DE102010055678A1 - Process for the preparation of unsaturated hydrocarbon compounds - Google Patents

Abstract

The present invention relates to a process for producing unsaturated hydrocarbon compounds by converting a heteroatom-containing hydrocarbon compound to an unsaturated hydrocarbon compound in the presence of a catalyst comprising titano (silico) aluminophosphate.

Description

The present invention relates to 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. Further, 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 only listed under the collective name Zeolithe.

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) are understood to mean molecular sieves obtained from aluminophosphates (general formula (AlPO ₄ -n)) by isomorphous exchange of phosphorus with silicon, and the general formula (Si _x Al _y P _z ) O 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where x + y + z = 1 and the species has negative charges, the number of which depends on how many phosphorus atoms have been replaced by silicon atoms, or the number of which depends on the excess of aluminum atoms with respect to the phosphorus atoms ,

Structures of this group are classified according to the International Union of Pure and Applied Chemistry (IUPAC) according to the Structure Commission of the International Zeolite Association because of their pore size. They 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 used in a desired ratio, preferably such that the sum of the Si and P values Component is stoichiometric to the Al component. The crystallization of the obtained silico-aluminophosphates (SAPOs) is achieved by adding structure-directing templates, crystallization nuclei or elements ( EP 103 117 A1 . US 4,440,871 . US 7,316,727 ).

The framework structure of the SAPOs is built up of regular, three-dimensional spatial networks with characteristic pores and channels, which can be linked together in one, two or three dimensions. The structures mentioned above are formed by corner-sharing tetrahedral building blocks (AlO ₄ , SiO ₄ , PO ₄ ), each consisting of four times 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 do not require any counterions in cavities for charge compensation. Thus, catalytically active metal ions can not be effectively incorporated into these cavities by ionic bonding. Therefore, these aluminophosphates are poorly suited as molecular sieves in catalysts for producing unsaturated hydrocarbon compounds from 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 compensate, and thus the maximum possible loading of the compounds with positively charged cations, e.g. For example, hydrogen or metal ions. By incorporating the cations, the acidic catalytic properties of the silico-aluminophosphates are determined, and can be used by targeted ion exchange in terms of their activity and selectivity as catalyst components. 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. These silico-aluminophosphates possess but the disadvantage that they are thermally relatively unstable in the aqueous phase. So amorphizes z. B. SAPO-34 even at low temperatures - including in the preparation of the catalyst in aqueous phases. Therefore, silico-alumino-phosphates are only limited use as molecular sieves in catalysts for the preparation of unsaturated hydrocarbon compounds, since in the production of these a great stability to water at moderate temperatures is necessary, since 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 undesirably 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 art are known as suitable catalyst components for the conversion of oxygen or heteroatom-containing hydrocarbons to olefins. Particularly SAPO-34 was used because it is characterized by its hydrothermal stability, which has proven in the aqueous atmosphere during the conversion of oxygen-containing hydrocarbons to olefins at about 450 ° C. However, in the catalytic conversion of oxygen or heteroatom-containing hydrocarbons to olefins no such high temperature is 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 severely damage the structure of the SAPO used. Ie. 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 already known during the formulation of the catalyst z. B. in the washcoat preparation or in the production of wet masses for extrusion heavily damaged.

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 producing unsaturated hydrocarbon compounds by reacting a heteroatom-containing hydrocarbon compound to form 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. Due to its high phase purity and its high hydrothermal stability, the titano- (silico) -alumino-phosphate according to the invention is outstandingly suitable as a molecular sieve for a catalyst in the conversion of heteroatom-containing hydrocarbon compounds to olefins. Since in the reaction of heteroatom-containing hydrocarbons, in particular oxygen-containing hydrocarbons, such as aliphatic alcohols, water is obtained as a by-product in large quantities, the hydrothermally stable titano (silico) -alumino-phosphates are particularly suitable as molecular sieves for these catalysts.

