1448results about "Molecular-sieve and base-exchange phosphates" patented technology

The present invention relates to a silicoaluminophosphate molecular sieve comprising at least one intergrown phase of molecular sieves having AEI and CHA framework types, wherein said intergrown phase has an AEI / CHA ratio of from about 5 / 95 to 40 / 60 as determined by DIFFaX analysis, using the powder X-ray diffraction pattern of a calcined sample of said silicoaluminophosphate molecular sieve. It also relates to methods for its preparation and to its use in the catalytic conversion of methanol to olefins.

The synthesis of a crystalline aluminophosphate or silicoaluminophosphate molecular sieve having a chabazite-type framework type is conducted in the presence of an organic directing agent having the formula (I) [R1R2R3N—R4]+X−  (I) wherein R1, R2 and R3 are independently selected from the group consisting of alkyl groups having from 1 to 3 carbon atoms and hydroxyalkyl groups having from 1 to 3 carbon atoms; R4 is selected from the group consisting of 4- to 8-membered cycloalkyl groups, optionally substituted by 1 to 3 alkyl groups having from 1 to 3 carbon atoms; 4- to 8-membered heterocyclic groups having from 1 to 3 heteroatoms, said heterocyclic groups being optionally substituted by 1 to 3 alkyl groups having from 1 to 3 carbon atoms and the heteroatoms in said heterocyclic groups being selected from the group consisting of O, N, and S; and aromatic groups optionally substituted by 1 to 3 alkyl groups, said alkyl groups having from 1 to 3 carbon atoms; and X− is an anion.

The invention discloses a universal preparation process for aluminosilicophosphate (SAPO) molecular sieve materials from natural lamellar aluminosilicate minerals. According to the invention, on the basis of the cheap natural lamellar aluminosilicate minerals, the SAPO molecular sieve materials are prepared by carrying out activation, slurrying of ingredients, hydrothermal crystallization and removal of structure directing agents; the natural lamellar aluminosilicate minerals can be fully used as a composite silicon aluminum source, are enabled to completely dissolve by utilizing the reaction activity of an alumina layer with phosphorous species and structure directing agent species under a hydrothermal condition and utilizing dissolving and coordination capacity of a silica layer in a medium, and can assemble anew to form a variety of SAPO molecular sieve materials under the action of the structure directing agents. The process provided in the invention substantially reduces synthesis cost for SAPO molecular sieves; the prepared molecular sieves have variable structure and composition, controllable silicon content and silicon distribution and adjustable acidic site intensity and acidic site distribution; the prepared SAPO molecular sieve materials have a wide application prospect in the fields of catalysis, adsorption, ion exchange, functional materials, etc.

The present invention discloses microporous aluminophosphate (AlPO4) molecular sieve membranes and methods for making and using the same. The microporous AlPO4 molecular sieve membranes, particularly small pore microporous AlPO-14 and AlPO-18 molecular sieve membranes, are prepared by three different methods, including in-situ crystallization of a layer of AlPO4 molecular sieve crystals on a porous membrane support, coating a layer of polymer-bound AlPO4 molecular sieve crystals on a porous membrane support, and a seeding method by in-situ crystallization of a continuous second layer of AlPO4 molecular sieve crystals on a seed layer of AlPO4 molecular sieve crystals supported on a porous membrane support. The microporous AlPO4 molecular sieve membranes have superior thermal and chemical stability, good erosion resistance, high CO2 plasticization resistance, and significantly improved selectivity over polymer membranes for gas and liquid separations, including carbon dioxide / methane (CO2 / CH4), carbon dioxide / nitrogen (CO2 / N2), and hydrogen / methane (H2 / CH4) separations.

The invention discloses a preparation method of a mesoporous-microporous composite molecular sieve. The preparation method comprises the following steps of adding a microporous molecular sieve subjected to hydrothermal treatment into a mixed system of a silicon source, an acid solution and a surfactant, then carrying out crystallization, filtration and washing, and then carrying out drying and calcination to obtain the mesoporous-microporous composite molecular sieve. The preparation method fully utilizes non-framework aluminum falling from the microporous molecular sieve, avoids an aluminum source used by the conventional molecular sieve preparation technology, is conducive to improvement of a silica-alumina ratio of the mesoporous-microporous composite molecular sieve, realizes a high degree of crystallization, and improves hydrothermal stability and thermostability of the mesoporous-microporous composite molecular sieve. The mesoporous-microporous composite molecular sieve is suitable for the field of macromolecule catalysis, is conducive to improvement of a reaction conversion ratio and reaction selectivity, and is especially suitable for being used in a cracking catalyst for maximum-degree production of middle distillate from heavy oil as a raw material.

