measure the final product of each experiment and form, and calculate C in each product
2-C
4the content of alkene and molecular sieve service life, and the results are shown in following table 3.
Table 3
As can be seen from Table 1: the low silicon ALPO-5/ of symbiosis of the present invention is low, and silicon ALPO-18 composite molecular screen (molecular sieve-4 A-D) has longer service life and excellent catalytic activity simultaneously, and shows good C in methanol to olefins reaction
4olefine selective and C
2-4alkene selective.With existing molecular sieve (molecular sieve-4 A-1 and molecular sieve-4 A-3) in the comparative example, compare, it is selective that the low silicon ALPO-18 composite molecular screen of the low silicon ALPO-5/ of the present invention has higher butylene.
Test case 3: the active assessment of catalyst
The molecular sieve catalyst obtained in embodiment 5 and comparative example 5-1 and 5-2 is carried out to catalytic activity and test in service life.
Adopt other miniature fixed bed methanol-to-olefins (MTO) reactor of laboratory-scale, this reactor inside diameter is 3 centimetres.
Take respectively the molecular sieve catalyst obtained in the embodiment 5 of the 1.0 about 60-80 microns in gram particle footpath and comparative example 5-1 and 5-2, with 4 gram 100-500 order quartz sands, evenly mix, and they are put into respectively to above-mentioned reactor, pass into nitrogen and activate above-mentioned catalyst 1 hour under 500 ℃, then, temperature of reactor is down to 450 ℃, methanol solution mixes with nitrogen carrier gas after the flow measurement pump as raw material, and enter preheating furnace under nitrogen carrier gas carries in, methanol solution is gasificated into gas in preheating furnace, then, enter again in above-mentioned reactor, carry out reaction for preparing light olefins from methanol under above-mentioned molecular sieve catalyst effect.
In said process, nitrogen flow rate: 150 ml/min, methyl alcohol weight space velocity: 3.0/ hour, product is carried out constituent analysis with the off-line gas chromatograph, while in gas chromatogram, alcohol and ether occurring, illustrate that methanol conversion has not been 100%, now, stop test, the reaction of usining started to time now as catalyst service life.
Measure the final product of each experiment and form, and calculate C in each product
2-C
4the content of alkene and molecular sieve service life, and the results are shown in following table 4.
Table 4
| |
5 | Comparative example 5-1 | Comparative example 5-2 |
| The catalyst numbering | A | A-1 | A-2 |
| Methanol conversion (volume %) | 100 | 100 | 100 |
| C 2H 4 | 29.45 | 40.31 | 30.85 |
| C 3H 6 | 42.32 | 33.47 | 38.47 |
| C 4H 8 | 22.03 | 8.15 | 13.96 |
| C 3H 6+C 4H 8 | 64.35 | 41.62 | 52.43 |
| C 2H 4+C 3H 6+C 4H 8 | 93.80 | 81.93 | 83.28 |
| Service life (minute) | 120 | 95 | 80 |
As can be seen from Table 4: the low silicon ALPO-18 composite molecular sieve catalyst (catalyst A) of the low silicon ALPO-5/ of the present invention also has longer service life and excellent catalytic activity simultaneously, and shows good C in methanol to olefins reaction
4olefine selective and C
2-4alkene selective, particularly, show higher butylene selective.With existing catalyst (catalyst A-1 and A-2), compare, it is selective that the low silicon ALPO-18 composite molecular sieve catalyst of the low silicon ALPO-5/ of the present invention has higher butylene.
The term that this specification is used and form of presentation only are used as descriptive and nonrestrictive term and form of presentation, the feature that when using these terms and form of presentation, will mean and describe unintentionally or any equivalent exclusion of its part.
Although meaned 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 that in the situation that do not break away from principle of the present invention and spirit can be carried out any accommodation and improvement to these embodiments, protection scope of the present invention is determined by appended claim and equivalent thereof.
Claims (15)
1. a composite molecular screen, formed by low silicon ALPO-5 molecular sieve and the symbiosis of low silicon ALPO-18 molecular sieve, it is characterized in that: prepare this composite molecular screen raw material used and meet following ratio:
Al
2o
3: P
2o
5: SiO
2mol ratio is 1:(0.7-1.3): (0.05-0.3).