Like the abovementioned SAPOs, the titano- (silico) -alumino-phosphates in the context of the present invention are crystalline substances with a spatial network structure consisting of TiO ₄ / (SiO ₄ ) / AlO ₄ / PO ₄ tetrahedra and owing to common oxygen atoms linked to a regular three-dimensional network. All these tetrahedral units together form the so-called "framework". Further units that do not consist of the tetrahedral units of the backbone are called "extra frameworks".

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 that are normally wetted with water molecules and additional framework cations that can be exchanged. In the case of the so-called aluminophosphates, at least in the "framework" of the titano (silico) -alumino-phosphate, an aluminum atom is replaced by one phosphorus atom, so that the charges balance each other. 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 is determined by the P / Al / Ti / (Si) ratio, which is the largest proportion of the catalytic, in addition to the parameters in the preparation, ie use or type of template, pH, pressure, temperature, presence of seed crystals Character of a titano-alumino-phosphate or titano (silico) -alumino-phosphate. By 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. The negative charges are compensated by the incorporation of cations into the pores of the zeolite material. 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 are distinguished, as in the prior art, mainly according to the geometry of the cavities formed by the rigid network of the TiO ₄ / AlO ₄ / (SiO ₄ ) / PO ₄ tetrahedra become. The entrances to the cavities are formed by 8, 10 or 12 ring atoms with respect to the metal atoms which form the entrance opening, the skilled person speaking here of narrow, medium and wide-pore structures. According to the invention, narrow-pore structures are preferred here. These titano- (silico) -alumino-phosphates may have a uniform structure structure, e.g. B. show a VFI or AET topology with linear channels, but. Other topologies are conceivable in which connect larger cavities behind the pore openings. Titano- (silico) -alumino-phosphates having openings of eight tetrahedral atoms, ie narrow-pore materials, are preferred according to the invention. 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 preparation of unsaturated hydrocarbon compounds. The titano- (silico) -alumino-phosphates are excellently suitable as molecular sieves for catalysts in the preparation of unsaturated hydrocarbon compounds from heteroatom-containing hydrocarbon compounds because of their high phase purity, their temperature stability and their high possible loading fraction with transition metal ions.

The term "catalyst" in the process according to the invention is preferably understood to mean a support 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 coated with a composition containing the molecular sieve.

The step of reacting is preferably carried out in the process according to the invention at a temperature in the range from 200 to 1000 ° C., preferably in the range from 300 to 700 ° C. and particularly preferably at 400 to 600 ° C.

The starting compound used in the process according to the invention, namely the heteroatom-containing hydrocarbon compound, is preferably a linear, branched or cyclic saturated or unsaturated alcohol or ether, or a nitrogen, sulfur or halogen-containing analogue of the alcohol or ether. Here, it is particularly preferred that when the starting compound is an unsaturated heteroatom-containing hydrocarbon compound, the product produced, namely the unsaturated hydrocarbon compound, is a compound having more C-C-π bonds than the starting compound.

The following components may be mentioned as examples of the heteroatom-containing hydrocarbon compounds to be used: methanol, ethanol, n-propanol, isopropanol, C ₄ -C ₁₀ -alcohols, methylethyl ether, dimethyl ether, diethyl ether, diisopropyl ether, methylmercaptan, methylsufide, methylamines, ethylmercaptan , Diethyl sulfides, diethylamines, ethyl chlorides, formaldehydes, dimethyl carbonates, dimethyl ketone, acetic acid, n-alkyl amines, n-alkyl halides, n-alkyl sulfides with n-alkyl groups having 3 to 10 carbon atoms, and mixtures thereof. Particularly suitable are methanol, dimethyl ether and mixtures thereof, and is very suitable methanol.

The reaction in the process according to the invention is preferably an elimination reaction in which, for example, starting from ethanol, one molecule of H ₂ O is split off to form a double bond to ethene. However, it is also possible, for example, to form 2-butene or a tautomer thereof by reacting two molecules of ethanol with elimination of two molecules of water. Generally speaking, dehydration forms a double bond either intra- or intermolecularly.

