Method of obtaining molecular sieves by continuous addition of raw material components

FIELD: chemistry.

SUBSTANCE: elaborated is method of various molecular sieves synthesis. Method includes formation of reaction mixture, which includes reaction-able sources of frame elements plus, at least, one template agent, interaction of mixture to, at least, partial crystallisation of molecular sieves and creation of suspension of crystal germs and addition to them of raw material (sources) of frame elements, for instance, aluminium and silicon for crystal germ growth. Rate of adding raw material components is regulated in such way that it is in fact the same as the rate of crystal growth, and nucleation of new crystals is in fact absent. Crystal germs can be the same or different from added raw material components, which allows to obtain foliated molecular sieves. When crystal size reaches desirable value, they are isolated by common methods.

EFFECT: method ensures growth of crystals from crystal germs without nucleation of new crystals.

10 cl, 5 ex

 

Molecular sieve type crystalline aluminosilicate zeolite is widely represented in the prior art and currently includes more than 150 species of natural and synthetic zeolites. In General, the crystalline zeolites are formed from AlO2and SiO2tetrahedra with a common vertex and are characterized by the presence of open pores of the same size with significant ion-exchange capacity, capable of reversible desorption and adsorption phases, distributed on the internal voids of the crystal without any noticeable shifts of the atoms that make up the permanent crystal structure.

Known to other crystalline microporous compositions that are not of the zeolite, but possess ion-exchange and/or adsorption characteristics of the zeolites. They include: 1) pure polymorph of silicon dioxide, silicalite with a neutral structure that includes no cations or cationic positions, as disclosed in US-A-4,061,724; 2) crystalline aluminophosphate compositions disclosed in US-A-4,310,440; 3) alumophosphate, replaced by silicon, as disclosed in US-A-4,440,871 and 4), alumophosphate, replaced by titanium as disclosed in US-A-4,500,651.

Molecular sieves are usually synthesized hydrothermally from a reaction mixture in the reactor of periodic action. In this type of process, all the ingredients are added into the reactor with the formation thus the om gel. Then the gel is stirred and heated for a time sufficient length crystallization of zeolite. Disadvantages commonly used method include restrictions control the size and morphology of crystals, limit the content of solid components, the receipt of waste that cannot be recycled, and large capital expenditures. According to industry continuously conduct research to improve the production of molecular sieves.

For example, US-A-4,314,979 discloses a continuous method of producing zeolite A. the Method involves mixing solutions containing aluminum and silicon, and the flow of the mixture in the reactor crystallization for crystallization of zeolite A. US 5,389,358 discloses a method for the synthesis of zeolites first nucleation of crystals and then the addition of solutions containing the reagents, followed by curing for crystallization of zeolite. Finally, US 3,425,800 describes a continuous method for the synthesis of zeolite a or X, in which a mixed aqueous solutions of reagents for the formation of the gel, the gel is heated and then fed to a multi-layer crystallization zone, which formed crystals.

C.S.Cundy et al., in Zeolites, Vol.15, 353-372 (1995), discloses a method for the synthesis of zeolite ZSM-5. The method includes filling the reactor with a suspension of nuclei of crystals in a suitable liquid. To this mixture continuously add sources of aluminum and credit the Deposit with periodic removal of the product, the reactor is filled to a constant level. In the second article of the same authors Zeolites, Vol.15, 400-407 (1995)found that when aluminum and silicon type with greater speed than the growth of crystals, there is a high rate of nucleation.

Finally, US 6,773,694 B1 discloses a method for the synthesis of molecular sieves is added to the suspension of nuclei of the crystal raw material, which is the source of the frame elements, for example, Al, Si molecular sieves. Raw material type at a speed essentially equal to the velocity of crystal growth, so that the gel is not formed and there is no nucleation of new crystals.

The method of the present invention relates to crystal growth of molecular sieves of the germ crystals, essentially, without nucleation of new crystals. In one implementation of the invention, the same molecular sieve as the germ, that is, the same elements of the framework and structure, but not necessarily the same for these elements will grow on the nuclei of crystals. In another implementation of molecular sieves, growing on the germ crystals will have the same frame structure, but with other elements of the framework, that is, at least, one element will be different.

Accordingly, one essential element of the present invention are germ crystals molecular sieves. Molecular sieves are acroporidae compositions with three-dimensional framework with crystallographically homogeneous pores. These sieves are classified into the zeolite and neoreality molecular sieves. Zeolites are aluminosilicate compositions, in which the frame structure is composed of tetrahedra oxides SiO2and lO2. Nezeritis molecular sieves are those that contain elements other than aluminum and silicon. Examples include silicoaluminate and aluminophosphate molecular sieves. Zeolite and neoreality molecular sieves, which can be obtained by the method of the present invention have a three-dimensional frame structure and composition frame, presents the General empirical formula:

where El is an element capable of forming a three-dimensional frame oxide cell, as described below, and P, Al and Si elements of the carcass that are present in the form of tetrahedrons oxides. The mole fraction of El presents "w" and has a value of 0-0,5, "x"is the mole fractions of Al and has a value of 0-0,5, "y" is the mole fraction of P and has a value of 0-0,5, and "z" is the mole fractions of Si and has a value of 0-1, w+x+y+z=1 and "y" and "z" are not simultaneously equal to zero. When "El" includes two or more elements, "w" represents the molar fraction of these elements (El1El2, El3El4and so on) and "w" equals the sum of w1", "w2" "w3", "w4"and so on, which represent, respectively, m the global share El 1El2, El3El4and so the Acronym of these molecular sieves is E1APSO and they are described in detail in US-A-4,793,984. Selection criteria element E1 is also presented in the patent '984. El is characterized by at least one of the following criteria:

