EP2655256A2 - Titano-silico-alumo-phosphate - Google Patents

Abstract

The invention relates to a titano-silico-alumo-phosphate which contains tetradrically coordinated titanium in the framework, which comprises a free coordination point for CO, which can be detected by means of a characteristic IR-band at 2192 ± 5 cm^-1. Said titano-silico-alumo-phosphate displays exceptionally high hydrothermal stability and has a good adsorption capacity even at high temperatures. Based on the high hydrothermal stability, the titano-silico-alumo-phosphate can be obtained by a hydrothermal method from a synthesis gel mixture made of an aluminium, phosphor, silicon and a titanium source, and corresponding templates.

Description

 Titano-silico-alumino-phosphate

The present invention relates to a titano-silico-aluminophosphate, and a process for its preparation. Alumo-silicates (zeolites), aluminophosphates (AlPO ^'s ) and silico-aluminophosphates (SAPO ^'s ) have long been known in the art as refinery and petrochemical active catalyst components. Furthermore they will be in

stationary, as well as used in the mobile phase in the emission control.

Alumino-silicates (zeolites) are found in many different structures in nature, but are also produced synthetically. Alumo-silicates (zeolites) have a high

Adsorption capacity, and can be water and others

reversibly take up low molecular weight substances which are

Heating can be given again without damaging its structure. Structural diversity and high

However, not only alumino-silicates (zeolites) but also the group of alumino-phosphates show adsorption capacity. The structures of this group of substances are classified according to the IUPAC rules (International Union of Pure and Applied Chemistry) according to the Structure Commission of the International Zeolite Association

Microporous compounds have pore sizes between 0.3 nm to 0.8 nm. The crystal structure and thus the size of the pores and channels formed are controlled by synthesis parameters such as pH, pressure and temperature. Through the use of templates in the synthesis, as well as the Al / P / (Si) ratio the porosity is further influenced. They crystallize in more than two hundred different variants, in more than two dozen different structures that have different pores, channels and cavities.

In addition to alumino-silicates and alumo-phosphates, there are also modified alumino-silicates and alumo-phosphates. Known here are in particular the titano-alumino-phosphates, and the

Silico-aluminophosphates. Alumo-phosphates are charge-neutral due to the balanced number of aluminum and phosphorus atoms. Through isomorphous exchange of phosphorus by titanium, titano-aluminophosphates are formed from alumino-phosphates and titano-silico-aluminophosphates (TAPSO) are exchanged by silicon. Exchanges result in excess negative charges due to the incorporation of additional cations into the pore and channel system

be compensated. The degree of phosphorus-titanium and

Phosphorus-silicon substitution thus determines the number of cations needed to balance, and thus the maximum loading of the compound with positively charged cations, e.g.

 Hydrogen or metal ions. By the storage of the

Cations can be adjusted and changed the properties of the titano-silico-aluminophosphate (TAPSO). The framework structures of titano-alumino-phosphates are composed of regular, three-dimensional spatial networks

characteristic pores and channels constructed, the one-, two- or three-dimensional with each other via common

Oxygen atoms are linked.

The crystalline structures consist of corner-sharing tetrahedral building blocks (AIO ₄ , PO ₄ , T1O ₄ , possibly S1O ₄ ), consisting of four times of oxygen coordinated titanium, aluminum and phosphorus, as well as silicon. The tetrahedra are considered primary Designates units whose link leads to the formation of secondary units.

These structures contain cavities that fit each one

Structure type are characteristic. The titano-aluminophosphates are classified into different structures according to their topology. The crystal framework contains open cavities in the form of channels and cages, which are usually with

Water molecules and additional skeletal cations are occupied, which can be replaced. On each aluminum atom comes a phosphorus atom, so that the charges

compensate each other. Will phosphorus against titanium

exchanged, the titanium atoms form excess negative charges, which are compensated by cations. The interior of the pore system represents the catalytically active surface. The more titanium contained in a titano-alumino-phosphate, the denser the negative charge in its lattice and the more polar its internal surface.

The pore size and structure is influenced by the synthesis parameters as well as by the use of templates. Thus, by the pH, the pressure, the temperature, the type of template, the presence of seed crystals or their nature, and by the P / Al / Ti ratio, the catalytic character of a titano-alumino-phosphate can be determined.

In addition to titanium, phosphorus atoms can also be replaced by silicon. Replacement creates additional negative ones

Charges that are compensated by the incorporation of cations in the pores of the zeolite material.

Titano-Alumo-Phosphate, Silico-Alumo-Phosphate and Titano-Silico-Alumo-Phosphate are typically used by

Hydrothermal synthesis obtained starting from reactive gels, or the individual Ti, Al, P, and possibly Si sources which are used in stoichiometric proportions. The preparation of the titano-silico-aluminophosphates (TAPSO) is similar to silico-aluminophosphates (SAPO) (DE 102009034850.6). With the addition of structure-directing

 Templates, crystallization nuclei or elements can be obtained in crystalline form (EP 161 488 A1).

Titano-Alumo-Phosphate is mainly used as

Catalysts in MTO (methanol-olefin conversion) processes in which, starting from methanol, a mixture of ethene and propene can be obtained.

Alumo-phosphates are still used in

Dehydration reactions (EP 2 022 565 AI) due to their good hydrophilic properties and their high

Adsorption capacity.

Although titano-silico-aluminophosphates (EP 161 488 Al) have been known for many years, they are hardly used in the field of catalysis.

Due to their adsorptive capacity and ability due to their microporous framework structure they are used in addition to titano-aluminophosphates especially as an adsorber, as they can adsorb on its large surface many molecules.

A pure, non-ion-exchanged zeolite is usually present in its H form, in which H ⁺ ions balance the negative charges by incorporation into the lattice. The zeolite obtains Brønsted acid properties through the embedded protons. Besides H ⁺ can also other cations

be subsequently stored by a cation exchange in the grid. So these can be against, for example Exchange metal cations, whereby the zeolite, for example, receives different or improved catalytic properties.

Since pure alumino-phosphates do not contain excess negative charges, pure alumino-phosphates have no

Brønsted acid properties, and therefore have no acidic character. Due to the missing stored

Protons also can not exchange metals in the lattice, which eliminates the possibility of metal modification and other properties.

The group of silico-aluminophosphates or titano-silico-aluminophosphates has additional negative due to the partial replacement of phosphorus by silicon or titanium

Charges on. These can be as well as in zeolites through

 Cations, such as protons, are compensated. For various technical applications, these compounds can also be exchanged with different metal cations. The titano-silico-aluminophosphates are mainly distinguished by the geometry of the cavities formed by the rigid network of the TiG ^ / SiG ^ / AlG ^ / PG ^ tetrahedra, where the skeletal structure of the aluminophosphates is always linked is formed by rings. The pore openings are composed of 8, 10 or 12 rings. They are differentiated due to the pore size in narrow, medium, and wide-pore structures. Certain aluminophosphates have a uniform structure, e.g. a VFI or AET structure with linear channels, with others

Topology can also connect larger cavities behind the pore openings.

