FR2964962A1 - MANUFACTURE OF ALUMINOPHOSPHATES WITH RECOVERY OF STRUCTURING AGENTS - Google Patents

Abstract

The present invention relates to the manufacture of aluminophosphates with recovery of the structuring agent, comprising the steps of a) preparing a reaction mixture from a source of aluminum, a source of phosphate and of a structuring agent in water, b) transformation of the reagents under the effect of hydrothermal conditions in a reactor into an aluminophosphate, c) release of the pressure in the reactor and capture of a mixture containing a stabilizing agent. outgoing structuring of the reactor, d) separation of the structuring agent from the mixture, e) return of the structuring agent to step a) to obtain a more advantageous method in terms of costs and more respectful of the environment, since the recovery of structuring agents again allows to obtain aluminophosphates.

Description

Stolmâr Scheele & Partner -1/36 - 19 September 2011 34947-SÜD-P-DE / DrJun Applicant: Süd-Chemie AG Manufacture of aluminophosphates with recovery of structuring agents The present invention relates to the manufacture of aluminophosphates with recovery of structuring agents. The structural classification of porous aluminophosphates is carried out according to the International Union of Pure and Applied Chemistry (IUPAC) rules on the basis of their pore sizes

15 according to the "Structure Commission of the International Zeolite Association". These crystalline substances are contained in more than two hundred different bonds in two dozen different structures (topologies). Classified as small, medium and large pore links, they have

20 pores ranging from 0.3 nm to 0.8 nm. During the synthesis, the characteristic pore size is influenced not only by synthesis parameters such as pH, pressure and temperature, but also by the organic structuring agents used.

Aluminophosphates are used as absorption agents, as active and selective catalyst components for processes in crude oil refining, in stationary and mobile exhaust gas cleaning as well as for oxygenate conversion reactions. or aromatics, etc. The framework structures of aluminophosphates are composed of three-dimensional regular space networks, with Stolmâr Scheele & Partner -2/36 - 19 September 2011 34947-SÜD-P-DE / DrJun pores and characteristic channels, networks that can be interconnected with each other. uni-, bi- or three-dimensional way. The calcined structures are composed of tetrahedrons (AlO4r PO4r, where appropriate SiO4) connected by a wedge, consisting respectively of aluminum and phosphorus in quadruple coordination with oxygen, as well as silicon, where appropriate (SAPO). The tetrahedra are called primary structural units, the bond of which leads to the formation of secondary structural units (pores, channels, etc.).

In aluminophosphates, charge neutrality is ensured due to the balanced number of aluminum and phosphorus atoms. Due to the isomorphous substitution of phosphorus by silicon, excess negative charges occur in silicoaluminophosphates (SAPO), which negative charges are compensated by depositing additional cations in the pore and channel system. The degree of phosphorus-silicon substitution thus determines the number of cations necessary for the compensation, and therefore the maximum loading of the bond with positively charged cations, eg hydrogen or metal ions. The insertion of the cations makes it possible to define the catalytic properties of aluminophosphates, whose activity and selectivity as catalyst components can be improved by means of a targeted ion exchange. The metal-substituted aluminophosphates are used in various ways because of their multiple catalytic properties. Metal-substituted aluminophosphates are known with silicon (SAPO), iron (FeAPO), titanium (TiAPO), chromium (CrAPO), manganese (MnAPO), gallium (GaAPO), zinc (ZnAPO), cobalt (CoAPO), nickel (NiAPO), etc. Aluminophosphates can be made by different methods. They are manufactured mostly Stolmâr Scheele & Partner -3/36 - September 19, 2011 34947-SÜD-P-DE / DrJun by hydrothermal crystallization, from reactive sources of aluminum, phosphate or silicon (in the case silicoaluminophosphates).

According to the state of the art, various processes for manufacturing aluminophosphates are known, providing for the use of structuring agents. The addition of structuring agents thus makes it possible to obtain the structures

desired.

Thus the invention DE 38 73 726 T2 describes a method for manufacturing non-zeolitic molecular sieves, from pre-molded bodies of alumina or alumina-silica with the addition of various oxides and organic structuring agents.

The invention US 4,440,871 describes a hydrothermal process for obtaining substituted silicoaluminophosphates, aluminophosphates, from silicon, aluminum and phosphorus, in the presence of organic structuring agents. The aluminophosphates substituted with a metal can, according to the invention EP 0 132 708, be obtained in the presence of metals, sources of aluminum and phosphorus, by means of structuring agents. The invention EP 0 159 624 B2 also describes the preparation of metal-substituted silicoaluminophosphates by means of hydrothermal synthesis, from corresponding sources of silicon, aluminum and phosphate as well as structuring agents. Nitrogen-containing organic and inorganic substances are used as structuring agents, including quaternary ammonium cations, amines (primary, secondary, tertiary or cyclic), azines, imines or alkanolamines. It is also possible to use different metal complexes or ionic liquids, which are both structuring agent and solvent.35 Stolmàr Scheele & Partner -4/36 - 19 September 2011 34947-SÜD-P-DE / DrJun The molecules of The structuring agent is deposited in the pores of the aluminophosphates and thus influences the size of the secondary structural units during the synthesis. The use of the same structuring agent can lead here to the formation of different aluminophosphate structures; also, the same structure can be obtained by using different structuring agents. In these methods known from the state of the art, however, the disadvantage lies in the need to use very large amounts of structuring agents. A large part of the structuring agent used remains in the mother liquor during the separation of the products, before being discarded. On the other hand, is also contained in the pore and cage system of crystalline aluminophosphates a large amount of the structuring agent, which must first be removed in a complex additional work step either by calcining at elevated temperatures (350 ° C - 500 ° C) or by absorption (EP 1 873 470 A2). A need therefore existed for the provision of a process for producing crystalline aluminophosphates by means of synthesis with a structuring agent, in which the consumption of organic structuring agents is low and the structuring agents can be recovered. from the synthesis mixture without additional efforts, efficiently and cost-effectively.

