WO2012085154A1

WO2012085154A1 - Method for producing unsaturated hydrocarbon compounds

Info

Publication number: WO2012085154A1
Application number: PCT/EP2011/073690
Authority: WO
Inventors: Silke Sauerbeck; Arno Tissler
Original assignee: Süd-Chemie AG
Priority date: 2010-12-22
Filing date: 2011-12-21
Publication date: 2012-06-28
Also published as: CN103429343A; DE102010055678A1; WO2012085154A4

Abstract

The invention relates to a method for producing unsaturated hydrocarbon compounds by reacting a hydrocarbon compound containing heteroatoms to form an unsaturated hydrocarbon compound in the presence of a catalyst comprising a titano-(silico)-alumo-phosphate. The invention also relates in particular to the use of a titano-(silico)-alumo-phosphate with a CHA-structure for converting methanol into olefins.

Description

Process for the preparation of unsaturated hydrocarbon compounds

The present invention relates to a method for

Preparation of unsaturated hydrocarbon compounds by reacting a heteroatom-containing

Hydrocarbon compound to an unsaturated

A hydrocarbon compound in the presence of a catalyst comprising a titano-alumino-phosphate or a titano-silico-aluminophosphate (hereinafter both compounds are collectively referred to as titano (silico) -alumino-phosphate).

Furthermore, the present invention also relates to the use of a catalyst comprising titano (silico) -alumino-phosphate in the reaction of a heteroatom-containing

Hydrocarbon compound to an unsaturated

Hydrocarbon compound.

Alumo-silicates (zeolites), aluminophosphates (ALPOs) and silico-aluminophosphates (SAPOs) have long been known as active components for refinery, petrochemical and chemical catalysts as well as for the purification of exhaust gases in both stationary and in-situ known mobile applications. These groups are often just under the collective name

Led zeolites.

These zeolites are usually in the form of a honeycomb formed body with an active metal doped, which represents the catalytically active component, in catalyst housings before. Generally, silico-aluminophosphates (SAPOs)

Understood molecular sieves, which are obtained from alumino-phosphates (general formula (AIPO ₄ - /)) by isomorphous exchange of phosphorus with silicon, and the general formula (Si _x Al _y P _z ) 0 ₂ (anhydrous) correspond (EP 0 585 683), where x + y + z = 1 and the species has negative charges, the number of which depends on how many

Phosphorus atoms were replaced by silicon atoms, or their number depends on how large the excess of

Is aluminum atoms with respect to the phosphorus atoms.

Structures of this group are named according to the "Structure

Commission of the International Zeolite Association "because of their pore size according to the IUPAC rules (International Union of Pure and Applied Chemistry)

crystallize in more than 200 different compounds in two dozen different structures. They are classified based on their pore sizes. SAPOs are typically available by hydrothermal synthesis, starting from reactive alumino-phosphate gels or the individual Al, Si, P components, which in one

desired ratio are used, preferably such that the sum of the Si and P component is stoichiometric to the Al component. The crystallization of the resulting silico-aluminophosphates (SAPOs) is achieved by adding structure-directing templates, crystallization nuclei or elements (EP 103 117 AI, US 4,440,871, US 7,316,727). The framework structure of the SAPOs is made up of regular,

built three-dimensional space networks with characteristic pores and channels that can be linked one, two or three-dimensional. The structures mentioned above are formed by corner-sharing tetrahedral building blocks (A10 ₄ , Si0 ₄ , P0 ₄ ), consisting of four times of oxygen coordinated aluminum, silicon and phosphorus. The tetrahedra are called primary building blocks, the linkage of which leads to the formation of secondary building units. Silico-aluminophosphates (SAPOs) crystallize, among others, in the known CHA structure (chabazite), classified according to IUPAC due to their specific CHA unit.