For technical applications, these materials are often modified with other components. So will zeolites in the exhaust gas catalysis usually modified with transition metals and precious metals. In oxidation catalysis, precious metals are often used, whereas for reduction catalysts, iron, copper, cobalt, etc. are usually used.

Zeolites are usually used in the form of powders, which are then formed into extrudates, mostly for stationary applications. With admixture of oxidic and

organic binders, these are then formed to Vollextrudaten or honeycomb catalysts, or as a washcoat on

applied ceramic or metallic honeycombs and moldings.

The group of silico-alumino-phosphates has many

Applications. In particular, SAPO-34 is particularly important in the field of catalysis. As a small-pore silico-alumino-phosphate, SAPO-34 crystallizes in the known CHA structure according to IUPAC due to the specific 8-unit units and has a pore opening of 3.5 Å. SAPO-34 has been thermally stable for some time as a more active

Catalyst for the reduction of nitrogen oxides (N0 _X ) used. Both for the reduction with hydrocarbons, such as

Propene, or in conjunction with ammonia. Furthermore, in the literature, the use of SAPO-34 as

Catalyst in the reaction of oxygen-containing

Hydrocarbons to olefins described.

Despite good catalytic properties, the use of SAPO-34 is not always possible. In the presence of water, or in an aqueous phase, SAPO-34 can not be used because of its low hydrothermal stability, since even at low thermal stress of 30 ° C to 50 ° C more than 70% of the structure is amorphized and thus unusable. In particular, the amorphization already contributes to the structure the preparation of the catalysts in the aqueous phase. This is particularly disadvantageous since the production

 Cost reasons usually done from aqueous phase. In the prior art, therefore, no alternative to SAPO-34 is known, in addition to good Katalyseeigenschaften, high

Adsorption capacity also high hydrothermal stability, especially over extended periods of time, as in the

large-scale catalysis are common has.

Object of the present invention was therefore, a

Small pore material, the good Katalyseeigenschaften, a high adsorption capacity and hydrothermal stability, especially in aqueous solutions and in hot

Steam atmospheres for prolonged periods, such as e.g. are common in large-scale catalysis,

to provide.

According to the invention, this object is achieved by a titano-silico-aluminophosphate with tetrahedrally coordinated titanium, which has a free CO coordination site.

Surprisingly, it has been found that the titano-silico-aluminophosphate (TAPSO) according to the invention, eg TAPSO-34, has greater thermal stability in aqueous phases than non-titanium-containing SAPO-34. Therefore, TAPSOs can be obtained by a hydrothermal process, and moreover have high structural stability in aqueous phases and in a hot steam atmosphere. Of great advantage is the high stability in particular with respect to the so-called hydrothermal stress defined below, in particular with respect to hydrothermal stress over long periods of time in the aqueous phase, in particular in the temperature ranges of 50 ° C to 100 ° C, and in the gas phase in the temperature ranges from 500 ° C to 900 ° C.

By "hydrothermal stress" is meant herein that high temperatures prevail in the presence of water.

 Examples are the hydrothermal synthesis of chemical compounds, adsorption or desorption processes. Among them is also the repeated process of adsorption and

Desorption understood because here repeatedly heat-induced adsorbed water or other low molecular weight compounds desorb, so that water or other low molecular weight compounds can be adsorbed again. Advantageously, TAPSOs in particular retain their titanium-containing TAPSO-34

Structure also in a hydrothermal treatment at

Temperatures of greater than 70 ° C in the aqueous phase, while the structure of SAPOS, e.g. SAPO-34 is already attacked at 30 ° C, and from 70 ° C its structure completely loses and completely amorphized. TAPSOs retain their structures under hydrothermal conditions even at 80 ° C

Conditions. A comparison of the BET surface area showed that, in contrast to the pure SAPOs, the titano-silico-alumino-phosphates were also hydrothermal

Treatment at 80 ° C have a constant BET surface area of about 630 m ² / g.

According to the invention, the titano-silico-aluminophosphate contains tetrahedrally coordinated titanium. These titanium-containing silico-aluminophosphates according to the invention thus have a much higher hydrothermal stability in comparison to pure non-titaniferous silico-aluminophosphate, and even after prolonged hydrothermal treatment remain

elevated temperatures still their characteristic

Structure at. This is due to stabilization

built-in tetrahedral coordinated titanium atoms. Titano-silico-aluminophosphates according to the invention have exceptionally high stability to hydrothermal stress, and water even at high temperatures, owing to the tetrahedrally coordinated titanium atoms. This can also be done

repeated adsorption and Desorptionsvorgänge be performed. Due to their high long-term stability against water and high temperatures at repeated adsorption and

Desorptionsvorgängen can thus be reduced, the process costs, if titano-silico-aluminophosphates in

Presence of water used for catalytic processes.

The tetrahedrally coordinated titanium of N.N. Panchenko, E.

Roduner, Langmuir 21, 10545-10554 (2005) shows a vacant coordination site for CO, resulting in five-coordinate titanium at CO adsorption. Addition of CO to the tetrahedrally coordinated titanium can be used to detect by IR spectroscopy a Ti-CO stretching band at 2199-2181 crrT ¹ typical of meso- and microporous titano-silicates, as well as other titanium-containing species

Silico derivatives occurs. The IR band occurs only in microporous and mesoporous titano-silico materials, in which the titanium atoms are incorporated in the framework and not as

isolated tetrahedra present. Thus, this can

characteristic IR band in pure T1O ₂ or non-titanium-containing silico-aluminophosphates or in titanium-containing silico-aluminophosphates in which titanium is not incorporated in the framework, can not be detected. The broadening of the Ti-CO-IR band is due to the CO-coordinated environment of the titanium atom, which has at least one other titanium or silicon atom in its vicinity.

Evidence of the characteristic vibrational band at

2192 ± 5 crrT ¹ in the IR spectrum is further an indication that the inventive titano-silico-alumino-phosphate a high Brønsted acidity. This is for the catalytic properties of titano-silico-alumino-phosphate

responsible, because of a high Brønsted acidity

Conversion rate in particular acid-catalyzed

Catalysis processes can be increased. Such a

Titano-Silico-Alumo-Phosphate-Catalyst has on it

Surface acidic centers where reactions or

Reaction steps can proceed. The type and number of these acidic centers has a decisive effect on the

reaction-related characteristics such as activity, selectivity or deactivation behavior. For the development and optimization of chemical processes with acidic heterogeneous catalysts, it is therefore often necessary to investigate these catalysts in terms of their Brønsted acidity. If a titano-silico-alumino-phosphate is present in its H-form, the number of Brønsted acidic centers will be determined by the number of

Protons defined.

Brønsted acidity is determined by the number of free ones

defines negative charges in the framework of the titano-silico-aluminophosphates, which is determined by the (Si + Ti) / Al ratio. Due to the lack of valence electron, the Al atom shows a higher electron affinity than the Si atom or Ti atom, which leads to the attachment of a proton to a Α10 ι ^~ tetrahedron and increases the Brønsted acidity.

