EP3083050A1 - Catalyst containing phosphorus for converting oxygenates into olefins - Google Patents

Catalyst containing phosphorus for converting oxygenates into olefins

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Publication number
EP3083050A1
EP3083050A1 EP20140809025 EP14809025A EP3083050A1 EP 3083050 A1 EP3083050 A1 EP 3083050A1 EP 20140809025 EP20140809025 EP 20140809025 EP 14809025 A EP14809025 A EP 14809025A EP 3083050 A1 EP3083050 A1 EP 3083050A1
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EP
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Patent type
Prior art keywords
catalyst
phosphorus
preferably
step
wt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP20140809025
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German (de)
French (fr)
Inventor
Markus Tonigold
Manfred Frauenrath
Goetz Burgfels
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Clariant Produkte (Deutschland) GmbH
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Clariant Produkte (Deutschland) GmbH
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    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7023EUO-type, e.g. EU-1, TPZ-3 or ZSM-50
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J29/70Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7034MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3
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    • B01J29/70Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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    • B01J37/28Phosphorising
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    • C01B39/02Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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    • C01B39/36Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C01B39/38Type ZSM-5
    • C01B39/40Type ZSM-5 using at least one organic template directing agent
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    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
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    • B01J2229/10After treatment, characterised by the effect to be obtained
    • B01J2229/18After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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    • B01J2229/00Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30After treatment, characterised by the means used
    • B01J2229/36Steaming
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01J29/00Catalysts comprising molecular sieves
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    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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    • B01J35/1004Surface area
    • B01J35/1019100-500 m2/g
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    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • C07C2527/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/14Phosphorus; Compounds thereof
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    • C07C2529/00Catalysts comprising molecular sieves
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    • C07C2529/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11

Abstract

The invention relates to a novel process for preparing a catalyst containing phosphorus, wherein the catalyst is steamed. Also disclosed are the catalyst obtainable by said process as well as the use thereof in a process for preparing olefins from oxygenates. The catalyst is usually steamed before being modified with a compound containing phosphorus.

Description

Phosphorhaitiger catalyst for conversion of oxygenates to

olefins

The present invention relates to a process for the preparation of phosphorus-containing zeolite-based catalysts, the catalysts prepared by this process and their use in a process for conversion of oxygenates to olefins. The invention particularly relates to the conversion of methanol or dimethyl ether to olefins (CMO) method. In particular, the invention relates to the conversion of methanol to propylene.

Background of the Invention

The catalyzed conversion of oxygenates to olefins,

in particular of methanol to propylene, is an attractive value-added by the processing of the starting materials.

Zeolite-based catalysts for the conversion of oxygenates to olefins are described for example in EP 0448000 Al and EP 1424128 Al.

A general problem with the use of zeolite-based catalysts in the conversion of oxygenates to olefins is the tendency of the catalysts during the proceedings

losing catalytic activity. This is effected on the one hand by the increasing coking of the surfaces and pores. This results from the fact that during the conversion of

Oxygenates to olefins resulting by-products

condense longer chain or cyclic species, and may be deposited on the catalyst, whereby the catalytically active sites are masked. Therefore, after a certain running time, a so-called regeneration is necessary, in which the

carbonaceous deposits are removed from the catalyst under mild conditions. On the other hand cause

Reaction conditions, a progressive dealumination of the zeolite material. This is caused by the water vapor, for example, when using

water-feed and / or produced during the conversion reaction of oxygenates to olefins. The dealumination has the consequence that gradually decreases according to the number of catalytically active sites, the catalyst is irreversibly deactivated and decreases the rate of conversion of the oxygenate used.

To influence the activity, stability, or selectivity of the prior art describes the modification of

Zeolite-based catalysts with phosphorus at different times of the manufacturing process and the use of detergents or steam treatments.

In WO 2012/123558 and WO 2012/123556 the preparation of a phosphorus-modified zeolite-based catalyst by coating a phosphorus compound is described on an extruded and calcined zeolites. WO 2012/123557 describes the preparation of a phosphorus-containing catalyst

Zeolite by extrusion of a phosphorus-modified zeolites followed by Abschlusskalzinierung. These

Preparation methods include no steam treatment, however, the catalysts obtained must be subjected before being used i an MTO process to a water vapor treatment.

The US 4,356,338 describes a method of reducing carbon deposits and extension of the duration of a zeolitic catalyst in which the steam treatment and / or a treatment with phosphorus-containing compounds is subjected. This catalyst is characterized by a lower coking tendency in the use as a catalyst for the aromatization of 1-heptene out, at the same time can be observed a decrease in the output yields. The catalyst has phosphorus contents 2-15 wt .-% on.

WO 2011/044037 describes a zeolite-based catalyst which is prepared by treating a zeolite with a phosphorus compound. The treated with phosphorus zeolite is mixed with a binder, extruded,

calcined and contacted with liquid water, a proportion of phosphorus is removed from the phosphorus-treated zeolite. The catalyst described in WO 2011/044037 is by prior treatment with steam in the alkylation process of aromatics used.

EP 2348004 Al describes a method for preparing a phosphorus modified zeolite-based catalyst and the use of the catalyst in a MTO process. Here is reduced by steam treatment of the aluminum content of a ZSM-5 zeolite. The catalyst is then by applying phosphorus to the zeolite and then mixing the phosphorus modified zeolite with one or more

Binders, alkaline earth, rare earth, clays and shaping additives prepared.

WO 2009/156434 describes a process for preparing lower olefins by providing an XTO reaction zone, an OC reaction zone and a catalyst regeneration zone using a phosphorus-modified zeolite-based catalyst. Prior to the application of phosphor with a solution of a zeolite at a temperature of 400 ° C to 870 ° C for 0.01 to 200 is subjected h a steam treatment, optionally mixed with a binder and a part of the aluminum is removed by leaching with an aqueous acid solution ,

WO 2007/076088 relates to a method for preparing a phosphorus modified zeolite-based catalyst and the use of the catalyst in a Toluolmethylierungsverfahren. The zeolite is modified with phosphorus and then bound with an inorganic oxide binder which has been treated with a mineral acid.¬ process before use in the Toluolmethylierungs the catalyst less treated with steam at a temperature of 300 ° C or. The major disadvantage of known, not

phosphorus-modified catalysts for the conversion of

Oxygenates such as methanol or dimethyl ether into lower olefins and particularly the conversion of methanol to propylene is further deactivation by coking within a cycle and the dealumination of the catalysts due to the presence of water during the catalytic conversion over several cycles. Although evident from the use of phosphorus-modified catalysts is that although the modification causes an increase in the methanol conversion rate, but the existing manufacturing methods other hand, lead to a (depending on the modification methods, and phosphorus content is more or less drastically precipitated) adversely reduced

Propylene yield or Propylenselektivitat. but a decreased Propylenselektivitat reduces the efficiency of the process.

Already with the known processes for conversion of methanol to propylene using non-phosphorus-modified

Catalysts propylene selectivities that can still be optimized. In general, the Propylenselektivitat takes in the conversion of oxygenates, such as methanol or dimethyl ether into lower olefins, especially of methanol to propylene, with increasing temperature. On the other hand, however, the deactivation by coking and dealumination increases dramatically in processes for the conversion of oxygenates to olefins with increasing temperature. An increase in selectivity by increasing the temperature in the reactor in the conversion of oxygenates such as

Methanol or dimethyl ether to olefins is therefore desirable, if the known disadvantages to the performance of the catalyst can be overcome.

From the prior art it is known that phosphorus modifications zeolite-based catalysts can prolong their lifespan. The term "lifetime" in this context, tests on manufactured according to the prior art modified catalysts is the duration of the catalyzed conversion to hydrocarbons by the same conversion is achieved, for example, not less than 95%, to understand. Show that

Phosphorus modifications shaped extrudates under relevant

Process conditions (for example, addition of water, for example in

Weight ratio of water: methanol 2: 1) detrimental to the

can particularly on the selective release of propylene, impact olefin. The cumulative total propylene yield obtained through a cycle can be obtained by

Temperature increase will not increase maximum because either the drastic shortening of life in the event

phosphorus-free catalysts, or the reduction of

in the case of phosphorus-modified catalysts affect propylene selectivity disadvantageous. Thus, it is not possible with the catalysts of the prior art to achieve the process of conversion of oxygenates, such as methanol or dimethyl ether to olefins by increasing the temperature a maximum increase in olefin yield.

OBJECT OF THE INVENTION

An object of the present invention is to provide a

provide manufacturing method of a catalyst, the increased methanol conversion rate without lowering the

having selectivity for propylene. In particular, should the

Catalyst increased olefin yield at least the same service life by increasing the temperature in the process of

allow conversion of oxygenates, such as methanol or dimethyl ether to lower olefins, ie have an increased resistance to coking and dealumination.

Another object of the invention is to provide a simplified method for producing a catalyst, in the further process steps, such as subsequent washing after applying a phosphorus-containing compound, a repeated modification with a phosphorus containing compound in a later process step or an additional treatment with acid to reduce the aluminum content dispensed after the steam treatment. Another object of the invention is therefore also a

provide methods comprising the preparation of a

Catalyst allowed, which directly without time-consuming and cost-intensive steam treatment prior to the catalytic process by traveler

Conversion reaction can be used.

These objects are achieved by the inventive method and the catalyst thus obtainable.