The task of the present invention was therefore to provide a process for manufacturing aluminophosphates for the synthesis of crystalline aluminophosphates with a low consumption of structuring agents. Stolmâr Scheele & Partner -5/36 - September 19 This task is solved according to the invention by a process for the manufacture of aluminophosphates comprising the steps of a) preparing a reaction mixture from a source of aluminum, aluminum oxide or aluminum oxide. a source of phosphate and a structuring agent in water,

b) transformation of the reagents under the effect of hydrothermal conditions in a reactor into an aluminophosphate, c) release of the pressure in the reactor and capture of a mixture containing a structuring agent leaving the reactor, d) separation of the agent structuring the mixture, e) returning the structuring agent to step a). Surprisingly, up to 50 of the structuring agent employed can be recovered from the reaction mixture by loosening and used again for the manufacture of aluminophosphates.

The structuring agent contained in the mixture is obtained by separation of the condensate and can be repeated in step a) of the process according to the invention. Aluminophosphates (general formula (A1PO4-n)) in the context of the invention are understood to mean microporous aluminophosphates. Among them are aluminophosphates (AlPO) of the type

Next: AlPO-5, AlPO-8, AlPO-11, AlPO-16, AlPO-17, AlPO-18, AlPO-20, AlPO-31, AlPO-34, AlPO-35, AlPO-36, AlPO-37 , AlPO-40, AlPO-41, AlPO-42, AlPO-44, AlPO-47, AlPO-56. In particular, AlPO-5 is preferred. 10 15 Stolmâr Scheele & Partner -6/36 - 19 September 2011 34947-SÜD-P-DE / DrJun The term aluminophosphate in the context of the present invention, according to the definition of the International Mineralogical Association ( DS Coombs et al., Can. Mineralogist, 35, 1997, 1571), a crystalline substance of the aluminophosphate group, with a cross-linked spatial structure. The aluminophosphates under consideration are classified according to IUPAC (International Union of Pure and Applied Chemistry) and the Structure Commission of the International Zeolite Association on the basis of the size of their pores.

The cross-linked spatial structure has characteristic pores and channels, which can be connected to each other in a single, two or three-dimensional manner by tetrahedra connected by a wedge (A1O4r SiO4, PO4). Al / P / Si tetrahedra are referred to as primary structural units, the binding of which leads to the formation of the typical framework structure. Are obtained from aluminophosphates by isomorphous substitution of phosphorus, for example by silicon, so-called silicoaluminophosphates, which correspond to the general formula (SiXAlyPZ) 02 (anhydrous). Aluminophosphates having a partial replacement of phosphorus with silicon are particularly suitable, with an Si / (Al + P) ratio of 0.01: 1 to 0.5: 1, preferably 0.02: 1 to 0.2 : 1. In one embodiment of the invention, it is possible to use SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO, silicoaluminophosphates (SAPO) of the following type. -18, SAPO-34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-44, SAPO-47, SAPO-48, SAPO-56. SAPO-20, SAPO-31, SAPO-41, SAPO-42, SAPO-5, SAPO-11, SAPO-34 are particularly preferred. Stolmâr Scheele & Partner -7/36 - 34947-SÜD-P-DE / DrJun September 2011 Part of the phosphorus of the aluminophosphates according to the invention can also be replaced by titanium, iron, manganese, copper, cobalt, chromium, zinc and / or nickel. They are generally called FeAPO, TiAPO, MnAPO, CuAPO, CoAPO, CrAPO, ZnAPO, CoAPO or NiAPO. The MAPO-5, MAPO-8, MAPO-11, MAPO-16, MAPO-17, MAPO-18, MAPO-20, MAPO-31, MAPO-34, MAPO-35, MAPO-36, MAPO-37 types, MAPO-40, MAPO-41, MAPO-42, MAPO-44, MAPO-47, MAPO-48, MAPO-56 (with M = Ti, Fe, Mn, Cu, Co, Cr, Zn, Ni) are particularly suitable. .

In addition to silicon, the aluminophosphates according to the invention may also have other metals. Ion exchange is particularly advantageous with titanium, iron, manganese, copper, cobalt, chromium, zinc and nickel. TiSAPO, FeSAPO, MnSAPO, CuSAPO, CoSAPO, CrSAPO, ZnSAPO, NiSAPO are particularly suitable.

According to the invention, SAPOs can also exist spiked, when metal is incorporated framework. Doping with titanium, iron, manganese, copper, cobalt, chromium, zinc and nickel is particularly advantageous. FeAPPO, TiSAPO, MnAPSO, CuAPSO, CrAPSO, ZnSPPO, CoAPSO and NiAPSO are particularly suitable.

They can exist in the form of microporous MAPSO (M = Ti, Mn, Cu, Cr, Zn, Co, Ni), such as MAPSO-5, MAPSO-8, MAPSO-11, MAPSO-16, MAPSO-17, MAPSO- 18, MAPSO-20, MAPSO-31, MAPSO-34, MAPSO-35, MAPSO-36, MAPSO-37, MAPSO-40, MAPSO-41, MAPSO-42, MAPSO-44, MAPSO-47, MAPSO-56.

MAPSO-5, MAPSO-11 or MAPSO-34 are preferably employed. An aluminophosphate according to the invention may also contain at least one other metal, selected from the group consisting of silicon, titanium, iron, manganese, copper, Stolmâr Scheele & Partner -8/36 - September 19, 2011 34947 -SUD-P-DE / DrJun cobalt, chromium, zinc and nickel. The incorporation of one or more other metals makes it possible to further improve the adsorption properties of the aluminophosphates. They are generally called SiMAPO, FeMAPO, TiMAPO, MnMAPO, CuMAPO, CoMAPO, CrMAPO, ZnMAPO or NiMAPO. On the other hand, it is also possible to obtain zeolites according to the process of the invention. Zeolites in particular have hollow spaces, in addition to channels that characterize each zeolite. Zeolites are classified according to different structures according to their topology. The zeolite framework has open channel and cage shaped hollow spaces, which are normally occupied by water molecules and additional framework cations that can be exchanged. An excess negative charge is created on an aluminum atom, which charge is compensated by cations. The interior of the pore system prepares the catalytically active surface. The more a zeolite contains aluminum and the less it contains silicon, the denser the negative charge in its network and the more its interior surface is polar. The pore size and the structure are defined not only by the parameters in the manufacturing context (ie the use and the type of structuring agents, the pH, the pressure, the temperature, the presence of inoculation crystals ), but also by the Si / Al ratio, which determines most of the catalytic character of a zeolite. Due to the presence of bivalent or trivalent cations as a tetrahedral center in the zeolite framework, the zeolite receives a negative charge in the form of said anionic holes, near which are the corresponding cationic positions. The negative charge is compensated by the insertion of cations into the pores of the zeolite material.