As a result of the addition of the proton, the OH bond on the AI is weakened, as a result of which H ₂ 0 is formed at elevated temperatures

can be split off. This results in unsaturated Al ³⁺ ions which are strong electron acceptors and strong Lewis acid centers. These three-coordinate (and thus strongly Lewis acidic) aluminum atoms no longer belong to the periodic crystal lattice, which is why this process is also referred to as dealuminization. This reduces the number of Brønsted acidic centers with simultaneous increase of the Lewis acidic centers. As strong Lewis acid, these centers can continue to undergo Lewis acid-base reactions, which allows the properties of the titano-silico-aluminophosphates to be altered as a catalyst.

The acidity of titano-silico-alumino-phosphates is not only determined by the number of aluminum atoms in the skeleton, but also due to the negatively charged A10 _4/2 ^~ tetrahedra, the neutral Si0 _{4/2-tetrahedron,} the neutral Ti0 _{4/2-tetrahedron} and the positively charged P0 _{a 4/2} ⁺ tetrahedra. Because of the titano-silico-aluminophosphates of Brønsted acidity desired for catalysis, this is a negatively charged backbone

required by a replacement of phosphorus by

Silicon or titanium is formed. This is missing per replaced

Phosphorus atom a positive charge, so that in total results in a negative excess charge. When the charge balance is by protonation, a titano-silico-aluminophosphate of Brønsted acidity is present. Thus, the higher the Brønsted acidity, i. the more acid sites available for catalysis, the higher the catalytic activity of the titano-silico-alumino-phosphate.

However, since Ti is incorporated into the framework as well as Si as a charge-neutral tetrahedron, the Brønsted acidity in

 Titano-silico-aluminophosphates determined by the replacement of phosphorus by titanium / silicon. Due to the formation of a pentaedrisch coordinated titanium by CO addition

(Adsorption), Br0nsted acidity can thus be determined from the adsorbed amount of CO by IR spectroscopy. This can indirectly the acidity of the

Determine titano-silico-alumino-phosphate. Thus, the framework structure is stabilized and offers no attack possibilities for water and thus leads to an extremely high stability to hydrothermal stress.

The Ti-CO-IR band has an intensity of 0.005 to 0.025. This characteristic IR band at 2192 ± 5 crrT ¹ is shown in FIG. This Ti-CO-IR band marked by an arrow can be recognized as a shoulder, since the adjacent CO band for CO adsorbed on silicon is much more intense at 2173 cm ± 5 cm. It has been found according to the invention that the improvement of the hydrothermal stability with a certain intensity of 0.005-0.025 in the IR spectrum

accompanied. So that the titano-silico-alumino-phosphate the

desired hydrothermal stability should have the

 Intensity at least 0. 005, preferably 0.016 + _ 0. 005.

The titano-silico-aluminophosphate according to the invention contains a proportion of 0.06 to 5% by weight of titanium in others

 Embodiments of 0.15 to 4 wt .-%, further from 0.15 to 3.6 wt .-%, or 0.15 to 3 wt.% In the framework. It has been shown that in particular a proportion of 0.06 wt .-% or more in the framework of the titano-silico-aluminophosphates leads to an increase in the hydrothermal stability. If the proportion is lower, the BET surface area of the titano-silico-aluminophosphate used to determine the intact framework structure is more strongly amorphized after a hydrothermal treatment than if the proportion of titanium in a range between 0.06 and 5 wt .-% lies.

The titano-silico-aluminophosphate according to the invention has a Ti / Si / (Al + P) ratio of 0.01: 0.01: 1 to 0.2: 0.2: 1. Particularly suitable are titano-silico-aluminophosphates, In addition to a certain ratio of Si: P by the replacement of phosphorus by silicon in the framework structure, also a certain proportion of titanium in the framework structure

exhibit. Titano-Silico-Alumo-Phosphate with the

Ratio of the invention are characterized by a

hydrothermal long-term stability, with a high

Resistance to hydrothermal stress, whereby also the adsorption capacity e.g. stays high for CO.

Titano-silico-aluminophosphate according to the invention can be used as catalyst because of the high adsorption capacity, or for the adsorption of water in the drying, for example in dishwashers, dryers,

Heat exchangers or air conditioners, etc. The adsorption capacity determines how many molecules in the framework of the

Titano-silico-alumino-phosphate according to the invention can be included. The titano-silico-aluminophosphate of the present invention has a (Si + Ti) / (Al + P) molar ratio of 0.01 to 0.5 to 1, preferably 0.02 to 0.4 to 1, more preferably from 0.05 to 0.3 to 1, and most preferably from 0.07 to 0.2 to 1, whereby the stability to hydrothermal stress is particularly high. This is evident from the significantly higher BET surface area after hydrothermal stress compared to SAPO-34 (Table 1).

The titano-silico-aluminophosphate according to the invention has negative charges due to the exchanged by titanium or silicon atoms phosphorus atoms, which are compensated by cations. By exchanging with the metal cations, the catalytic properties of the titano-silico-aluminophosphates are defined or changed. The lend in the interior of the framework structure present metal cations of the structure the catalytic properties.

The ion exchange of H ⁺ or Na ⁺ by a metal cation can be carried out both in the liquid and in the solid phase. In addition, gas phase exchange processes

known, which are too expensive for technical processes.

A disadvantage of the current state of the art is that during fixed ion exchange, although a defined amount of

Metal ions can be introduced into the framework of the titano-silico-alumino-phosphates, but no homogeneous distribution of the metal ions takes place. On the other hand, when the ion exchange is carried out in liquid, usually in the aqueous phase, a homogeneous metal ion distribution in the titano-silico-aluminophosphate can be achieved. For small pore zeolites is the aqueous

Ion exchange disadvantageous that the hydrate shell of the

Metal ions is too large, that the metal ions can pass through the small pore openings and the exchange rate is thus very low. In addition to the mentioned methods, the doping or modification with one or more

 Metal cations by aqueous impregnation or the

Incipient-wetness procedure. This Dotierbzw. Modification methods are known in the art. It is particularly preferred that the doping or modification be carried out by means of one or more metal compounds by aqueous ion exchange, wherein both metal salts and metal complexes are used as metal ion sources.

Surprisingly, titano-silico-aluminophosphates according to the invention have a high hydrothermal stability up to 900. This is especially beneficial for applications in

Catalysis processes, which are carried out in the presence of water and at higher temperatures. The non-titanium-containing silico-aluminas known from the prior art Phosphates show only a very low stability in the aqueous phase, and amorphize even at low temperatures.

This increased hydrothermal stability is particular

advantageous, since in particular the hydrothermal stability at high and low temperatures of importance, since even at a low desorption temperature of 20 ° C to 100 ° C, titanium-silico-alumino-phosphates are regenerated again, preferably at a temperature of 30 ° C 90 ° C,

more preferably at a temperature of 40 ° C to 80 ° C. By showing no tendency to amorphization like silico-aluminophosphates, but a much higher

Have structural stability, at lesser

 Desorption temperature compared to zeolites or Alumo- phosphates, so several cycles of adsorbing and desorbing can be run through without the

 Adsorption must be replaced. Furthermore, the energy costs have been reduced, which contribute to the regeneration of the

Adsorbent are needed. In the long-term hydrothermal stress test, it was found that titano-silico-aluminophosphates according to the invention, compared to silico-aluminophosphates at 30 ° C., for up to 90 ° C. for longer periods of time, treated with water without amorphization, i. in particular reduction of the BET surface area or structural deformation survive.