It is further preferred for the molecular sieve in the process according to the invention to have a BET surface area in the range from 400 to 850 m ² / g, particularly preferably 500 to 750 m ² / g, even more preferably 580 to 680 m ² / g. The BET surface area of the molecular sieve should not be too low, since then sufficient contact of the starting compounds to be reacted with the catalytically active components is present and thus the reaction does not take place sufficiently. Too high a BET surface area has the disadvantage that due to the low density of the material, it is no longer sufficiently stable in temperature. The BET surface area is reduced by adsorption of nitrogen DIN 66132 certainly.

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 molecules such. As methanol to olefins are suitable.

It is preferred that the molecular sieve of the process of the invention is a titano-silico-alumino-phosphate 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 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 various processes due to their microporous structure and because they are very well suited as an adsorbent 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. According to the invention, the use of microporous titano-silico-aluminophosphates with CHA structure is particularly suitable.

Particularly preferred is the used in the process according to the invention titano (silico) -alumino-phosphate TAPSO-34, as in the prior art, for example, from EP 161 488 and US 4,684,617 is known. 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 charges due to the exchange of phosphorus atoms by titanium or silicon atoms, which are compensated by cations. In the synthesis of titano (silico) -alumino-phosphates, which has been used for several years from the EP 161 488 is known, the molecular sieve preferably exists in the protonated or in the Na ⁺ form, ie the negative charges, which are preferably in the interior of the framework structure, the cavities are compensated by H ⁺ - or Na ⁺ ions. In the process according to the invention, however, the molecular sieve can also be present in a modified form in which metal cations are present as counterions, preferably in the cavities, for compensating the negative charges. The metal cations preferably present in the interior of the framework structure impart the catalytic properties to the structure. 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 are known, but these are too expensive for technical processes. A disadvantage of the current state of the art is that during solid ion exchange, although a defined amount of metal ions can be brought into the titano (silico) -alumino-phosphate skeleton, but there is no homogeneous distribution of the metal ions. In the case of liquid ion exchange, by 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. These doping or modifying 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 ) O ₂ ] ^-a [M ^{b +} ] _{a / b} , where the symbols and indices used have the following meanings: x + y + z + q = 1; 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 ^{b +} 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 each of the Ti, Al, Si and P atoms has two oxygen atoms, these units would have the following charges: The unit TiO ₂ and the unit SiO ₂ are charge neutral, the unit AlO ₂ is due to the trivalent aluminum has a negative charge and the unit PO ₂ has a positive charge due to the pentavalentity of phosphorus. 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 overall. 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 PO ₂ ⁺ units are substituted by charge-neutral TiO ₂ or SiO ₂ units.

In addition to the aforementioned SiO ₂ , TiO ₂ , AlO ₂ and PO ₂ ⁺ units, which form the framework of the molecular sieve and whose ratio determines the valency of the molecular sieve, the molecular sieve may also contain Al and P units which be viewed as such formally charge neutral are, for example, because it is not O ₂ ^- units occupying the coordination sites, but because other units, such as OH ^- or H ₂ O sit at this point, preferably when this is present terminally or marginal in the structure are. This proportion of these units is called the so-called "extraframework" of the molecular sieve.

The molecular sieve used in the process 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.

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, d. H. that of the framework and extra framework of the titano (silico) alumino-phosphate is preferably in the range of 0.5 to 1.5, more preferably in the range of 0.70 to 1.25. The Al / P ratio only with respect 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 formed into extrudates, in particular with the aid of oxidic and / or organic binders to Vollextrudaten / honeycomb catalysts deformed or applied via the intermediate stage of a washcoat on ceramic or metallic carrier body, in particular honeycomb-shaped carrier body. The molecular sieve used in the process 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 the carrier bodies coated with the bulk extrudate 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.

If the catalyst used in the process according to the invention is in the form of a bulk extrudate, the bulk extrudate preferably comprises 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, particularly in SCR catalysts. In addition to the binders, said composition may also contain other metal oxides, promoters, stabilizers and / or fillers. In this composition, the titano- (silico) -alumino-phosphate is preferably present in the range of 5 to 95% by weight, more preferably 20 to 80% by weight, based on the total composition.