Stolmâr Scheele & Partner -9/36 - 19 September 2011 34947-SÜD-P-DE / DrJun In a pure zeolite that has not known an ion exchange, it is usually H + ions, which induce properties of Bronsted acids, but which can also be exchanged in the lattice against other Mn + ions. In the case of conventional zeolites containing aluminum, these trivalent cations inducing a Brdnsted acidity are A13 + ions. Therefore, pure silicates and titanosilicates do not contain Brönsted acidity and do not allow the exchange of H + ions against other ions. Zeolites are differentiated mainly by the geometry of the cavities, which are formed by the rigid network of SiO4 / AlO4 tetrahedra. The entrances of the hollow spaces are formed by 8, 10 or 12 rings, corresponding to zeolites with narrow pores, medium or wide. Some zeolites have a uniform structural organization, eg ZSM topology 5 or MFI topology, with linear or zigzag channels. In other zeolites, there are larger hollow spaces behind the pore openings, eg for Y or A zeolites, with the FAD and LTA topologies. According to a preferred embodiment of the zeolite according to the invention, it is selected from a group consisting of AEL, BEA, CHA, EUO, FAU, IRON, KFI, LTA, LTL, MAZ, MOR, MEL, MTW. , LEV, OFF, TON and CHA. In principle, it is possible in the context of the present invention to use any zeolite, in particular all the zeolites with 10 and 12 rings. According to the invention, the zeolites selected in the group of topologies AEL, BEA, CHA, EUO, FAU, IRON, KFI, LTA, LTL, MAZ, MFI, MOR, MEL, MTW, LEV, OFF, TON and CHA, Stolmâr Scheele & Partner -10/36 - 19 September 2011 34947-SÜD-P-DE / DrJun topologies BEA, MFI, FER, MOR, MTW and CHA benefit from a very particular preference. According to the invention, the term "structuring agent" is understood to mean in particular organic and inorganic nitrogen bonds, which are added to the reaction mixture as structuring agents (SDA) in order to obtain crystalline aluminophosphates. Structuring agents influence the formation of the crystal lattice during synthesis. They support crystal growth, since the tetrahedral units (A1O4r PO4, SiO4) bind to the molecules of the structuring agents, thus forming the preliminary stage of the characteristic framework structure. In addition, addition of structuring agents also modifies the chemical potential, whereby the energy to be used for network formation is decreased during synthesis by the insertion of the agents.

structuring. This energy stabilization is achieved through interactions between the structuring agent and the tetrahedral units (such as hydrogen bridge bonds, Van der Waals forces, London electrostatic interactions and interactions). Thus the size, shape and chemical properties of the structuring agents act on the resulting structure, knowing that a special framework structure with pores and channels is formed and stabilized by the structuring agent. The influence of the structuring agent during the crystalline formation of aluminophosphates also depends on its solubility and stability under the corresponding hydrothermal synthesis conditions. The structural directing effect can be induced both by the addition of organic molecules and inorganic molecules, which can exist with a neutral charge or in ionic form.

Stolmâr Scheele & Partner -11/36 - 19 September 2011 34947-SÜD-P-DE / DrJun Here we have to differentiate between "true" structuring agents, such as the tetrapropylammonium cation, and non-structuring agents. than "mouth-pores". Depending on the silicon content, it is possible in the case of SAPOs, for example, to stabilize the existing crystal lattice by hydrophobic interactions with filler blocks such as bifunctional amines.

long chain, bulky amines or alcohols.

Ammonium salts, quaternary ammonium salts, amines (primary, secondary, tertiary or cyclic), alkanolamines, azines, diamines, nitrogenous heterocyclic substances, amines substituted by alkyl, imines. For this purpose, the structuring agents are selected from a group consisting of: hydroxide / fluoride / chloride / bromide / iodide / tetramethylammonium nitrate / tetraethylammonium / tetrapropylammonium / tetrathylammonium / n-butylammonium, di-n-propylamine, tripropylamine, triethylamine, triethanolamine, diethanolamine, polyamines, 1,6-hexanediamine, 1,3-propandiamine, hydroxide / fluoride / chloride / bromide / iodide / triethylenetetramine nitrate, piperidine, cyclohexylamine, 2-methylpyridine, N, N-dimethylbenzylamine, N, N- diethylethanolamine, dicyclohexylamine, N, N-dimethylethanolamine, choline, N, N'-dimethylpiperazine, 1,4-diazabicyclo [2,2,2] octane, N-methyldiethanolamine, N-methylethanolamine, N-methylpiperidine, chinuclidine, N, N 1,4-dimethyl-1,4-diazabicyclo [2,2,2] octane di-n-butylamine, neopentylamine, di-n-pentylamine, isopropylamine, t-butylamine, n-butylamine, ethylenediamine, pyrrolidine, 2- Stolmar Scheele & Partner -12/36 - 19 September 2011 34 947-SÜD-P-DE / DrJun imidazolidone, hexamethylimine, 4,4-dimethyl-4-azonia-tricyclo [5.2.2.02,6] undec-8-ene hydroxide (OSDA). According to a preferred embodiment of the process according to the invention, however, triethylamine (TEA) is used as structuring agent. In addition, it is also understood by structuring agents

other organic bonds such as polymers, alcohols (monovalent and multivalent alcohols), ketones,

polyethylene glycol or sulfur-containing bonds. In the following it is understood by hydrothermal conditions that the reaction takes place in a reactor under a pressure of from 1 to 50 bar, preferably from 1 to 25 bar, at a temperature of 50 to 300.degree. 70 to 250 ° C over a period ranging from a few hours, 1 to 24 hours, up to several days, 1 to 10 days, transformation of a source of aluminum, a source of phosphate and, where appropriate, a source of silicon and metals M (with M = Ti, Fe, Mn, Cu, Co, Cr, Zn, Ni), with organic structuring agents, in an aqueous solution. The addition of the structuring agents makes it possible, under the hydrothermal conditions in place, to "erect" the desired pore and cage structure around the corresponding molecules of the structuring agents, which means that they act as germs of crystallization. The frame structure can still be influenced by the variation of hydrothermal conditions such as pressure and temperature.