The titano-silico-aluminophosphates according to the invention are selected from TAPSO-5, TAPSO-8, TAPSO-11, TAPSO-16, TAPSO-17, TAPSO-18, TAPSO-20, TAPSO-31, TAPSO-34, TAPSO- 35, TAPSO-36, TAPSO-37, TAPSO-40, TAPSO-41, TAPSO-42, TAPSO-44, TAPSO-47, TAPSO-56. Particularly suitable according to the invention is the use of microporous titano-silico-aluminophosphates with CHA structure. Particularly preferred are TAPSO-5, TAPSO-11 or TAPSO-34, especially TAPSO-34, since they have a particularly high hydrothermal stability to water. TAPSO-5, TAPSO-11 and TAPSO-34 are also particularly suitable because of their good properties as a catalyst in

different processes due to their microporous structure, which makes them very suitable as adsorbents due to their high adsorption capacity. In addition, they also show a low regeneration temperature, as they already give adsorbed water or adsorbed other small molecules reversibly at temperatures between 30 ° C and 90 ° C. Regenerable means that the water-containing adsorbent reversibly releases the adsorbed water under heat. As a result, the titano-silico-alumino-phosphate is recovered, and can be re-adsorbed or in catalytic processes

be used.

Metal-exchanged titano-silico-aluminophosphate according to the invention has a metal content which is in the range from 1% by weight to 20% by weight, based on the total weight of the titano-silico-aluminophosphate. The metal exchange determines the catalytic properties, whereby

Silico-aluminophosphates, in particular by their long-term hydrothermal stability, become suitable materials for catalytic processes in the presence of water at high temperatures. It is particularly advantageous that the metal exchange in the liquid phase, i. can be carried out in the aqueous phase of microporous and small-pore titano-silico-alumino-phosphates without destroying the framework structure. This results in higher exchange rates compared to the prior art, whereby a higher proportion of metal can be introduced into the framework structure of the titano-silico-alumino-phosphate. In addition, by an aqueous metal exchange starting from

Metal salt solutions etc. a uniform distribution of metal ions in the framework of the titano-silico-aluminophosphates allows, with typically a metal content of 0.01-20 wt .-% is advantageous.

Therefore, according to the invention, titano-silico-aluminophosphates contain at least one further embodiment of the invention

Metal selected from lithium, sodium, potassium, magnesium, calcium, strontium, barium, scandium, titanium, vanadium, chromium, manganese, iron, nickel, copper, zinc, gallium, germanium,

Cobalt, boron, rubidium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, lanthanum, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, and / or bismuth ,

According to the invention, the term "metal exchange" also means a doping with metal or semimetal, in which case it is synonymous whether the exchange in the framework

takes place, and metal ions have been integrated into the structure, or whether the replacement has been carried out subsequently, and only cations X are replaced by other metal cations M.

According to the invention, the titano-silico-aluminophosphates may also be doped, i. where metal is installed in the framework. Particularly advantageous are dopings with iron, manganese, copper, cobalt, chromium, zinc and nickel.

Particularly suitable are FeTAPSO, MnTAPSO, CuTAPSO, CrTAPSO, ZnTAPSO, CoTAPSO and NiTAPSO.

Particularly suitable are microporous MTAPSOs (M = Mg, Mn, Cu, Cr, Zn, Co, Ni), such as MTAPSO-5, MTAPSO-8, MTAPSO-11, MTAPSO-16, MTAPSO-17, MTAPSO-18, MTAPSO- 20, MTAPSO-31, MTAPSO-34,

MTAPSO-35, MTAPSO-36, MTAPSO-37, MTAPSO-40, MTAPSO-41, MTAPSO-42, MTAPSO-44, MTAPSO-47, MTAPSO-56. Particular preference is given to using MTAPSO-5, MTAPSO-11 or MTAPSO-34, where M is as defined above. This is particularly advantageous since the adsorption properties and the hydrothermal stability of the titano-silico-aluminophosphates are usually further increased by the incorporation of one or more further metals.

Surprisingly, titano-silico-aluminophosphates according to the invention, which are used in a heat exchanger module according to the invention, have a high hydrothermal stability up to 900.degree. This is especially beneficial since

In particular, the hydrothermal stability at high and low temperatures of importance, since even at a low desorption temperature of 20 ° C to 100 ° C, titanium silico-alumino-phosphates are regenerated again, preferably at a temperature of 30 ° C to 90 ° C. , more preferably at a temperature of 40 ° C to 80 ° C. By showing no tendency to amorphization like silico-aluminophosphates, but a much higher structural stability, with lesser

Desorption have compared to zeolites or Alumo- phosphates, so clearly several cycles of adsorbing and desorbing can be run through without the adsorption must be replaced. Next, the energy costs that can be used to regenerate the

Adsorbent needed are lowered.

The (primary) crystallite sizes of the titano-silico-aluminophosphates according to the invention are between 0.1 μπι and 10 μπι. It is particularly advantageous if the crystallite size is about 0.5 to 3 μπι. So the material can be directly without

Further processing, such as milling etc. are used. However, milling processes can be performed using ball mills, planetary mills, jet mills, etc. without damaging the material. The titano-silico-alumino-phosphate can be used both as extrudate, binder-containing or binder-free granules, extruded granules or pellets.

Advantageously, the titano-silico-aluminophosphate can also be present in a coating on a shaped body. It is advantageous if the material already exists in the form of small crystallites. The molding can take any geometric shape, such. Hollow bodies, plates,

Nets or honeycombs. The application is usually carried out via a suspension (washcoat) and can be carried out with any other methods known to the person skilled in the art. Furthermore, the shaped body may also consist entirely of a titano-silico-aluminophosphate, which is produced by pressing,

optionally with the addition of a binder and / or

Excipient, and drying can be obtained.

In this case, the use of the titano-silico-alumino-phosphate as a shaped body in catalytic processes is particularly advantageous, since the material can be integrated to save space, and also allows easy handling.

It is also advantageous if the titano-alumino-phosphate as loose granules or a shaped body in the form of beads,

Cylinders, beads, threads, strands, platelets, cubes, or agglomerates is present, since so the adsorptive surface of the titano-silico-alumino-phosphate is increased, which allows a particularly efficient catalysis, or adsorption of water vapor and water.

The use as a shaped body is advantageous because so the

Titano-silico-aluminophosphates in different Catalysis processes, adsorbents or as im

Heat exchanger material can be used to save space.

The Titano-Silico-Alumo-Phosphate can also be used as a fixed bed or loose bulk material. A loose titano-silico-alumino-phosphate bed or titano-silico-alumino-phosphate introduced in a fixed bed is particularly suitable since handling is easier.