In the aluminophosphates, charge neutrality prevails due to the balanced number of aluminum and phosphorus atoms. These systems thus have the disadvantage that they are in

Cavities require no counterions to charge balance. Thus, in these cavities also not effective

catalytically active metal ions are incorporated by ionic bonding. Therefore, these aluminophosphates are poorly suited as molecular sieves in catalysts for the production of

unsaturated hydrocarbon compounds of heteroatom-containing hydrocarbon compounds. Through isomorphous exchange / replacement of phosphorus with silicon, silico-alumino-phosphates produce excess negative charges, which are compensated for by incorporation of additional cations into the pore and channel system. The degree of phosphorus-silicon substitution from alumino-phosphates thus determines the number of cations needed to balance, and thus the maximum possible loading of the compounds with positively charged cations, e.g. Hydrogen or

Metal ions. The incorporation of the cations determines the acidic catalytic properties of the silico-aluminophosphates, and can be achieved by targeted ion exchange

in terms of their activity and selectivity as

Catalyst components are used. The so-called SAPO-34 with CHA structure and pore openings of about 3.5 Å is particularly preferred as the molecular sieve in catalysts. However, these silico-aluminophosphates have the disadvantage that they are thermally relatively unstable in the aqueous phase. For example, SAPO-34 already amorphizes at low temperatures - even during the preparation of the catalyst in aqueous phases. Therefore, silico-aluminophosphates are only partially suitable as molecular sieves in catalysts for the preparation of unsaturated hydrocarbon compounds, as in the

Production of these a great stability to water at moderate temperatures is necessary because a high water content meets the catalyst. In the case of the SAPOs mentioned, the surface decreases rapidly and the acidity is greatly reduced. This leads to an undesirable premature

Inactivation of the catalyst. For example, in particular the silico-aluminophosphates SAPO-34 and SAPO-18 both individually and as a mixture in the prior art are suitable catalyst components for the reaction of oxygen or heteroatom-containing

Hydrocarbons known to olefins. In particular, SAPO-34 was used, as it was characterized by its

hydrothermal stability, which is reflected in the

aqueous atmosphere during the implementation of

Oxygen-containing hydrocarbons to olefins at about 450 ° C has proven. However, in the catalytic

Reaction of oxygen or heteroatom-containing

Hydrocarbons to olefins no such high temperature required. If the reaction is carried out at lower temperatures, the resulting water is not sufficiently evaporated in the gaseous state. However, water in a liquid state can greatly enhance the structure of the SAPO used

to damage. That is to say, the stability of, for example, SAPO-34 is not very pronounced at low temperatures in water or in the moist state, and the structure is also already formed during the formulation of the catalyst, for example in the washcoat. Preparation or heavily damaged in the production of moist masses for extrusion.

Therefore, it was an object of the present invention to increase the stability of the SAPO-34 in the presence of water, especially at low temperatures, while maintaining the excellent high temperature property.

The present object has been achieved by a process for the preparation of unsaturated hydrocarbon compounds by reacting a heteroatom-containing

Hydrocarbon compound to an unsaturated

Hydrocarbon compound in the presence of a catalyst comprising a titano (silico) -alumino-phosphate (TAPSO).

In other words, it has surprisingly been found that titanium-containing aluminophosphates are particularly suitable as active components in the conversion of heteroatom-containing hydrocarbon compounds to olefins. The titano- (silico) -alumino-phosphate according to the invention is suitable because of its high phase purity and its high

hydrothermal stability excellently as a molecular sieve for a catalyst in the conversion of heteroatom-containing hydrocarbon compounds to olefins. As in the reaction of heteroatom-containing hydrocarbons, in particular oxygen-containing hydrocarbons, such as aliphatic alcohols, water in large quantities as

By-product is obtained, the hydrothermally stable titano (silico) -alumino-phosphates are particularly suitable as molecular sieves for these catalysts.

Like the aforementioned SAPOs, the titano- (silico) -alumino-phosphates in the context of the present invention are crystalline substances with a spatial network structure consisting of Ti0 ₄ / (Si0 ₄ ) / A10 ₄ / P0 ₄ tetrahedra and by common oxygen atoms to a regular three-dimensional

Network is linked. All these mentioned

Tetrahedral units together form the so-called

"Framework." Other units that are not from the

Tetrahedral units of the skeleton exist, referred to as a so-called "extra framework".