The additional influence of microwave radiation makes it possible to reduce the particle size of crystalline aluminophosphates, making it possible to obtain nanoparticulate aluminophosphates.35 Stolmâr Scheele & Partner -13/36 - 19 September 2011 34947-SÜD-P-DE / DrJun A reactor according to the invention is for example a pressurized steel tank pressure-tight, heatable and cylindrical. The reactor may further be provided with a mixing screw and mixing members. The reactor has a choice of lifting and lowering device. The capacity of such a reactor is from 1 to 200 liters, but can also reach 1000 to 100,000 liters.

It can be operated at temperatures between 70 and 250 ° C, for example by electric heating, in an oil bath or in steam, and in a pressure range of 1 to 100 bar. The reactor can be equipped for example with a high-pressure safety system with quick-closing, pressure-tight valves and a conventional double jacket. According to the invention, aluminum oxide, pseudoboehmite, sodium aluminate, aluminosilicates and the like can be used as aluminum sources.

On the other hand, it is possible to use as phosphate source in the process according to the invention all phosphorus oxide, hydrogen / dihydrogenphosphate, phosphoric acid, etc., in a corresponding purity, as well as phosphates. MPO4 with M = Li, Na, K, Ca, Mg, Sr, B, Al, Ga, In, Ti, Si, Ge, Sn, Zn, Pb, Ti, Fe, Mn, Cu, Ag, Au, Pd , Pt, Co, Cr, Zn, Ni, Rh, Ru, Te, Tl. The metal bonds used for the synthesis can be employed in the form of oxides, salts with inorganic or organic residues, depending on the reaction mixture, so to ensure good solubility.

In the process according to the invention, it is possible to use any source of silicon, such as SiO 2 powder, sodium brine, silica, aluminosilicates, etc.

A Malvern Mastersizer (obtained from Malvern Instruments GmbH, Germany) was used to determine the average particle size of the SiO 2 powder. The SiO 2 powder was preliminarily exposed to absolute n-hexane for analysis for measurement.

According to the invention, it is also possible to use SiO 2 with a purity of> 99.99%. The particular advantage here lies in the fact that the use makes it possible to obtain silicoaluminophosphates having a stability at the particularly high temperature at high temperatures. According to a preferred embodiment of the process according to the invention, the SiO 2 powder has a BET surface area of 35 m 2 / g to 70 m 2 / g. SiO 2 powder having a BET surface area of 40 m 2 / g at 65 m 2 / g and more preferably an area of 45 m 2 / g at 55 m 2 / g is preferred. The high BET surface of the SiO 2 powder causes an increase in reactivity during the transformation into silicoaluminophosphates.

The BET surface of the SiO 2 powder is defined according to DIN 66131 and DIN 66132 by nitrogen adsorption. A publication of the BET method is found in: J. Am. Chem. Soc. 60, 309 (1938). According to another advantageous adaptation of the process according to the invention, the aluminum hydroxide powder has an average particle size of 20 gm to 150 gm and in particular from 20 gm to 100 μm.

Stolmâr Scheele & Partner -15/36 - 19 September 2011 34947-SÜD-P-DE / DrJun The recovery of the structuring agent from the reaction mixture is carried out according to the invention by the opening of the very hot reactor located under pressure. The very hot reaction mixture under pressure, containing the structuring agent, gas, water, optionally a solvent, possibly dirt, is transferred via a connection to another reactor or a closed vessel, in which the reaction mixture is captured, the latter cooling by expansion and condenses. Thus, a solution of the reaction mixture is obtained in the other reactor and can be separated into its components. The particular advantage lies in the fact that no additional energy supply is necessary, due to the expansion of the reaction mixture under pressure, to obtain a solution and, consequently, to easily separate the structuring agent from the first reactor from the reaction mixture. According to the invention, the solution obtained by condensation in the other reactor, containing the structuring agent, water, optionally a solvent, etc., is separated into its various components in order to allow the reuse of the structuring agent in a new synthesis. The particular advantage here lies in the fact that the mixture contained in the reaction mixture can be removed by the opening of the very hot reactor under pressure, thanks to the fact that this reaction mixture cools by loosening (Joule-Thomson effect) and is in the form of a solution in another reactor. It is possible to do this to control the composition of the "outgoing" reaction mixture. At the beginning, a reaction mixture is obtained under pressure consisting essentially of a structuring agent and slightly volatile organic components; the longer an open connection between the first reactor and the second reactor is maintained, the more the reaction mixture is collected and is aqueous. It is therefore particularly advantageous to open the first reactor only "briefly", depending on the amount of reaction mixture, thus allowing a solution containing a structuring agent to occur in the other reactor. A connection maintained longer open is in particular because of a larger transfer of soils from the first reactor to the second reactor, which makes it more difficult to separate to obtain a pure structuring agent. The separation can be removed if necessary, or at least will be much simpler, if the amount of water contained is lower, thus saving costs and resources.

The advantage lies in the fact that very hot reaction mixture which is under pressure is essentially removed from water and the structuring agent, thus making it possible to obtain the pure structuring agent after separation on the part of water. By-products or reagent residues contained in the reaction mixture remain in the reactor and are subsequently obtained with the product and separated in another step.

According to the invention, only a part of the mixture containing a structuring agent is removed from the reactor. Just the required amount is removed so that the product is still present in the reactor as a suspension, thus allowing easy removal of the reactor, for example by pumping.

According to the invention, a structuring agent is used which is soluble in water only under condition. The particular advantage here lies in the fact that the structuring agent is insoluble in polar solvents. This has the advantage of facilitating recovery from condensate, again saving time and money. A facilitated separation of the structuring agent and the condensate is thus possible and can then be carried out for example by decantation.

The process according to the invention can be carried out under a pressure of 1 to 50 bar, the pressure conditions vary greatly depending on the desired structure of the aluminophosphate. A pressure range of between 4 and 25 bar is particularly preferred because the hydrothermal synthesis undergoes an optimal course under these pressure conditions.

The reaction of the reactants with aluminophosphates according to the invention preferably takes place at a temperature of 120 to 250 ° C., the conversion being carried out in a preferred manner at a temperature of 160 to 200 ° C. This has the advantage of having a very high conversion rate at the indicated temperatures, the reaction time being further reduced depending on the desired structure.

According to the invention, the reactor is released after the transformation and while it is still very hot and is under pressure. This can be done slowly or abruptly by means of a regulating unit (valve, regulator, passage valve, etc.). Depending on the volume of the reactor, the relaxation can also be carried out in stages, in this case the amount of condensate required in order to keep the product remaining in the reactor in the form of a suspension, in this way, is taken in another reactor. easy removal of the reactor, for example by pumping or with a flow valve.