The invention relates to an SAPO (silicoaluminophosphate) molecular sieve with an RHO skeleton structure. The molecular sieve is formed by a PO2+, AlO2- and SiO2 tetrahedron and has a three-dimensional skeleton structure, the anhydrous chemical composition can be shown as mR.(SixAly Pz)O2. The preparation process comprises the following steps of: mixing a silicon source, an aluminum source, a phosphorous source, a surfactant, a template with deionized water to obtain an initial gel mixture; moving the prepared initial gel mixture material to a synthesis reactor for airtight temperature rise and crystallization; and washing and drying a solid crystallized product to obtain SAPO molecular sieve raw powder with the RHO structure; or the preparation process comprises the following steps of: mixing a silicon source, an aluminum source, a phosphorous source with the deionized water to obtain a gel mixture; evaporating the moisture content of the gel mixture to prepare a dry gel; moving the dry gel mixture, the template and the deionized water to the synthesis reactor for airtight rotation and crystallization; and washing and drying the solid crystallized product to obtain the SAPO molecular sieve raw powder with the RHO structure.

This invention relates to a continuous microwave synthesis process of inorganic materials and its apparatus and more particularly, to the process of synthesizing inorganic materials prepared in a manner such that after preparing a mixed solution of precursor materials for various inorganic materials such as porous molecular sieve, layered compounds and ceramics, this mixed solution is continuously added to a tube-type microwave reactor using a slurry pump for the synthesis and crystallization of inorganic materials. Thus the manufacturing process of this invention has the following advantages: (1) the reaction time is further shortened by several to tens of minutes for crystallization, compared to the conventional hydrothermal reaction requiring a prolonged time, (2) the continuous manufacturing and collection processes of this invention can give access to mass-scale production of inorganic materials with relatively small facility, compared to the conventional batch hydrothermal or microwave synthesis, and (3) less amount of organic templating agent can be required during the manufacture of porous molecular sieve.

The invention relates to a method of molecular sieve catalyst synthesis using the kaolin for the synthesis of silicon aluminum phosphate molecular sieve, belonging to the technical field of the preparation of the catalyst materials. The invention is characterized in utilizing the low-cost kaolin as materials. Through (1) roasting the kaolin in the high temperature to gain the crystal aluminum sources and silicon sources; (2) mixing the kaolin with the phosphorus sources and the template agent with the deionized water, processing hydro-thermal crystallization, and roasting and activating the products after washing and drying, the catalyst of the silicon aluminum phosphate molecular sieve can be gained. The structure of the silicon aluminum phosphate molecular sieve is CHA or the intergrowth of CHA and AEI. The invention has the advantages of smaller or lamellar structure molecular sieve gains of the prepared catalyst, which can be used for the process of making olefin from the oxygenic compounds like the limited diffuse alcohol ether to gain the good activity of reaction and the product selectivity, and further the directly application of the catalyst carried by the kaolin micro sphere into fluidized bed reactor.

A silicoaluminophosphate molecular sieve is disclosed that comprises first and second intergrown phases of a CHA framework type and an AEI framework type, wherein said first intergrown phase has an AEI / CHA ratio of from about 5 / 95 to about 40 / 60 as determined by DIFFaX analysis, the second intergrown phase has an AEI / CHA ratio of about 30 / 70 to about 55 / 45 as determined by DIFFaX analysis and said molecular sieve has a silica to alumina molar ratio (Si / Al2) from about 0.13 to about 0.24.

The invention relates to a solvent thermal synthesis method of an SAPO (silicoaluminophosphate) molecular sieve and a catalyst prepared by the SAPO molecular sieve. The solvent thermal synthesis method provided by the invention is characterized in that organic amine is directly used as a solvent and a template agent of a synthesis system, and the SAPO molecular sieve is prepared through solvent thermal synthesis.

The invention discloses an AEI / CHA eutectic molecule sieve containing triethylamine. An anhydrous chemical composition of the AEI / CHA eutectic molecule sieve is expressed as mR.(Six.Aly.Pz)O2, wherein x, y and z are molar fractions of Si, Al and P respectively; the x is between 0.001 and 0.98; the y is between 0.01 and 0.6; the z is between 0.01 and 0.6, x+y+z is equal to 1; the R is a template agent, and the m is a mole number of the R; and the value of the m is between 0.02 and 0.6. A preparation method for the AEI / CHA eutectic molecule sieve comprises the following steps: a) according to the mol ratio of oxides of various components, stirring and mixing evenly a silicon source, an aluminum resource, a phosphorus source, the template agent, and water are to obtain an initial gel mixture; and b) transferring the initial gel mixture into a stainless steel synthesis kettle to be sealed, then heating the kettle to a crystallization temperature of between 160 and 250 DEG C, and performing crystallization at constant temperature for 1 to 120 hours under the self-generated pressure, and separating a solid product, washing the solid product to be neutral, and drying the solid product to obtain the AEI / CHA eutectic molecule sieve. The molecule sieve can be used as a catalyst for an acid catalytic reaction after the template agent is removed through the baking.