The object of the present invention is further achieved by a process for the preparation of the titano-silico-aluminophosphate according to the invention comprising the steps of a) providing an aqueous

 A synthesis gel mixture containing, at least one aluminum source, a phosphorus source, a silicon source, a template and another titanium source,

 b) stirring for several hours at a

 Temperature of 180 ° C,

 c) filtering, and drying in a

 Temperature of 100 ° C,

 d) calcining at a temperature of 550 ° C, e) obtaining a titaniferous silico-aluminophosphate.

The inventive method for producing a titano-silico-alumino-phosphate is based on a

Synthetic gel mixture performed in aqueous medium. The process may also be under pressure in an autoclave

be performed. The synthesis gel mixture contains a

Aluminum source, a phosphorus source, a silicon source, a template and a titanium source. In some embodiments of the invention, a titaniferous titanium source is used Silicon source used. The components are combined in aqueous solution using a synthesis gel mixture

is obtained. The synthesis gel mixture is reacted with stirring for 12 to 100 hours, preferably 24-72 hours at a temperature of 150 ° C to 350 ° C, preferably at 160 ° C to 185 ° C, then filtered and at a temperature of 100 ° C. dried. The obtained titano-silico-aluminophosphate is calcined at a temperature of 400 ° C to 600 ° C, preferably 550 ° C, to obtain crystalline titania containing silico-alumino-phosphate.

As a titanium source, titanium-oxygen compounds or

Titanium-metal-organic compounds such as T1O ₂ , T1OSO ₄ , Ti-tetra isopropylate, Tetraethylorthot itanat used.

The aluminum source is preferably alumina,

 Sodium aluminate, aluminum hydroxide, or an aluminum salt.

Preferably, in the inventive method as

Silicon source silicon dioxide, sodium silicate, a

 Silica sol, silicic acid, colloidal silica, precipitated silica, silicon-doped titanium oxide or pyrophoric

Silica used. As a phosphorus source is preferred according to the invention

 Phosphoric acid, a metal phosphate, hydrogen phosphate or

Dihydrogen phosphate used.

In the method according to the invention, various

ionic templates are used, selected from the group tetramethylammonium, tetraethylammonium,

Tetrapropylammonium, tetrabutylammonium hydroxides and bromides, di-n-propylamine, tri-n-propylamine, triethylamine, triethanolamine, piperidine, cyclohexylamine, 2-methylpyridine, N, N-dimetylbenzylamine, N, N-dimethylethanolamine, choline, Ν, Ν'-dimethylpiperazine, 1, 4-diazabycyclo (2, 2, 2) octane, N-methyldiethanolamine, N-methylethanolamine, N-methylpiperidine, 3-methylpiperidine , N-methylcyclohexylamine, 3-methylpyridine, 4-methylpyridine, quinuclidine, N, N'-dimethyl-1, 4-diazabicyclo (2,2,2) octane, di-n-butylamine, t-butylamine,

Ethylenediamine, pyrrolidine, 2-imidazolidone. In some

Embodiments of the invention will be particularly

Tetraethylammonium hydroxide used.

In a development of the method according to the invention, preference is given to using a titanium source, such as T1O _2, which contains 0.5 to 25% by weight of silicon dioxide. The titanium source preferably has a proportion of 5 to 20% by weight of silicon. The proportion of titanium in the titano-silico-aluminophosphates according to the invention determines the hydrothermal stability since, with the proportion of titanium in the structure, the hydrothermal long-term stability also decreases. According to the process of the invention, a titano-silico

Alumo-phosphate obtained, which has a Si / Ti ratio of 0.02 to 40.

The Si / Ti ratio of the silico-aluminophosphate of the invention is preferably in the range of 0 to 20, more preferably in the range of 0.5 to 10, even more preferably in the range of 0.5 to 8. The Al / P Ratio is preferably in the range of 0.9 to 1.8, more preferably 1 to 1.6, and most preferably in the range of 1.3 to 1.5.

The titano-silico-aluminophosphate obtained by the process according to the invention has an Si / Al ratio of 0.05 to 0.3. The titano-silico-aluminophosphate according to the invention has a much higher acid strength than titano-silico-aluminophosphates, which are known from the prior art, since no Na ₂ O is used in the process for its preparation. Na ₂ Ü is known for its extremely high base strength. Becomes

Sodium oxide used in the synthesis reduces the acid strength of the titano-silico-alumino-phosphate, which due to acid-base reactions leads to a reduction of the acid centers, i. The catalytic centers leads, so that the

catalytic activity, which is based on the acidity of the titano-silico-alumino-phosphate, decreases. Thus, the titano-silico-aluminophosphate obtainable by the process described above has a much higher acid strength, and thus a much higher catalytic activity, especially at

acid catalyst processes.

To illustrate the present invention and its advantages, this is based on the following figure and the

Examples are described without these being to be understood as limiting.

It shows :

Figure 1: the IR bands of TAPSO-34, SAPO-34 and a

Mixture of SAPO-34 and Ti0 ₂ .

Method part:

The following are the methods and devices used

but should not be construed as limiting.

Determination of the BET surface area:

The determination of the BET surface area was carried out in accordance with DIN 66131 (multipoint determination), as well as with the provisions of DIN ISO 9277, the European Standard 2003-05

specific surface area of solids by gas adsorption by the BET method (according to Brunauer, S., Emett, P., Teller, E.J. Am Chem Chem 1938, 60, 309.).

The determination was carried out using a Gemini Micromeritics, taking into account the manufacturer's information. Röngtendiffraktometrie was carried out using a D4Endeaver Bruker, taking into account the

Information from the manufacturer. To determine the IR bands, a Thermo Nicolet 4700 FTIR spectrometer with Thermo Scientific MCT detector was used according to the manufacturer's instructions. For the synthesis, a stainless steel autoclave (0.5 1 volume) of Juchheim GmbH was used.

For the synthesis example, hydrargillite (aluminum hydroxide SH10) from Aluminum Oxid Stade GmbH, Germany was used.

Next was silica sol (Krosrosol) with 1030.30%

Silicon dioxide used by the company CWK Chemiewerk Bad Köstritz GmbH, Germany.

The silicon-doped titanium dioxide T1O ₂ 545 S was available from Evonik, Germany.

For the comparative example, SAPO-34 from Süd-Chemie AG was used.

Example 1: Preparation of TAPSO-34 according to the invention

100.15 parts by weight of deionized water and 88.6

Parts by weight of hydrargillite (aluminum hydroxide SH10) were mixed. To the resulting mixture were added 132.03 parts by weight of phosphoric acid (85%) and 240.9 parts by weight of TEAOH

(Tetraethylammonium hydroxide) (35% in water), as well

then 33.5 parts by weight silica sol and 4.87

Parts by weight of silicon doped titanium dioxide added, so that a synthesis mixture having the following composition was obtained:

A1 ₂ 0 ₃ : P ₂ O ₅ : 0.3 Si0 ₂ : 0.1 Ti0 ₂ : 1 TEAOH: 35 H ₂ 0

The synthesis gel mixture having the above composition was transferred to a stainless steel autoclave. The autoclave was stirred and heated to 180 ° C, this

Temperature was kept 68 hours. After cooling, the product obtained was filtered off, washed with deionized water and dried in an oven at 100 ° C. One

X-ray diffraction of the resulting product showed that the product was pure TAPSO-34 according to the invention. The elemental analysis showed a composition of 1.5% Ti, 2.8% Si, 18.4% Al and 17.5% P, giving a

 Stoichiometry of Tio, 023S10, 073AI0, 494P0, 410 corresponds. According to a SEM analysis (Rastereleketronenmikroskopie) of the product whose crystal size was in the range of 0.5 μπι to 2 μπι.