1) "El" is characterized by the electron orbital configuration selected from the group consisting of d0d1d2d5d6d7or d10where the low crystal field stabilization energy of the metal ligand "-O-El" favors tetrahedral coordination element El O2-as described in "Inorganic Chemistry" J.E.Huheey, Harper Row, p.348 (1978):

2) "El" is characterized as capable of forming stable oxo or hydroxo complexes in aqueous solutions, as evidenced by the first hydrolysis constant K11larger 10-14as described in "The Hydrolysis of Cations", C.F.Baes and R.E.Mesmer, John Wiley& Sons (1976);

3) "El" is selected from the group of elements that occur in the types of crystal structures are geometrically associated with the various modifications of silicon dioxide, quartz, cristobalite or tridymite, as described in .Parthe, "Crystal Chemistry of Tetrahedral Structures", Gordon and Breach, tew York, London, pp.66-68 (1964); and

4) "E1" is the element that in its cationic form is classified by Pearson (Pearson) (J.E. Huheey, 'Inorganic Chemistry", Harper & Row, p.276 (1978) as "hard" or "borderline" to the slot, which interacts with a "hard" based On2-with the formation of more stable relationships than cations are classified as "soft" acids. Specific items include, but are not limited to arsenic, beryllium, boron, chromium, cobalt, Nickel, gallium, germanium, iron, lithium, magnesium, manganese, titanium, vanadium, tin and zinc.

Of the General formula described above, several classes of molecular sieves can be described and received. For example, when "w" and "y" are both zeros, the molecular sieves are zeolites or zeolite molecular sieves. In this case the formula (I) becomes

where the value x is 0-0,5. Specific examples of zeolites which can be obtained by the present invention include, but are not limited to zeolite a, zeolite X, mordenite, silicalite, zeolite beta, zeolite Y, zeolite L, ZSM-12, UZM-4 and UZM-5. UZM-4 and UZM-5, described in US 6,419,895 B1 and US 6,613,302 B1, respectively. When x is zero, the zeolite is silicalite. In the case when the "x" in the formula (I) is greater than zero, the result is the formula (III)

where "w", "y" and "z" are defined as in formula (I) and the value x' is from more than 0 to 0.5. In addition, when "w" and "z" is zero in formula (III) or when the "w" and "z" is zero and "x" more than 0 in the formula (I), the result is a collection neoreality ALPO molecular sieves to the e described in detail in US-A-4,310,440 and US-A-4,500,651. In addition, when "w" is zero and "z" more than zero in the formula (I) or (III) (and "x" more than zero in the formula (I)), then the family neoreality molecular sieves SAPO, non-limiting examples of which include SAPO-34 and SAPO-11, described in US-A-4,440,871. When "z" is zero and all other subscripts in the formula (I) or (III) is greater than zero, the result is a collection neoreality molecular sieves l. Finally, when all subscripts in the formula (I) or (III) is greater than zero, the result is a collection neoreality molecular sieves E1APSO described above, one example of which is MAPSO-31.

In addition to frame elements of the structure of molecular sieves in anhydrous condition or after synthesis will contain in its then part of the template agent used to obtain the molecular sieves. These template agents known in the art and include, but are not limited to alkali metals, alkaline earth metals and organic compounds. Organic compounds are any compounds of the prior art and include, but are not limited to amines, such as piperidine, Tripropylamine, dipropylamine, diethanolamine, triethanolamine, cyclohexylamine and Quaternary ammonium compounds, such as Galenia or hydroxide compounds ions Tetramethylammonium, tetrabutylammonium, tetraethylammonium and tet is Propylamine.

The first stage in the method of the present invention includes obtaining germ crystals molecular sieves. Germ crystals of any of the above molecular sieves can be obtained by conventional methods described in the cited and included in the description of the patents, which include the mixing of reagents frame elements, for example, the source of aluminum, a source of silicon and at least one template structure-forming agent, plus the water in the vessel, and heated to a temperature (with or without pressure)to obtain a crystalline product. For molecular sieves, represented by formula (II), the reaction mixture will have a composition, expressed in molar relationship oxides:

where the value "a/s is 0-4, preferably 0-2, n is the valence of M and is 1 or 2, the value "b" is 0-4, preferably 0-2, the value of "d/c" is 2-200, preferably 10-50, and the interaction of the reaction mixture in the reaction conditions includes a temperature of 50-200°C for 4 hours to 14 days, at least to a partial crystallization germ crystals molecular sieves and gives the suspension germ crystals; adding to the suspension of nuclei in the face of rising raw materials to ensure items frame germ crystals, thereby creating conditions for the growth of germs Krista is the catch; adding a speed essentially equal to the growth rate, and for a time sufficient to obtain molecular sieves. For molecular sieves, represented by formula (III), the reaction mixture composition expressed by the empirical formula expressed in molar relationship oxides:

where the value b'/e' is 0.4 to 7 and preferably from 0.8 to 3.2, the value of C'/e' is 0-0,5 and preferably 0-0,3, the value of d'/e' is 0.2 to 1.6 and preferably 0.6 to 1.4, the value of f/e is 0-3,6, and preferably 0-1,0, the value of g/e' is 4-200 and preferably 20-80.