The structures of titano- (silico) -alumino-phosphates contain cavities that are characteristic of each type of structure. They are divided 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 framework cations are wetted, which can be replaced. In the case of the so-called aluminophosphates, at least in the "framework" of the titano (silico) -alumino-phosphate, there is one phosphorus atom on each aluminum atom, so that the charges are mutually exclusive

compensate. If titanium atoms substitute the phosphorus atoms, the titanium atoms form an excess negative charge that is compensated by cations. The interior of the pore system represents the catalytically active surface. The less

Phosphorus in relation to aluminum contains a titano (silico) -alumino-phosphate in the framework, the denser the negative charge in its lattice and the more polar is its inner surface. The pore size and structure will be next to the

Parameters in the production, i. Use or type of template, pH, pressure, temperature, presence of

Seed crystals determined by the P / Al / Ti / (Si) ratio, which accounts for the largest part of the catalytic character of a titano-alumino-phosphate or titano (silico) -alumino-phosphate. The substitution of phosphorus atoms by titanium atoms with respect to the framework results in a deficit of positive charges, so that the molecular sieve is negatively charged overall is. The negative charges are due to the installation of

Cations in the pores of the zeolite material compensated.

In addition to titanium atoms, as apparent from the above parenthetical optional presence of silicon, silicon atoms can also replace the phosphorus atoms. These then also cause negative charges, which must be compensated by cations.

The titano- (silico) -alumino-phosphates according to the invention

As in the prior art, a distinction is made mainly according to the geometry of the cavities formed by the rigid network of Ti0 ₄ / A10 ₄ / (Si0 ₄ ) / P0 ₄ tetrahedra. The entrances to the cavities are made of 8, 10 or 12 ring atoms with respect to the metal atoms that the

Form input opening, formed, the expert speaks here of narrow, medium and wide-pore structures.

According to the invention, narrow-pore structures are preferred here.

These titano (silico) -alumino-phosphates can have a

uniform structure, e.g. show a VFI or AET topology with linear channels, but other topologies are also conceivable, which are behind the

Pore openings larger cavities connect. According to the invention, preference is given to titano (silico) -alumino-phosphates having openings of eight tetrahedral atoms, ie. narrow-pored materials. These preferably have an opening diameter of about 3.1 to 5 Å, particularly preferably 3.4 to 3.6 Å.

By the term "molecular sieve" is meant natural and synthetic skeletal structures with cavities and channels, such as zeolites and related materials, which have high absorbance for gases, vapors, and solutes having particular molecular sizes. It has surprisingly been found that titanium-containing

(Silico) -alumino-phosphates are particularly suitable as

Molecular sieves in catalysts for the production of

unsaturated hydrocarbon compounds. The titano- (silico) -alumino-phosphates are suitable because of their high phase purity, their temperature stability and their high possible loading with transition metal ions

Excellent as molecular sieves for catalysts in the

Preparation of Unsaturated Hydrocarbon Compounds from Heteroatom-Containing Hydrocarbon Compounds.

The term "catalyst" in the process according to the invention is preferably understood as meaning a carrier body which comprises a titano (silico) -alumino-phosphate The carrier body can be formed as a bulk extrudate from the molecular sieve or in the form of a carrier body which is provided with a

Composition containing the molecular sieve is coated.

The step of the reaction is preferably carried out in the process according to the invention at a temperature in the range of 200 to 1000 ° C, preferably in the range of 300 to 700 ° C and

particularly preferably carried out at 400 to 600 ° C.

The used in the process according to the invention

Starting compound, namely the heteroatom-containing

Hydrocarbon compound, is preferably a linear, branched or cyclic saturated or unsaturated alcohol or ether, or a nitrogen, sulfur or

Halogenated analogue of alcohol or ether. Here, it is particularly preferred that when the starting compound is an unsaturated heteroatom-containing

Hydrocarbon compound is the product produced, namely the unsaturated hydrocarbon compound, one Compound with more CCn bonds than the

Starting compound.

Examples of the heteroatom-containing hydrocarbon compounds to be used, the following components can be mentioned: methanol, ethanol, n-propanol, iso-propanol, C ₄ -Cio alcohols, methyl ethyl ether, dimethyl ether, diethyl ether, diisopropyl ether, methylmercaptan, methylsufides, methylamines, ethylmercaptan, Diethyl sulfides, diethylamines, ethyl chlorides, formaldehydes, dimethyl carbonates, dimethyl ketone, acetic acid, n-alkyl amines, n-alkyl halides, n-alkyl sulfides having n-alkyl groups having from 3 to 10 carbon atoms, and mixtures thereof. Particularly suitable are methanol,

Dimethyl ether and mixtures thereof, and is very suitable methanol.