According to the invention, the relaxation of the reaction mixture in the reactor makes it possible to remove a greater proportion of structuring agent from the reaction mixture than water. This is due to the Stolmâr Scheele & Partner -18/36 - 19 September 2011 34947-SÜD-P-DE / DrJun lower boiling point of the component of the structuring agent in comparison with that of the mother-water aqueous. There is therefore sufficient water in the reactor for the product to remain present as a slurry.

A particular advantage of removing the organic structuring agent from the reaction mixture is that the water remains in the reaction mixture mainly as waste water. Disposal of waste water is therefore simplified, it is more advantageous in terms of costs and above all it is more respectful of the environment. Depending on the size of the preparation to be processed in the reactor, about a quarter of the liquid contained therein is removed to about half of the liquid. It is important that the reaction product is still present as a suspension. In one embodiment according to the invention, because of the reaction conditions (high temperatures and high pressures) in the reactor, thanks to the relaxation of the reactor, the reaction mixture containing a structuring agent is captured in another reactor in the form of outgoing gas and is condensed therein.

On the other hand, a change in temperature occurs according to the invention, by releasing the mixture under pressure, and that the very hot gas under pressure cools and is condensed in the other reactor. The strength and orientation of the temperature change here depends on the Joule-Thomson effect, which is described by the Joule-Thomson PJT coefficient. Release of the outgoing gas causes cooling, resulting in a solution containing the condensate.

The Stolmâr Scheele & Partner equation -19/36 - 34947-SÜD-P-DE / DrJun september 2011 describes the Joule-Thomson effect.

Depending on the temperature and the pressure of the condensate in the reactor it is possible using the coefficient 1JT to optimize the loosening and obtaining the condensate. While maintaining the enthalpy H, it is possible to transfer the gaseous condensate starting from a volume V1 with T1 and a pressure p1 (in the reactor) in another reactor, in which there is a volume V2, a temperature T2 and a pressure p2. So that the gas can not develop kinetic energy, the transfer of V1 to V2 is done by a connecting element between the reactor and the second reactor, element through which the gas containing the condensate flows "of itself" starting from the volume V1 because of the pressure pl to p2. A volume work is provided here, with pressure compensation. The amount of energy released p1V1 therefore corresponds to the maximum temperature cooling that the gas containing the condensate can know. As a result, the internal energy U of the condensate is also changed due to the volume work provided. The work here needed p2V2 must be provided by the gas. To do this, energy conservation is used: The internal energy U of the gas is modified because of the work done and because of the energy conservation rate U1 + p1V1 = U2 + p2V2. Knowing that the internal energy depends on the temperature, it is modified with the change of the temperature T1 and the pressure p1 in the reactor at T2 and P2 by cooling and expansion of the gas. We therefore apply for the Joule-Thomson coefficient I ~ rr = AT (T1-T2) / Lp (pl-p2)> 0 and usr = AT (T1-T2) / Ap (p1-p2) <0 Stolmâr Scheele & Partner -20/36 - September 19, 2011 34947-SÜD-P-DE / DrJun The Joule-Thomson coefficient can take here values pjr> 0 and pjr <O. In the presence of positive values, the energy is emitted in the environment in the form of heat; in the presence of negative values, the gas absorbs energy in the environment. In this case, one must apply pjr> 0 so that the gas can cool and cool in the other reactor.

When the very hot reaction mixture under pressure is removed from the reactor and transferred to another reactor, it cools due to loosening (Joule-Thomson effect). The mixture can optionally be further actively cooled by cooling the other reactor or by integrating for example a heat exchanger, or by active cooling, eg icing bath, dry ice, refrigerant mixtures, the other reactor connected downstream. Such cooling has the consequence that the very hot gaseous reaction mixture cools more rapidly and that a solution of the reaction mixture, which contains the structuring agent, is more rapidly present. The advantage here lies in the fact that the operation can be performed very quickly and that the synthesis process does not experience long waiting periods before a new synthesis can be started or before obtaining the mixture residual reaction in the form of condensate. It is particularly advantageous for a freeze separation of the water contained in the condensate to take place thanks to the additional active cooling which completes the cooling operation by means of the Joule-Thomson effect. Temperatures ranging from 0 to about -5 ° C are used here to separate the condensate by freezing. Knowing that the water already separates by freezing at temperatures higher Stolmâr Scheele & Partner -21/36 - 19 September 2011 34947-SÜD-P-DE / DrJun elevated (0 ° C), and knowing that the structuring agent The organic matter separates by freezing only at lower temperatures, it is then easy and simple to separate the condensate to obtain the structuring agent and the water, thus making a new separation step unnecessary, separation by freezing the condensate allowing to separate at the same time the solids possibly contained. However, too low temperatures present a disadvantage here, knowing that one ends up by freezing a too large amount of the structuring agent, which can not subsequently be recovered. The other reactor may be here a heatable reactor or, as an alternative, cooling, which can be adjusted to a certain temperature depending on the temperature of the gas, so that it follows an optimized condensation of the very hot reaction mixture in the reactor. other reactor. In addition, the latter can also be provided with a valve so that the gas supply from the reactor can be regulated.

It can also present a flow device such as a tap for the solution. The other reactor may still be connected to a purification device or be in a position to use as purification device for example a container adapted to a rotary evaporator.

The purification can be carried out here by mechanical methods such as decantation, shaking, separation, distillation, extraction, etc. The advantage here lies in the simplicity, speed and efficiency of the separation. It is also possible to employ chromatographic methods such as HPLC or apparatus, eg a rotary evaporator, which allows separation of the condensate using vacuum. The specialist is aware of other methods that can be used here.35 Stolmâr Scheele & Partner -22/36 - 19 September 2011 34947-SÜD-P-DE / DrJun If additional cleaning steps are necessary, eg. in order to separate from the structuring agent any solids, optionally unconverted reagents, it may follow an additional filtration step in order to obtain a pure structuring agent suitable for use in a new synthesis . According to the invention, the condensate obtained is separated into its various components. These consist of an aqueous phase and a non-mixing organic phase in the first or only under condition. The water component is separated, making it possible to recover a very pure structuring agent that can be reused in step a) of the process according to the invention without any other form of cleaning.