The invention discloses a slice-shaped nanometer SAPO-34 molecular sieve with relatively low silicon content, a preparation method and an application thereof, and belongs to the technical field of molecular sieves. Tetraethylammonium hydroxide is used as a template, the slice-shaped nanometer SAPO-34 molecular sieve with relatively low silicon content is synthesized by using the traditional hydrothermal method or a solvothermal synthesis method. The synthesized nanometer SAPO-34 sample is a slice-shaped feature, of which the average crystal granularity size is 50-250nm and the thickness is 50-100nm. The synthetic method is simple and efficient; the solvent consumption is low; the yield of the synthesized nanometer SAPO-34 sample is extremely high and can be up to 85-90 percent; the synthesized nanometer SAPO-34 sample is high in low carbon olefin selectivity during reaction of methanol to olefin (MTO), particularly, the total yield of ethylene and propylene can be up to more than 83 percent, and the molecular sieve is very suitable for industrial amplification application.

The present invention provides a synthesis process of SAPO-11 molecular sieve. Available technology adopts conventional hydrothermal method, which is non-repeatable and easy to produce many Si areas to degrade catalytic performance. The present invention is that in a water-surfactant-organic alcohol system, nano level SAPO-11 molecular sieve with high repeatability, less Si areas and more strong B acid is synthesized. After carrying noble metal, the molecular sieve has high selectivity, yield and repeatability while being used in hydrogensing isomerization reaction of long-chain alkane.

A method for producing zeolite films or membranes at essentially ambient pressure, which includes preparing a synthesis mixture comprising an ionic liquid solvent and an aluminum and / or silicon and / or phosphate source and converting the synthesis mixture to form a continuous zeolite layer. In addition, a method of synthesizing zeolite nanocrystals, which includes preparing a synthesis mixture, the synthesis mixture having a silica or a silica and alumina source, and a template; and synthesizing the synthesis mixture to form zeolite nanocrystals.

The invention relates to a preparation method for a silicoaluminophosphate (SAPO)-34 molecular sieve with a small crystal particle, which mainly solves the problem of larger product particle diameter in the SAPO-34 synthesis process in the prior art. The preparation method comprises the following steps: a) preparing an initial gel mixture at the following molar ratio: 0.5-10 moles of SiO2, 0.05-10 moles of Al2O3, 0.2-3 moles of P2O5, 0.001-0.02 moles of hydrogen fluoride (HF) and 20-200 moles of H2O, and stirring and ageing at the room temperature for 1-24h; b) adding the aged mixed solution into a crystallization kettle, carrying out hydrothermal crystallization at the temperature of 170-220DEG C for 0.1-20h, taking out, and quenching to obtain crystallization directing agent; c) according to the step a), preparing the gel mixture again, adding the crystallization directing agent obtained in the step b) to be evenly mixed, loading into the crystallization kettle, and carrying out hydrothermal crystallization at the temperature of 150-260DEG C for 5-48h; and d) recovering a molecular sieve product. According to the technical scheme, the problem is better solved, and the preparation method can be used for the industrial preparation of the SAPO-34 molecular sieve.

The invention relates to a synthetic method of SAPO-5 and SAPO-34 symbiotic molecular sieves and mainly solves the problems of single aperture and low activity of a porous material synthesized by the prior art. The synthetic method provided by the invention comprises the following steps of: using a phosphor source, an aluminium source, a silicon source and an organic template as raw materials, mixing the raw materials according to a certain proportion to form a mixed solution, and carrying out hydrothermal crystallization to obtain a series of SAPO-5 and SAPO-34 symbiotic molecular sieves. The synthesized symbiotic molecular sieves have the following molar ratio: AlO3: P2O5: SiO2: R: H2O=1: 0.2-1-2: 0.1-2.0: 0.5-2.5: 20-100, wherein R is the organic template. The technical scheme provided by the invention greatly solves the problems, and can be used in the industrial production of low carbon olefin prepared by methanol.