Summary of the Invention

The invention relates to a process for preparing a phosphorus-containing catalyst comprising the steps of:

(A) extruding a mixture comprising a zeolite and a binder,

(B) calcining the step (a) extrudate,

(C) treating the product obtained in step (b) the calcined extrudate with water vapor,

(D) applying a phosphorus-containing compound to the treated with water vapor extrudate from step (c), and

(E) calcining the phosphorus modified extrudate from step (d),

wherein the weight percentage of phosphorus in the after step (e) the obtained catalyst from 0.8 to 2.5 wt .-%, preferably from 1.0 to 1.8 wt .-%, and even more preferably from about 1.4. - is related%, based on the total weight of the catalyst.

It has surprisingly been found that the catalysts obtained with the inventive method in the production of lower olefins from oxygenates, particularly from methanol or dimethyl ether, an improved conversion rate of oxygenate and an increased service life for the same selectivity,

have, in particular propylene. Especially at elevated process temperature, the catalyst enables by its increased resistance to coking and dealumination an increase in propylene yield at least the same service life as compared to a non-phosphorus-modified catalyst.

The invention therefore also relates to a according to this

The method of catalyst available, the use of the

Catalyst for the conversion of oxygenates, such as methanol or dimethyl ether to olefins, especially of methanol to propylene and to a process for the preparation of lower olefins from oxygenates, such as methanol or dimethyl ether, wherein a feed gas, preferably comprising methanol, dimethyl ether or a mixture thereof, is passed over the catalyst becomes. The catalyst of the invention is typically in a isothermal or

adiabatic fixed bed reactor used.

Brief Description of Drawings

Figure 1 shows the conversion of methanol to propylene in

0 reference catalyst at 450 ° C and according to the invention

Catalyst 1 at 475 ° C. Cat. 0: methanol conversion ■,

Propylene yield □; Cat. 1: ♦ methanol conversion, propylene yield 0. steam treatment in each case for 48 h.

Figure 2 shows the conversion of methanol to propylene in

0 reference catalyst and comparative catalyst 2 at each 450 ° C. Cat. 0: methanol conversion ■, propylene yield □; Cat. 2:

Methanol conversion ♦, propylene yield 0. steam treatment in each case for 48 h.

Figure 3 shows the conversion of methanol to propylene to the Comparative Catalysts 3 and 4 and reference catalyst at 0 to 450 ° C, respectively. Cat. 3: Methanol conversion propylene yield Δ;

Cat 4: methanol conversion ·, propylene yield o;. Kat 0th:

Methanol conversion ■, □ propylene yield. Steam treatment in each case for 24 h.

Figure 4 shows the conversion of methanol to propylene in

Reference catalyst 0 and of inventive catalyst 1 at 450 ° C, respectively. Cat. 0: methanol conversion ■, propylene yield □; Cat. 1: ♦ methanol conversion, propylene yield 0. steam treatment in each case for 48 h.

Figure 5 shows the conversion of methanol to propylene in

Reference catalyst 0 and of inventive catalyst 1 at 475 ° C, respectively. Cat. 0: methanol conversion ■, propylene yield □;

Cat. 1: ♦ methanol conversion, propylene yield 0. steam treatment in each case for 48 h.

Figure 6 shows the conversion of methanol to propylene in

Reference catalyst 0 and of inventive catalyst 6 in each case at 450 ° C. Cat. 0: methanol conversion ■, propylene yield □;

Cat. 6: ♦ methanol conversion, propylene yield 0. steam treatment in each case for 24 h.

Figure 7 shows the dependence of the yield of propylene from the

Phosphorus content of the catalyst for the novel

Catalysts 1 and 7 to 10 and for the comparative catalysts 13 to 16.

Detailed Description of the Invention

The invention relates to a process for preparing a phosphorus-containing catalyst comprising the steps of:

(A) extruding a mixture comprising a zeolite and a binder,

(B) calcining the of step (a) extrudate,

(C) treating the obtained in step (b) the calcined extrudate with water vapor,

(D) applying a phosphorus-containing compound to the treated with water vapor extrudate from step (c), and

(E) calcining the phosphorus modified extrudate from step (d)

wherein the weight proportion of phosphorus obtained in the after step (e) catalyst from 0.8 to 2.5 wt .-%, preferably from 1.0 to 1.8 wt .-%, and more preferably about 1.4 parts by weight % by weight based on the total weight of the catalyst.

In a preferred embodiment of the zeolite in step (a) used has a phosphorus content of 0 wt .-% to 0.01 wt .-%, preferably from 0 wt .-% to 0.001 wt .-% to. It is particularly preferred that the zeolite in step (a) used, under the limit of detection, is phosphate-free.

It has surprisingly been found that contrary to the teaching of the prior art, the washing of the catalyst by

Phosphorus modification does not improve the Propylenselektivitat or life. In the inventive catalyst rather a negative effect on the life was determined by washing after modification.

Without wishing to be bound by the following theory, the unmodified propylene selectivity of the catalyst of the invention explained by the supposed influence of

Preparation steps on the acidity of the catalyst obtained. The acidity of a (non phosphorus-modified) zeolite can be lower by steam treatment. As in Lago et. al. New Developments in Zeolite Science and Technology, editors

Y.Murakami, A.Iijima, and JW Ward, Elsevier, Tokyo, 1986, pp 677 et seq., Takes the activity of the remaining acid centers in the conversion of oxygenates to olefins to this. The zeolite thus obtained is distinguished from a non-steamed zeolites, both through improved hydrothermal stability as well as by increased

Propylene selectivity.

From the prior art it is known that a

Phosphorus modification may increase the hydrothermal stability of a zeolite. If the phosphorus modification to the zeolite prior to steaming, so a stabilization of the acidic centers on the interaction with the available phosphorus-containing compounds should be carried out so that the above-described effect of the steam treatment compared to non-phosphorus-containing zeolites, losing effectiveness. If the steam treatment according to the invention carried out with a phosphorus-containing compound prior to modification, the steam treatment is effective in effect, and the subsequent phosphorus modification protects the previously modified to steam treatment centers and contributes to the further increase in stability without loss of selectivity (by the

otherwise less efficient steam treatment) in.

In addition, depending on other phosphorus-containing compounds or a different distribution between the phosphorus-containing compounds by treatment of the catalyst (eg. B. isolated mono-phosphate, oligo-phosphates) may probably arise, with consequent changes in the interaction between the phosphorus-containing compounds and the acidic centers of

Zeolites, but also between the phosphorus-containing compounds and the acidic centers of the binder.

In a preferred embodiment of the present invention (steps (a) to (e) comprehensive) process takes place

Treatment with steam only in step (c). This means that between the extrusion of the zeolite and binder

comprising mixture in step (a) and calcining the (in step (a) obtained) extrudate in step (b) there is no treatment with steam. Also, preferably according to the

Applying a phosphorus-containing compound in step (d) no treatment carried out with water vapor. It is particularly preferred that either between steps (a) and (b) or after step (d) takes place a water treatment.

a In a preferred embodiment of the present invention (steps (a) to (e) comprehensive) method is carried out

Applying a phosphorus-containing compound only in step (d). This means that in particular not prior to treatment of the extrudate with water vapor in step (c) or after calcination, the phosphorus modified extrudate in step (e) a

is carried out applying a phosphorus-containing compound. An increased catalyst life without reducing the propylene selectivity as well as a greatly increased life at an elevated temperature in the process of conversion of oxygenates, such as methanol or dimethyl ether into lower olefins: by the inventive manufacturing method of the catalyst, the following advantages over the prior art arise. There is no more time and cost intensive steam treatment by the

Process operators needed. Compared with other post-synthetic modifications in accordance with the prior art there omitted necessary further processing steps subsequent washing after

Applying the phosphorus-containing compound, a repeated modification with a phosphorus containing compound in a later process step or an additional treatment with acid to reduce the aluminum content after the steam treatment.

Under oxygenates is understood in the context of the present invention, oxygen compounds, in particular organic

Oxygenates such as alcohols and ethers. Both

According to the invention unreacted oxygen compounds are preferably methanol (conversion of methanol to olefins, CMO) or dimethyl ether. The present invention relates to

preferably a process for producing lower olefins from oxygenates, wherein the term "lower olefins" is preferably olefins having a chain length of C2 are to be understood to Cg.

Wherein in step (a) used zeolites are usually crystalline aluminosilicate is a zeolite. The zeolite may have a structure such as (in the "Atlas of Zeolite Framework Types" Ch. Baerlocher, WM Meier, DH Olson,

Elsevier, Fifth Revised Edition, 2001) describes the relevant disclosure of which is hereby incorporated into the description. Suitable zeolite materials include, for example zeolites having TON-structure (eg ZSM-22, ISI-1, KZ-2), MTT-structure (eg ZSM-23, KZ-1), MFI-structure (eg ZSM-5), MEL structure (eg ZSM-11), MTW-structure (eg ZSM-12), zeolites with structure type EUO, or ZSM-21, ZSM-35, ZSM-38, ZSM-4, ZSM-18 or ZSM-57 Amendment.

In particular, the zeolite has a TON structure MTT structure, an MFI structure, MEL structure, MTW structural or EUO structure. It can also be used mixtures of zeolites with different structures. Preferably, wherein in step (a) used zeolite a zeolite of the pentasil type; more preferably the zeolite has a MFI structure,

in particular of the ZSM-5 type on. It is further preferred that the zeolites in the H form, that is the protonated form.

The manufacturing process of the conversion of oxygenates, such as methanol or dimethyl ether into lower olefins particularly

suitable crystalline aluminosilicate zeolite is generally described in EP 1424128 Bl, the relevant disclosure of which is hereby expressly incorporated into the present specification.