2. composite molecular screen according to claim 1, wherein, described silicon source comes from ethyl orthosilicate, Ludox, white carbon, waterglass, white carbon or they mixture arbitrarily; The aluminium source comes from boehmite, pseudobochmite, aluminium colloidal sol, aluminium isopropoxide, aluminium salt, aluminate, activated alumina or they mixture arbitrarily; The phosphorus source comes from phosphoric acid, phosphorous acid, phosphate and/or phosphorous oxides.
3. composite molecular screen according to claim 1 and 2, wherein, by adjusting above-mentioned Al
2o
3: P
2o
5: SiO
2mol ratio, adjust the relative scale of low silicon ALPO-5 molecular sieve and low silicon ALPO-18 molecular sieve, and then adjust pore passage structure distribution and the acidity of described composite molecular screen.
4. the preparation method according to one of any described composite molecular screen of claim 1-3, it comprises the following steps successively:
(1) in proportion template, ,Lin source, ,Lv source, silicon source and water are mixed at the temperature of 20 ℃-90 ℃, control the rate of addition of each step raw material, obtain comprising the mixed solution of template, ,Lin source, ,Lv source, silicon source and water, template in above-mentioned mixed solution: SiO
2: Al
2o
3: P
2o
5: H
2the mol ratio of O is (0.7-1.6): (0.05-0.3): 1:(0.7-1.3): (30-80);
(2) stir described mixed solution until each component of mixed solution is uniformly dispersed, the standing mixed solution 2-24 hour of ageing subsequently, until form the colloid mixed liquor;
(3) the colloid mixed liquor of the standing rear formation of ageing is put into to 160 ℃ of-180 ℃ of reactors and carried out Hydrothermal Synthesis crystallization 3-8 days;
(4) separate the formed solid crystal thing of crystallization, then under 80 ℃-120 ℃ dry described solid crystal thing 2-12 hour;
(5) at the 450-650 ℃ of above-mentioned dried solid crystal thing 2-8 hour of lower roasting, to remove template wherein, thereby, obtain the composite molecular screen by low silicon ALPO-5 molecular sieve and the symbiosis of low silicon ALPO-18 molecular sieve.
5. preparation method according to claim 4, wherein, described template is N, the N-diisopropyl ethyl amine; Described silicon source is ethyl orthosilicate, Ludox, white carbon, waterglass, white carbon or they mixture arbitrarily; Described aluminium source is boehmite, pseudobochmite, aluminium colloidal sol, aluminium isopropoxide, aluminium salt, aluminate, activated alumina or they mixture arbitrarily; Described phosphorus source is phosphoric acid, phosphorous acid, phosphate and/or phosphorous oxides.
6. preparation method according to claim 4, wherein, in step (4), the formed solid crystal thing of described separation crystallization refers to: the formed solid crystal thing of centrifugal filtration, the crystal mother liquor produced to remove the Hydrothermal Synthesis crystallization, wash described solid crystal thing at least one times by deionized water, the more described solid crystal thing of centrifugal filtration at least one times.
7. preparation method according to claim 4, wherein, by controlling relative consumption, hybrid mode and/or the feeding sequence of template, ,Lin source, ,Lv source, silicon source and water, and then control pore passage structure and the acidity of described composite molecular screen.
8. preparation method according to claim 4, wherein, prepared by described mixed solution by the following method:
(1) respectively He Lin source, ,Lv source, silicon source is mixed with water, form silicon source solution, aluminium source solution and phosphorus source solution;
(2) lentamente phosphorus source solution is added drop-wise to aluminium source solution, forms the mixed solution in He Lv source, phosphorus source;
(3) lentamente silicon source solution is added drop-wise in the mixed solution in He Lv source, phosphorus source, forms the mixed solution in He Gui source, ,Lv source, phosphorus source;
(4) add described template again in the mixed solution in He Gui source, ,Lv source, described phosphorus source, thereby form the mixed solution that comprises ,Gui source, ,Lv source, phosphorus source, template and water.
9. the catalyst of an organic oxygen-containing compound producing light olefins, the catalytic active component of described catalyst is one of any low silicon ALPO-18 composite molecular screen of described low silicon ALPO-5/ of claim 1-3.
10. catalyst according to claim 12, wherein, described organic oxygen-containing compound is methyl alcohol and/or dimethyl ether; Described low-carbon alkene is ethene, propylene and/or butylene.