It is in the implementation of the invention

Method preferably to an elimination reaction in which, for example, starting from ethanol, a molecule of H ₂ O is cleaved to form a double bond to ethene. It can, however, for example, under reaction of two

Molecules of ethanol with elimination of two molecules of water form 2-butene or a tautomer thereof. Generally

Expressed with elimination of water, a double bond is formed either intra- or intermolecularly.

It is further preferred that the molecular sieve in

according to the invention has a BET surface area in the range of 400 to 850 m ² / g, more preferably 500 to 750 m ² / g, even more preferably 580 to 680 m ² / g. The BET

Surface of the molecular sieve should not be too low, because then no sufficient contact of the reacted

Starting compounds with the catalytically active components is present and thus the reaction is not sufficient Dimensions takes place. Too high a BET surface area brings the

Disadvantage that due to the low density of the material this is no longer sufficiently stable in temperature. The BET surface area is determined by adsorption of nitrogen according to DIN 66132.

Preferably, the titano (silico) -alumino-phosphate has a so-called CHA structure, as is known from the classification of the various topologies of zeolites.

Materials with CHA structure preferably have

Pore openings of about 3.5 Å, which are excellent for the selective implementation of small size due to their size

Molecules, e.g. Methanol to olefins are suitable. It is preferred that the molecular sieve of the process of the invention is a titano-silico-aluminophosphate selected from the group consisting of 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 and TAPSO-56 exists. Particularly preferred are TAPSO-5, TAPSO-11 or

TAPSO-34, since these are a particularly high hydrothermal

Have stability to water. Particularly suitable are TAPSO-5, TAPSO-11 and TAPSO-34 also because of their good

Properties as a catalyst in various processes due to their microporous structure and because they are very good as due to their high adsorption capacity

Adsorbents are suitable. In addition, they also show a low regeneration temperature, as they already adsorbed water or adsorbed other small molecules

Release temperatures between 30 ° C and 90 ° C reversibly.

According to the invention, the use of

microporous titano-silico-aluminophosphates with CHA structure. Particularly preferred is the titano (silico) -alumino-phosphate TAPSO-34 used in the process according to the invention, as is known in the prior art from, for example, EP 161 488 and US Pat. No. 4,684,617. The excellent hydrothermal

Stability of TAPSO-34 as well as the small pore openings predestine TAPSO-34 as a selective catalyst for the conversion of oxygen-containing or heteroatom-containing hydrocarbons to olefins. The titano- (silico) -alumino-phosphate used in the process according to the invention has negative effects due to the exchange of phosphorus atoms by titanium or silicon atoms

Charges that are compensated by cations. In the synthesis of titano (silico) -alumino-phosphates, which has been known for some years from EP 161 488, this exists

Molecular sieves, preferably in the protonated or in the Na ⁺ form, ie the negative charges, which are preferably located inside the framework structure, the cavities, are compensated by H ⁺ or nations. In the inventive method, the molecular sieve but also in a

modified form in which as counterions

Metal cations for compensation of negative charges

preferably present in the cavities. The metal cations preferably present in the interior of the framework structure

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

known, but 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 brought into the titano (silico) -Alumo-Phosphatgerüst, but no homogeneous distribution of

Metal ions present. In liquid ion exchange can In contrast, a homogeneous metal ion distribution in the titano (silico) -alumino-phosphate can be achieved. In addition to the methods mentioned, doping or modification with one or more metal cations can be carried out by aqueous impregnation or the incipient wetness method. This Dotierbzw. Modification methods are known in the art. It is particularly preferred that the doping or modification is carried out by means of one or more metal compounds by aqueous ion exchange.