Subsequently, the obtained product was calcined at 550 ° C for 1 hour. The titano-silico-aluminophosphate according to the invention exhibits a CO-Ti oscillation band in the IR spectrum

2192 ± 5 cm.

Example 2:

Hydrothermal long-term stress test:

An inventive titano-silico-alumino-phosphate (TAPSO-34) with 3.4 wt .-% Ti (obtained as in Example 1 with correspondingly adapted composition of the synthesis gel), a non-inventive titano-silico-alumino-phosphate (TAPSO -34) with 0.5% by weight of Ti and a non-titanium-containing silico-aluminophosphate (SAPO-34) were used to determine the hydrothermal Long-term stability treated with water for a long time at different temperatures.

Small pore molecular sieves with CHA structure have high

Adsorptionskapazitäten, but show different hydrothermal stability depending on the titanium content in the structure. Therefore, in addition to inventive titano-silico-aluminophosphate (TAPSO-34), a non-inventive titano-silico-aluminophosphate (TAPSO-34), with a low titanium content and a non-titanium-containing silico-aluminophosphate (SAPO) 34), and tested by the same method in the hydrothermal long-term stress test.

A long-term hydrothermal stress test was carried out to show that the structure of the titano-silico-aluminophosphate according to the invention survives treatment with and in water at 30 ° C., 50 ° C., 70 ° C. and 90 ° C. for 72 h , in contrast to the structure of the non-inventive titano-silico-aluminophosphates and the non-titaniferous silico-aluminophosphates. This was determined using the BET surface area

Information about the degree of amorphization

in terms of structural deformation.

Experimental procedure:

For the hydrothermal long-term stress test in each case the same amount of inventive TAPSO-34, noninventive TAPSO-34 and non-titanium-containing SAPO-34 at 30 ° C, 50 ° C, 70 ° C and 90 ° C in each case for 72 h in Water treated. Subsequently, the material was filtered off, dried at 120 ° C and the BET surface area determined. The non-inventive TAPSO-34 and the non-titanium-containing SAPO-34 already untreated shows a lower BET surface area than a comparable TAPSO-34 according to the invention. While TAPSO-34 according to the invention only a small destruction of the BET surface area by water as a function of the

Temperature remains, and still retains over a period of 72 h over 50% of the original BET surface area after a treatment at 90 ° C, the BET surface area in non-inventive TAPSO-34 and non-titanium-containing SAPO-34 already drops after one Treatment with water at 30 ° C over a period of 72 h to 80% and 77% of the original BET surface area. In contrast, TAPSO-34 according to the invention still has more than 99% of the original BET surface area even after treatment with water at 30 ° C. for 72 hours. After a treatment with water for 72 h at 50 ° C, the structure of the non-inventive TAPSO-34 and SAPO-34 is almost completely destroyed, after 72 h at 70 ° C hardly crystalline structure is no longer present, and after a

 Treatment at 90 ° C both non-inventive TAPSO-34 and non-titanium-containing SAPO-34 is completely amorphized and completely destroyed the typical crystalline structure. The hydrothermal long-term stress test thus shows that non-inventive TAPSOs and non-titanium-containing SAPOs already lose their structure after 72 hours of treatment at 50 ° C. and already become amorphous at 70 ° C. In contrast, titano-silico-aluminophosphates (TAPSOs) according to the invention exhibit enormous resistance to hydrothermal long-term stress.

TAPSOs according to the invention also retain one

Long-term stress test with and in water at 70 ° C their structure, and show only after a treatment at 90 ° C, an amorphization of 50% (see Table 1).

The hydrothermal long-term stress test thus clearly shows that only titano-silico-aluminophosphates according to the invention, in which a certain proportion of titanium between 0.06 and 5% by weight is incorporated in the framework, also have such a high content Show stability in hydrothermal environment. Such inventive titano-silico-aluminophosphates also show a corresponding, slightly broadened band in the IR

 2192 ± 5 cm. If this band is missing, as with non-inventive titano-silico-aluminophosphates or non-titaniferous silico-aluminophosphates, the structure amorphizes even at low temperatures due to hydrothermal stress.

Table 1: Hydrothermal long-term stress test of

 according to the invention TAPSO-34, non-inventive TAPSO-34 and non-titanium-containing SAPO-34 with respect to the BET surface area after hydrothermal treatment as a function of temperature.

Example 3:

IR spectroscopy:

To determine the titanium position in the lattice, the

 Titano-silico-aluminophosphate according to the invention investigated by IR spectroscopy. Since by incorporation of the titanium atoms in the framework of the titano-silico-alumino-phosphate, the

hydrothermal stability is increased or defined by determining the incorporated titanium in the framework structure the increased hydrothermal stability of the titano-silico-alumino-phosphate can be determined.

The determination of titanium atoms by means of indirect

Determination by adsorption of CO to the free binding site of the tetrahedrally coordinated titanium to form a pentahedrally coordinated titanium. After a CO adsorption of the titano-silico-aluminophosphate according to the invention (TAPSO-34), a characteristic CO-Ti oscillation band at 2192 ± 5 cm ^-1 in the IR spectrum can be detected.

To determine the increase in stability of

Comparative substances, non-titanium-containing SAPO-34 and a mixture consisting of non-titanium-containing SAPO-34 and 3.4 wt .-% T1O ₂ (anatase) also by IR spectroscopy after

CO adsorption investigated. Since non-titanium-containing SAPO-34 and inventive TAPSO-34 have the same structure, this was chosen as the comparison substance. As another

Comparative substance, the mixture of non-titanium-containing SAPO-34 and T1O _{2 was} examined by the same method to show that by not built into a framework structure titanium atoms no increase in stability, resulting in a lack of characteristic IR band at 2192 ± 5 crrT ¹ can be shown.