According to the method of the invention, an already recovered used structuring agent can again be reused and recovered. The number of recovery cycles is not limited here. The process is therefore particularly advantageous since the amount of fresh structuring agent to be fed can be kept low. Methodical part: The methods and apparatus used are presented below, but without being limiting in nature. X-ray diffractograms were measured with an X-ray diffractometer from Pananalytical with CuKa radiation. The syntheses were carried out in a 2.0 liter stirring vessel of type 3 and in a Kiloclave autoclave (10 1) from Büchi AG (Switzerland) with maximum volume. 35 Stolmâr Scheele & Partner -23/36 - 34947-SÜD-P-DE / DrJun september 2011 Examples of realization:

The invention is explained in greater detail below with the support of non-limiting examples.

Example 1: Synthesis of A1PO-5 with recovery of the structuring agent

AlPO-5 was obtained by hydrothermal synthesis starting from a molar gel composition in a ratio of 1.1 TEA: 1.0 Al 2 O 3: 53 H 2 O: 1.0 P 2 O 5. To this end, 2000 g of the molar gel composition was converted to A1PO-5 at 185 ° C over a period of 12 h in a 2.0 l stirred vessel of type 3 from Büchi AG. The pressure in the autoclave was 18 bar. After successful conversion of the reagents, the still very hot and pressurized autoclave was opened and connected by a tube system to another pressure vessel cooled in an ice bath (0 ° C). The opening allowed the exit of the autoclave from the reaction mixture under pressure, which was collected in the pressure vessel. The connection remained open for about 30 minutes, so that about 50% of the mainly gaseous reaction mixture was removed. A solution was obtained by condensation due to relaxation and active cooling in the icing bath. The solution contained mainly TEA, since it was only later that water and other components came out of the reactor. The solution obtained was stripped of the water residues by shaking to be pure TEA. The share of the TEA agent recovered here was 50% of the amount used. The resulting AlPO-5 reaction product was pumped out of the reactor as a slurry, containing mainly water; the soils were separated and the product dried. The yield, relative to non-Stolmâr Scheele & Partner oxides -24/36 - September 19, 2011 34947-SÜD-P-DE / DrJun volatile employees, was 86%. The crystallinity and purity of the product were analyzed using X-ray diffractometry (XRD). X-ray analysis revealed that the crystallinity of the A1PO-5 thus obtained was 97%. The position of the reflections in the X-ray diffractogram clearly indicates that it is A1PO-5 of good quality and crystallinity.

Example 2: Synthesis of AlPO-5 using regenerative structuring agent AlPO-5 was obtained by hydrothermal synthesis starting from a molar gel composition in a ratio of 1.1 TEA: 1.0 Al 2 O 3: 53 H 2 O: 1.0 P 2 O 5. 50% of the TEA employed here was TEA recovered from a previous synthesis of A1PO-5. For the synthesis, 2000 g of the molar gel composition was converted to A1PO-5 at 185 ° C, at a pressure of 18 bar and over a period of 12 h in a 2.0 l stirred vessel of the following type. 3 from Büchi AG. After successful conversion of the reagents, the still very hot autoclave under pressure was opened and connected by a tube system to another pressure vessel cooled in an ice bath (0 ° C). The opening allowed the exit of the autoclave from the reaction mixture under pressure, which was collected in the pressure vessel. The connection remained open for about 30 minutes, so that about 50% of the mainly gaseous reaction mixture was removed. A solution was obtained by condensation due to relaxation and active cooling in the icing bath. The solution contained mainly TEA, since it was only later that water and other components came out of the reactor. The resulting solution was stripped of water by shaking to be pure TEA. The share of Stolmâr Scheele & Partner -25/36 - September 19, 2011 34947-SÜD-P-DE / DrJun the TEA agent recovered here was 50% compared to the quantity used. The reaction product A1PO-5 obtained was pumped out of the autoclave as a suspension, mainly containing water; the dirt was separated and the product dried. The yield, relative to the nonvolatile oxides employed, was 86%. Crystallinity and purity of the product were analyzed using X-ray diffractometry (XRD) and compared with synthesized A1PO-5 and obtained only from unrecovered fresh TEA. It was found that the AlPO-5 thus obtained exhibits characteristic reflection positions despite the use of recovered TEA and X-ray analysis revealed that its crystallinity was 98%. The position of the reflections in the X-ray diffractogram clearly indicates that it is A1PO-5 of good quality and crystallinity. The use in the synthesis of A1PO-5 from recovered TEA does not therefore have a negative impact on the quality of the product. Example 3 Synthesis of FeAPO-5 with recovery of the structuring agent FeAPO-5 was obtained by hydrothermal synthesis starting from a molar gel composition in a ratio of 1.1 TEA: 0.9 Al 2 O 3: 0.2 FeSO 4: 53 H 2 O: 1.0 P 2 O 5. For this purpose, 2000 g of the molar gel composition was converted to FeAPO-5 at 175 ° C over a 12 hour period in a 2.0 L type 3 stirring vessel of Büchi AG. The pressure in the autoclave was 18 bar. After successful conversion of the reagents, the still very hot and pressurized autoclave was opened and connected by a tube system to another pressure vessel cooled in an icing bath (0 ° C). The opening allowed the autoclave to exit the pressurized reaction mixture, which was collected in the pressure vessel. The connection remained open for about 45 minutes, so that about 50 of the mainly gaseous reaction mixture was discharged. A solution was obtained by condensation due to relaxation and active cooling in the icing bath. The solution contained mainly TEA, since it was only later that water and other components came out of the reactor. The resulting solution was decanted from the water remains to be pure TEA.

The share of the TEA agent recovered here was 50% of the amount used. The reaction product obtained FeAPO-5 was pumped out of the autoclave as a suspension, mainly containing water; the dirt was separated and the product dried. The yield, relative to the nonvolatile oxides employed, was 87. The crystallinity and purity of the product were analyzed using X-ray diffractometry (XRD) and compared with a synthesized FeAPO-5 and obtained solely from TEA. fee not recovered. It has been found that the FeAPO-5 thus obtained has characteristic reflection positions and X-ray analysis has revealed that its crystallinity is 98. The position of the reflections in the X-ray diffractogram clearly indicates that it is It acts of FeAPO-5 of good quality and crystallinity.