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 suitable for coating carrier bodies in order to produce the coated carrier body. Such a washcoat preferably comprises from 5 to 70% by weight, more preferably from 10 to 50% by weight, particularly preferably from 15 to 50% by weight, of the titano- (silico) -alumino-phosphate used in the process according to the invention, based on the pure fractions namely titanium, aluminum, silicon, phosphorus and oxygen. The washcoat according to the invention may contain a solvent in addition to the above-mentioned components of the composition. The binder of the composition serves to bind the molecular sieve when applied to a carrier body. The solvent serves to enable both the molecular sieve and the binder to be applied in a coatable form to the catalyst support.

In the process according to the invention, the carrier body comprising the molecular sieve is preferably present 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, the starting compound is preferably passed through a reactor bed at a space velocity in the range of 0.01 h ^-1 to 600 h ^-1 . The space velocity results from the quotient 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 catalyst for the reaction of a heteroatom-containing hydrocarbon compound into an unsaturated hydrocarbon compound.

The present invention also relates to a so-called reducing-elimination catalyst comprising a titano (silico) -alumino-phosphate. By a reducing-elimination catalyst is meant inter alia in the present invention a catalyst as defined above which is capable of a heteroatom-containing hydrocarbon compound with elimination of, for example, H ₂ O, alkyl-OH, H ₂ S, alkyl-SH, NH ₃ or Alykl-NH ₂ to reduce an unsaturated hydrocarbon compound.

All of the features of the molecular sieve mentioned in the method according to the invention also apply to the uses according to the invention.

The present invention will now be illustrated by the following nonlimiting examples:

Examples:

Example 1:

100.15 parts by weight of deionized water and 88.6 parts by weight of hydrargillite (aluminum hydroxide SH10, available from Aluminum Oxide Stade GmbH, Germany) 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 (TiO ₂ 545 S, Evonik, Germany), so that a synthesis gel mixture having the following molar composition was obtained: Al ₂ O ₃ : P ₂ O ₅ : 0.3 SiO ₂ : 0.1 Ti ₂ : 1 TEAOH: 35 H ₂ O

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 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 1.5 Ti, 2.8 Si, 18.4 Al and 17.5 P, which corresponds to a stoichiometry of Ti _0.023 Si _0.073 Al _0.494 P _0.410 . 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:

For the catalytic test, 10 mg of the sample of Example 1 were taken and subjected to an oxygenateto-olefin process in a fixed-bed microreactor. For this purpose, methanol was chosen as the starting material to obtain mainly olefin-containing, carbon-based products. Methanol was passed undiluted at 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 stream of nitrogen. 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 Table 1. Table 1

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• EP 0585683 [0004]
• EP 103117 A1 [0006]
• US 4440871 [0006]
• US 7316727 [0006]
• EP 161488 [0027, 0028]
• US 4684617 [0027]

Cited non-patent literature

• DIN 66132 [0024]

Claims (12)

A process for producing 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. A process according to claim 1, wherein the reaction is carried out at a temperature in the range of 200 to 1000 ° C. The process of 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. A method according to any one of claims 1 to 3, wherein the molecular sieve has a CHA structure. The process of claim 4 wherein the titano (silico) -alumino-phosphate is TAPSO-34. A process according to any one of claims 1 to 5, wherein the titano (silico) -alumino-phosphate has a (Si + Ti) / (Al + P) molar ratio in the range of 0.01 to 0.5, A process according to any one of claims 1 to 6, wherein the titano (silico) alumino-phosphate 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 having. Method according to one of claims 1 to 7, wherein the titano (silico) -alumino-phosphate is formed as a bulk extrudate 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 is present in a reactor bed. The process of claim 8, wherein the step of reacting in the reactor bed is performed at a space velocity in the range of 0.01 hr ^-1 to 600 hr ^-1 . Use of a catalyst comprising a titano- (silico) -alumino-phosphate in the reaction of a heteroatom-containing hydrocarbon compound to an unsaturated hydrocarbon compound. Use of titano- (silico) -alumino-phosphate for the preparation of a catalyst for the reaction of a heteroatom-containing hydrocarbon compound to an unsaturated hydrocarbon compound. Reductive elimination catalyst comprising a titano (silico) alumino-phosphate.