The molecular sieve modified with the transition metal cation preferably has the following formula:

[(Ti _x Al _y Si _z P _q ) 0 ₂ r ^a [M ⁺ ] _{a / b} , where the symbols and indices used are as follows

Have meanings: x + y + z + q = l; 0.010 <x <0.110; 0.400 <y <0.550; 0 <z <0.090; 0.350 <q <0.500; a = y - q (with the proviso that y is preferably greater than q); M ⁺ represents the cation with the charge b +, where b is an integer greater than or equal to 1, preferably 1, 2, 3 or 4, even more preferably 1, 2 or 3 and most preferably 1 or 2. The number of negative charges a of the molecular sieve results from the excess number of aluminum atoms to the number of phosphorus atoms. Assuming that two oxygen atoms are on each Ti, Al, Si and P atom, these units have the following charges: The unit T1O ₂ and the unit S1O ₂ are electrically neutral, the unit has _two AIO due the trivalent aluminum has a negative charge and the unit PO ₂ is due to the

Pentavalence of phosphorus on a positive charge. It is particularly preferred according to the invention that the number of Aluminum atoms is greater than the number of phosphorus atoms, so that the molecular sieve is negatively charged. This is expressed in the above formula by the subscript a, which represents the difference of the aluminum atoms present minus the phosphorus atoms. This is especially the case because positively charged PC> ₂ ⁺ units by

Charge-neutral T1O ₂ - or SiC> ₂ units are substituted.

In addition to the above-mentioned S1O ₂ , T1O ₂ , A1C> ₂ ^~ and PC> ₂ ⁺ units, which form the framework of the molecular sieve and whose ratio determines the valency of the molecular sieve, the molecular sieve can also have AI and P units which, as such, are formally considered to be charge-neutral,

for example, because C> ₂ ^~ units do not

Occupy coordination sites, but because other units, such as OH ^~ or H ₂ O sit at this point, preferably if they are present in the structure or terminally marginal. This proportion of these units is called the so-called "extraframework" of the molecular sieve.

The molecular sieve used in the method of the present invention preferably has a (Si + Ti) / (Al + P) molar ratio of 0.01 to 0.5 to 1, more preferably 0.02 to 0.4 to 1, even more preferably 0 0.05 to 0.3 to 1, and most preferably 0.07 to 0.2 to 1. Especially with regard to improved catalyst activity and improved

Ethene / propene ratio, the above-mentioned molar ratio of in the range of 0.05 to 0.3 is particularly advantageous. In addition, it is particularly preferred that the molecular sieve used in the process according to the invention contains Si as an essential element in addition to Ti. The Si / Ti ratio 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 1 to 7. The Al / P ratio with respect to all units of the molecular sieve, that is, the framework and extra framework of the titano (silico) alumino-phosphate is preferably in the range of 0.5 to 1.5, stronger

preferably in the range of 0.70 to 1.25. The Al / P ratio only relative to the framework of the titano (silico) -alumino phosphate is preferably in the range of greater than 1 to 1.5, more preferably in the range of 1.05 to 1.25.

After the production of the molecular sieve, this is usually in the form of a powder. These then present as a powder molecular sieves are then either deformed into extrudates, in particular with the aid of oxidic and / or organic binders to Vollextrudaten / honeycomb catalysts deformed or via the intermediate stage of a washcoat on ceramic or metallic carrier body, in particular

applied honeycomb carrier body. The im

Molecular sieve used according to the invention is preferably present as a bulk extrudate or on a carrier body in the form of a coating.

In particular, the bulk extrudates are produced in the form of honeycombs or those coated with the solid extrudate

Carrier bodies are preferably honeycomb-shaped carrier bodies.

Particularly suitable catalysts are spray-dried molded articles with a size of 5 to 100 μm. In addition, both rolled balls or dripping balls with a diameter of 1-10 mm are suitable.

Is the used in the method according to the invention

Catalyst in the form of a Vollextrudats, so includes the bulk extrudate preferably the titano- (silico) -alumino-phosphate and at least one oxidic and / or organic binder. The bulk extrudate is preferably prepared by extruding a composition comprising the titano- (silico) -alumino-phosphate and at least one oxidic and / or organic binder and by spray-drying or granulation. The bulk extrudate is preferably a honeycomb extrudate, as is commonly used in automotive applications, in particular

SCR catalysts is used. In addition to the binders, the said composition may also contain other metal oxides,

Promoters, stabilizers and / or fillers. In this composition, the titano (silico) -alumino-phosphate is preferably in the range of 5 to 95% by weight, more preferably 20 to 80% by weight, based on the whole

Composition before.