Sources of aluminum include aluminum alkoxide, pseudoboehmite, gibbsite, colloidal alumina, colloidal solution of alumina, sodium aluminate, trichloride aluminum hydrochloride and aluminum. From the above preferred sources of aluminum are pseudoboehmite, sodium aluminate and aluminum alkoxides, such as isopropoxide aluminum. Sources of silicon include Sol of silica, colloidal silica, pyrogenic silica, silica gel, alkoxides of silicon, silicic acid and alkali metal silicates such as sodium silicate. Sources of phosphorus include phosphoric acid, organic phosphates such as triethyl phosphate.

Item(s) "El" can be introduced into the reaction system in any form which enables the formation in situ is actionspanel form element, that is capable of forming a frame oxide cell element "El". Connection element(s) "El", which can be used include the oxides, hydroxides, alkoxides, nitrates, sulfates, halide, carboxylates and mixtures thereof. Typical compounds that can be used include, without limitation: the carboxylates of arsenic and beryllium; uranyl chloride cobalt, alpha iodide divalent cobalt sulfate divalent cobalt; cobalt acetate; bromide of divalent cobalt; chloride of divalent cobalt; alkoxides of boron; chromium acetate; the gallium alkoxides; zinc acetate; zinc bromide; zinc formate; iodide of zinc; heptahydrate zinc sulfate; Germany dioxide; acetate of iron (II); lithium acetate; magnesium acetate; chloride of magnesium; magnesium chloride; magnesium iodide; nitrate of magnesium; magnesium sulfate; manganese acetate; bromide manganese; manganese sulfate; titanium tetrachloride; titanium carboxylates; acetate titanium; zinc acetate; tin chloride; and the like

When template/structure-forming agent is a cation of an alkaline or alkaline earth metal sources include, without limitation hydroxides, such as hydroxide and halide sodium. If the template agent is a Quaternary ammonium cation, the sources include, without limitation hydroxide and Galenia connection, as described above. Finally, add shortcuts is just water to obtain a usable mixture.

The reaction mixture is then heated to the reaction temperature under autogenous pressure or pressure with or without stirring. Specific reaction conditions for the various molecular sieves listed above are known and are disclosed in various patents listed above and incorporated into the description by reference.

For completeness, the overall reaction or crystallization conditions include a temperature of 50-200°C for molecular sieves of the formula (II) and 50-250°C for molecular sieves of the formula (III). The reaction mixture is maintained at the desired temperature for a time sufficient for at least partial receipt of the germ crystals molecular sieves. Although the mixture can react to the complete crystallization of all possible germs crystals molecular sieves, there is no need to perform to carry out the invention. However, there may be times when it is desirable to completely crystallize the reaction mixture. Time for at least partial formation of germ crystals molecular sieves can vary considerably, but usually is 1-48 hours for the molecular sieves of the formula (III) and from 4 hours to 14 days for the molecular sieves of the formula (II).

The reaction mixture containing the germs of crystals, that is, the suspension of the embryo is now the starting mixture or suspension for the second stage of the method. To the E. is the second suspension of germs add sources to the desired frame elements, hereafter referred to as raw materials for cultivation of molecular sieves on the germ crystals. Thus, raw material or combination of materials, which add, is any raw material from which to form the molecular sieve. These combinations are: 1) a source of silicon; (2) sources of aluminum and silicon, 3) sources of aluminum, phosphorus and silicon; 4) sources of aluminum and phosphorus; 5) sources El, aluminum and phosphorus; and (6) sources El, aluminum, silicon and phosphorus. It should be noted that it may be necessary to add additional template/structure-forming agent. This can be done by adding the desired source agent with one of the components of the raw material or in a separate thread. In some cases, the suspension of nuclei may contain unreacted excess template agent, thus making the method more economical due to the expenditure of this additional template in the second stage, i.e. the stage of growth method.

The raw materials that are added may be such that provides the same molecular sieve, and that the germs of crystals or other molecular sieves. Even if formed of the same molecular sieves, the ratio of the raw material components and, thus, the ratio of the frame elements may differ between embryos of molecular crystals and what it growing then the germ crystals. For example, the nuclei of crystals of zeolite X with an Si/Al 1,25 you can add raw materials of silicon and aluminum at concentrations for the cultivation of zeolite X in the nuclei of crystals, but at the Si/Al and 1.0.

In the case where the germ crystals and molecular sieve-grown embryos crystals have different elements of the framework, it is necessary that the germ crystals or Central molecular sieves and external molecular sieve had the same frame structure. This requires that the core and outer molecular sieve differed, at least one element of the framework. For example, the core molecular sieves can be ARO-34 and outer molecular sieves can be SAPO-34, chabazite, Soara-44, LZ-218, GaAPO-34, zeolite Phi, etc. Molecular sieves which have the same structure can be determined using W.M.Meier, D.H.Olson and In.Baulocher, Atlas of Zeolite Structure Types, Fifth Revised Edition, Elsevier, Amsterdam, 001 or Ch.Baulocher and L.B.McCusker, Database of Zeolite Structures, http://www.iza-tructure.org/databases/. It should be noted that in some systems, molecular sieves may occur intergrowth of two or more frames. So with the growth of molecular sieves on the core instead of one type of frame is an intergrowth of two or more frames. For example, if the layer of SAPO-34 is growing on the core, the layer can be essentially SLEEP structure with negligible AEI. Of course, it is desirable site and is preferably to grow one frame structure.

