958results about "Molecular-sieve silicoaluminophosphates" patented technology

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 preparation method of a metal-modified SAPO-34 molecular sieve. The method includes: first mixing a template agent with metal salt solution to form a metal complex in the preparation process of raw powder of the molecular sieve; then adding materials such as aluminum source, phosphorus source, silicon source to prepare gel mixture; and finally obtaining the metal-modified SAPO-34 molecular sieve through ageing, hydrothermal crystallization, washing, drying, roasting and the like. The metal-modified SAPO-34 molecular sieve prepared by the method has comparatively high degree of crystallinity and can effectively improve the selectivity of ethene and propylene as reaction catalyst for preparing olefins by methanol. The invention discloses a preparation method of the metal-modified SAPO-34 molecular sieve and a catalyst containing the molecular sieve.

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 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.

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.

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.

Disclosed is a method for the manufacture of silicoaluminophosphate (SAPO) and/or aluminophosphate (ALPO) molecular sieves. The method includes maintaining the slurry of the as crystallized molecular sieve under substantially static conditions when stored after substantially complete crystallization and prior to recovery of the product.

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 present invention relates to an improved process for the preparation of porous crystalline aluminophosphate molecular sieves, which are useful as catalysts and adsorbents.

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 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.

The invention discloses a preparation method of a high-performance SAPO (silicoaluminophosphate)-34 molecular sieve membrane. The preparation method comprises the following steps: (1) obtaining an SAPO-34 molecular sieve crystal seed; (2) coating the SAPO-34 molecular sieve crystal seed on the inner surface of a porous carrier; (3) putting the prepared porous carrier coated with the SAPO-34 molecular sieve crystal seed into synthesizing mother liquor of the molecular sieve membrane and synthesizing an SAPO-34 molecular sieve membrane tube; (4) roasting to remove a template agent, thereby obtaining the SAPO-34 molecular sieve membrane without the template agent. The preparation method disclosed by the invention has the advantages that the uniformity and stability of the synthesizing mother liquid are greatly improved, the synthesis repeatability of the SAPO-34 molecular sieve membrane is improved, and the synthesized SAPO-34 molecular sieve membrane has higher gas permeability and CO2/CH4 selectivity. Furthermore, the SAPO-34 molecular sieve membrane prepared by the preparation method can be applied to gas separation of CO2-CH4, CO2-H2 and CO2/N2 and the like.

The invention discloses a method for preparing multistage-channel SAPO-n (n=34, 18) through solvent volatilization. According to the invention, a zeolite template agent is added into a mixed solution of an aluminum source, a silicon source, and a phosphorus source; stirring and a reaction are sufficiently carried out; the solution is completely delivered into a culture dish, and is air-dried into gel; under the effect of steam formed by water added into an autoclave, the gel is subjected to hydrothermal synthesis; powder converted from the gel is subjected to a heat treatment under high temperature, such that the multistage-channel SAPO-n zeolite is formed. The method provided by the invention has the advantages of simple process, easy control, easy realization, low cost, and environment friendliness.

The invention relates to a preparation method of a hierarchical porous structure silicon-phosphorus-aluminum SAPO molecular sieve. The technical scheme adopted by the invention for mainly solving the problem that the hierarchical porous structure SAPO molecular sieve is hard to prepare in the prior art is as follows: the preparation method of the hierarchical porous structure silicon-phosphorus-aluminum SAPO molecular sieve comprises the following steps: hydrolyzing a mixture prepared by a high-molecular polymer R1, water, an organic template agent R2, a phosphorus source, an aluminum source and an alkali-treated silicon source at -20 DEG C to 100 DEG C to prepare sol, then putting the sol in a reaction kettle for crystallizing; and washing, drying and roasting a sample after crystallizing to prepare the hierarchical porous structure SAPO molecular sieve. The preparation method of the hierarchical porous structure silicon-phosphorus-aluminum SAPO molecular sieve can be applied to industrial production of the hierarchical porous structure molecular sieve.

