EP3083050A1 - Catalyseur contenant du phosphore pour la conversion de composés oxygénés en oléfines - Google Patents

Catalyseur contenant du phosphore pour la conversion de composés oxygénés en oléfines

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Publication number
EP3083050A1
EP3083050A1 EP14809025.1A EP14809025A EP3083050A1 EP 3083050 A1 EP3083050 A1 EP 3083050A1 EP 14809025 A EP14809025 A EP 14809025A EP 3083050 A1 EP3083050 A1 EP 3083050A1
Authority
EP
European Patent Office
Prior art keywords
phosphorus
catalyst
range
zeolite
methanol
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
EP14809025.1A
Other languages
German (de)
English (en)
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
Original Assignee
Clariant Produkte Deutschland GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Clariant Produkte Deutschland GmbH filed Critical Clariant Produkte Deutschland GmbH
Publication of EP3083050A1 publication Critical patent/EP3083050A1/fr
Pending legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7023—EUO-type, e.g. EU-1, TPZ-3 or ZSM-50
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7034—MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7042—TON-type, e.g. Theta-1, ISI-1, KZ-2, NU-10 or ZSM-22
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7046—MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/23—
    • B01J35/30—
    • B01J35/393—
    • B01J35/40—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/28—Phosphorising
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline 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
    • C01B39/026—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline 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
    • C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C01B39/38—Type ZSM-5
    • C01B39/40—Type ZSM-5 using at least one organic template directing agent
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/36—Steaming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/37—Acid treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J35/615—
    • B01J35/633—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0063—Granulating
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/14—Phosphorus; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11

Definitions

  • the present invention relates to a process for the preparation of zeolite-based phosphorus catalysts, to the catalysts prepared by this process, and to their use in a process for the conversion of oxygenates to olefins.
  • the invention particularly relates to the conversion of methanol or dimethyl ether into olefins (CMO process).
  • the invention also relates to the conversion of methanol into propylene.
  • Zeolite-based catalysts for the conversion of oxygenates into olefins are described, for example, in EP 0 448 000 A1 and EP 1 424 128 A1.
  • Reaction conditions also a progressive dealumination of the zeolitic material. This is caused by the water vapor, for example, in use
  • WO 2012/123558 and WO 2012/123556 describe the preparation of a zeolite-based phosphorus-modified catalyst by applying a phosphorus compound to an extruded and calcined zeolite.
  • WO 2012/123557 describes the preparation of a phosphorus-containing catalyst
  • Manufacturing processes do not involve steam treatment, whereas prior to use, the resulting catalysts must be subjected to a steam treatment in an MTO process.
  • US 4,356,338 describes a process for reducing carbon deposits and extending the life of a zeolitic catalyst by subjecting it to a steam treatment and / or a treatment with phosphorus-containing compounds.
  • This catalyst is characterized by a lower coking tendency in use as a catalyst for the aromatization of 1-heptene, at the same time a reduction in the starting yields can be observed.
  • the catalyst has phosphorus contents between 2 and 15% by weight.
  • WO 2011/044037 describes a zeolite-based catalyst obtained by treating a zeolite with a zeolite Phosphorus compound is prepared.
  • the phosphorus-treated zeolite is mixed with a binder, extruded,
  • EP 2 348 004 A1 describes a process for the preparation of a zeolite-based catalyst modified with phosphorus and the use of the catalyst in an MTO process.
  • the aluminum content of a ZSM-5 zeolite is reduced by steam treatment.
  • the catalyst is then prepared by applying phosphorus to the zeolite and then mixing the phosphorus-modified zeolite with one or more
  • Binders alkaline earth metal salts, rare earth metal salts, clays and molding additives.
  • WO 2009/156434 describes a process for producing lower olefins by providing an XTO reaction zone, an OC reaction zone and a catalyst regeneration zone using a zeolite-based phosphorus-modified catalyst.
  • a zeolite is subjected to steaming at a temperature of 400 ° C to 870 ° C for 0.01 to 200 hours, 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 process for preparing a phosphorus-modified zeolite-based catalyst and the use of the catalyst in a toluene-methylation process.
  • the zeolite is modified with phosphorus and then bound with an inorganic oxide binder which has been treated with mineral acid.
  • the catalyst is treated at a temperature of 300 ° C or less with steam.
  • phosphorus-modified catalysts shows that although the modification brings about an increase in the methanol conversion rate, the previous preparation methods on the other hand lead to a disadvantageously reduced (depending on the modification method used and phosphorus content more or less drastically precipitating)
  • Catalysts achieve propylene selectivities that can be optimized.
  • oxygenates such as methanol or dimethyl ether
  • methanol or dimethyl ether to lower olefins
  • propylene selectivity increases with increasing temperature.
  • deactivation by coking and dealumination in processes for converting oxygenates to olefins increases dramatically with increasing temperature.
  • Methanol or dimethyl ether in olefins is thus desirable, provided that the known disadvantages can be overcome on the performance of the catalyst.