From the above it is seen that it is possible to obtain molecular sieves, which have many layers of different composition. In this case, the core molecular sieves must be made of several layers with the final layer being the outer molecular sieves. Using straightforward process, you can also obtain the molecular sieve with the same frame elements throughout the crystal, but with layers with different relations of the elements of the framework, for example by the ratio of Si/Al. Thus, you can start with a ZSM-5 core, to increase the ratio of Si/Al on stage in the following layers and, finally, to get the layer silicalite as the outer layer.

Regardless of the choice of the raw materials it may be added by any suitable means. These tools include the preparation of solutions of raw materials, preparation of suspensions of solids or sludge, direct addition of solid substances and adding pure raw components. Of course, one component of the raw materials can be added in one way, while another component(s) of raw materials can be added in another way. Additionally, depending on the specific component materials may be necessary to add additional acid or base to achieve the desired pH. For example, when using sodium silicate as a raw material or source of silicon, you may need to add acid to n is strelitzia sodium hydroxide, which can be formed.

When you add more than one component of the raw materials, such as Si and Al, they may be added simultaneously or sequentially. When using successive addition requires the use of only one pump in the case of liquids or suspensions. Simultaneous addition can be done in one of three ways. First: each component of the raw material fed into the reactor containing the suspension of the embryo, through individual nozzles or injectors. Second: the individual components of the raw material can be directed into a collecting tank mixed and then submitted as a single stream into the reactor containing the suspension of the embryo. Third: raw material components can be combined to education the minimum number of threads in which the components of each thread selected to minimize unwanted reactions in each thread until the final add. Finally, the raw materials may be added continuously or intermittently. If adding exercise periodically, the addition can be carried out uniformly or at irregular intervals. With the continuous or periodic addition it is necessary that the raw material is moved with such speed that the germ or nucleus crystals grew on the merits without further nucleation of new crystals or the formation of amorphous solids. the od "nucleation of new crystals" refers to the formation of crystals in the mixture, when the concentration of the raw material components above the critical concentration supersaturation. The crystal growth of the embryos in large crystals, is not considered as "nucleation of new crystals. To achieve this, the speed of addition of the raw material should be essentially the same as the growth rate of crystals. One way of determining the speed of adding is to first determine the size of the crystal nuclei of crystals by methods such as scanning electron microscopy (SEM). Then assume that the crystal growth (determined empirically) is homogeneous and linear, and the crystals have the shape of a cube. From these data can be calculated growth rate.

Another way of controlling the number of components of the raw materials that should be added, is to maintain the concentration of each component of the raw materials above saturation, but below the critical limit of supersaturation. If the concentration is above the critical limit of supersaturation, it will start the nucleation of new crystals, whereas if the concentration is equal to or below saturation, such growth does not occur.

Reaction conditions for growing crystals are the same as used in conventional methods, and include autogenous pressure and temperature from room temperature (20°C) to 250°C. Can be used, higher pressures, and they can usually reach 30 lb/inch 2. Adding components raw materials continue, until the desired size of the crystals. The size of the nuclei of the crystals can vary considerably and is not a critical parameter of the present invention. Although the nuclei of crystals can be used with any size, usually the crystallite size of embryos ranges from 10 nanometers to five micrometers. Also there is no upper limit of the finite crystallite size of the product, but can be formed crystallites with a size of 10 micrometers. Upon reaching the desired size of the crystals stop adding materials and molecular sieves are separated from the aqueous phase or mother liquor by means of the prior art, such as filtration, centrifugation, etc.

When the size of the crystals is determined by the number of added materials, the crystals can aglomerirovanie or aggregated into particles. Thus, the particles can be larger than any single crystal. Control of particle size, i.e. the degree of agglomeration is achieved by the application of shearing forces to the reaction mixture. The shearing force can be effected by mechanical means, hydraulic means, etc. Certain ways of applying the shearing forces include, but are not limited to mixers, impellers, ultrasonic, counter flows of liquid, etc. E. and tools are designed to break up the agglomerates, but they can also destroy the individual crystals, which can grow further. The fragmentation of the single crystals is not nucleation.

The size of the crystals and/or the distribution of particle size can be controlled by adding more embryos during the process. This can be done once, periodically or continuously during the process. In addition, the nuclei of crystals that add later can be greater than the original germ of the crystals, providing, thus, a narrow distribution of the crystals and/or particle size. Alternatively, the embryos crystals that add later can be smaller than the original germ of the crystals, providing, thus, a wider distribution of the crystals and/or particle size.

The following examples are provided to illustrate the invention. It should be understood that the examples are only a means of illustration and are not intended for being too restrictive of the broad scope of the claims formulated in the attached claims.

Example 1

Molecular sieve SAPO-34 was prepared as follows. Prepare the reaction mixture with a total weight of 500 grams with the following structure.