The zeolite in step (a) used is preferably made of aluminosilicate primary crystallites which have an average

Diameter in the range of 0.010 to 0.100 μπι μπι, more preferably in the range of 0.010 to 0 μπι, 060 μπι, and most preferably in the

Μπι range of 0.015 to 0, have μπι 050th It has been shown that the primary crystallite size of the zeolite employed is usually not or changes only slightly when carrying out the inventive method. Preferably, therefore, the catalyst is also available with the inventive method contains a zeolite with an average diameter in the range of 0.010 μπι from aluminosilicate primary crystallites to 0.100 μπι, more preferably μπι in the range of 0.010 to 0 060 μπι, and on

preferably in the range of 0.015 to 0 μπι, 050 μπι exists.

The average diameter of the primary crystallites is defined as the arithmetic mean of the average diameter of a plurality of crystallites (eg., From 10 to 100, preferably 10 to 20, for example 14 or 15), wherein the average diameter of the individual crystallites as the arithmetic mean between is defined the largest and the smallest diameter of a single crystallite, wherein the largest or smallest diameter of a crystallite based on scanning electron microscopy

Investigations determined at a magnification of 80,000. This definition has its importance in crystallites with an irregular crystal habit, eg. Example in rod-shaped

Crystallites. For spherical or approximately spherical crystallites the largest and the smallest diameter coincide.

In step (a) zeolite used preferably has a Si / Al atomic ratio in the range of 50 to 250, preferably in the range of 50 to 150, especially ranging from 75 to 140, more preferably in the range of 85 to 125.

Wherein in step (a) the binder employed is in the inventive process usually inorganic oxides, in particular aluminum oxide, magnesium oxide, titanium oxide, zinc oxide, niobium oxide, zirconium oxide, silicon oxide, and / or their hydrates, and mixtures thereof, z. B. mixtures of the aforementioned oxides (other than aluminum oxide) to aluminum oxide. For example, amorphous aluminosilicates, and non-oxide binders may be used such as, for example, aluminum phosphates. Preferably, wherein in step (a) the binder employed to an alumina as alumina hydrate or as

modified alumina may be used. at

modified alumina is, for example, phosphorus-modified alumina. Particularly preferred is the use of finely divided alumina which is z. example by

Hydrolysis of aluminum trialkyls or aluminum alkoxides is obtained from, or in the form of peptisierbarem

Alumina hydrate is used. Very particularly preferably used as a binder peptizable alumina. Preferably at least 95% of the particles of

peptizable alumina hydrate μπι an average diameter of ^ 100, as measured by laser diffraction on. To determine a MALVERN Mastersizer 2000 with dispersing 2000 S

used; the measurement was made according to ISO 13320th

It is preferred that the binder in step (a) in an amount ranging from 5 to 60 wt .-%, more preferably in the range of 8 40 wt .-%, particularly preferably in the range of 10 to 35 wt .-%, based on the total weight of zeolite and inserted

to use binders.

It is further preferred that the mixture in step (a) an inorganic or organic acid, in particular sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid or

Citric acid, preferably nitric acid, acetic acid or

Citric acid, more preferably citric acid and / or

nitric acid. It is further preferred that the mixture in step (a), the acid, when present contains, in aqueous solution.

Furthermore, the mixture in step (a) or additives

(Eg oils, paraffin wax, methyl cellulose or

Polyethylene oxide) included.

In step (a) extruded mixture comprising a zeolite, a binder and for example, an inorganic or organic acid and / or additives, is usually obtained by mixing the components with a commercially available

Mixer, such as a mixer with moving mixing tools and fixed chamber or a mixer with moving mixing tools and portable chamber.

The extrusion of the binder-zeolite mixture (the term binder zeolite mixture, as used herein, with also includes mixtures which may also contain other ingredients such as an inorganic or organic acid and / or additives) in step (a) is carried out by using a commercially available

Extruder such as a single-screw or

Zweiwellenxtruder. In particular, the design (ie can

Extrusion) (in step a) assume a plastifiable mass of the binder zeolite mixture, which, after shaping, in step (b) is subjected to calcination to obtain the desired stability. The method according to the invention the calcination step or in step (e) is usually for 10 minutes to 15 hours, preferably for 1 h carried out to 10 hours. The

Calcination temperature is usually in a range from 350 ° C to 700 ° C, preferably in a range from 400 ° C to 700 ° C, in particular in a range from 500 ° C to 600 ° C,

most preferably at about 550 ° C. It is particularly preferred that the calcination h in step (b) for 1 to 10 h,

particularly for 5 h, at a temperature ranging from 400 ° C to 700 ° C, in particular in a range from 500 ° C to 600 ° C, and is particularly preferably carried out for about 5 hours at about 550 ° C. It is further preferred that the calcination in step (e) for 1 h to 10 h, h, in particular 5, at a temperature in

Range of 400 ° C to 700 ° C, in particular in the range from 500 ° C to 600 ° C, and is particularly preferably carried out for about 5 hours at a temperature of about 550 ° C.

In a particularly preferred embodiment, the

Calcination in both steps (b) and (e) for 1 h to 10 h, in particular for 5 h, at a temperature ranging from 400 ° C to 700 ° C, in particular in the range from 500 ° C to 600 ° C, and particularly preferably carried out for about 5 hours at about 550 ° C.

From step (a) or step extrudate (d) obtained is preferably dried before it is subjected to the calcination step (b) and the calcination step (e). The drying is usually 5 minutes to 24 hours at a temperature ranging from 50 ° C to 150 ° C, preferably for 1 to 10 h at a temperature ranging from 80 ° C to 150 ° C, and more preferably for about 5 h carried out at about 120 ° C.

In a preferred embodiment, the invention relates to a method for preparing a phosphorus-containing catalyst comprising the steps of:

(A) extruding a mixture comprising a zeolite and a binder,

(B) drying and calcining the of step (a) obtained extrudate, (c) treating the resulting from step (b) the obtained calcined extrudate with water vapor,

(D) applying a phosphorus-containing compound to the treated with water vapor extrudate from step (c), and

(E) drying and calcining the phosphorus modified extrudate from step (d),

wherein the weight proportion of phosphorus obtained in the after step (e) catalyst from 0.8 to 2.5 wt .-%, preferably from 1.0 to 1.8 wt .-%, and more preferably about 1.4 parts by weight % by weight based on the total weight of the catalyst.

In a more preferred embodiment, the invention relates to a method for preparing a phosphorus-containing catalyst comprising the steps of:

(A) extruding a mixture comprising a zeolite and a binder,

(B) drying and calcining the extrudate of step (a) obtained,

(C) treating the obtained in step (b) the calcined extrudate with water vapor,

(D) applying a phosphorus-containing compound to the treated with water vapor extrudate from step (c), and

(E) drying and calcining the phosphorus modified extrudate from step (d),

wherein the weight proportion of phosphorus obtained in the after step (e) catalyst from 0.8 to 2.5 wt .-%, preferably from 1.0 to 1.8 wt .-%, and more preferably about 1.4 parts by weight %, based on the total weight of the catalyst, and

wherein the drying both in step (b) and in step (e) at a temperature ranging from 80 ° C to 150 ° C for 1 to 10 hours, preferably 6 to 8 hours, and calcining both

in step (b) and in step (e) at a temperature in the range of 500 ° C to 600 ° C for 6 to 8 hours is performed.

Usually is avoided in the present process that the catalyst after the calcination step (e) is brought into contact with water, especially after step (e) is no more steam treatment prior to use in a process for conversion of oxygenates, such as methanol or

Dimethyl ether performed in olefins.

The treatment with steam in step (c) is bar usually at a water vapor in the range of 0.1 to 1, a temperature in the range of 400 ° C to 850 ° C, a WHSV

(Weight hourly space velocity) ranging from 0.01 to 10 h _ l and for 0.5 to 100 hours, preferably at a water vapor partial pressure of about 1 bar, a temperature of 400 ° C to 650 ° C (especially from 480 ° C to 550 ° C) a WHSV of about 1 h _ conducted l and a duration of about 48 h.

The phosphorus-containing compound can be applied in step in solution (d) as a solid or. It is preferred that the phosphorus-containing compound is used in solution.

In the inventive method, the phosphorus-containing compound is preferably selected from inorganic phosphorus-containing acids, organic phosphorus acids, alkaline, alkaline-earth and / or ammonium salts of inorganic phosphorus containing acids or organic phosphorus-containing acids, phosphorus (V) halides, phosphorus (III) halides, Phosphoroxidhalogeniden,

thereof phosphorus (V) oxide, phosphorus (III) oxide and mixtures thereof.

In the inventive process it is further preferred that the phosphorus-containing compound is independently selected 2 Η 3 _ (χ + ζ) from PY5, PY3 ^ POY3, χ Ε ζ / Ρ0 4, χ Ε ζ / (ζ χ +) 2 Η3_ Ρ0 3, P 2 0 5 and P 4 0 6 in which Y is F, Cl, Br or I, preferably Cl, x = 0, 1, 2 or 3, z = 0, 1, 2, or 3 wherein x + z -S 3,

M is independently an alkali metal and / or means ammonium, and alkaline earth metal e.

In a more preferred embodiment, when used in the inventive method the phosphorus-containing compound is H3PO4, (NH 4) H 2 P0 4, (NH 4) 2 HP0 4, and / or (NH 4) 3 P0. 4 I method of the invention, it is preferred that it is in de phosphorus-containing compound is H or POZ j (H 4) H2P0 4, and especially preferred that it is in the phosphorus-containing

Connection to H j is POZ.