If the molecular sieve is present on a carrier body in the form of a coating, the said composition is preferably processed to form a washcoat which is used to coat the coated carrier body

Carrier bodies is suitable. Preferably, such includes

Washcoat 5 to 70 wt .-%, more preferably 10 to 50 wt .-%, particularly preferably 15 to 50 wt .-% of the titano (silico) -alumino-phosphate used in the process according to the invention based on the pure components, namely titanium , Aluminum, silicon, phosphorus and oxygen. The washcoat according to the invention may, in addition to the above-mentioned components of

Composition containing a solvent. The binder of the composition serves when applied to a

Carrier body to bind the molecular sieve. The solvent serves to ensure that both the molecular sieve and the Binder can be applied in a formable form on the catalyst support.

In the method according to the invention are the

Molecular sieve comprising carrier body preferably in a reactor bed, which may be a fluid or fixed bed (as bulk material) of a catalyst component through which the gaseous or liquid heteroatom-containing hydrocarbon compound (starting compound) is passed. Here is the

Starting compound preferably at a space velocity in the range of 0.01 h ¹ to 600 h ^{1 passed} through a reactor bed. The space velocity results from the

Ratios of the volume flow (m ³ / h) of the starting compound to the volume of the reactor bed (m ³ ).

The present invention also relates to the use of a catalyst comprising a titano (silico) -alumino-phosphate in the reaction of a heteroatom-containing

Hydrocarbon compound to an unsaturated

Hydrocarbon compound.

The present invention also relates to the use of a titano (silico) -alumino-phosphate for the preparation of a

A catalyst for the conversion of a heteroatom-containing hydrocarbon compound to an unsaturated one

Hydrocarbon compound.

The present invention also relates to a so-called reducing-elimination catalyst comprising a titano (silico) -alumino-phosphate. Under a reductive

Elimination catalyst is understood inter alia in the present invention, a catalyst as defined above, which is capable of a heteroatom-containing

Hydrocarbon compound with elimination, for example of H ₂ O, alkyl-OH, H ₂ S, alkyl-SH, NH ₃ or allyl-NH ₂ to reduce an unsaturated hydrocarbon compound.

All mentioned in the process according to the invention of the molecular sieve also apply to the invention

Uses.

The present invention will now be described with reference to the following

Non-limiting examples are illustrated:

Examples: Example 1: 100.15 parts by weight of deionized water and 88.6

Parts by weight of hydrargillite (aluminum hydroxide SH10, from

Aluminum Oxid Stade GmbH, Germany available) were mixed. To the resulting mixture was added 132.03 parts by weight of phosphoric acid (85%) and 240.9 parts by weight of TEAOH (35% in water) and then 33.5 parts by weight of silica sol (Köstrosol 1030, 30% silica, available from CWK Chemiewerk Bad

Köstriz, Germany) and 4.87 parts by weight of silicon

doped titanium dioxide (Ti0 ₂ 545 S, Evonik, Germany) was added, so that a synthesis gel mixture having the following molar composition was obtained:

A1 ₂ 0 ₃ : P ₂ 0 ₅ : 0, 3 SiO ₂ : 0, 1 Ti0 ₂ : 1 TEAOH: 35 H ₂ 0

The synthesis gel mixture having the above composition was transferred to a 0.5 liter stainless steel autoclave made by Juchheim GmbH. The autoclave was stirred and heated to 180 ° C, this temperature being maintained for 68 hours. After cooling, the resulting product was filtered off, washed with deionized water and heated in an oven at 100 ° C dried. An X-ray diffractogram of the resulting product showed that the product was pure TiAPSO-34. The elemental analysis showed a composition of 1.5% Ti, 2.8% Si, 18.4% Al and 17.5% P, giving a

Stoichiometry of Ti ₀ , 023S10, 073AI0, 494P0, 410 corresponds. According to an SEM (Scanning Electron Microscope) analysis of the product, its crystal size was in the range of 0.5 to 2 μm. Subsequently, the obtained product was calcined at 550 ° C for 1 hour. Example 2:

453.3 parts by weight of deionized water and 232.5

Parts by weight of phosphoric acid (85%) were mixed. To the resulting mixture were added 428.5 parts by weight of aluminum isopropoxide (Sigma Aldrich), then 90.89 parts by weight of Ludox LS 30 (30% silica, Sigma Aldrich) and 129.04