Experimental procedure:

The powder samples of TAPSO-34 of the invention, non-titaniferous SAPO-34 and a mixture consisting of non-titaniferous SAPO-34 and 3.4% by weight of T1O ₂ , became self-supporting tablets having a diameter of 13 mm and a weight from 10 to 20 mg pressed at a pressure of about 0 to 3 metric tons. The FTIR measurements of

adsorbed carbon monoxide were used on a Thermo Nicolet 4700 Spectrometer recorded with MCT detector. The plant had a custom built high vacuum system

connected low-temperature cell (window material ZnSe). The IR spectra were in the transmission mode with a

Resolution of 4 crrT ¹ at a range of 400 to 4000 crrT ¹ and recorded with 128 scans, or carried out determinations of CO loading. The activation of the sample was carried out under high vacuum (max 1 x 10 ^{~ 5} mbar) for 2 h at a temperature of 450 ° C. Subsequently, the cell with the help of liquid

Nitrogen cooled to -196 ° C. After that was long

 Carbon monoxide adsorbed until a pressure of 10 mbar has set. Subsequently, the cell was gradually evacuated again until no more CO bands were seen or had set a constant state. Before everyone

Spectrum was a constant amount of helium in the cell passed to ensure a constant sample temperature. The amount of CO adsorbed on titanium was through

Integration of the area of the CO band (at 2192 cm ⁴ ) determined. For this, the spectrum of the TAPSO-34 is based on the specific

Surface of reference sample SAPO-34 normalized.

FIG. 1 shows the IR spectra of TAPSO-34 (according to the invention and not according to the invention), SAPO-34 and the mixture of SAPO-34 and T1O ₂ . It was found that only the titano-silico-

Alumino-phosphate has a CO IR band in the IR spectrum at 2192 ± 5 cm ^{" 1} , which is due to tetrahedrally coordinated titanium with free coordination point for CO. The

characteristic IR band at 2192 ± 5 cm ⁴ results from a CO-Ti stretching vibration characteristic of

is tetrahedral titanium incorporated into the framework, and thus neither in non-titanium-containing SAPO-34 nor in with T1O ₂

mixed non-titanium SAPO-34. The Broadening of the vibrational band results from the first or second coordination sphere of titanium.

Table 2: Determination of the relative intensity and the

relative area of the CO band of the titano-silico-aluminophosphate according to the invention (TAPSO-34), of the non-inventive titano-silico-aluminophosphate (TAPSO-34), of the non-titanium-containing SAPO-34 and not mixed with T1O ₂ - titaniferous SAPO-34.

In contrast to the titano-silico-aluminophosphate according to the invention, the non-inventive titano-silico-aluminophosphate has only a very small proportion of titanium in the framework.

The comparison substances were prepared by the same method

examined. It was found that in non-titanium-containing SAPO-34, as well as mixed with Ti0 ₂ SAPO-34 no CO band at 2192 crrT ^{1 is} observed and therefore no Ti ⁴⁺ centers are present. Example 4 Adsorption of Water on Titano-Silico-Alumo-Phosphate According to the Invention (TAPSO-34)

Due to the high adsorption capacity, this will

Titano-silico-aluminophosphate according to the invention as a catalyst, or used for the adsorption of water in the drying.

To determine the adsorption capacity, the

Titano-silico-aluminophosphate according to the invention (TAPSO-34), a non-inventive titano-silico-aluminophosphate (TAPSO-34) and a non-titanium-containing silico-aluminophosphate (SAPO-34) were investigated by the following method.

General part of the experiment description:

The adsorption capacity of a titano-silico-aluminophosphate according to the invention (TAPSO-34), of a non-inventive titano-silico-aluminophosphate (TAPSO-34) and of a non-titaniferous silico-alumo was measured in a heatable, steam-filled pressure chamber Phosphate (SAPO-34) depending on the treatment temperature.

For this, the water vapor pressure in the pressure chamber was set to 20 mbar (at 20 ° C.) and the adsorbed water of the material treated at different temperatures (30 ° C., 50 ° C., 70 ° C. or 90 ° C.) was measured. Table 3 shows how inventive TAPSO-34, compared to non-inventive TAPSO-34 and non-titanium-containing SAPO-34 in terms of a Water adsorption capacity depending on

 Treatment temperature behaves.

Table 3:

The temperature was adjusted in the pressure chamber with a thermostat, and only after keeping the temperature constant for 10 minutes, a corresponding amount of adsorbent was added to the pressure chamber via a corresponding valve.

It was found that depending on the treatment temperature, a different amount of water is adsorbed. Example 5 with TAPSO-34 according to the invention:

In embodiment 5, TAPSO-34 according to the invention (with 3.4% by weight of Ti) was used. The test series at 20 mbar steam pressure show for TAPSO-34, which was treated at temperatures of 23 to 70 ° C that much water is adsorbed, and the amounts of

adsorbed water (Table 3) is reduced only from a temperature of 70 ° C. The values of the adsorbed water here were in a range from 33.5% by weight to about 34.9% by weight, based on the total weight of the TAPSO-34 according to the invention. From a temperature of 70-75 ° C, the amount of water decreases slightly, but at 90 ° C is still over 50% of

initial amount of water adsorbed.

The adsorption capacity of a maximum of 34.9% at the beginning decreases with increasing temperature, since at temperatures above 70 ° C the BET surface, i. slowly amorphizes the active, adsorbing surface of the titano-silico-alumino-phosphate.

However, titano-silico-aluminophosphates according to the invention are so stable even in the presence of water that more than 50% of the surface is still intact even at a temperature of 90 ° C., and therefore it can adsorb water (see Table 1).

Comparative example

In the comparative example, in each case a corresponding amount of non-inventive titano-silico-alumino-phosphate

(TAPSO-34) and non-titanated silico-alumino-phosphate (SAPO-34). The non-inventive TAPSO-34 and the non-titaniferous SAPO-34 were chosen to be in

Dependence on the built-in titanium in the structure, the

To compare adsorption capacity with that of the adsorption capacity of the inventive titano-silico-alumino-phosphate (TAPSO-34).

The comparative examples of the non-inventive TAPSO-34 and the non-titaniferous SAPO-34 show (Table 2) that the adsorption capacity is very much different from the

Treatment temperature is affected. Already from a temperature of 30 ° C, the adsorption capacity of

Water vapor. For a material that is at a temperature treated by 70 ° C, hardly any more water at the

Surface of the non-inventive TAPSO-34 and the non-titan SAPO-34 adsorbs SAPO-34, which was treated at 90 ° C, adsorbs no more water, since the structure is completely amorphized, while non-inventive TAPSO-34 after treatment at 90 ° C still low

Has adsorption capacity (see also Table 3).

By the proportion of tetrahedral according to the invention

coordinated titanium in the framework structure in titano-silico-aluminophosphates according to the invention are thus a constant adsorption capacity, also depending on the

Treatment temperature achieved. This can be done by a

characteristic IR-Ti vibration band can be detected and is reflected in a higher temperature stability of the

 Framework. If too little titanium is contained in the framework structure, the adsorption capacity remains longer compared to pure silico-alumino-phosphates, but sinks in

Dependent on the treatment temperature also strong.