The application of the phosphorus-containing compound from aqueous solution (impregnation solution) is carried out for example by a "Wet impregnation" method or an "incipient wetness" method. The "Wet Impregantion" method, the extrudate is usually first suspended in the phosphorus-containing solution and the suspension for an improved interaction of the

phosphorus-containing compound with the extrudate optionally heated to a temperature ranging from 45 ° C to 95 ° C. Connecting the water of the impregnating solution is removed in the gaseous state, in particular by distillation at elevated temperature in the range from 75 ° C to 115 ° C and / or a pressure of 0.01 MPa to 0.1 MPa completely removed. The distillative removal of the water of the impregnating solution can for example be carried out using a rotary evaporator.

The "incipient wetness" method (also referred to as pore-filling) the extrudate is brought into contact with the phosphorus-containing solution, wherein the volume of the phosphorus-containing solution corresponds to the pore volume of the extrudate. That is, the volume of the phosphorus-containing solution is in the adsorption volume of the extrudate water is added adapted such that after impregnation no excess solution is no longer present. the volume required for this can be determined by an accurately weighed amount of the impregnated extrudate in a solution consisting least from., the extrudates completely covered by the aqueous solution be. After the solution for a sufficient time was allowed to stand, usually H h, the solution is decanted and weighed, the still moist extrudates again. from the weight increase in the volume taken up can be calculated with knowledge of the density of the solution, even in the case de r "incipient wetness" with the phosphorus-containing solution corresponding to the volume loading of the phosphorus-containing solution. The water of the phosphorus-containing solution can then in

subsequent drying and calcination partially or

is completely removed. By such an approach, a precise and reproducible application of the phosphorus-containing compound is possible. Alternative methods of "incipient wetness" - processes are coating methods, for example using a Aircoaters ™ or Hüttlin coater (Innojet Herbert Hüttlin, Germany).

(D) if the the phosphorus-containing compound in step

Extrudate is applied in the form of a solution, is usually dried as described above, the product obtained before being subjected to the calcination step (e). The drying is usually min in the range of 5 to 24 h at a temperature ranging from 50 ° C to 150 ° C, preferably at a temperature ranging from 80 ° C to 150 ° C, and preferably for about 5 hours at about 120 ° C.

The phosphorus content is preferred by the method of

Applying controlled particularly preferably by applying about incipient wetness, whereby the entire existing in solution

Amount of phosphorus is deposited on the extrudates.

The catalyst obtainable by the process of this invention preferably has a phosphorus content of 0.8 to 2.5 wt .-%, more preferably from 1.0 to 1.8 wt .-%, and most preferably from about 1.4 wt .-% on, based on the total weight of the catalyst. The catalyst obtainable by the inventive process preferably has a BET surface area in the range of 250 to 450 m ^ / g, in particular in the range of 270 to 410 m ^ / g and particularly preferably in the range of 300 to 390 m ^ / g as determined according to DIN 66131 on. By sufficiently long synthesis time in the production of the zeolite powder, the BET surface area is maximized, but lowers by the subsequent phosphorus modification with increasing phosphorus content. Also, the parameters have

(E.g. duration or temperature) the calcination and steaming decisive influence on the surface.

Preferably, the pore volume of the present invention

Catalyst, determined by the mercury porosimetry method according to DIN 66133, 0 3 to 0.8 cm - ^ / g, in particular from 0.30 to 0.45 cm - ^ / g.

The catalyst of the invention can be particularly advantageously used in processes for the production of olefins by the conversion of oxygenates, such as methanol or dimethyl ether.

However, in principle, the use of carbon in other conversion reactions, such as in particular dewaxing process,

Alkylation reactions, the conversion of paraffins to aromatic compounds (CPA) and related reactions are possible.

Part of the invention is therefore a process for the production of olefins from oxygenates, preferably from methanol, dimethyl ether or mixtures thereof, wherein a starting material gas, that is, the gaseous starting material is passed over the catalyst of this invention. Under oxygenates is understood in the context of the present invention, oxygen compounds, in particular organic

Oxygenates such as alcohols and ethers. The present invention therefore preferably relates to a process for the production of lower olefins, especially C ^ - to Cg olefins, oxygen compounds (oxygenates to olefins, OTO), preferably from alcohols and / or ethers, more preferably from methanol (Conversion of methanol to olefins, CMO) or dimethyl ether by reaction, for example a methanol or dimethyl ether and water vapor, the reaction mixture in a reactor in an indirectly cooled catalyst of this invention.

Directly in front of the catalytic reaction, the catalyst according to the invention to a steam treatment may be subjected. In a particularly preferred embodiment, the catalyst according to the invention is produced directly, ie, used in the catalytic reaction without a preceding steam treatment.

According to the inventive method is especially

Methanol conversion increased in a reaction cycle, without lowering the propylene selectivity as with other modifying routes. By improving the hydrothermal stability of the methanol conversion is less strongly reducing than with the unmodified catalyst, so that also increases the lifetime of the catalyst, especially in the later cycles of reaction (after accelerated total run time). Moreover, the

Propylene yield and selectivity to propylene by

Increase in temperature can be further increased, whereby the lifetime is less decreased, as would be the case for the unmodified catalyst at the same temperature increase. Under life is the life of the catalyzed conversion to

to understand hydrocarbons, even to that of sales to the same value (for example, not less than 95%) decrease. Thus, it is possible to provide a maximum increase in propylene yield without sacrificing the life by increasing the temperature in the process for the conversion of oxygenates, such as methanol or

to reach dimethyl ether to olefins. In addition, the lateral compressive strength increased with respect to the underlying

unmodified catalyst. the invention

Preparation method reduces the number of necessary

Process steps, it is unnecessary repeated modification with a phosphorus-containing compound in a later

Step and a further treatment with acid to

Reduction of the aluminum content after the steam treatment.

Moreover, a method is provided which allows the production of a catalyst which can be used directly by the process user no time and cost intensive steam treatment prior to the catalytic conversion reaction.

It turns out that the order of treatment of the

zeolite extrudate assumes a decisive influence on the product composition in the conversion of methanol to olefins and increases the lifetime of the catalyst significantly.

Thus, the process according to the invention, in which first a steam treatment of the extrudate leads, followed by

Phosphorus treatment, an increase in the propylene yield, for example, while a modification as it is known from DE 10 2011 013 909, in the first one

Phosphorus modification, followed by a subsequent

Steam treatment is performed, a decrease in the

Propylene yield (see FIG. 6 test run, the catalysts 7 to 10 and test run 8, comparative catalysts 13 to 16) leads.

In addition, an increase in the life of the catalyst according to the invention is observed over the unmodified catalyst. So increases in test run 6, the life of the catalyst, which is approximately 260 hours for the unmodified reference catalyst 0, with increasing phosphorus content significantly and results

in particular in a nearly twice as high service life of about 516 h (s. Table 2, test run 6, the catalyst 0 and 9).

Although, in contrast, leads a phosphorus modification, as is known from DE 10 2011 013 909 to a measurable

However, increasing the life of the catalyst, this increase is significantly lower than for the invention

Catalyst and also can not affect on the amount of applied phosphor (s. Table 2 Test Run 8, comparative catalysts 13 to 16).

Furthermore, it is observed that the amount of the applied phosphorus affects propylene yield. So with taking

increasing phosphorus content to the propylene yield until they wt .-% assumes a maximum value at a phosphorus content of about 1.4. In contrast, a higher phosphorus content again leads to a decrease in propylene yield.

In addition, there is an opposite trend, which is located

expresses that with increasing phosphorus content the formation of aromatics is reduced. The minimum value is for a

Phosphorus content of about 1.6 wt .-% was reached. Since the formation of aromatics in a conversion of oxygenates is brought into connection to olefins with the formation of carbonaceous deposits, a catalyst of the invention is characterized by a phosphorus content of about 1.6 wt .-% by increasing the propylene yield, prolong life and a minimum formation of aromatics as by-products.

The reaction of methanol with the catalyst of this invention is preferably carried out at a total pressure in the range of 0.1 to 1.5 bar, in particular at a total pressure ranging from 0.5 to 1.4 bar, at a weight ratio of water and methanol or methanol equivalents in the range of 0.1 to 4.0, in particular ranging from 0.5 to 3, and at a temperature of reactor coolant medium in the range of 280 ° C to 570 ° C, preferably in the range of 400 ° C to 550 ° C. Such a process is described in EP 0448000 Al, the relevant disclosure of which is hereby incorporated in the description. More preferred processes are described in EP 1289912 Al and DE 10 2006 026 103 Al, whose relevant disclosures of which are hereby incorporated into the description.

The present invention is illustrated by the following non-limiting examples.

Hereinafter, preferred embodiments of the invention are described.

1. A process for preparing a phosphorus-containing

Catalyst comprising the steps of:

(A) extruding a mixture comprising a zeolite and a binder, (b) calcining the extrudate of step (a) obtained,

(C) treating the obtained in step (b) the calcined extrudate with water vapor,

(D) applying a phosphorus-containing compound to the treated with water vapor extrudate from step (c), and

(E) calcining the phosphorus modified extrudate from step (d),

wherein the weight percentage of phosphorus in the after step (e) the obtained catalyst from 0.8 to 2.5 wt .-%, based on the total weight of the catalyst. A method according to embodiment 1, wherein the weight proportion of phosphorus in the after step (e) the obtained catalyst 1.0 to 1.8 wt .-%, based on the total weight of

is the catalyst. Method according to embodiment 2, wherein the weight proportion of phosphorus in the after step (e) the obtained catalyst is about 1.4 wt .-%, based on the total weight of

is the catalyst. Method according to embodiment 1.2 or 3, wherein the zeolite in step (a) used has a phosphorus content of 0 wt .-% to 0.01.%, Preferably from 0 wt .-% to 0.001 wt .-%, and in particular, a phosphorus-free zeolite. A method according to one of the preceding embodiments, wherein

(I) both between the extrusion in step (a) and calcination in step (b) and after the application of a phosphorus-containing compound in step (c) no treatment with water vapor and

(ii) In both before the treatment of the extrudate with water vapor in step (c) and after calcining the phosphorus modified extrudate m step (e) no application of a phosphorus-containing compound.