  • lifetime in this context means the duration of the catalyzed conversion into hydrocarbons until the same conversion of, for example, not less than 95% is achieved prepared modified catalysts show that
  • Process conditions e.g., addition of water, such as in
  • Olefin selectivity especially on the selective release of propylene, can affect.
  • the cumulative yield of propylene obtained over a cycle can be determined by
  • An object of the present invention is a
  • Catalyst an increased Olefinausbeute with at least the same life by increasing the temperature in the process
  • a further object of the invention is to provide a simplified method of preparation of a catalyst, in which further process steps such as subsequent washing after application of a phosphorus-containing compound, repeated modification with a phosphorus-containing compound in a later process step or further treatment with acid to reduce the aluminum content omitted after the steam treatment.
  • a further object of the invention is therefore also a
  • the invention relates to a process for preparing a phosphorus-containing catalyst, comprising the following steps:
  • step (b) calcining the extrudate obtained in step (a),
  • step (c) treating the calcined extrudate obtained in step (b) with steam,
  • step (d) applying a phosphorus-containing compound to the steam-treated extrudate from step (c), and
  • the weight proportion of phosphorus in the catalyst obtained after step (e) is 0.8 to 2.5% by weight, preferably 1.0 to 1.8% by weight, and more preferably about 1.4% by weight. %, based on the total weight of the catalyst.
  • the catalyst allows by its increased resistance to coking and dealumination an increase in Propylene yield at least the same lifetime compared with a non-phosphorus-modified catalyst.
  • the invention therefore further relates to a after this
  • the catalyst of the invention is typically in an isothermal or
  • FIG. 1 shows the conversion of methanol to propylene
  • FIG. 2 shows the conversion of methanol to propylene
  • FIG. 3 shows the conversion of methanol to propylene over the comparative catalysts 3 and 4 and to the reference catalyst 0 at 450 ° C.
  • Cat. 3 Methanol conversion Propylene yield ⁇ ;
  • FIG. 4 shows the conversion of methanol to propylene
  • FIG. 5 shows the conversion of methanol to propylene
  • FIG. 6 shows the conversion of methanol to propylene
  • FIG. 7 shows the dependence of the propylene yield on
  • the invention relates to a process for preparing a phosphorus-containing catalyst, comprising the following steps:
  • step (c) treating the calcined extrudate obtained from step (b) with steam,
  • step (d) applying a phosphorus-containing compound to the steam-treated extrudate from step (c), and
  • the weight fraction of phosphorus in the catalyst obtained after step (e) is 0.8 to 2.5% by weight, preferably 1.0 to 1.8 wt .-%, and more preferably about 1.4 wt .-%, based on the total weight of the catalyst.
  • the zeolite used in step (a) has a phosphorus content of from 0 wt% to 0.01 wt%, preferably from 0 wt% to 0.001 wt%. It is particularly preferred that the zeolite used in step (a) is phosphate-free within the detection limit.
  • Phosphorus modification does not improve the propylene selectivity or lifetime.
  • the washing after modification rather determined a negative influence on the service life.
  • zeolite thus obtained is distinguished from a non-steamed zeolite by both improved hydrothermal stability and increased
  • Phosphorus modification can increase the hydrothermal stability of a zeolite. If the phosphorus modification is carried out on the zeolite before the steam treatment, the acidic centers should be stabilized via the interaction with the phosphorus-containing compounds present, so that the above-described effect of the steam treatment, compared with non-phosphorus zeolites, loses effectiveness. If the steam treatment according to the invention is carried out before the modification with a phosphorus-containing compound, the steam treatment is effectively effective, and the subsequent phosphorus modification protects the previously modified via steam treatment centers and contributes to further stability increase without selectivity losses (by the
  • Zeolites but also between the phosphorus-containing compounds and the acidic centers of the binder.
  • step (c) Treatment with water vapor only in step (c). That means that between extruding the zeolite and binder
  • step (a) preferably after the
  • step (d) Applying a phosphorus-containing compound in step (d) carried out no treatment with water vapor. It is particularly preferred that neither between steps (a) and (b) nor after step (d) takes place a water treatment.
  • step (d) Applying a phosphorus-containing compound only in step (d). This means that in particular neither before treating the extrudate with water vapor in step (c) nor after calcination of the phosphorus-modified extrudate in step (e)
  • the catalyst preparation process according to the invention has the following advantages over the prior art: increased catalyst life without reduction in propylene selectivity and greatly increased elevated temperature life in the process of converting oxygenates such as methanol or dimethyl ether into lower olefins. There is no further time and cost intensive steam treatment by the
  • oxygenates are understood as meaning oxygen compounds, in particular organic ones
  • Oxygen compounds such as alcohols and ethers.
  • the oxygen compounds reacted according to the invention are preferably methanol (conversion of methanol to olefins, CMO) or dimethyl ether.
  • CMO conversion of methanol to olefins
  • lower olefins are preferably to be understood as meaning olefins having a chain length of from 2 to 4 Cg.
  • the zeolite used in step (a) is usually a crystalline aluminosilicate zeolite.