A process for preparing molecular sieve SAPO-34 includes such steps as adding deionized water to the container with stirrer, proportionally and sequentially adding the compounds of Al, P and Si and organic amine while stirring, evaporating water in baker to obtain dried substance, putting it on the upper position of a gas-phase reactor, filling the mixture of organic amine and water into its bottom, reaction, cooling, washing, drying and calcining.

The present invention is directed to the synthesis of novel delaminated layered zeolite precursor materials prepared by fluoride / chloride anion-promoted exfoliation. The method comprises, for example, using a combination of fluoride and chloride anions at a mild pH in aqueous solution to affect delamination of a layered zeolite precursor. The method can also comprise using a combination of fluoride and chloride anions in a non-aqueous solution comprising an organic solvent. The method may be used in conjunction with either acidification or sonication, or both. The resulting delaminated zeolite precursors are then isolated. Precursors that are then isolated lack amorphous silica content. The UCB-1 product is an example of such a novel oxide material and is obtained in yields in excess of 90% without the need for sonication.

The invention relates to a method for preparing a molecular sieve with small crystal of SAPO-11, which does not use any other organics additives except template. The method prepares the molecular sieve with small crystal of SAPO-11 which has a size ranging from 300mm to 800mm and has an AEL structure comprising water, phosphorus source, aluminum source, template, and silica source. The preparation method includes the following steps: (1) the preparation of colloid slurry: according to the total material mole ration of P2O5: (0.5 to 1.5)AL2O3: (0.4 to 2.0) R: (0 to 1.0)SiO2:(17 to 60) H2O, the water, the phosphorus source, the aluminum source, the template and the silica source are added under the condition of temperature of 5 to 80 DEG C, fast mixing and the PH value controlled between 3.5 to 7.0, wherein, R is the template; (2) the aging of slurry: the reaction mixture acquired from step (1) is gel static aged under the temperature of 80 to 190 DEG C for 0.5 to 24 hours then is cooled to the room temperature; (3) the crystallization of the slurry: under the stirring condition, 0 to 200 percent of distilled water of the total mixture is put into the aging solution, then the solution is heated up to 100 to 220 DEG C for continuous crystallization for 4 to 72 hours to get the product by filtering, washing and drying after the crystallization.

The invention discloses a nano SAPO (silicoaluminophosphate)-34 molecular sieve with a spherical or flaky appearance, a synthetic method of the nano SAPO-34 molecular sieve and a methanol to olefin catalyst prepared by the molecular sieve. The SAPO-34 molecular sieve is prepared in a microwave heating manner. The nano spherical or flaky SAPO-34 molecular sieve can be obtained by controlling microwave synthesis conditions, is a sphere having a crystal grain size less than 30nm or a sheet having a thickness less than 70nm, and the has the characteristics of short synthetic time, controllable crystal grain appearance and the like. A molecular sieve catalyst prepared by the molecular sieve is used for reactions of methanol to olefin, such as methanol to ethylene, methanol to propylene and the like, wherein a methanol conversion rate can reach 100%, the selectivity of C2 to C4 can reach 89.85%, the single pass life of the catalyst can reach 350 minutes.

The invention discloses a method for preparing SAPO-34 molecular sieve, which is characterized in that Al2O3, P2O5, SiO2, R and H2O which have the mol ratio of 1:0.5-1.02:0.1-0.8:0.32-3:50-200 are mixed together into crystallization liquid and processed by aging treatment at the temperature of 2-110 DEG C for 10-24hr; or the crystallization liquid is processed by ultrasonic treatment at the temperature of 20-90 DEG C for 0.5-1hr, the ultrasonic frequency is 40-60 Hz, and the power is 200-400W. After being pretreated by the technique, the crystallization liquid is crystallized at the temperature of 180-200 DEG C for 18-48hr, and the solid product is washed in a centrifugal way and dried at the temperature of 105-115 DEG C; then, the obtained solid product is calcined at the temperature of 530-560 DEG C for 5-6hr, so that the SAPO-34 molecular sieve is obtained.

The invention belongs to the technical field of molecular sieves and particularly relates to a cubic or sheet-shaped nano SAPO-34 molecular sieve and application thereof in conversion, separation and absorption of all kinds of hydrocarbons. The dimension range of the molecular sieve is within 20-300nm and is rapidly prepared by using tetraethyl ammonium hydroxide as template agent, mixing the tetraethyl ammonium hydroxide with an aluminum source, a silicon source and a phosphorus source and adding specific solvent to control gel concentration through the traditional hydrothermal or microwave heating method. The nano-scale SAPO-34 molecular sieve synthesized by adopting the method has the characteristics that the cost of raw materials for gel is low, the production speed of the molecular sieve is rapid, the preparation time of crystallized start materials is short, the reaction energy consumption is low, the yield of the molecular sieve is high, the catalytic application life is long and the catalytic effect of the molecular sieve in catalytic reaction can be obviously improved.