A method according to any one of embodiments 1 to 5, wherein the mixture in step (a) an acid selected from

Sulfuric acid, nitric acid, acetic acid, formic acid, oxalic acid and citric acid, preferably selected from

nitric acid, acetic acid and citric acid, and particularly preferably citric acid and / or nitric acid.

A method according to any one of embodiments 1 to 6, wherein the treatment with water vapor in step (c) at a water vapor partial pressure in the range of 0.1 to 1 bar, a temperature ranging from 400 ° C to 850 ° C, a WHSV in the range of 0.01 to 10 h _ l and for 0.5 to 100 hours, preferably at a water vapor partial pressure of about 1 bar, a temperature in the range of 400 ° C to 650 ° C, a WHSV of about 1 hl for about 48 h performed becomes.

A method according to any one of embodiments 1 to 7, wherein the zeolite has a TON structure MTT structure, an MFI structure, MEL structure, MTW, EUO structure or structure, and / or

Mixtures thereof, preferably a MFI structure, more preferably a structure of the ZSM-5 type having.

A method according to any one of embodiments 1 to 7, wherein the zeolite has a Si / Al atomic ratio in the range of 50 to 250, preferably in the range of 50 to 150, more preferably in the range of 75 to 140, most preferably in the range from 85 to 125 comprising ,

A method according to any one of embodiments 1 to 9, wherein the zeolite is selected from aluminosilicate primary crystallites μπι having an average diameter in the range of 0.010 μπι to 0.100, more preferably in the range of 0.010 μπι to 0, 060 μπι, and most preferably in the range of 0.015 μπι to 0, 050 μπι is. A method according to any one of embodiments 1 to 10, wherein the zeolite is in the H form. A method according to any one of embodiments 1 to 11, wherein the binder contained in the step (a) the extruded mixture of alumina, magnesia, titania,

Zinc oxide, niobium oxide, zirconium oxide, silicon oxide, preferably alumina or alumina hydrate, alumina hydrate is more preferably their hydrates and / or a mixture thereof. A method according to any one of embodiments 1 to 12, wherein the extruded wherein in step (a) mixture of binder contained in an amount ranging from 5 to 60 wt .-%, preferably in the range of 8 to 40 wt .-%, more preferably in range of 10 to 35 wt .-%, based on the total weight of zeolite and binder employed, is used. A method according to any one of embodiments 1 to 13, wherein said calcining in steps (b) and / or (e) at a temperature in the range of 400 ° C to 700 ° C, preferably at a temperature in the range of 500 ° C to 600 ° C, for a period of 1 h to 10 h, preferably for about 5 hours, and more preferably at a temperature of about 550 ° C for about 5 h effected. A method according to any one of embodiments 1 to 14, wherein the phosphorus-containing compound in step (d) is independently selected from phosphorus-containing inorganic acids, organic phosphorus acids, alkaline salts, alkaline earth salts and / or ammonium salts of

inorganic phosphorus-containing acids, or organic phosphorus acids, phosphorus (V) halides,

Phosphorus (III) halides, Phosphoroxidhalogeniden,

thereof phosphorus (V) oxide, phosphorus (III) oxide and mixtures thereof. A method according to any one of embodiments 1 to 14, wherein the phosphorus-containing compound in step (d) is independently selected from PY5, ΡΟ γ 3 'M x E z / 2 H 3- (x + z) PO4 <

M x E z / 2 H 3- (x + z) P0 3 'P 2 O 5 and p 4 ° 6' wherein

Y is F, Cl, Br or I, preferably Cl, x = 0, 1, 2 or 3, z = 0, 1, 2, or 3 wherein x + z ^ 3,

M is independently an alkali metal and / or means ammonium, and alkaline earth metal e.

Is 17. The method according to embodiment 16, wherein the phosphorus-containing compound is selected from H3PO4, (NHz ^ i ^ pos j, (j ^ NHz HPC ^ and (H 4) 3P04, especially H3PO4 or (NH4) H2P04.

18. A catalyst obtainable by a process according to any of embodiments 1 to 17.

19. A catalyst according to embodiment 18, the one

Phosphorus content, based on the total weight of the

Comprising catalyst in the range of 0.8 to 2.5 wt .-%, preferably in the range of 1.0 to 1.8 wt .-%, and more preferably from about 1.4 wt .-%.

20. A process for producing olefins from oxygenates in which a feed gas, preferably a gas containing methanol,

Dimethyl ether and / or a mixture thereof, is passed over a catalyst according to embodiment 18 or 19th

21. Use of a catalyst according to embodiment 18 or 19 for the conversion of oxygenates to olefins, in particular for the conversion of methanol to olefins.

Examples Measuring methods

The average primary as described above with the aid of scanning electron investigations determined.

The scanning electron microscope examinations were performed with a LEO Field Emission Scanning Electron Microscope (LEO Electron

Microscopy Inc., USA) based on powder samples of the catalyst, previously redispersed in acetone for 30 seconds with ultrasonic, and then applied to a support (Sample Current Range were: 4 pA to 10 nA). The measurement was made at 80,000 times magnification. The values ​​could be confirmed at 253,000-fold magnification.

The mean side crushing strength was determined from the force applied to the side surface (longest side) of the molded body is applied until fracture occurs. These were from a

representative sample of moldings having a length in the range of 5.5 to 6.5 mm selected 50 moldings and measured individually. The moldings were free of cracks and just formed. A molded article was placed (a movable and an immovable) between two measuring jaws. The movable measuring jaw is then smoothly moved to the molded body until the breakage of the molded article occurred. The break measured value in kiloponds (kp), measured with a measuring instrument of the Schleuniger, was divided by the length of the molding to the lateral compressive strength of

to obtain the molding. From 50 individual measurements then the average side crushing strength was determined as the arithmetic mean.

The specific surface (BET surface) was determined according to DIN 66131 using nitrogen.

The measurement of the pore volume after the Quecksilberporosimetrie- method and the calculation of pore diameter were carried out according to DIN 66,133th

The average methanol conversion as indicated in the following

Application Example 1 were measured. Reference Example 1: Preparation of H-zeolite having an average primary crystallite size of 0.03 μπι

A reaction mixture was a by intimately mixing

Suspension and a solution at room temperature in a 40-liter autoclave made. The suspension was prepared by adding 2218 g of tetrapropylammonium bromide were dissolved in 11 kg of deionized water and then 5000 g of a commercial silica were added. The solution was prepared by dissolving 766 g of NaOH and then 45,6 g were dissolved NAALC> 2 in 5.5 liters of deionized water. The still warm (25 ° C-50 ° C) solution was added to the suspension. The autoclave was then closed and, with stirring at about 60 rev / min. brought to the reaction temperature. The reaction was stopped after about 23 h to complete the growth of primary crystallites with a mean particle diameter of 0.03 cancel μπι. After cooling, the autoclave was opened, the reaction mixture was removed from the reaction vessel and filtered. The filter cake was deionized in about 40 liters of water

slurried with about 5 liters of a 0.4 wt .-% aqueous suspension of a commercial flocculant (Praestol BC 11L, copolymer of acrylamide and a cationic

Acrylic acid derivative) is added and decanted after stirring and settling, the pre-agglomerates of the solid. the described

Washing process was repeated until the wash water had a pH value of 7 to 8 and a Br-concentration of less than 1 ppm. The slurry could be seen in the pre-agglomerates of primary crystallites which were held together by the flocculant, was filtered. The filter cake was then h at 120 ° C for 12 dried.

The dried filter cake was ground with a commercial granulator to a grain size of 2 mm.

The granules were placed at a rate of l ° C / minute under nitrogen (1000 Nl / h) at 350 ° C and at 350 ° C for 15 under nitrogen (1000 Nl / h) h calcined. Then, the temperature was raised at a heating rate of l ° C / minute to 540 ° C, and the

Granules were calcined 24 hours at this temperature in air to burn off the remaining tetrapropylammonium bromide; Finally, a calcined Na zeolite was obtained.

The calcined Na zeolite was suspended in the 5-fold amount of a 1-molar aqueous HCl solution and brought to 80 ° C. At this temperature, stirring for one hour. Then, about 1 liter of a 0.4 wt .-% suspension of flocculant was added and the supernatant acid was decanted after settling of the solid. The process thus described was repeated once more. The solid was suspended in about 10 washes each in 60 liters of deionized water with stirring and treated with an average of 100 ml of a 0.4 wt .-% suspension of the flocculant. After the solids have settled, the supernatant solution was decanted. When the content of Cl in the wash water was ~ <5 ppm, the suspension was filtered and the filter cake at 120 ° C for 15 h dried to obtain a zeolite in the H form (ZSM-5 H-zeolite).

The dried H-zeolite was commercially available with a

Granulator crushed to 2 mm, placed in air at a heating rate of l ° C / minute to 540 ° C and calcined at this temperature in air 10th

The BET surface of the zeolite thus obtained was 434 m ^ / g.