11. the preparation method according to claim 9 or 10 described catalyst, it comprises the following steps successively:
(1) respectively the low silicon ALPO-18 composite molecular screen of one of any described low silicon ALPO-5/ of claim 1-3, molding adhesive, additive, peptizing agent are mixed to each self-forming solution or slurries with water;
(2) above-mentioned each solution or slurries are mixed, form even mixed serum, and standing or ageing;
(3) the mixed slurries after standing or ageing are carried out to spray drying forming, obtain shaped granule, then through roasting, thereby, obtain described low silicon ALPO-5/ALPO-18 composite molecular sieve catalyst,
Wherein, the weight ratio of the low silicon ALPO-18 composite molecular screen of low silicon ALPO-5/, molding adhesive, additive, peptizing agent is 1:0.1-0.6:0.5-1.5:0.01-0.25.
12. preparation method according to claim 11, wherein, in above-mentioned steps (2), mix described composite molecular screen slurries successively with molding adhesive solution, additive slurries, peptizing agent solution, finally form even mixed serum, and standing or ageing.
13. preparation method according to claim 11, wherein, described molding adhesive is boehmite, aluminium colloidal sol, Ludox, silicon-aluminum sol, aluminum phosphate, zirconia, titanium oxide or they one of mixture arbitrarily; Described additive is diatomite, kaolin (stone), imvite (stone), talcum, bentonite or they one of mixture arbitrarily, and they are activated by acid treatment before use; Described peptizing agent is inorganic acid and/or organic acid.
14. preparation method according to claim 13, wherein, described inorganic acid comprises nitric acid, hydrochloric acid and/or sulfuric acid; Described organic acid comprises formic acid, acetic acid, propionic acid and/or citric acid.
15. preparation method according to claim 11, wherein, in step (2), based on the slurries gross weight, described mixed serum solid content is 15-40%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104828842A (en) * | 2014-12-18 | 2015-08-12 | 神华集团有限责任公司 | Preparation method of SAPO-5 and SAPO-34 symbiotic composite molecular sieve |
| CN104923294A (en) * | 2015-04-29 | 2015-09-23 | 天津众智科技有限公司 | Composite molecular sieve for MTO (Methanol to Olefins) and preparation method therefor and application thereof |
| CN106554026A (en) * | 2015-09-24 | 2017-04-05 | 天津工业大学 | A kind of preparation of the magnesium-modified low silicon SSZ-13 molecular sieves of metal and its MTO reactivity worth |
| CN107952470A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | The synthetic method of composite molecular screen and application |
| CN113582801A (en) * | 2020-04-30 | 2021-11-02 | 中国石油化工股份有限公司 | Process for preparing isooctene by selective superposition of mixed C4 |
| CN114038602A (en) * | 2021-09-16 | 2022-02-11 | 武汉市莎卡娜尔科技有限公司 | Radiation protection material for inorganic fiber one-dimensional multi-element nano-micron composite crystal |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104828842A (en) * | 2014-12-18 | 2015-08-12 | 神华集团有限责任公司 | Preparation method of SAPO-5 and SAPO-34 symbiotic composite molecular sieve |
| CN104923294A (en) * | 2015-04-29 | 2015-09-23 | 天津众智科技有限公司 | Composite molecular sieve for MTO (Methanol to Olefins) and preparation method therefor and application thereof |
| CN104923294B (en) * | 2015-04-29 | 2020-04-10 | 天津众智科技有限公司 | Composite molecular sieve for preparing olefin from methanol, preparation method and application |
| CN106554026A (en) * | 2015-09-24 | 2017-04-05 | 天津工业大学 | A kind of preparation of the magnesium-modified low silicon SSZ-13 molecular sieves of metal and its MTO reactivity worth |
| CN107952470A (en) * | 2016-10-14 | 2018-04-24 | 中国石油化工股份有限公司 | The synthetic method of composite molecular screen and application |
| CN113582801A (en) * | 2020-04-30 | 2021-11-02 | 中国石油化工股份有限公司 | Process for preparing isooctene by selective superposition of mixed C4 |
| CN113582801B (en) * | 2020-04-30 | 2023-09-05 | 中国石油化工股份有限公司 | Process for preparing isooctenes by mixing carbon four selective overlapping |
| CN114038602A (en) * | 2021-09-16 | 2022-02-11 | 武汉市莎卡娜尔科技有限公司 | Radiation protection material for inorganic fiber one-dimensional multi-element nano-micron composite crystal |
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