Example 4 Synthesis of FeAPO-5 Using Structurizer Recovered

FeAPO-5 was obtained by hydrothermal synthesis starting from a molar gel composition in a ratio of 1.1 TEA: 0.9 Al 2 O 3: 0.2 FeSO 4: 53 H 2 O: 1.0 P 2 O 5. 50 TEA employed here was TEA recovered from a previous FeAPO-5 synthesis. For the synthesis, 2000 g of the molar gel composition were converted into FeAPO-5 at 175 ° C. under a pressure of 18 bar and over a period of 12 hours. Stolmâr Scheele & Partner -27/36 - 34947-SÜD-P -DE / DrJun september 2011 in a stirring vessel of 2.0 1 type 3 from Büchi AG.

After successful conversion of the reagents, the still very hot autoclave under pressure was opened and connected by a tube system to another pressure vessel cooled in an ice bath (0 ° C). The opening allowed the exit of the autoclave from the reaction mixture under pressure, which was collected in the pressure vessel. The connection remained open for about 30 minutes, so that about 50% of the mainly gaseous reaction mixture was removed. A solution was obtained by condensation due to relaxation and active cooling in the icing bath. The solution contained mainly TEA, since it was only later that water and other components came out of the reactor. The resulting solution was decanted from the water remains to be pure TEA. The share of the TEA agent recovered here was 50% of the amount used.

The reaction product obtained FeAPO-5 was pumped out of the autoclave as a suspension, mainly containing water; the dirt was separated and the product dried. The yield, relative to the nonvolatile oxides employed, was 87%. The crystallinity and purity of the product were analyzed using X-ray diffractometry (XRD) and compared with synthesized FeAPO-5 and obtained only from unrecovered fresh TEA. It was found that FeAPO-5 thus obtained exhibited characteristic reflection positions despite the use of recovered TEA and X-ray analysis revealed that its crystallinity was 98%. The position of the reflections in the X-ray diffractogram clearly indicates that it is FeAPO-5 of good quality and crystallinity. The use of TEA in the synthesis of Stolmâr Scheele & Partner -28/36 - September 19, 2011 34947-SÜD-P-DE / DrJun FeAPO-5 recovered does not therefore have a negative impact on the quality of the product. Example 5: Synthesis of SAPO-34 with recovery of the structuring agent. SAPO-34 was obtained by hydrothermal synthesis starting from a molar gel composition in a ratio of

1 isopropylamine: 1 Al 2 O 3: 1 P 2 O 5: 0.4 SiO 2: 40 H 2 O. To do this, 2000 g of the molar gel composition was converted to SAPO-34 at 165 ° C. over a period of 48 h in a 2.0 l stirred vessel of type 3 from Büchi AG. The pressure in the reactor was 15 bar. After successful transformation of the reagents, the autoclave is still very

The pressure vessel was heated and pressurized and was opened and connected to a round bottom flask with pressure relief, which was cooled in an icing bath. The opening allowed the autoclave to exit the reaction mixture under pressure, which was collected in the round bottom flask 20 with pressure safety. The connection remained open for about 40 minutes, so that about 50 of the mainly gaseous reaction mixture was removed. A solution was obtained by condensation due to relaxation and active cooling in the icing bath. In addition to

Isopropylamine, the solution contained essentially water. The resulting solution was distilled off water to be pure isopropylamine. The share of the isopropylamine agent recovered here was 50% of the amount used. The resulting SAPO-34 reaction product was pumped out of the autoclave as a slurry, containing mainly water; the dirt was separated and the product dried. The yield, relative to the nonvolatile oxides employed, was 90%. The crystallinity and purity of the product were analyzed using X-ray diffractometry (XRD). Analysis by Stolmâr Scheele & Partner -29/36 - September 19, 2011 34947-SÜD-P-DE / DrJun X-ray revealed that the crystallinity of SAPO-34 thus obtained was 98%. Example 6: Synthesis of SAPO-34 using the recovered structuring agent. SAPO-34 was obtained by hydrothermal synthesis starting from a molar gel composition in a ratio of

1 isopropylamine: 1 Al 2 O 3: 1 P 2 O 5: 0.4 SiO 2: 40 H 2 O. 50% of the isopropylamine employed here was a structuring agent recovered from a previous SAPO-34 synthesis. For the synthesis, 2000 g of the molar gel composition were transformed into SAPO-34 at 165 ° C. over a period of 48 h in a 2.0 l stirred vessel of type 3 of the company.

15 Büchi AG. The pressure in the autoclave was 15 bar. After successful conversion of the reagents, the autoclave still very hot and under pressure was opened and connected by a tube system to a round bottom flask with pressure safety, which was cooled in an icing bath. The opening allowed the exit of the autoclave from the reaction mixture under pressure, which was collected in the round-bottomed flask. The connection remained open for about 40 minutes, so that about 50% of the mainly gaseous reaction mixture was removed. A solution was obtained by condensation due to relaxation and active cooling in the icing bath. In addition to isopropylamine, the solution contained essentially water. The resulting solution was distilled off water to be nothing more than isopropylamine

30 pure. The share of the isopropylamine agent recovered here was 50% of the amount used. The resulting SAPO-34 reaction product was pumped out of the reactor as a slurry, containing mainly water; the dirt was separated and the product dried. The yield, relative to the nonvolatile oxides employed, was 83%. Stolmâr Scheele & Partner -30/36 - 19 September 2011 34947-SÜD-P-DE / DrJun crystallinity and product purity were analyzed using X-ray diffractometry (XRD) and compared to a synthesized SAPO-34 and obtained only from fresh unrecovered isopropylamine. X-ray analysis revealed that the crystallinity of SAPO-34 thus obtained was 95. The position of the reflections in the X-ray diffractogram clearly indicates that it is SAPO-34 of good quality and crystallinity. The use of isopropylamine recovered in the synthesis of SAPO-34 does not therefore have a negative impact on the quality of the product. Example 7: Synthesis of ZSM-5 with recovery of the structuring agent

A sodium aluminate solution is produced from aluminum oxide, NaOH, silicon dioxide, triethylamine and water.