  • the zeolite may have a structure as described in the "Atlas of Zeolite Framework Types" (Ch. Baerlocher, W. M. Meier, D. H. Olson,
  • Suitable zeolite materials are, for example, zeolites with a 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 EUO structure or also ZSM-21, ZSM-35, ZSM-38, ZSM-4, ZSM-18 or ZSM-57.
  • zeolites with a 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 EUO structure or also ZSM-21, ZSM-35, ZSM-38, ZSM-4, ZSM-18 or ZSM-57 zeolites with EUO structure or also ZSM-21, ZSM-35
  • the zeolite has a TON structure, MTT structure, MFI structure, MEL structure, MTW structure or EUO structure. It is also possible to use mixtures of zeolites of different structures.
  • the zeolite used in step (a) is a pentasil-type zeolite; more preferably, the zeolite has an MFI structure,
  • the zeolites are in the H form, i. in the protonated form.
  • suitable crystalline aluminosilicate zeolites is generally described in EP 1 424 128 B1, the disclosure of which is hereby expressly incorporated into the present description.
  • the zeolite used in step (a) preferably consists of aluminosilicate primary crystallites which have a middle
  • the catalyst obtainable by the process according to the invention also contains a zeolite consisting of aluminosilicate primary crystallites having an average diameter in the range of 0.010 ⁇ to 0.100 ⁇ , more preferably in the range of 0.010 ⁇ to 0, 060 ⁇ , and on
  • the average diameter of the primary crystallites is defined as the mean diameter arithmetic mean of a plurality of crystallites (eg, from 10 to 100, preferably 10 to 20, for example, 14 or 15), the average diameter of the individual crystallites being an arithmetic mean between is defined as the largest and the smallest diameter of a single crystallite, wherein the largest or smallest diameter of a crystallite on the basis of scanning electron microscopy
  • Crystallites In the case of spherical or approximately spherical crystallites, the largest and the smallest diameter coincide.
  • the zeolite used in step (a) preferably has a Si / Al atomic ratio in the range from 50 to 250, preferably in the range from 50 to 150, in particular in the range from 75 to 140, more preferably in the range from 85 to 125.
  • the binder used in step (a) is 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, eg. B. to mixtures of the aforementioned oxides (except alumina) with alumina.
  • 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, eg. B. to mixtures of the aforementioned oxides (except alumina) with alumina.
  • amorphous aluminosilicates and non-oxidic binders for example aluminum phosphates.
  • the binder used in step (a) is preferably an aluminum oxide which is also present as alumina hydrate or as
  • modified alumina can be used.
  • Modified alumina is, for example, phosphorus-modified alumina. Particularly preferred is the use of finely divided aluminum oxide, the z. B. by
  • Alumina hydrate is used. Very particular preference is given to using peptisable alumina hydrate as binder. Preferably, at least 95% of the particles of the
  • the binder in step (a) is present in an amount ranging from 5 to 60 wt.%, More preferably in the range of 8 to 40 wt.%, Particularly preferably in the range of 10 to 35 wt. based on the total weight of zeolite used and
  • Binder to use.
  • the mixture in step (a) is 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
  • step (a) Contains nitric acid. It is further preferred that the mixture in step (a) contains the acid, if present, in aqueous solution.
  • the mixture may still contain additives in step (a)
  • oils for example, oils, paraffin wax, methyl cellulose or
  • step (a) 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 one
  • Mixers e.g. a mixer with movable mixing tools and fixed chamber or a mixer with movable mixing tools and moving chamber.
  • step (a) The extrusion of the binder-zeolite mixture (wherein the term binder-zeolite mixture as used herein also includes mixtures which may also contain other ingredients such as an inorganic or organic acid and / or additives) in step (a) done by using a commercial binder-zeolite mixture (wherein the term binder-zeolite mixture as used herein also includes mixtures which may also contain other ingredients such as an inorganic or organic acid and / or additives) in step (a) done by using a commercial
  • Extruder such as a single-screw extruder or
  • step (a) Extrusion) in step (a) from a plastifiable mass of the binder-zeolite mixture which, after shaping, is subjected to calcination in step (b) in order to obtain the desired stability.
  • the calcination in step or step (e) is usually carried out for 10 minutes to 15 hours, preferably carried out for 1 h to 10 h.
  • Calcining temperature is usually in a range of 350 ° C to 700 ° C, preferably in a range of 400 ° C to 700 ° C, in particular in a range of 500 ° C to 600 ° C,
  • step (b) most preferably at about 550 ° C. It is particularly preferred that the calcination in step (b) for 1 h to 10 h,
  • step (e) for 1 h to 10 h, in particular for 5 h, at a temperature in the range of 400 ° C to 700 ° C, in particular in a range of 500 ° C to 600 ° C, and more preferably for about 5 h at about 550 ° C is performed. It is further preferred that the calcination in step (e) for 1 h to 10 h, in particular for 5 h, at a temperature in
  • the extrudate obtained from step (a) or from step (d) is preferably dried before being subjected to the calcination step (b) or the calcination step (e).