TEON is a hydroxide of tetraethylammonium. This mixture is produced by combining on / over the 85% orthophosphoric acid, H2O, 35% TEON, Ludox™ AS-40, and Versal™ 250 aluminum oxide. The mixture is heated to 100°C and kept at it for one hour. Subsequently, it is heated to 175°C and kept at it for two hours. To this partially crystallized reaction mixture add two streams of raw materials for 15 hours at 175°C. the Weight of the first stream 446,8 grams and its composition: 2.3% of SiO2; 27,5% R2About5; 27,4% DEA; and 42.8% N2O. DEA is diethanolamine. The weight of the second component 443,2 grams and its composition is 20% Al2O3and 80% H2O. Final composition of the gel is as follows:

At the end of the 15-hour period added, the reactor is cooled to room temperature and the product is separated by centrifugation, washed and dried, obtaining 199,0 g of powder, which identify x-ray phase analysis as SAPO-34. Elemental analysis of the dried powder of the following (wt.%): 22,00 Al, 23,00 R, 2,63 Si, 10,9, 1,5 N. This corresponds to the Al0,494P0,450Si0,057O2expressed in normalized mole fractions.

Example 2

Molecular sieve SAPO-34 was prepared as follows. Prepare the reaction mixture with a total weight of 500 grams with the following structure.

TEON is a hydroxide of tetraethylammonium. This mixture is produced by combining, in order, 85% orthophosphoric acid, H2ABOUT 35% OF EON, Ludox AS-40, and Versal 250 alumina. Addition of 18.0 grams of embryos SAPO-34 add to this mixture. The mixture is heated to 100°C for five hours and kept at it for nine hours. Subsequently, it is heated to 175°C for six hours and kept at it for two hours. To this partially crystallized reaction mixture add two streams of raw materials for 15 hours at 175°C. the Weight of the first stream 507,4 grams and its composition: 0.8% of SiO2; 20,6% P2O5; 13,2% DEA; and 4.0% TEON and 61,4% N2O. DEA is diethanolamine. The weight of the second stream 374,6 grams and composition of 20% Al2O3and 80% N2O. Final composition of the gel is as follows:

At the end of the 15-hour period added, the reactor is cooled to room temperature and the product is separated by centrifugation, washed and dried, obtaining 268,9 g of powder, which identify x-ray phase analysis as SAPO-34 with a small bonding with the AEI. Elemental analysis of the dried powder of the following (wt.%): 22,50 Al, 23,60 P, 2,05 Si, 10,8, 1,4 N. This corresponds to the Al0,500P0,457Si0,044O2expressed in normalized mole fractions.

Example 3

Molecular sieve SAPO-34 was prepared as follows. Prepare the reaction mixture with a total weight of 500 grams with the following structure.

TEON is a hydroxide of Tetra is Ramone. This mixture is produced by combining, in order, 85% orthophosphoric acid, H2O, 35% TEON, Ludox AS-40, and Versal 250 alumina. The mixture is heated to 100°C and kept at it for one hour. Subsequently, it is heated to 175°C for six hours and kept at it for two hours. To this partially crystallized reaction mixture add two streams of raw materials for 15 hours at 175°C. the Weight of the first stream 446,8 grams and its composition: 0.8% of SiO2; 27.5% of the P2O5; 13,7% DEA; and 58,0% N2O. DEA is diethanolamine. The weight of the second stream 443,2 grams and composition of 20% Al2O3and 80% H2O. Final composition of the gel is as follows:

At the end of the 15-hour period added, the reactor is cooled to room temperature, and the product is separated by centrifugation, washed and dried, obtaining AZN 264.2 g of powder, which identify x-ray phase analysis as SAPO-34 with a small bonding with the AEI. Elemental analysis of the dried powder shows (wt.%): 23,20 Al, 23,50 R, 1,31 Si, 10,2, 1,6 N. This corresponds to the Al0,516P0,456Si0,028O2expressed in normalized mole fractions.

Example 4

Molecular sieve SAPO-34 was prepared as follows. Prepare the reaction mixture with a total weight of 500 grams with the following structure.

TEON is hydroxide is Tetramethylammonium. This mixture is produced by combining, in order, 85% orthophosphoric acid, H2O, 35% TEON, Ludox AS-40, and Versal 250 alumina. The mixture is heated to 100°C for five hours and kept at it for nine hours. Subsequently, it is heated to 175°C for six hours and kept at it for two hours. To this partially crystallized reaction mixture add two streams of raw materials for 15 hours at 175°C. the Weight of the first stream 446,8 grams and composition: 0.7% of SiO2; 27.5% of the P2O5; 27,4% DEA; and 44.4% N2O. DEA is diethanolamine. The weight of the second stream 443,2 grams and composition of 20% Al2O3and 80% N2O. Final composition of the gel is as follows:

At the end of the 15-hour period added, the reactor is cooled to room temperature, and the product is separated by centrifugation, washed and dried, obtaining 165,5 g of powder, which identify x-ray phase analysis as SAPO-34 with a small bonding with the AEI.

Example 5

Molecular sieves BETA obtained as follows. Prepare the reaction mixture with a total weight of 600 grams with the following structure.

TEON is a hydroxide of tetraethylammonium. This mixture is produced by combining, in order, sodium hydroxide, N2O, sodium aluminate, 35% TEON and Ludox AS-40. The mixture is stirred for 12 hours. Bafter is under her heated to 150°C and incubated for twenty-four hours. To this partially crystallized reaction mixture add two streams of raw materials for 12 hours at 150°C. the Weight of the first stream 384,9 grams and composition: 32% SiO2; 0,12 Na2O; and 67,88% N2O. the Weight of the second stream 284,9 grams and composition of 3.13% Al2O3; 2,94 Na2O and 93,93% N2O. Final composition of the gel is as follows:

At the end of the 12-hour period added, the reactor is cooled to room temperature and the product is separated by centrifugation, washed and dried, obtaining 189,7 g of powder, which identify x-ray phase analysis as Beta zeolite.