The invention provides a method for preparing a SAPO-34 molecular sieve. The method comprises the following steps of: 1, uniformly mixing a proper amount of phosphorus source, aluminum source, silicon source, template, auxiliary template and water at a proper temperature and under a stirring condition to obtain mixed solution, of which a molar ratio of all components, namely, the molar ratio of R to F- to SiO2 to Al2O3 to P2O5 to H2O, is a:b:c:1:d:e, wherein R represents the template, a is 0.2 to 5.0, b is 0 to 1.0, c is 0.2 to 1.5, d is 0.2 to 2.0 and e is 20 to 200; 2, ageing the mixed solution; and putting the aged mixed solution in a crystallization kettle, sealing the crystallization kettle, heating the mixed solution to a crystallization temperature, and crystallizing the mixed solution at the constant crystallization temperature; 3, performing centrifugal separation of the crystallized mixed solution, filtering, washing the mixed solution until a pH value of the mixed solution is 7 to 8, and drying a solid sample to obtain the SAPO-34 raw powder; and 4, baking the SAPO-34 raw powder at the temperature of between 450 and 650 DEG C for 4 to 8 hours to obtain the SAPO-34 molecular sieve. The SAPO-34 molecular sieve prepared by the method is characterized by high crystallinity and can show better low carbon olefin selectivity in an MTO reaction.

Layered silicate materials and applications are disclosed. In one aspect, the invention features layered silicate materials having pores that run generally perpendicular to the layers. In another aspect, the invention features composite materials including layered framework materials (e.g., layered silicate materials, layered Aluminophosphate materials, layered tin sulfides) having pores or openings that run generally perpendicular to the layers.

The invention relates to a preparation method and application of a hierarchical porous molecular sieve membrane. A mesoporous structure guiding agent is added to limit the growth of a molecular sieve crystal, and is subjected to self-assembly in a crystallization process of the molecular sieve crystal, so as to generate a mesoporous structure. The hierarchical porous molecular sieve membrane is synthesized by using a seed crystal inducing secondary nucleation mechanism and a hydrothermal one-step synthesis method; synthesis conditions are mild and controllable, the simplicity in preparation and good repeatability are realized, energy consumption is reduced, and the cost is reduced. The hierarchical porous molecular sieve membrane prepared by adopting the method shows good retention performance, and the retention molecular weight is controllable between 200 and 500000 Da. The method for preparing the hierarchical porous molecular sieve membrane, provided by the invention, can be used for synthesizing the hierarchical porous molecular sieve membrane with other micropore skeleton structures, and has high cost performance and a broad industrial production prospect; the application of the preparation method also can be popularized to the field of catalysis.

The present invention relates to a method of preparing a microporous crystalline molecular sieve Inorganic gel having mesoporous skeleton, comprising following steps: (a) adding a meso-SDA (meso-Structure Directing Agent) into a gel composition of synthesizing molecular sieve, (b) subjecting the mixture obtained in the above step (a) to crystallization by a hydrothermal reaction, a microwave reaction, a dry-gel synthesis, etc., and (c) removing selectively organic materials from the resulted material obtained in the above step (b) by a calcination or a chemical treatment. Molecular sieve having mesoporous skeleton synthesized by the present invention exhibits, as compared with conventional zeolite, a good molecule diffusion ability and a greatly improved catalytic activity.

The invention provides an SAPO-34 molecular sieve and a synthesis method thereof. A hysteresis loop is arranged between nitrogen adsorption isotherm and desorption isotherm of the molecular sieve; and a molecular sieve crystal comprises topographies such as hollow shells, holes, concave-convex, cracks, nuclear shells and the like. The molecular sieve is obtained by mixing an aluminum source, a phosphorous source, a silicon source and an organic template agent to form gel and hydrothermally crystallizing the gel for 4 to 500 hours at the temperature of between 100 and 250 DEG C, wherein the organic template agent is added in two steps, one part is added during forming the gel, and the rest is added during hydrothermal crystallization. The molecular sieve is a catalyst of active components, can be used for conversion reaction of oxygenated organic compounds, and also can be used for conversion reaction of hydrocarbons, or used as a hydrogen conversion catalyst of hydrocarbons after supporting metals.