The average particle diameter of the primary crystallites was μπι 0.03. The Si / Al ratio was 105: first

Reference Example 2: Preparation of reference catalyst

catalyst 0

3400 g of ZSM-5 H-zeolite prepared in Reference Example 1 was mixed with 848 g of alumina and 136 g of paraffin wax. This mixture was then least 1190 g. H2O, 233.7 g of a nitric acid solution (5 wt .-% HNO3) and 495 g distilled water. H2O is added. This gives a plasticizable mass. This was mixed with 272 g of steatite yet. The molding (extrusion) was performed using a commercial extruder. The extruded catalyst body had a diameter of about 3 mm and a length of about 6 mm. The extruded catalyst bodies were dried at 120 ° C and calcined at 550 ° C for 5 h and is obtained catalyst 0. The BET surface area of ​​the catalyst was determined to be 391 m ^ / g. The side crushing strength was 0.66 kgf / mm (6.47 N / mm), the

Pore ​​volume 0.33 ml / g determined.

Example 1: Preparation of the catalyst 1 according to the invention

32 g of the catalyst prepared in Reference Example 2 0 were heated under a nitrogen flow of 400 mL / min at a rate of l ° C / min to 480 ° C. The catalyst was then without nitrogen flow with water vapor at 480 ° C for 48 treated h, conveyed continuously at a partial pressure of 1 bar, 32 g of liquid water per hour with an HPLC pump and vaporized, heated to 480 ° C and passed over the catalyst has been. This corresponds to a WHSV = 1 g (water) / (g (catalyst) * h).

Finally, it was cooled under nitrogen flow at room temperature.

25 g of the treated with water vapor catalyst (in a 1 L round bottom flask with 250.42 g of a phosphoric acid solution consisting of 249 g water and 1.42 g of 85 wt .-% phosphoric acid (H3PO4), corresponding to approximately 0.48 wt % H3PO4 in water was added) and on the rotary evaporator at 85 ° C - 95 ° C (initially 85 ° C, with

As time progresses, up to 95 ° C increased) at a pressure of 250 mbar over a period of about 3 hours evaporated to dryness.

Thereafter, the product for 5 h was dried and calcined for 5 hours at 550 ° C in air at 120 ° C. 25 g of the steamed and phosphorus-modified catalyst 1 is obtained.

The phosphorus content of the catalyst was 1.4 wt .-%. The BET surface area of ​​the catalyst was determined to be 333 m ^ / g. The side crushing strength was 0.96 kgf / mm (6.43 N / mm), the

Pore ​​volume 0.31 ml / g determined. Example 2: Preparation of Catalyst 6 according to the invention

Two batches each of 20 g of the catalyst prepared in Reference Example 2 0 were ground in a mortar and the sieve fraction of 200-280 μπι heated under nitrogen flow to 480 ° C. Thereafter, the catalyst was treated without nitrogen flow with water vapor at 480 ° C for 24 h, and conveyed continuously at a partial pressure of 1 bar 1 g of liquid water per hour per gram of catalyst were heated to 480 ° C and passed over the catalyst. This corresponds to a WHSV = 1 g (water) / (g (catalyst) * h).

Finally, it was cooled under nitrogen flow at room temperature.

30 g of the treated with water vapor catalyst (in a 1 L round bottom flask with 300.24 g of a phosphoric acid solution consisting of 298 g of water and 2.24 g of 85 wt .-% phosphoric acid (H3PO4), corresponding to about 0.6 weight % H3PO4 was added in water) and on the rotary evaporator at 95 ° C at a pressure of 250 mbar over a period of about 5 hours evaporated to dryness.

Thereafter, the product for 5 h was dried and calcined for 5 hours at 550 ° C in air at 120 ° C. 29 g of the steamed phosphorus-modified catalyst and 6 is obtained.

The phosphorus content of the catalyst was 1.8 wt .-%. The BET surface area of ​​the catalyst was determined to be 340 m ^ / g. The pore volume was determined to be 0.30 ml / g.

Comparative Example 1: Preparation of Comparative Catalyst 2

To 12 g of Catalyst 1 prepared in Example 1 58 g of dist. H2O added, stirred for 1 h at 90 ° C, filtered, washed, dried (15 h, 120 ° C) and calcined (10 h, 540 ° C) to give Catalyst 2 having a phosphorus content of 1.5 wt .-% was obtained.

Comparative Example 2: Preparation of Comparative Catalyst 3 1400 g of ZSM-5 H-zeolite prepared in Reference Example 1 was dissolved in 7066 g of phosphoric acid solution (wt .-% in water is about 0.8) at 80 ° C to 90 ° C for 2 h suspended , The suspension was by a spray drying process to

Dryness. The suspension was initiated via a nozzle at a temperature of about 220 ° C in a NIRO spray dryer. a finely divided powder is obtained. The powder was then separated in a cyclone. The powder was then calcined for about 10 h at 540 ° C. The phosphorus content of the powder was 1.2 wt .-%. The BET surface area was determined to be 394 m ^ / g.

850 g of the powder was least in 4130 ml. H2O slurried and stirred for 1 h at 90 ° C. The powder was then

filtered, washed with 25000 ml of water, and calcined, after drying at 120 ° C for 18 h at 540 ° C for 10 h. a powder having a phosphorus content of 0.09 wt .-% is obtained. The BET surface area was determined to be 409 m ^ / g.

700 g of the powder was mixed with 176 g of alumina and 28 g of paraffin wax. This mixture was then least 245 g. H2O and 48.3 g of a solution of nitric acid (wt .-% HNO3 5) was added, followed by further 120 g of distilled water. H2O. This gives a plasticizable mass. This was mixed with 56 g of steatite yet.

The molding was conducted using a commercially available extruder. The extruded catalyst body had a diameter of about 3 mm and a length of about 6 mm. The

Catalyst bodies were at 120 ° C for 18 h and dried at 550 ° C for 5 h and calcined to obtain a catalyst 3. The

Phosphorus content of the catalyst was 0.086 wt .-%. The BET surface area of ​​the catalyst was determined to be 387 m ^ / g. The side crushing strength was 0.90 kgf / mm (8.85 N / mm), the

Pore ​​volume 0.34 ml / g determined.

Comparative Example 3: Preparation of Comparative Catalyst 4 1400 g of ZSM-5 H-zeolite prepared in Reference Example 1 was dissolved in 7200 g of phosphoric acid solution (wt .-% in water is about 2.4) at 80 ° C to 90 ° C for 2 h suspended , The suspension was by a spray drying process to

Dryness. The suspension was initiated via a nozzle at a temperature of about 220 ° C in a NIRO spray dryer. a finely divided powder is obtained. The powder was then separated in a cyclone. The powder was then calcined for about 10 h at 540 ° C. The phosphorus content of the powder was 3.4 wt .-%. The BET surface area was determined to be 296 m ^ / g.

850 g of the powder was least in 4076 ml. H2O slurried and stirred for 1 h at 90 ° C. The powder was then

filtered, washed with 26000 ml of water, and after drying at 120 ° C for 17 h again at 540 ° C for 10 h calcined. Of the

Phosphorus content of the powder was 0.30 wt .-%. The BET surface area was determined to be 374 m ^ / g.

700 g of the powder was mixed with 179 g of alumina and 28 g of paraffin wax. This mixture was then least 245 g. H2O and 49.1 g of a solution of nitric acid (wt .-% HNO3 5) was added, followed by further 115 g of distilled water. H2O. This gives a plasticizable mass. This was mixed with 56 g of steatite yet.

The molding was conducted using a commercially available extruder. The extruded catalyst body had a diameter of about 3 mm and a length of about 6 mm. The

Catalyst bodies were at 120 ° C for 16 h and dried at 550 ° C for 5 h and calcined to obtain a catalyst 4. The

Phosphorus content of the catalyst was 0.24 wt .-%. The BET surface area was determined to be 374 m ^ / g. The side crushing strength was determined to be 0.91 kg / mm (8.91 N / mm), pore volume 0.33 ml / g.

Comparative Example 4: Preparation of Comparative Catalyst 5 1,200 g of a prepared analogously to Example 1-H-ZSM-5 zeolite having an average particle diameter of the

Primary crystallites of 0.03 μπι, a Si / Al ratio of 99: 1 were and a BET surface area of ​​427 m ^ / g in 6050 g of a

Solution of phosphoric acid (wt .-% in water 1.5) at 80 ° C for 2 h suspended. Subsequently, the suspension was by means of a

Spray-drying process to dryness concentrated. The

Suspension was initiated via a nozzle at a temperature of about 220 ° C in a NIRO spray dryer. a finely divided powder is obtained. The powder was then separated in a cyclone. The powder was then calcined for about 10 h at 540 ° C. The phosphorus content of the powder was 2.3 wt .-%. The BET surface area was determined to be 327 m ^ / g.

700 g of the powder was mixed with 179 g of alumina and 28 g of paraffin wax. This mixture was then least 245 g. H2O and 48.0 g of a solution of nitric acid (wt .-% HNO3 5) was added, followed by further 127 g of distilled water. H2O. This gives a plasticizable mass. This was mixed with 56 g of steatite yet.

The molding was conducted using a commercially available extruder. The extruded catalyst body had a diameter of about 3 mm and a length of about 6 mm. The

Catalyst bodies were dried at 120 ° C and at 550 ° C for 5 h and calcined to obtain a catalyst 5. The

Phosphorus content of the catalyst was 2.00 wt .-%. The BET surface area was determined to be 337 m ^ / g. The pore volume was 0.43 cm - ^ / g. Measurement of the average side crushing strength gave a value of about 0.14 kp / mm (1.37 N / mm).