1. The method of synthesis of molecular sieves with three-dimensional microporous frame structure and composition of the frame represented by the empirical formula

where Al and Si are framework elements present as oxide tetrahedra, the value of x is 0-0,5; including the formation of a reaction mixture comprising reactive sources of the framework elements, M and optional R, where M is selected from the group consisting of alkali metals, alkaline earth metals and mixtures thereof, R is an organic template agent selected from the group consisting of cations of Quaternary ammonium, amines and mixtures thereof; and the reaction mixture has a composition, expressed in molar relationship oxides:

where is the a/C is 0-4, n is the valence of M and is 1 or 2, the value of b/C is 0-4, the value of d/C is 2-200, and the interaction of the reaction mixture in the reaction conditions at a temperature of 50-200°C for 4 h to 14 days prior to at least partial crystallization germ crystals molecular sieves with the formation of a suspension of nuclei of crystals; adding to the suspension of the embryo, in terms of growth, raw materials (sources) to provide framework elements germ crystals, thereby causing the growth of germs of crystals; and adding exercise at a speed essentially equal to the growth rate, and for a time sufficient to obtain molecular sieves.

2. The method of synthesis of molecular sieves with three-dimensional microporous frame structure and composition of the frame represented by the empirical formula

where El, Al, P are framework elements present as oxide tetrahedra, w is the molar fractions of El with a value of 0-0,5, x is the molar fractions of Al with the value of 0-0,5, y' is the mole fraction of R with a value of from more than 0 to 0.5, and z is the molar fractions of Si with a value of 0-0,98, w+x+y'+z=1, including the formation of a reaction mixture comprising reactive sources of the framework elements and R, where R is an organic template agent, wybran the m group, consisting of cations of Quaternary ammonium, amines and mixtures thereof; and the reaction the reaction mixture has a composition, expressed in molar relationship oxides:

where the value b'/e' is 0.4 to 7, and the C'/e' is 0-0,5, the value of d'/e' is 0.2 to 1.6, the value of f/e is 0-3,6, the value of g/e' is 4-200; the interaction of the reaction mixture in the reaction conditions at a temperature of 50-250°C for 1 h to 48 h before, at least partial crystallization germ crystals molecular sieves with the formation of a suspension of nuclei of crystals; adding to the suspension of nuclei in terms of growth, raw (sources), to ensure germ crystals frame elements, thus causing the growth of germs of crystals; and adding exercise at a speed essentially equal to the rate of crystal growth, and for a time sufficient to obtain molecular sieves.

3. The method according to claims 1 and 2, in which the raw material is selected from the group consisting of 1) a source of aluminum and phosphorus; 2) a source of aluminum, silicon and phosphorus; 3) source El, aluminum and phosphorus, and 4) source El, aluminum, phosphorus and silicon.

4. The method according to claim 2, in which the frame structure of molecular sieves selected from the group consisting of SAPO-34, SAPO-11 and MAPSO-31.

5. The method of synthesis of molecular sieves with three-dimensional microporous frame structure is Oh, including the Central molecular sieves and external molecular sieves, with the same frame structure, where the composition of the Central molecular sieves presents empirical formula

where Al and Si are framework elements present as oxide tetrahedra, and the value of x is 0-0,5; including the formation of a reaction mixture comprising reactive sources of the framework elements, M and optional R, where M is selected from the group consisting of alkaline and alkaline-earth metals and mixtures thereof, R is an organic template agent selected from the group consisting of cations of Quaternary ammonium, amines and mixtures thereof; and the reaction mixture has a composition, expressed in molar relationship oxides:

where is the a/C is 0-4, n is the valence of M and is 1 or 2, the value of b/C is 0-4, the value of d/c is 2-200, and the interaction of the reaction mixture in the reaction conditions at a temperature of 50-250°C for 4 h to 14 days to at least partial crystallization germ crystals molecular sieves; adding to the suspension germ raw materials to ensure germ frame elements, thus causing the growth of external molecular sieves in the nuclei of crystals, and the outer molecular sieves are of the same structure is ur frame, as the Central molecular sieve, but the Central and outer molecular sieves differ, at least one element of the frame, the outer molecular sieves have a composition represented by the empirical formula

where El, Al, P and Si are framework elements present as oxide tetrahedra, w is the molar fractions of El with a value of 0-0,5, x is the molar fractions of Al with the value of 0-0,5, y is the molar fraction of R with a value of more than 0 to 0.5, and z is the molar fractions of Si with a value of 0-1, w+x+y+z=1, and y and z are not simultaneously equal to zero; and adding exercise at a speed essentially equal to the rate of growth of external molecular sieves, and during sufficient for receiving the molecular sieve.