  • the drying is usually carried out for 5 minutes to 24 hours at a temperature in the range of 50 ° C to 150 ° C, preferably for 1 to 10 hours at a temperature in the range of 80 ° C to 150 ° C, and more preferably for about 5 hours performed at about 120 ° C.
  • the invention relates to a process for preparing a phosphorus-containing catalyst, comprising the following steps:
  • step (b) drying and calcining the extrudate obtained from step (a), (c) treating the calcined extrudate obtained from step (b) with steam,
  • step (d) applying a phosphorus-containing compound to the steam-treated extrudate from step (c), and
  • the weight fraction of phosphorus in the catalyst obtained after step (e) is from 0.8 to 2.5% by weight, preferably from 1.0 to 1.8% by weight, and more preferably about 1.4% by weight. %, based on the total weight of the catalyst.
  • the invention relates to a process for preparing a phosphorus-containing catalyst, comprising the following steps:
  • step (b) drying and calcining the extrudate obtained from step (a),
  • step (c) treating the calcined extrudate obtained from step (b) with steam,
  • step (d) applying a phosphorus-containing compound to the steam-treated extrudate from step (c), and
  • the weight fraction of phosphorus in the catalyst obtained after step (e) is from 0.8 to 2.5% by weight, preferably from 1.0 to 1.8% by weight, and more preferably about 1.4% by weight. %, based on the total weight of the catalyst, and
  • step (b) and step (e) at a temperature in the range of 80 ° C to 150 ° C for 1 to 10 h, preferably 6 to 8 h, and calcining both
  • step (b) as well as in step (e) at a temperature in the range of 500 ° C to 600 ° C for 6 to 8 h becomes .
  • the catalyst is brought into contact with water after the calcination step (e), in particular after step (e) no further steam treatment is required prior to use in a process for the conversion of oxygenates such as methanol or
  • the treatment with water vapor in step (c) is usually carried out at a partial water vapor pressure in the range of 0.1 to 1 bar, a temperature in the range of 400 ° C to 850 ° C, a WHSV
  • Weight hourly space velocity in the range of 0.01 to 10 h _ l and for 0.5 to 100 h, preferably at a water vapor partial pressure of about 1 bar, a temperature of 400 ° C to 650 ° C (in particular of 480 ° C to 550 ° C) a WHSV of about 1 h _ l and a duration of about 48 h performed.
  • the phosphorus-containing compound can be applied in step (d) as a solid or in solution. It is preferable that the phosphorus-containing compound is used in solution.
  • 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 acids or organic phosphorus acids, phosphorus (V) halides, phosphorus (III) halides, phosphorus oxyhalides,
  • Phosphorus (V) oxide Phosphorus (V) oxide, phosphorus (III) oxide and mixtures thereof.
  • M is independently alkali metal and / or ammonium
  • E is alkaline earth metal
  • the phosphorus-containing compound used in the process according to the invention is H 3 PO 4 , (NH 4 ) H 2 PO 4 , (NH 4 ) 2 HPO 4 and / or (NH 4 ) 3 PO 4 .
  • the application of the phosphorus-containing compound from aqueous solution is carried out for example by a "wet impregnation” method or an “Incipient Wetness” method.
  • the extrudate is usually first suspended in the phosphorus-containing solution and the suspension for improved interaction of the
  • the phosphorus-containing compound with the extrudate optionally heated to a temperature in the range of 45 ° C to 95 ° C.
  • the water of the impregnating solution is removed in the gaseous state, in particular completely removed by distillation at elevated temperature in the range from 75 ° C. to 115 ° C. and / or from 0.01 MPa to 0.1 MPa.
  • the distillative removal of the water of the impregnating solution can be carried out, for example, using a rotary evaporator.
  • the extrudate is contacted with the phosphorus-containing solution, the volume of the phosphorus-containing solution corresponding to the pore volume of the extrudate, that is, the volume of phosphorus-containing solution becomes the adsorption volume of the extrudate adjusted so that after impregnation no excess solution is no longer available Volume can be determined by a precisely weighed amount of the extrudate material to be impregnated in a solution consisting of dist. Water is added, the extrudates are completely covered by the aqueous solution. After allowing the solution to stand for a sufficient time, usually H h, the solution is decanted off and the still moist extrudates are weighed again. If the density of the solution is known, the recorded volume can be calculated from the increase in weight, which also corresponds to the volume of the phosphorus-containing solution in the case of incipient wetness loading with the phosphorus-containing solution
  • Extrudate is applied in the form of a solution, the product obtained is usually dried as described above, before it is subjected to the calcination step (e).
  • the drying is usually in the range of 5 minutes to 24 hours at a temperature in the range of 50 ° C to 150 ° C, preferably at a temperature in the range of 80 ° C to 150 ° C, and preferably for about 5 hours at about 120 ° C performed.
  • the phosphorus content is preferred by the method of
  • Controlled application more preferably by application via Incipient Wetness, whereby the entire existing in solution
  • Phosphorus amount is applied to the extrudates.