Titanium isopropoxide ((Sigma Aldrich)) was mixed in until a homogeneous mixture formed, and 466.75 parts by weight of TEAOH (35% in water) were added to obtain a synthesis gel mixture having the following molar composition:

1 A1 ₂ 0 _3: 1 P ₂ O _5: 0.3 SiO _2: 0.3 Ti0 _2: l, l TEAOH: 50 H ₂ 0 The Synthesegelgemisch having the above composition was transferred to a 2 1 stainless steel autoclave from Buchi. The autoclave was stirred and heated to 200 ° C, this temperature being held for 312 hours. After cooling, the product obtained was filtered off, washed with deionized water and dried in an oven at 100 ° C. An X-ray diffractogram of the resulting product showed that the product was pure TiAPSO-34. The elemental analysis showed a composition of 5.37% Ti, 7.50% Si, 12.37% Al and 14.94% P, giving a Stoichiometry of Ti ₀ , oss S io, 203AI0, 3 ₄ 7P0, 365 corresponds. According to an SEM (Scanning Electron Microscope) analysis of the product, its crystal size was in the range of 0.5 to 2 μm. Subsequently, the obtained product was calcined at 550 ° C for 1 hour.

Example 3: catalytic test results:

For the catalytic test, 10 mg each of a sample from Examples 1 and 2 were taken and subjected to an oxygenate-to-olefins process in a fixed-bed microreactor. This was

Methanol was chosen as the starting material to mainly

to obtain olefin-containing, carbon-based products.

Methanol was passed neat with a vapor pressure of 2.5 bar at a space velocity per hour of 100 h ¹ through a stainless steel reactor at 450 ° C. Before methanol was added, the catalyst sample was activated at 550 ° C for 30 minutes in a nitrogen stream. The product stream was analyzed online by means of a gas chromatograph equipped with an FID detector. The results of the analysis are summarized in Tables 1 and 2.

Table 1

Table 2

Claims

claims

Process for the preparation of unsaturated

Hydrocarbon compounds by reacting a

Heteroatom-containing hydrocarbon compound to an unsaturated hydrocarbon compound in the presence of a catalyst comprising a titano-alumino-phosphate or a titano-silico-alumino-phosphate.

A process according to claim 1, wherein the reaction is carried out at a temperature in the range of 200 to 1000 ° C.

A process according to claim 1 or 2, wherein the heteroatom-containing hydrocarbon compound is a linear, branched or cyclic saturated or unsaturated alcohol or a nitrogen, sulfur or halogen containing analog of the alcohol. 4. The method according to any one of claims 1 to 3, wherein the

Titano alumino-phosphate or the titano-silico-alumino-phosphate has a CHA structure.

The process of claim 4 wherein the titano-silico-aluminophosphate is TAPSO-34.

6. The method according to any one of claims 1 to 5, wherein the

Titano-Alumo-Phosphate or Titano-Silico-Alumo-Phosphate has a (Si + Ti) / (A1 + P) molar ratio in the range of 0.01 to 0.5,

7. The method according to any one of claims 1 to 6, wherein the

Titano-alumino-phosphate or the titano-silico-aluminophosphate has a Si / Ti molar ratio in the range of 0 to 9 and / or an Al / P ratio in the range of greater than 1 to 1.5. Method according to one of claims 1 to 7, wherein the titano-alumino-phosphate or the titano-silico-alumino-phosphate is formed as Vollextrudat in the form of a shaped body or in the form of a coating on a carrier body, wherein the shaped body or the coated carrier body in a reactor bed is present.

A process according to claim 8, wherein the step of reacting in the reactor bed is carried out at a space velocity in the range of 0.01 hT ¹ to 600 hT ¹ .

Use of a catalyst comprising a titano-alumino phosphate or a titano-silico-aluminophosphate in the reaction of a heteroatom-containing

Hydrocarbon compound to an unsaturated

Hydrocarbon compound.

11. Use of titano-alumino-phosphate or titano-silico-alumino-phosphate for the preparation of a catalyst for the

Reaction of a heteroatom-containing

Hydrocarbon compound to an unsaturated

Hydrocarbon compound. 12. A reductive elimination catalyst comprising a titano-alumino-phosphate or a titano-silico-alumino-phosphate.