Example 5: Preparation of the catalysts 7-10 according to the invention:

The catalysts 7-10 according to the invention were prepared by the reference catalyst obtained in Reference Example 2 was 0 subjected to steam treatment according to Example 2 first. Each 35 g of this steam-treated catalyst was phosphor modified by using a rotary evaporator analog described in Example 1 process by per 175 g of a phosphoric acid solution, containing 1.32 g (catalyst 7), 1.85 g (catalyst 8), 2.39 g ( catalyst 9) and 2.93 g (catalyst 10) of a 85 GE .-% phosphoric acid (H 3 P0 4) (the difference to 175 g consisted of dist. H 2 0 were concentrated) to dryness. Thereafter, the product for 4 h was dried and calcined for 5 hours at 550 ° C in air at 120 ° C. 35-36 g of the steam-treated and phosphorus-modified catalysts 7-10 are obtained. The phosphorus content of the catalyst was 0.95, 1.22, 1.63 and 2.10 wt .-%.

Comparative Example 6: Preparation of Comparative Catalysts Comparative Catalysts 13-16 13-16 were prepared according to the teaching of DE 10 2011 013 909.

For this purpose, not previously treated with water vapor reference catalyst was loaded by an 0 incipient wetness method with phosphorus by 50 g each of the reference catalyst were applied with 0 19 g of a phosphoric acid solution. The 19 g of phosphoric acid solution consisted in this case of a 85 wt .-% phosphoric acid (H 3 P0 4) (1.9 g for the preparation of

Comparative Catalyst 13, 2.6 g for Comparative Catalyst 14, 3.4 g for Comparative Catalyst 15 and 4.2 g for Comparative Catalyst 16), and the difference with 19 g of dest. H 2 0. After the respective product for 4 hours at 120 ° C was dried and calcined for 5 hours at 550 ° C in air. Following the catalysts were treated with steam.

P Si Al Specific pore volume page printing surface strength

Wt. - weight. - weight. -

/ G cm ^ / g kgf / mm

Reference catalyst 0 0 37 6 8, 4391 0, 33 0, 66

Catalyst 1 1 4 37 9 8, 3333 0, 31 0, 96

Comparative catalyst

1, 5 37, 3 8,2 343 0 33-2

Comparative catalyst

0,09 38, 1 8, 7387 0, 34 0, 90 3

Comparative catalyst

0, 24 37, 5 9 0 374 0, 33 0, 91 4

Comparative catalyst

2, 0 35, 2 8, 7337 0.43 0, 14 5

Catalyst 6 1, 8 36, 9 8,2 340 0 30 -

Catalyst 7 0 95 37 9 8 5 346 0 31 -

Catalyst 8 1 22 37 8 8 4 344 0 31 - 9 catalyst 1, 63 37, 7 8, 3341 0, 30 -

Catalyst 10 2, 10 37, 0 337 8.2 0.29 -

Comparative 39, 1 8, 6

1 0 374 0 31 - Catalyst 13

Comparative 38, 8 8, 5

1, 4362 0, 30 - Catalyst 14

Comparative 38, 1 8, 3

1, 8357 0, 30 - Catalyst 15

Comparative 38 4 8 3

2, 3361 0.29 - Catalyst 16

Table 1: Chemical composition, specific surface area, pore volume and side crush strengths of the catalysts 0 to 10 and 13 to the 16th

Application Example 1: Comparison of catalysts 0 to 4 and 6 in the reaction of methanol to olefins.

The catalyst samples were tested for their catalytic behavior in the conversion of methanol to olefins. This

Example shows data on the basis of the catalytic CMO process (conversion of methanol-to-olefin process) in an isothermal fixed-bed reactor, the advantages of the catalyst according to the invention.

300 mg of catalysts 0 to 4 and 6 were ground in a mortar, the

Sieve fraction from 200 to 280 μπι with silicon carbide (SiC) in

Volume ratio 1: 4 (Catalyst: SiC) and in each case in a vertical isothermal fixed-bed reactor with a

Inner diameter of 8 mm filled.

Before the catalytic test, the catalysts were heated at 0, 3 and 4 under nitrogen flow to 480 ° C. Thereafter, the

Catalyst without nitrogen flow with water vapor at 480 ° C

(Partial pressure of 1 bar) for 24 h or 48 h treated (see Table 2), continuously conveyed at a partial pressure of 1 bar 1 g of liquid water per 1 g of catalyst per hour and evaporated, heated to 480 ° C and passed over the catalyst has been. This corresponds to a WHSV = 1 g (water) / (g (catalyst) * h).

Finally, it was cooled under nitrogen flow at room temperature. The lifetime of the standards in this case depends heavily on the contamination of the feed. Therefore, the absolute lifetimes can be compared only to those catalysts in the same test run, so using the same feed tested (Table 2). To check the results everyone will

catalyst measured in the same test run in at least two of the ten reactors, wherein an error-free test run on the basis of matching results (life and selectivity) was found in all cases.

The composition of the products at the output of CMO-catalyst reactor was determined by gas chromatographic analysis techniques.

The selectivity S j _ results from the molar carbon content of component i with respect to the converted carbon,

calculated as the sum of all received carbonaceous products. The starting materials methanol (MeOH) and thus in

Balance standing dimethyl ether (DME) are not included among the products:

The yield Y j _ a product resulting from the molar

Carbon fraction of component i with respect to the total of the carbon used. The carbon used in total is calculated as the sum of all carbon-containing products, plus the starting materials used methanol (MeOH) and thus in equilibrium dimethyl ether (DME):

n

y = 100% · - i from ε;1

i = N

MeOH from £ MeOH + DME from '£' DME + Σ "i, Sales X-j_ obtained results from the sum of all

Carbonaceous products based on the total

Carbon used. The carbon used in total is calculated as the sum of all carbon-containing products, plus the starting materials used methanol (MeOH) and thus in equilibrium dimethyl ether (DME):

i = N

Σ from

X = 100% · -

, C * C

MeOH from 'DME MeOH + n on' £ DME

S i: selectivity of component i

X i: conversion of methanol and dimethyl ether

Y i: yield of component i

c

Ι number of carbon atoms of component: £ i

h: molar flow rate of component i

The novel catalysts 1 and 6 and the

Comparative Catalyst Catalyst 2 were no further

subjected to steam treatment in the reactor.

The feed of methanol / water (parts by weight (MeOH: H20) = 1: 2) at a space velocity WHSV (methanol) = 1.5 g (methanol) /

(G (catalyst) * h), ie 4.5 grams total feed per gram

Of catalyst per hour at a pressure of 1 bar to

directed conversion of methanol over the catalyst in the reactor. 10 reactors are operated in parallel and provided each with its own HPLC pump with the methanol-water mixture. The HPLC pumps feed the feed a respective via capillaries into an empty pre-reactor in which the feed is vaporized at 260 ° C and is supplied via a capillary to the reactor. Each catalyst is measured simultaneously in the same test run in at least two reactors in order to determine an error-free test run using identical results. All products are separated by means of a gas chromatograph and determined quantitatively.

In Table 2, the propylene, ethylene and aromatics with the use of the catalysts of 0, 1, 2, 3, 4 and 6, and their service life at a reaction temperature of 450 ° C (temperature of the reactor) and the propylene, ethylene and aromatics in the use of the catalysts of 0 and 1 and the service life combined at a reaction temperature of 475 ° C (temperature of the reactor).

The lifetime is the time period of the catalytic reaction relative to the reference Catalyst Catalyst 0 at a

Reaction temperature of 450 ° C up to which the conversion is 95% or higher.

The propylene, ethylene and aromatics was determined as the mean value at a methanol conversion of greater than or equal to 99, 0% from the data of gas-chromatographic analysis the product.

The methanol content at the reactor outlet was charged with

gas chromatographic analysis method determined.

Application Example 2: Comparison of Catalysts 0, 7 to 10 and

13 to 16 in the conversion of methanol to olefins.

0 reference catalyst, catalysts of the invention 7 to 10 and the comparative catalysts 13 to 16 were tested according to the method described in Application Example 1 as catalysts in the conversion of methanol to olefins.

Here, the novel catalysts were subjected to further steam treatment, reference catalyst and the 0

were comparative catalysts as in Example 1

described subjected to a steam treatment, the duration was 24 h.

The reaction temperature was 475 ° C, the propylene, ethylene and aromatics in the use of catalysts and their

Life are summarized in Table 2 below. Table 2: Results of the catalytic tests on the catalysts 0 to 4, 6 to 10 and 13 to

6 10 24 475 ° C "48.4" 5, 1 1.2 "515

7 0 24 475 ° C "47.5 - -" 180

7 6 24 475 ° C "48.1 - -" 440

8 0 24 475 ° C "46 9 - -" 190

8 13 24 475 ° C "45.4 - -" 295

8 14 24 475 ° C "44.8 - -" 305

8 15 24 475 ° C "44.6 - -" 290

8 16 24 475 ° C "44.4 - -" 285

The duration of the steam treatment in Table 2 refers to the catalysts 1, 2 and 6 to 10 to the steam treatment during the synthesis, and for the catalysts of 0, 3 and 4 (the steam treatment before de reaction, this final steam treatment is not necessary for the catalysts 1 , 2 and 6 to 10).

As can be seen from Table 2, the catalysts of the invention are distinguished 1 and 6 to 10 is characterized in that the catalyst life is increased without causing a measurable negative effect on the propylene yield.

The advantage of the catalyst 1 according to the invention is especially the comparison of the reaction at 475 ° C with the implementation of the

significantly 0 reference catalyst at 450 ° C: The propylene yield (absolute) increases by about 5%, during the life of the

still increased catalyst 1 according to the invention by 35% compared to 0 reference catalyst at 450 ° C (see also Figure 1). Also for catalyst 6, shows that the propylene selectivity can be increased by increasing the temperature, without decreasing the lifetime (see also Figure 6).