  • the catalyst obtainable by the process according to the invention preferably has a phosphorus content of from 0.8 to 2.5% by weight, more preferably from 1.0 to 1.8% by weight, and most preferably about 1.4% by weight. based on the total weight of the catalyst.
  • the catalyst obtainable by the process according to the invention preferably has a BET surface area in the range from 250 to 450 m.sup.2 / g, in particular in the range from 270 to 410 m.sup.2 / g and particularly preferably in the range from 300 to 390 m.sup.2 / g according to DIN 66131, on.
  • the pore volume of the invention is preferably a pore volume of the invention
  • Catalyst determined by the mercury porosimetry method according to DIN 66133, 0, 3 to 0.8 cm - ⁇ / g, in particular 0.30 to 0.45 cm - ⁇ / g.
  • the catalyst according to the invention can be used particularly advantageously in processes for the production of olefins by the conversion of oxygenates such as methanol or dimethyl ether.
  • Part of the invention is therefore a process for the preparation of olefins from oxygenates, preferably from methanol, dimethyl ether or mixtures thereof, wherein a reactant gas, i. the gaseous starting material is passed over the catalyst according to the invention.
  • oxygenates are understood as meaning oxygen compounds, in particular organic ones
  • the present invention therefore preferably relates to a process for the preparation of lower olefins, in particular of C 1 -C 4 -olefins, from oxygenates (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, of a methanol or dimethyl ether vapor and Steam-containing reaction mixture in a reactor on an indirectly cooled catalyst of the invention.
  • oxygenates Oxygenates to olefins, OTO
  • OTO oxygenates to olefins
  • OTO oxygenates to olefins
  • methanol Conversion of Methanol to olefins, CMO
  • CMO conversion of Methanol to olefins
  • the catalyst according to the invention can be subjected to a steam treatment.
  • the catalyst prepared according to the invention is directly, i. without a preceding steam treatment, used in the catalytic reaction.
  • zeolite-containing extrudate has a decisive influence on the product composition in the conversion of methanol to olefins and significantly increases the service life of the catalyst.
  • Phosphorus treatment to increase the propylene yield, while, for example, a modification, as known from DE 10 2011 013 909, in the first a
  • Catalyst and can also not be influenced by the amount of phosphorus applied see Table 2, Test Run 8, Comparative Catalysts 13 to 16).
  • Phosphorus content of about 1.6 wt .-% achieved. Since the formation of aromatics in a conversion of oxygenates to olefins is associated with the formation of carbonaceous deposits, a catalyst according to the invention having a phosphorus content of about 1.6% by weight is characterized by an increase in propylene yield, a longer service life and minimal formation of aromatics as by-products.
  • the reaction of methanol with the catalyst of the 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 in the range of 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 in the range of 0.5 to 3, and at a temperature of the reactor cooling medium in the range of 280 ° C to 570 ° C, preferably in the range of 400 ° C to 550 ° C.
  • a total pressure in the range of 0.1 to 1.5 bar, in particular at a total pressure in the range of 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 in the range of 0.5 to 3, and at a temperature of the reactor cooling medium in the range of 280 ° C to 570 ° C, preferably in the range of 400 ° C to 550 ° C.
  • Catalyst comprising the following steps:
  • step (a) extruding a mixture comprising a zeolite and a binder, (b) calcining the extrudate obtained from step (a),
  • step (c) treating the calcined extrudate obtained from step (b) with steam,
  • step (d) applying a phosphorus-containing compound to the steam-treated extrudate from step (c), and
  • Catalyst is. Process according to embodiment 2, wherein the proportion by weight of phosphorus in the catalyst obtained after step (e) is about 1.4% by weight, based on the total weight of the catalyst
  • Catalyst is.
  • step (i) there is no treatment with water vapor both between the extrusion in step (a) and the calcination in step (b) and after the application of a phosphorus-containing compound in step (c)
  • step (ii) both before treating the extrudate with water vapor in step (c) and after calcining it with phosphorus modified extrudates m step (e) no application of a phosphorus-containing compound takes place.
  • step (a) comprises 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.
  • Mixtures thereof preferably having an MFI structure, more preferably a ZSM-5 type structure.
  • the zeolite has an 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 125 ,
  • a method according to any one of embodiments 1 to 9, wherein the zeolite of aluminosilicate primary crystallites having a mean diameter in the range of 0.010 ⁇ to 0.100 ⁇ , more preferably in the range of 0.010 ⁇ to 0, 060 ⁇ , and most preferably in the range of 0.015 ⁇ to 0, 050 ⁇ exists.
  • a process according to any one of embodiments 1 to 10, wherein the zeolite is in the H form.
  • a process according to any one of embodiments 1 to 11, wherein the binder contained in the mixture extruded in step (a) is alumina, magnesia, titania,
  • Phosphorus (V) oxide Phosphorus (III) oxide and mixtures thereof.
  • a method according to any of embodiments 1 to 14, wherein the phosphorus-containing compound in step (d) is independent is selected from PY5, ⁇ ⁇ 3 ' M x E z / 2 H 3- (x + z) PO4 ⁇
  • M is independently alkali metal and / or ammonium
  • E is alkaline earth metal
  • 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.