A process for synthesizing SiPAl molecular sieve used for preparing low-carbon olefin from methanol features that tetra-ethyl ammonium hydroxide and morpholine are used as composite template to prepare SAPO-34 molecular sieve with low cost and high crystallinity.

The invention relates to a method for preparing SAPO (SIlico-Aluminophosphate) molecular sieve material with a multi-level-hole structure, mainly solving the problem that the whole SAPO molecular sieve material with the multi-level-hole structure is difficult to obtain in the prior art. The method adopts the following technical scheme for better solving the problem: adopting and hydrolyzing a mixture of phase-separation inducer R1, a gel accelerator R2, an organic solvent R3, water, a phosphorus source, a silicon source and an aluminum source to obtain a precursor I of silicon-phosphorus-aluminum oxide material; carrying out gel aging on the precursor I, thus obtaining a precursor II of the silicon-phosphorus-aluminum oxide material; drying and roasting the precursor II of the silicon-phosphorus-aluminum oxide material, thus obtaining silicon-phosphorus-aluminum oxide material III with a double-continuous-large-hole structure; dipping the silicon-phosphorus-aluminum oxide material III into solution containing a template agent, drying the silicon-phosphorus-aluminum oxide material III, then arranging the silicon-phosphorus-aluminum oxide material III at the upper part of a reaction kettle, adding organic amine solution at the bottom of the reaction kettle, and then crystallizing; and after the crystallization, washing, drying and roasting a sample, thus obtaining the whole SAPO molecular sieve material with the multi-level-hole structure. The method can be used for industrial production of the molecular sieve with multi-level-hole structure.

Embodiments of the invention generally provide compositions of crystalline zeolite materials with tailored crystal habits and the methods for forming such crystalline zeolite materials. The methods for forming the crystalline zeolite materials include binding one or more zeolite growth modifiers (ZGMs) to the surface of a zeolite crystal, which results in the modification of crystal growth rates along different crystallographic directions, leading to the formation of zeolites having a tailored crystal habit. The improved properties enabled by the tailored crystal habit include a minimized crystal thickness, a shortened internal diffusion pathlength, and a greater step density as compared to a zeolite having the native crystal habit prepared by traditional processes. The tailored crystal habit provides the crystalline zeolite materials with an aspect ratio of about 4 or greater and crystal surfaces having a step density of about 25 steps/μm² or greater.

The invention relates to a method for preparing a small crystal grain SAPO-34 molecular sieve with high crystallinity and large specific surface area. The method for preparing the molecular sieve is mainly characterized in that a structure guide agent containing triethylamine and fluoride is added in the forming process of a colloid mixture; and at the same time, after an ageing process, the colloid mixture is crystallized. The SAPO-34 molecular sieve prepared by the method has the advantages of small grain diameter, large specific surface area and high crystallinity.

The invention relates to a one-step method for synthesizing a copper-containing CHA type molecular sieve with high hydro-thermal stability. The method comprises the steps of (1) firstly stirring an aluminium source in deionized water thoroughly, then slowly adding phosphoric acid to dissolve the aluminium source completely, adding a certain amount of a silicon source and a copper source, stirring uniformly, adding an organic amine template and a ligand reagent with vigorous stirring, stirring for 2-8 hours, adding an obtained solution into a stainless steel reaction kettle with a polytetrafluoroethylene or polyphenylene lining, crystallizing for 0.5-5 days at a temperature of 140-210 DEG C; and (2) washing the obtained product, drying for 3-8 hours at a temperature of 60-110 DEG C; and roasting a dried product for 2-8 hours at a temperature of 450-600 DEG C to obtain the copper-containing CHA type molecular sieve. The template used in the method is cheap and easily available. One-step synthesis of the copper-containing CHA type molecular sieve omits a plurality of copper-containing salt solution ion exchange and roasting processes, simplifies operation steps and saves energy. The prepared copper-containing CHA type molecular sieve has relatively high degree of crystallinity and specific surface area, and has good hydro-thermal stability.