Comparative Example 1

Preparation of non-inventive TAPSO-34

76.41 parts by weight of deionized water and 73.84

Parts by weight of hydrargillite (aluminum hydroxide SH10) were mixed. To the resulting mixture was added 110.04 parts by weight of phosphoric acid (85%) and 200.81 parts by weight of TEAOH

(Tetraethylammonium hydroxide) (35% in water), as well

then 38.09 parts by weight silica sol and 0.81

Silicon dioxide doped titanium dioxide was added to give a synthesis mixture having the following composition: There was a Synthesegelgemisch obtained with the following molar composition: A1 ₂ 0 _3: P ₂ O _5: 0.4 Si0 _2: 0 02 Ti0 _2: l TEAOH: 35 H ₂ 0

The synthesis gel mixture having the above composition was transferred to a stainless steel autoclave. The autoclave was stirred and heated to 180 ° C, this

Temperature was kept 68 hours. After cooling, the resulting product was filtered off, washed with deionized water and dried in the oven at 100 ° C. One

X-ray diffraction of the resulting product showed that the product was a TAPSO-34. The

Elemental analysis revealed a composition of 0.05% Ti,

3.7% Si, 17.9% Al and 17.2% P, which corresponds to a stoichiometry of Tio, ooiSio, 097AI0, 491P0, 411. The non-inventive titano-silico-alumino-phosphate obtained with 0.01% Ti has a lower titanium content than the minimum proportion of the titano-silico-aluminophosphate according to the invention of 0.2% by weight. According to a SEM analysis (Rastereleketronenmikroskopie) of the product whose crystal size was in the range of 0.5 μπι to 2.5 μπι.

 Subsequently, the product obtained was calcined at 550 ° C. for 1 h.

Comparative Example 3 IR spectroscopy of non-inventive TAPSO-34

To determine the tetrahedrally coordinated titanium atoms in the non-inventive titano-silico-alumino-phosphate this was investigated by IR spectroscopy. The tetrahedral Coordination of titanium can be detected after CO adsorption to a free coordination site of titanium by a characteristic CO-Ti vibrational band at 2192 ± 5 crrT ¹ by IR spectroscopy.

For comparison, samples of non-t itanehaltige SAPO-34 and a mixture consisting of non-t itanhaltiger SAPO-34 and 3.4 wt .-% Ti0 ₂ (anatase) were also examined by IR spectroscopy after CO treatment. Since non-inventive TAPSO-34 and non-t itanhaltiges SAPO-34 have the same structure, this was selected as a reference substance. As a further comparison substance, a mixture consisting of non-t itanhaltiger SAPO-34 and T1O _{2 was} investigated by the same method, since the titanium atoms are not incorporated here in the backbone of the silico-alumino-phosphate s.

Experimental procedure:

The powdered samples, non-inventive TAPSO-34, non-t itane-containing SAPO-34 and non-t itane-containing SAPO-34, and a mixture consisting of non-t itane-containing SAPO-34 and 3.4% by weight. T1O ₂ , were pressed into self-supporting tablets with a diameter of 13 mm and a weight of 10 to 20 mg with a pressure of about 0 to 3 metric tons. Adsorbed carbon monoxide FTIR measurements were taken on a Thermo Nicolet 4700 spectrometer with MCT detector. The plant had a special

manufactured high vacuum system with connected

Cryogenic cell (window material ZnSe). The IR spectra were in transmission mode with a resolution of 4 cm ^-1 at a range of 400 to 4000 cm ^-1 and with 128 scans

added. The activation of the sample was carried out under high vacuum (max 1 x 10 ^{~ 5} mbar) for 2 h at a temperature of 450 ° C. Subsequently, the cell with the help of liquid Nitrogen cooled to -196 ° C. Carbon monoxide was then adsorbed at 10 mbar and evacuated stepwise until no CO bands were visible or a

constant state had set. Prior to each spectrum, a constant amount of helium was fed into the cell to ensure a constant sample temperature.

FIG. 1 shows the IR spectra of TAPSO-34 according to the invention, non-inventive TAPSO-34, non-titanium-containing SAPO-34 and the mixture of non-titanium-containing SAPO-34 and T1O ₂ .

It was found that the non-inventive titano-silico-alumino-phosphate has no detectable CO band in the IR spectrum at 2192 ± 5 crrT ¹ . Since hardly any titanium is incorporated in the framework, therefore, almost no tetrahedrally coordinated titanium atoms are present. The characteristic IR band for tetrahedral titanium incorporated into the framework should be seen at 2192 ± 5 crrT ¹ , and it is also found neither in SAPO-34 nor in TiO ₂ mixed SAPO-34.

Claims

claims

1. Titano-silico-aluminophosphate with tetrahedral

 coordinated titanium, which has a free CO coordination site.

2. Titano-silico-aluminophosphate according to claim 1, characterized in that the tetrahedrally coordinated titanium in the IR spectrum has a Ti-CO band at 2192 ± 5 crrT ¹ .

3. Titano-silico-aluminophosphate according to claim 2, characterized in that the Ti-CO-IR band has an intensity of 0.005 to 0.025.

4. titano-silico-alumino-phosphate according to claim 3, characterized in that the titano-silico-alumino-phosphate 0.06 to 5 wt .-% titanium in the framework.

5. Titano-silico-aluminophosphate according to claim 4, characterized in that the titano-silico-aluminophosphate has a Ti / Si / (Al + P) ratio of 0.01: 0.01: 1 to 0, 2: 0.2: 1.

6. Titano-silico-aluminophosphate according to claim 5, characterized in that the titano-silico-alumino-phosphate has a Si / Al ratio of 0.05 to 3.

7. titano-silico-alumino-phosphate according to claim 6, characterized in that the titano-silico-alumino-phosphate has a hydrothermal stability up to 900 ° C.

8. Titano-silico-aluminophosphate according to claim 7, characterized in that it is selected from TAPSO-5, TAPSO-8, TAPSO-11, TAPSO-16, TAPSO-17, TAPSO-18, TAPSO-20, TAPSO -31, TAPSO-34, TAPSO-35, TAPSO-36, TAPSO-37, TAPSO-40, TAPSO-41, TAPSO-42, TAPSO-44, TAPSO-47, TAPSO-

56th

9. titano-silico-aluminophosphate according to claim 8, characterized in that the titano-silico-aluminophosphate contains at least one further metal selected from

Lithium, sodium, potassium, magnesium, calcium,

 Strontium, barium, scandium, titanium, vanadium, chromium, manganese, iron, nickel, copper, zinc, gallium, germanium, cobalt, boron, rubidium, yttrium, zirconium, niobium,

 Molybdenum, ruthenium, rhodium, palladium, silver,

 Cadmium, indium, tin, lanthanum, hafnium, tantalum,

 Tungsten, rhenium, osmium, iridium, platinum, gold,

 and / or bismuth.

10. Titano-silico-aluminophosphate according to claim 9, characterized in that the further metal-containing titano-silico-alumino-phosphate, metal in the range of 1 wt .-% to 20 wt .-% based on the total weight of Titano-silico-alumino-phosphate contains.

11. Titano-silico-alumino-phosphate according to one of the preceding claims, whose crystallite size is between 0.1 μπι and 10 μπι.

12. Process for producing a titano-silico-aluminoxane

Phosphate comprising the steps of a) providing an aqueous

A synthesis gel mixture containing at least one Aluminum source, a phosphorus source, a silicon source, a template and a

 Titanium source,

b) stirring for several hours at a

 Temperature of 180 ° C,

c) filtering, and drying at a temperature of 100 ° C,

d) calcining at a temperature of 550 ° C, e) obtaining a titaniferous silico-aluminophosphate.