  • a catalyst obtainable by a process according to any one of embodiments 1 to 17.
  • 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 .-%.
  • a process for the preparation of olefins from oxygenates wherein a reactant gas, preferably a gas, the methanol,
  • the mean primary crystallite size was determined as described above by means of scanning electronic investigations.
  • the median lateral compressive strength was determined from the force acting on the side surface (longest side) of the molded bodies until fracture occurs. These were from a
  • Representative sample of moldings 50 moldings selected with a length in the range of 5.5 to 6.5 mm and measured individually. The moldings were crack-free and straight. A shaped body was placed between two measuring jaws (one movable and one stationary). The movable jaw was then moved evenly toward the molded body until the breakage of the molded article occurred. The fracture reading in kiloponds (kp), measured with a Schleuniger measuring instrument, was divided by the length of the molding to give the lateral compressive strength of the mold
  • the specific surface area was determined according to DIN 66131 using nitrogen.
  • the pore volume was measured by the mercury porosimetry method and the pore diameter was calculated according to DIN 66133.
  • Reference Example 1 Preparation of an H-zeolite having an average primary crystallite size of 0.03 ⁇ m
  • reaction mixture was prepared by intimately mixing a
  • the washing process was repeated until the washing water had a pH of 7 to 8 and a Br concentration of less than 1 ppm.
  • the filter cake was then dried at 120 ° C for 12 h.
  • the dried filter cake was comminuted with a commercial granulator to a grain size of 2 mm.
  • the granules were brought to 350 ° C at a rate of 1 ° C / minute under nitrogen (1000 Nl / h) and calcined at 350 ° C for 15 hours under nitrogen (1000 Nl / h). Then, the temperature was raised to 540 ° C at a heating rate of 1 ° C / minute, and that
  • Granules were calcined in air for 24 hours at this temperature to to burn off the remaining tetrapropylammonium bromide; finally, a calcined Na zeolite was obtained.
  • the calcined Na zeolite was suspended in a 5-fold amount of a 1-molar aqueous HCl solution and brought to 80 ° C. At this temperature, it was stirred for one hour. Then, about 1 liter of a 0.4% by weight suspension of the flocculant was added and the supernatant was decanted after settling the solid. The process thus described was repeated once more.
  • the solid was suspended in about 10 washings each in 60 liters of deionized water with stirring and mixed with an average of 100 ml of a 0.4 wt .-% suspension of the flocculant. After settling the solid, the supernatant 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 mixed with a commercial one
  • Granulator comminuted to 2 mm, brought under air at a heating rate of l ° C / minute to 540 ° C and calcined at this temperature under air for 10 h.
  • the BET surface area of the zeolite thus obtained was 434 m 2 / g.
  • the average particle diameter of the primary crystallites was 0.03 ⁇ .
  • the Si / Al ratio was 105: 1.
  • the BET surface area of the catalyst was determined to be 391 m 2 / g.
  • the side crush strength was 0.67 kgf / mm (6.47 N / mm), the
  • Pore volume determined at 0.33 ml / g.
  • the phosphorus content of the catalyst was 1.4% by weight.
  • the BET surface area of the catalyst was determined to be 333 m 2 / g.
  • the side crush strength was 0.96 kp / mm (6.43 N / mm), the
  • the phosphorus content of the catalyst was 1.8% by weight.
  • the BET surface area of the catalyst was determined to be 340 m 2 / g.
  • the pore volume was determined to be 0.30 ml / g.
  • Comparative Example 2 Preparation of Comparative Catalyst 3 1400 g of the ZSM-5-H zeolite prepared in Reference Example 1 was suspended in 7066 g of phosphoric acid solution (about 0.8 wt% in water) at 80 ° C to 90 ° C for 2 hours. Subsequently, the suspension was applied by means of a spray-drying process up to
  • the suspension was introduced 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 deposited in a cyclone. The powder was then calcined at 540 ° C for about 10 hours. The phosphorus content of the powder was 1.2% by weight. The BET surface area was determined to be 394 m 2 / g.
  • the shaping was carried out by means of a commercially available extruder.
  • the extruded shaped catalyst bodies had a diameter of about 3 mm and a length of about 6 mm.
  • Catalyst moldings were dried at 120 ° C for 18 h and calcined at 550 ° C for 5 h to give catalyst 3.
  • Phosphorus content of the catalyst was 0.086 wt .-%.
  • the BET surface area of the catalyst was determined to be 387 m 2 / g.
  • the side crush strength was 0.90 kp / mm (8.85 N / mm), the
  • Pore volume determined at 0.34 ml / g.
  • Comparative Example 3 Preparation of Comparative Catalyst 4 1400 g of the ZSM-5-H zeolite prepared in Reference Example 1 was suspended in 7200 g of phosphoric acid solution (about 2.4 wt% in water) at 80 ° C to 90 ° C for 2 hours. Subsequently, the suspension was applied by means of a spray-drying process up to
  • the suspension was introduced 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 deposited in a cyclone. The powder was then calcined at 540 ° C for about 10 hours. The phosphorus content of the powder was 3.4% by weight. The BET surface area was determined to be 296 m 2 / g.