As can be seen from Table 2, the comparative catalysts are characterized by contrast, either through a lower

Life (Comparative Catalyst 2, see also Figure 2) or lower propylene yield (Comparative Catalyst 3 and

Comparative Catalyst 4, see also Figure 3) compared to the

Reference catalyst of 0.

Especially at higher reaction temperatures, the catalyst life is shortened to: If the reaction at 475 ° C instead of 450 ° C is performed, the life of the decreases

Reference catalyst 0 (to about 70% compared with

0 reference catalyst at 450 ° C). For the inventive

1, the catalyst life is reduced only to about 90% (compared to Catalyst 1 at 450 ° C) when the reaction is carried out at 475 ° C instead of 450 ° C. The increased

Stability against coking, the catalyst according to the invention 1 with respect to the reference catalyst 0 at 475 ° C, an almost twice as long (see Figures 4 and 5).

By washing the phosphorus-containing zeolite in the synthesis of the comparative catalysts 3 and 4, whose

original phosphorus content (Comparative Catalyst 3: 1.2 wt .-% P before washing; Comparative Catalyst 4: 3.4 wt .-% P before washing) reduced. Despite the low phosphorus content have the

Comparative Catalysts 3 and 4, an increased service life.

However, the propylene yield and is Propylenselektivitat

reduced. However, has a washing step after extrusion, which does not lead to reduction of the initial phosphorus content and no significant effect on the yield has Propylenselektivitat and propylene (Comparative Catalyst 2), a reduction in the service life.

Comparing the Propylenselektivitat the

Comparative Catalysts 3 and 4 in the conversion of methanol to propylene, it can be seen that increasing the

(Phosphorus content in the phosphorus modification of the zeolite powder cf. comparative catalyst. 3: 1.2 wt .-% P; increased in

Comparative Catalyst 4: 3.4 wt .-% P) followed by washing prior to extrusion, to a deterioration in the

Propylenselektivitat leads. To access this synthetic one

prepare catalyst comprising the inventive

Catalyst comprises 1 equivalent phosphorus content of the initial phosphorus content should still far above that of the catalyst 4 can be increased. This suggests that, in a prepared catalyst in this way a more significant reduced propylene selectivity would be expected. Thus, such a catalyst would be even less for the conversion of

Oxygenates suitable olefins.

A comparable for inventive catalyst 1 Catalyst with similar high phosphorus content (Comparative Catalyst 5), from about 2.0 wt .-%, of the phosphorus modification by

Zeolite powder is prepared without washing, is insufficient for further processing into a molded body, since its mechanical stability (side crushing strength of about 0.14 kp / mm (N / mm) is as low 1.37 that here problems during transport and filling the reactor arise because the moldings break very quickly apart. Furthermore shows that the order of treatment of the zeolite extrudate assumes a decisive influence on the product composition in the conversion of methanol to olefins and increases the lifetime of the catalyst significantly.

Thus, the process according to the invention, in which first a steam treatment of the extrudate leads, followed by

Phosphorus treatment, an increase in the propylene yield, for example, while a modification as it is known from DE 10 2011 013 909, in the first one

Phosphorus modification, followed by a subsequent

Steam treatment is performed, a decrease in the

Propylene yield (see FIG. 6 test run, the catalysts 7 to 10 and test run 8, comparative catalysts 13 to 16) leads.

In addition, an increase in the life of the catalyst according to the invention is observed over the unmodified catalyst. So increases in test run 6, the life of the catalyst, which is approximately 260 hours for the unmodified reference catalyst 0, with increasing phosphorus content significantly and results

in particular in a nearly twice as high service life of about 516 h (s. Table 2, test run 6, the catalyst 0 and 9).

Although, in contrast, leads a phosphorus modification, as is known from DE 10 2011 013 909 to a measurable

However, increasing the life of the catalyst, this increase is significantly lower than for the invention

Catalyst and also can not affect on the amount of applied phosphor (s. Table 2 Test Run 8, comparative catalysts 13 to 16).

Furthermore, it is observed that the amount of the applied phosphorus affects propylene yield. So with taking

increasing phosphorus content to the propylene yield until they wt .-% assumes a maximum value at a phosphorus content of about 1.4. In contrast, a higher phosphorus content again leads to a decrease in propylene yield.

Claims

claims
1. A process for preparing a phosphorus-containing
Catalyst comprising the steps of:
(A) extruding a mixture comprising a zeolite and a binder,
(B) calcining the of step (a) extrudate,
(C) treating the obtained in step (b) the calcined extrudate with water vapor,
(D) applying a phosphorus-containing compound to the treated with water vapor extrudate from step (c), and
(E) calcining the phosphorus modified extrudate from step (d),
wherein the weight percentage of phosphorus in the after step (e) the obtained catalyst is 0.8 to 2.5 wt .-%.
2. The method of claim 1, wherein the proportion by weight of
Catalyst obtained in the phosphor after step (e) 1.0 to 1.8 wt .-%, based on the total weight of
is the catalyst.
3. The method of claim 2, wherein the proportion by weight of
Phosphorus catalyst obtained in the after step (e) about 1.4 wt .-%, based on the total weight of the catalyst.
comprises 4. A method according to claim 1, 2 or 3, wherein the zeolite in step (a) used by weight, a phosphorus content of 0 wt .-% to 0.01.%, preferably from 0 wt .-% to 0.001 wt .-% , and in particular, a phosphorus-free zeolite.
5. The method according to any one of the preceding claims, wherein
(I) both between the extrusion in step (a) and calcination in step (b) and after the application of a phosphorus-containing compound in step (d) is no treatment with water vapor and
(Ii) both before the treatment of the extrudate with water vapor in step (c) and after calcining the phosphorus modified extrudate in step (e) there is no application of a phosphorus-containing compound.
6. The method according to any one of claims 1 to 5, wherein the
Zeolite has a TON structure MTT structure, an MFI structure, MEL structure, MTW, EUO structure or structure, and / or mixtures thereof, preferably a MFI structure, more preferably a structure of the ZSM-5 type having.
7. The method according to any one of claims 1 to 6, wherein the
Zeolite has a Si / Al atomic ratio in the range of 50 to 250, preferably in the range of 50 to 150, more preferably in the range of 75 to 140, most preferably in the range of 85 to 125th
8. The method according to any one of claims 1 to 7, wherein the
Zeolite is selected from aluminosilicate primary crystallites with a mean diameter in the range of 0.010 to 0.100 μπι μπι, more preferably in the range of 0.010 to 0 μπι, 060 μπι, and most preferably in the range of 0.015 to 0 μπι, 050 consists μπι.
9. The method according to any one of claims 1 to 8, wherein the binder contained in the step (a) the extruded mixture of alumina, magnesia, titania, zinc oxide, niobium oxide, zirconium oxide, silicon oxide, hydrates thereof and / or a mixture thereof, preferably alumina or alumina, more preferably alumina hydrate.
10. The method according to any one of claims 1 to 9, wherein the binder contained in the step (a) the extruded mixture in an amount in the range of 5 to 60 wt .-%, preferably in the range of 8 to 40 wt .-%, more preferably in the range of 10 to 35 wt .-%, based on the total weight of zeolite and binder employed, is used.
11. The method according to any one of claims 1 to 10, wherein the
Calcining in steps (b) and / or (e) at a temperature in the range of 400 ° C to 700 ° C, preferably at a temperature in the range of 500 ° C to 600 ° C, for a period of 1 h to 10 preferably takes place h for about 5 hours, and more preferably at a temperature of about 550 ° C for about 5 h.
12. The method according to any one of claims 1 to 11, wherein the
phosphorus-containing compound in step (d) independently
is selected from phosphorus-containing inorganic acids, organic phosphorus acids, alkaline salts, alkaline earth salts and / or ammonium salts of
inorganic phosphorus-containing acids, or organic phosphorus acids, phosphorus (V) halides,
Phosphorus (III) halides, Phosphoroxidhalogeniden,
thereof phosphorus (V) oxide, phosphorus (III) oxide and mixtures thereof.
13. The method according to any one of claims 1 to 11, wherein the
phosphorus-containing compound in step (d) independently
is selected from PY5, POY3, Μ χ Ε ζ 2Η3_ (x + z) PO4,
Mx e z / 2 H 3- (x + z) P0 3 'P 2 O 5 and p 4 ° 6' wherein
Y is F, Cl, Br or I, preferably Cl, x = 0, 1, 2 or 3, z = 0, 1, 2, or 3 wherein x + z ^ 3,
M independently represents alkali metal and / or ammonium, and
E alkaline earth metal is preferably selected from H3PO4, (NH ^ I ^ pos j, (j ^ NHz HPC ^ and (H 4) 3P04, especially H3PO4 or (NH4) H2P04 is.
14. A catalyst obtainable by a process according to any one of claims 1 to 13.
15. The catalyst of claim 14, the phosphorus content a,
based on the total weight of the catalyst, in the range of 0.8 to 2.5 wt .-%, preferably in the range of 1.0 to 1.8 wt .-%, and even more preferably from about 1.4 -.% having .
16. A process for producing olefins from oxygenates in which a feed gas, preferably a gas containing methanol,
Dimethyl ether and / or a mixture thereof, is passed over a catalyst according to claim 14 or 15 °.
Use of a catalyst according to claim 14 or 15 for the conversion of oxygenates to olefins, in particular for
Conversion of methanol to olefins.
EP20140809025 2013-12-20 2014-12-08 Catalyst containing phosphorus for converting oxygenates into olefins Pending EP3083050A1 (en)

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DE10117248A1 (en) 2000-05-31 2002-10-10 Mg Technologies Ag A method for producing propylene from methanol
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