6. The method of synthesis of molecular sieves with three-dimensional microporous frame structure, including the Central molecular sieves and external molecular sieves with the same frame structure, where the composition of the Central molecular sieves presents empirical formula

where El, Al, P and Si are framework elements present as oxide tetrahedra, w is the molar fractions of El with a value of 0-0,5, x is the molar fractions of Al with the value of 0-0,5, y' is the mole fraction of P with value more than 0 to 0.5, and z is the molar fractions of Si with a value of 0-0,98, w+x+y'+z=1, which includes education is the W of the reaction mixture, comprising reactive sources of the framework elements and R, where R is an organic template agent selected from the group consisting of cations of Quaternary ammonium, amines and mixtures thereof; and the reaction mixture has a composition, expressed in molar relationship oxides

where the value b'/e' is 0.4 to 7, and the C'/e' is 0-0,5, the value of d'/e' is 0-1,6, the value of f/e is 0-3,6, the value of g/e' is 4-200; the interaction of the reaction mixture in the reaction conditions at a temperature of 50-250°C for 1 h to 48 h before, at least partial crystallization germ crystals molecular sieves and education suspension germ crystals; adding to the suspension of nuclei in terms of growth, raw materials, to ensure germ frame elements, thus causing the growth of external molecular sieves on the crystals, where the outer molecular sieves have the same frame structure, and that the Central molecular sieve, but the Central and outer molecular sieves differ, at least one element of the frame, and the outer molecular sieves have a composition represented by the empirical formula

where El, Al, P and Si are framework elements present as oxide tetrahedra, w is the molar fractions of El with a value of 0-0,5, x is m the school of the shares of Al with the value of 0-0,5, y is the molar fraction of R with a value of more than 0 to 0.5, and z is the molar fractions of Si with a value of 0-1, w+x+y+z=1, and y and z are not simultaneously equal to zero; and adding exercise at a speed essentially equal to the rate of growth of external molecular sieves, and for a time sufficient to obtain molecular sieves.

7. The method according to claim 5 or 6, in which the outer molecular sieves have a frame structure selected from the group consisting of zeolite A, zeolite X, mordenite, silicalite, zeolite beta, zeolite Y, zeolite L, ZSM-12, UZM-4, UZM-5, SAPO-34, SAPO-11 and MAPSO-31.

8. The method according to claims 1, or 2, or 5, or 6, in which the raw material is added continuously.

9. The method according to claim 1 or 2, or 5, or 6, in which raw materials are added periodically.

10. The method according to claim 5 or 6, in which the raw material is selected from the group consisting of: 1) a source of silicon; (2) the source of aluminum and silicon; 3) source of phosphorus, aluminium and silicon; 4) source of phosphorus and aluminum; 5) source El, aluminum and phosphorus, and 6) source El, aluminum, phosphorus and silicon.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: zeolite is obtained using a continuous or semi-continuous method in the heated zone of a reactor at temperature from 200°C to 500°C and dwell time less than 24 hours. Reagents are solid and liquid substances. Content of solid reagents lies between 45 and 98 wt % of the total amount of reagents.

EFFECT: increased output and reduced amount of hazardous substances during production of zeolite.

13 cl, 8 dwg, 24 ex

FIELD: mining.

SUBSTANCE: invention refers to methods of zeolite production. The method of production of solid substance containing titanium-silicate-1 consists in stage (I): at least partial crystallisation of solid substance containing at least one zeolite out of synthesis mixture with production of mixture (I) including at least the said solid substance and also at least one template compound presenting tetrapropylammonia hydroxide as an additive; stage (II): concentration of solid substance which is present in mixture (I) by ultra-filtration with obtaining retentate and permeate; notably, that permeate contains the said at least one template compound; stage (III): agglomeration or granulation or agglomeration and granulation of particles of solid substance in retentate from stage (II); also permeate produced at stage (II) containing the said at least one template compound at least partially is returned to stage (I); while ultra-filtration is performed with implementing at least one membrane containing dividing layers with diametre of pores from 50 nm to 200 nm.

EFFECT: invention facilitates re-circulating template compounds to stage of re-crystallising.

9 cl, 1 dwg

FIELD: synthesis of zeolites.

SUBSTANCE: the invention is dealt with synthesis of zeolites, in particular, with a composition containing in the capacity of raw material a lime product of incineration or aluminum silicate, to which is added a water alkaline solution, and the mixture is heated up, treated with the help of a mixer producing an agitated mixture in the form of a suspension or a mash. The agitated mixture is continuously relocated and exposed to a direct radiation by electromagnetic waves with a frequency within the range of 300 MHz - 30 GHz, and so transforming it into zeolite. Zeolite is cleaned by means of a cleaning machine and dried in a drum-type steam drying installation. The indicated method may be used for production of synthetic zeolite. The production is characterized by a decreased amount of the applied and removed alkali at decreased power input and operational time.

EFFECT: the invention ensures production of synthetic zeolite using a decreased amount of the applied and removed alkali at reduced power input and operational time.

3 cl, 3 dwg, 3 ex

The invention relates to zeolites derived from anthropogenic aluminosilicate raw materials, particularly components of volatile ashes of thermal power plants, and can be used in nuclear power and chemical-metallurgical industry for the purification of liquid radioactive waste and wastewater from radionuclides ions of non-ferrous and heavy metals

The invention relates to zeolites, which are used as adsorbents or catalysts carriers

The invention relates to the refining and chemical industry, in particular to a method of increasing time stable operation of catalysts based on high zeolites (VCC), which may find wide use as adsorbents and catalysts for the processes of cracking, hydrocracking, isomerization, alkylation, reforming of methanol into hydrocarbons, etc

The invention relates to the field of petrochemistry and oil refining, in particular to methods of synthesis of zeolites are crystalline aluminosilicates, components, catalysts and adsorbents for petrochemicals and refining

FIELD: chemistry.