The molar composition of the mixture was 80 SiO2: 1 Al2O3: 3.6 Na2O: 7.2 TEA: 1168 H2O. The mixture was stirred until a homogeneous reaction mixture. The mixture (8 1) was poured into a Kiloclave autoclave (10 1) from Büchi AG and heated while continuing to stir. The reaction mixture was stirred for 6 hours under a pressure of 15 bar and a temperature of 150 ° C. The mixture was then stored at 150 ° C without further movement until the desired crystal size of ZSM-5 was reached. The still very hot autoclave under pressure was then opened and connected by a tube system to a steel pressure vessel, which was cooled in an NaCl icing bath mixture. The opening allowed the exit of the autoclave from the reaction mixture under pressure, which was collected in the pressure vessel. The autoclave was left open for about 20 minutes, so that about 50 of the mainly gaseous reaction mixture was removed. A solution was obtained Stolmâr Scheele & Partner -31/36 - 19 September 2011 34947-SÜD-P-DE / DrJun by condensation in the pressure vessel due to the relaxation and active cooling in the icing bath. In addition to triethylamine, the solution contained essentially water. The resulting solution was stripped of water by shaking to be pure triethylamine. The proportion of the triethylamine agent recovered here was 50% relative to the amount used. The resulting reaction product ZSM-5 was pumped out of the autoclave as a slurry, containing mainly water; the dirt was separated and the product dried. The yield, relative to the nonvolatile oxides employed, was 88. The crystallinity and purity of the product were analyzed using X-ray diffractometry (XRD) and compared with ZSM-5.

X-ray analysis revealed that the crystallinity of the ZSM-5 thus obtained was 99

The position of the reflections in the X-ray diffractogram clearly indicates that it is ZSM-5 of good quality and crystallinity.

Example 8: Synthesis of ZSM-5 using regenerative structuring agent A sodium aluminate solution is made from aluminum oxide, NaOH, silicon dioxide, triethylamine and water.

The molar composition of the mixture was 80 SiO2: 1 Al2O3: 3.6 Na2O: 7.2 TPABr: 1168 H2O. 50 of the TPABr used here was TPABr recovered from a previous ZSM-5 synthesis. The mixture (8 1) was poured into a Kiloclave autoclave (10 1) from the company Büchi and heated while continuing to stir. The reaction mixture was stirred for 6 hours under a pressure of 15 bar and a temperature of 150 ° C. The mixture was then stored at 150 ° C without further movement until the desired crystal size of ZSM-5 was Stolmâr Scheele & Partner -32/36 - 19 September 2011 34947-SÜD-P-DE / DrJun reached . The still very hot autoclave under pressure was then opened and connected by a tube system to a steel pressure vessel, which was cooled in an NaCl icing bath mixture. The opening allowed the exit of the autoclave from the reaction mixture under pressure, which was collected in the pressure vessel. The autoclave was left open for about 20 minutes, so that about 50 of the mainly gaseous reaction mixture was removed. A solution was obtained by condensation in the pressure vessel due to relaxation and active cooling in the icing bath. In addition to triethylamine, the solution contained essentially water. The resulting solution was stripped of water by shaking to be pure triethylamine. The proportion of the triethylamine agent recovered here was 50% relative to the amount used. The reaction product obtained ZSM-5 was pumped out of the reactor as a slurry, containing mainly water; the dirt was separated and the product dried.

The yield, relative to the nonvolatile oxides employed, was 88. The crystallinity and purity of the product were analyzed using X-ray diffractometry (XRD) and compared with a synthesized ZSM-5 obtained solely from triethylamine. fresh not recovered.

X-ray analysis revealed that the crystallinity of the ZSM-5 thus obtained was 95. The position of the reflections in the X-ray diffractogram clearly indicates that it is ZSM-5 of good quality and crystallinity. The use of triethylamine recovered in the synthesis of ZSM-5 does not therefore have a negative impact on the quality of the product. 10 15 20 25 30 35 Stolmâr Scheele & Partner -33/36 - 19 September 2011 34947-SÜD-P-DE / DrJun

Claims (11)

REVENDICATIONS1. A method of manufacturing aluminophosphates comprising CLAIMS. A process for manufacturing aluminophosphates comprising the steps of a) preparing a reaction mixture from an aluminum source, a phosphate source and a structuring agent in water, b) transformation reagents under the effect of hydrothermal conditions in a reactor made of an aluminophosphate, c) release of the pressure in the reactor and capture of a mixture containing a structuring agent leaving the reactor, d) separation of the structuring agent mixing, e) returning the structuring agent to step a). 2. Method according to claim 1, characterized in that an organic solvent is added to the reaction mixture. 3. Method according to claim 1 or 2, characterized in that the structuring agent is used as the structure directing agent. 4. Method according to claim 3, characterized in that a nitrogen-containing organic agent is used as structural directing agent, selected from the group consisting of di-n-propylamine, tripropylamine, triethylamine, triethanolamine, diethanolamine, polyamines. Stolmâr Scheele & Partner -34/36 - September 19, 2011 34947-SÜD-P-DE / DrJun 1,6-hexanediamine, 1,3-propandiamine, piperidine, cyclohexylamine, 2-methylpyridine, N, N-dimethylbenzylamine, N, N-diethylethanolamine, dicyclohexylamine, N, N-dimethylethanolamine, choline, N, N'-dimethylpiperazine, 1,4-diazabicyclo [2,2,2] octane, N-methyldiethanolamine, N-methylethanolamine, N methylpiperidine, chinuclidine, N, N'-dimethyl-1,4-diazabicyclo [2,2,2] octane, di-n-butylamine, neopentylamine, di-n-pentylamine, isopropylamine, t-butylamine, n-butylamine, ethylenediamine, pyrrolidine, 2-imidazolidone, hexamethylimine, 4,4-dimethyl-4-azonia-tricyclo [5.2.2.02,6] undec-8-en e (OSDA). 5. Method according to claim 4, characterized in that the agent containing nitrogen is insoluble in polar solvents. 6. Method according to claims 1 and 2, characterized in that a structuring agent soluble in water can be separated from the polar solvent by extraction or distillation. 7. Process according to any one of the preceding claims 1 to 6, characterized in that the conversion is carried out under a pressure of 1 to 50 bar. 8. Process according to any one of the preceding claims 1 to 7, characterized in that the conversion is carried out at a temperature of 50 to 300 ° C. 9. Process according to claim 8, characterized in that the mixture leaving, after loosening, is captured in another reactor in the form of outgoing gas and is condensed.Stolmàr Scheele & Partner -35/36 - 19 September 2011 34947-SÜD- P-DE / DrJun 10. The method of claim 9, characterized in that the condensate is separated into an aqueous phase and an organic phase. 11. The method of claim 10, characterized in that the organic phase of the condensate is reused.