  • Phosphorus content of the powder was 0.30 wt%.
  • the BET surface area was determined to be 374 m 2 / g.
  • the shaping was carried out by means of a commercially available extruder.
  • the extruded shaped catalyst bodies had a diameter of about 3 mm and a length of about 6 mm.
  • Catalyst shaped bodies were dried at 120 ° C. for 16 h and calcined at 550 ° C. for 5 h, giving catalyst 4
  • Phosphorus content of the catalyst was 0.24 wt .-%.
  • the BET surface area was determined to be 374 m 2 / g.
  • Side crush strength was determined to be 0.91 kp / mm (8.91 N / mm), pore volume to be 0.33 ml / g.
  • Comparative Example 4 Preparation of Comparative Catalyst 5 1200 g of a ZSM-5-H zeolite prepared analogously to Reference Example 1 with an average particle diameter of
  • Phosphoric acid solution (about 1.5 wt .-% in water) at 80 ° C for 2 h suspended. Subsequently, the suspension was by means of a
  • Suspension was introduced via a nozzle at a temperature of about 220 ° C in an NIRO spray dryer. A finely divided powder is obtained. The powder was then deposited in a cyclone. The powder was then calcined at 540 ° C for about 10 hours. The phosphorus content of the powder was 2.3% by weight. The BET surface area was determined to be 327 m 2 / g.
  • the shaping was carried out by means of a commercially available extruder.
  • the extruded shaped catalyst bodies had a diameter of about 3 mm and a length of about 6 mm.
  • Catalyst shaped bodies were dried at 120 ° C. and calcined at 550 ° C. for 5 hours, giving catalyst 5
  • Phosphorus content of the catalyst was 2.00% by weight.
  • the BET surface area was determined to be 337 m 2 / g.
  • the pore volume was 0.43 cm - ⁇ / g.
  • the measurement of average lateral compressive strength gave a value of about 0.14 kp / mm (1.37 N / mm).
  • the novel catalysts 7-10 were prepared by firstly subjecting the reference catalyst 0 obtained in Reference Example 2 to a steam treatment according to Example 2. In each case 35 g of this steam-treated catalyst were phosphorus-modified using a rotary evaporator analogous to the method described in Example 1, by each 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 an 85% by weight phosphoric acid (H 3 P0 4 ) (the difference to 175 g was distilled H 2 O) was concentrated to dryness.
  • 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 an 85% by weight phosphoric acid (H 3 P0 4 ) (
  • Comparative Example 6 Preparation of Comparative Catalysts 13-16 Comparative Catalysts 13-16 were prepared according to the teaching of DE10 2011 013 909.
  • the previously not treated with steam reference catalyst 0 was loaded by an Incipient Wetness method with phosphorus by each 50 g of the reference catalyst 0 were applied with 19 g of a phosphoric acid solution.
  • the 19 g of the phosphoric acid solution consisted of an 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 to 19 g from dist. H 2 0. Thereafter, the respective product was dried for 4 h at 120 ° C and calcined for 5 h at 550 ° C in air. Subsequently, the catalysts were treated with steam.
  • Table 1 Chemical composition, specific surface area, pore volume and lateral compressive strengths of catalysts 0 to 10 and 13 to 16.
  • the catalyst samples were examined for their catalytic behavior in the conversion of methanol to olefins. This
  • Application example shows the benefits of the catalyst according to the invention based on catalytic data of the CMO process (conversion of methanol-to-olefins process) in an isothermal fixed bed reactor.
  • volume ratio 1: 4 (catalyst: SiC) diluted and each in a vertical isothermal fixed bed reactor with a
  • catalysts 0, 3 and 4 Prior to the catalytic test, catalysts 0, 3 and 4 were heated to 480 ° C under nitrogen flow. After that, the
  • composition of the products at the exit of the CMO catalyst reactor was determined by gas chromatographic analysis methods.
  • the selectivity S j _ results from the molar carbon content of component i relative to the converted carbon
  • Carbon content of component i based on the total carbon used.
  • the total carbon used is calculated as the sum of all carbon-containing products, plus the starting materials methanol (MeOH) and the dimethyl ether (DME) in equilibrium:
  • the total carbon used is calculated as the sum of all carbon-containing products, plus the starting materials methanol (MeOH) and the dimethyl ether (DME) in equilibrium:
  • Table 2 are the propylene, ethylene and aromatics yield when using the catalysts 0, 1, 2, 3, 4 and 6 and their life at a reaction temperature of 450 ° C (temperature of the reactor) and the propylene, ethylene and Aromatenausbeute when using the catalysts 0 and 1 and their life at a reaction temperature of 475 ° C (temperature of the reactor) summarized.
  • the lifetime is the duration of the catalytic reaction relative to the reference catalyst Catalyst 0 at a
  • Reaction temperature of 450 ° C to which the conversion is 95% or higher.