SUBSTANCE: invention refers to the preparation of molecular sieves. The claimed method comprises the preparation of laminar composition including the inner seed domain and outer layer containing the molecular sieve. The said method includes provision of the suspension containing the particles of the inner seed domains and the sources of the elements of molecular sieve lattice. The starting materials that is the elements sources are added to the said suspension whereby the crystals of molecular sieves are formed and enlarge on the inner seed domain. This process is carried out during time interval enough for forming of the layer with desired thickness. The obtained product is used as catalyst for hydrocarbons conversion.

EFFECT: enhancing of the composition catalytical performance.

10 cl, 5 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the method of reactivating silicoaluminophosphate molecular sieve catalyst, subjected to hydrothermal deactivation. The catalyst is reactivated by putting it into contact with warm water, aluminium salts, dilute acids or water vapour at low pressure until the level of catalytic activity does not increase by at least 25%.

EFFECT: reactivation of catalytic activity of silicoaluminophosphates through simple processing.

10 cl, 1 tbl

FIELD: chemistry.

SUBSTANCE: described is method of regulation of crystal microporous silicoalumophosphte structure with structure SAPO, free of admixtures of other crystal microporous silicoalumophosphtes, by introduction in water initial reaction mixture, which contains sources of aluminium and silicon, of phosphoric acid, as well as organic structure-forming compound - di-n-dibytylamine, inoculating crystals of target phase, namely, crystal microporous silicoalumophosphtes, free of admixtures of other crystal microporous silicoalumophosphtes, with further crystallisation of prepared mixture in hydrothermal conditions,necessary for formation of crystals with zeolite-like structure, separation and drying of obtained material.

EFFECT: obtaining phase-pure product of crystallisation.

7 cl, 13 ex

FIELD: industrial inorganic synthesis.

SUBSTANCE: material, appropriate as molecular sieves, is prepared from mixture of binder with aluminum phosphate-containing solid. After calcination of the mixture, liquid reaction mixture containing metal source and structure-forming reagent is added and thus obtained mixture is in situ crystallized. In the other embodiment, mixture of binder with solid containing metal source and aluminum phosphate is calcined and supplemented by mixture containing structure-forming reagent and water, after which in situ crystallized. Product obtained can be used as olefin synthesis catalyst.

EFFECT: enlarged choice of olefin synthesis catalysts.

11 cl, 6 dwg, 36 ex

FIELD: inorganic synthesis.

SUBSTANCE: invention provides method of synthesis of crystalline microporous metalloaluminophosphate from solid substance, which substance is constituted by particles containing aluminophosphates wherein pores of the particles are completely or partially filled with reactive mixture including active metal source E1, organic structurizing agent, and water. Crystallization is carried out at elevated temperature and autogenous pressure. Metal E1 is selected from group consisting of silicon, magnesium, zinc, iron, cobalt, nickel, manganese, chromium, and mixtures thereof.

EFFECT: extended synthetic possibilities.

31 cl, 5 tbl, 51 ex

FIELD: chemical industry; methods of synthesis of the molecular sieves.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the synthesis of the molecular sieves. The method of synthesis of the various molecular sieves is developed. The method provides for the preparation of the suspension of the seed crystals and attachments to it of the feeding substances (sources) of the skeleton components, for example, aluminum and silicon for the purpose to provide the growth of the seed crystals. The rate of addition of the feeding substances is regulated so, that it was just the same, as the rate of the crystals growth and at that there was no nucleation of the new crystals. The seed crystals can be the same or distinct from added feeding substances, that allows formation of the multilayered molecular sieve. When the crystals reach the desirable dimension, they are separated by means of the traditional methods. The invention allows to regulate the distribution of the size of the crystals.

EFFECT: the invention ensures control over the distribution of the size of the crystals.

10 cl, 11 ex, 2 tbl

The invention relates to chemistry

The invention relates to the field of synthesis neoreality molecular sieves have three-dimensional microporous frame structure containing blocks [AlO2] and [PO2]

FIELD: chemical industry; methods of synthesis of the molecular sieves.

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the synthesis of the molecular sieves. The method of synthesis of the various molecular sieves is developed. The method provides for the preparation of the suspension of the seed crystals and attachments to it of the feeding substances (sources) of the skeleton components, for example, aluminum and silicon for the purpose to provide the growth of the seed crystals. The rate of addition of the feeding substances is regulated so, that it was just the same, as the rate of the crystals growth and at that there was no nucleation of the new crystals. The seed crystals can be the same or distinct from added feeding substances, that allows formation of the multilayered molecular sieve. When the crystals reach the desirable dimension, they are separated by means of the traditional methods. The invention allows to regulate the distribution of the size of the crystals.

EFFECT: the invention ensures control over the distribution of the size of the crystals.

10 cl, 11 ex, 2 tbl

FIELD: inorganic synthesis.

SUBSTANCE: invention provides method of synthesis of crystalline microporous metalloaluminophosphate from solid substance, which substance is constituted by particles containing aluminophosphates wherein pores of the particles are completely or partially filled with reactive mixture including active metal source E1, organic structurizing agent, and water. Crystallization is carried out at elevated temperature and autogenous pressure. Metal E1 is selected from group consisting of silicon, magnesium, zinc, iron, cobalt, nickel, manganese, chromium, and mixtures thereof.

EFFECT: extended synthetic possibilities.

31 cl, 5 tbl, 51 ex

Up!