  • the propylene, ethylene and aromatics yield was determined as the mean value at a methanol conversion of greater than or equal to 99.0% from the data of the gas chromatographic product analysis.
  • Reference catalyst 0, catalysts 7 to 10 according to the invention and 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.
  • the duration was 24 h.
  • the reaction temperature was 475 ° C, the propylene, ethylene and Aromatenausbeuten when using the catalysts and their
  • the duration of the steam treatment in Table 2 refers to the steam treatment during the synthesis for the catalysts 1, 2 and 6 to 10, and to the steam treatment before the reaction for the catalysts 0, 3 and 4 (this final steam treatment is omitted for the catalysts 1 , 2 and 6 to 10).
  • catalysts 1 and 6 to 10 of the invention are characterized in that the lifetime of the catalyst is increased without causing a measurable negative effect on the propylene yield.
  • the advantage of the catalyst 1 of the invention is especially when comparing the reaction at 475 ° C with the reaction on
  • Inventive catalyst 1 is still increased by 35% compared to reference catalyst 0 at 450 ° C (see also Figure 1).
  • Catalyst 6 also shows that the propylene selectivity can be increased by increasing the temperature without reducing the service life (see also FIG. 6).
  • the comparative catalysts are characterized by either a lower one
  • Catalyst 1 reduces the life to only about 90% (compared to Catalyst 1 at 450 ° C) when the reaction is carried out at 475 ° C instead of 450 ° C.
  • the catalyst 1 of the invention over the reference catalyst 0 at 475 ° C has a nearly twice as long life (see Figures 4 and 5).
  • Comparative catalysts 3 and 4 have an increased lifetime.
  • Comparative catalyst 4 3.4 wt .-% P) with subsequent washing before extrusion, to a deterioration of
  • Catalyst 1 has comparable phosphorus content, the initial phosphorus content would have to be increased far beyond that of the catalyst 4. It can be deduced from this that a significantly reduced propylene selectivity would be expected for a catalyst prepared in this way. Thus, such a catalyst would be less so for the conversion of
  • a comparable catalyst according to the invention with a similar high phosphorus content (comparative catalyst 5), of about 2.0 wt .-%, by phosphorus modification of
  • Zeolithpulvers is produced without washing, is insufficient for further processing into a molded article, since its mechanical stability (lateral compressive strength about 0.14 kp / mm (1.37 N / mm)) is so low that here problems during transport and Fill the reactor yield, since the moldings break apart very quickly. Furthermore, it is found that the order of treatment of the zeolite-containing extrudate has a decisive influence on the product composition in the conversion of methanol to olefins and significantly increases the lifetime of the catalyst.
  • Phosphorus treatment to increase the propylene yield, while, for example, a modification, as known from DE 10 2011 013 909, in the first a
  • Catalyst and can also not be influenced by the amount of phosphorus applied see Table 2, Test Run 8, Comparative Catalysts 13 to 16).

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Abstract

La présente invention concerne un nouveau procédé de production d'un catalyseur contenant du phosphore dans lequel le catalyseur est soumis à un traitement à la vapeur. L'invention concerne également le catalyseur qui peut être obtenu par ce procédé, ainsi que son utilisation dans un procédé de production d'oléfines à partir de composés oxygénés. Le traitement à la vapeur du catalyseur se fait généralement avant la modification dudit catalyseur avec un composé contenant du phosphore.
EP14809025.1A 2013-12-20 2014-12-08 Catalyseur contenant du phosphore pour la conversion de composés oxygénés en oléfines Pending EP3083050A1 (fr)

Applications Claiming Priority (2)

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DE102013021950 2013-12-20
PCT/EP2014/076938 WO2015091078A1 (fr) 2013-12-20 2014-12-08 Catalyseur contenant du phosphore pour la conversion de composés oxygénés en oléfines

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EP3083050A1 true EP3083050A1 (fr) 2016-10-26

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EP14809025.1A Pending EP3083050A1 (fr) 2013-12-20 2014-12-08 Catalyseur contenant du phosphore pour la conversion de composés oxygénés en oléfines

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US (1) US10293333B2 (fr)
EP (1) EP3083050A1 (fr)
JP (1) JP6545172B2 (fr)
CN (1) CN105828943B (fr)
RU (1) RU2635567C1 (fr)
WO (1) WO2015091078A1 (fr)

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CN112898110B (zh) * 2019-12-03 2022-06-24 中国科学院大连化学物理研究所 高碳醇脱水制α-高碳烯烃的方法
CN112898109A (zh) * 2019-12-03 2021-06-04 中国科学院大连化学物理研究所 一种α-高碳醇脱水制α-高碳烯烃的方法

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Publication number Publication date
JP6545172B2 (ja) 2019-07-17
US20160318007A1 (en) 2016-11-03
CN105828943A (zh) 2016-08-03
RU2635567C1 (ru) 2017-11-14
WO2015091078A1 (fr) 2015-06-25
JP2017501030A (ja) 2017-01-12
CN105828943B (zh) 2019-03-08
US10293333B2 (en) 2019-05-21

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