WO2014037192A1 - Traitement au méthanol de catalyseurs de craquage atae contenant de l'aluminosilicate - Google Patents

Traitement au méthanol de catalyseurs de craquage atae contenant de l'aluminosilicate Download PDF

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Publication number
WO2014037192A1
WO2014037192A1 PCT/EP2013/066919 EP2013066919W WO2014037192A1 WO 2014037192 A1 WO2014037192 A1 WO 2014037192A1 EP 2013066919 W EP2013066919 W EP 2013066919W WO 2014037192 A1 WO2014037192 A1 WO 2014037192A1
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Prior art keywords
catalyst
methanol
cleavage
mass
treatment
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PCT/EP2013/066919
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German (de)
English (en)
Inventor
Frank GEILEN
Markus Winterberg
Horst-Werner Zanthoff
Stephan Peitz
Dietrich Maschmeyer
Reiner Bukohl
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Evonik Industries Ag
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Publication of WO2014037192A1 publication Critical patent/WO2014037192A1/fr

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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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and alumina
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
    • 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
    • C07C2521/12—Silica and alumina
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the invention relates to a process for the preparation of an aluminosilicate-containing catalyst, which is intended for use in the cleavage of alkyl tert-alkyl ethers to olefins and alcohols. Furthermore, the invention relates to a
  • Alkyl tert-alkyl ethers are compounds of the formula II
  • radical R is an alkyl radical having 1 or 2 carbon atom (s)
  • radical R 1 is H, methyl or ethyl radical
  • radicals R 2 and R 3 are methyl or ethyl radicals, wherein the radicals R 2 and R 3 may be the same or different.
  • ATAE substance class methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE) and tert-amyl methyl ether (TAME).
  • MTBE methyl tert-butyl ether
  • ETBE ethyl tert-butyl ether
  • TAME tert-amyl methyl ether
  • Olefins also called alkenes, are unsaturated hydrocarbons of the formula I.
  • radical R is an alkyl radical having 1 or 2 carbon atom (s)
  • radical R 1 is H, methyl or ethyl radical
  • radicals R 2 and R 3 are methyl or ethyl radicals, wherein the radicals R 2 and R 3 may be the same or different.
  • Isobutene is an olefin in the sense of this definition.
  • Alcohol in the context of the invention is a compound of formula III R-OH III wherein the radical R is an alkyl radical having 1 or 2 carbon atom (s). Examples of alcohols include methanol and ethanol.
  • the synthesis of pure olefins can be accomplished by the selective, catalytic cleavage of the underlying ethers.
  • isobutene can be prepared by cleavage of methyl or ethyl-tert-butyl ethers (MTBE or ETBE).
  • MTBE or ETBE methyl or ethyl-tert-butyl ethers
  • the by-product of the reaction is the corresponding alcohol (methanol or ethanol).
  • the cleavage can be carried out technically in the gas phase, the liquid phase or in a gas / liquid mixed phase. Because when increasing the reaction temperature, the equilibrium position of the endothermic
  • reaction in favor of the products the reaction in the gas phase is often preferred.
  • the cleavage reaction can be carried out on acidic or basic catalysts.
  • Gas-phase processes are usually used catalysts based on Br ⁇ nsted acidic amorphous aluminosilicates or zeolites.
  • a number of undesirable side reactions and / or subsequent reactions may occur, especially at relatively high reaction temperatures.
  • the most frequently described in the literature are the formation of dimethyl ether from methanol (or diethyl ether from ethanol) and the oligomerization of the target olefin, for example isobutene to Cs or higher olefins.
  • Catalysts show distinctly different activities for the cleavage reaction and also different selectivities to the target products.
  • No. 5,225,754 describes a ZSM-5 zeolite catalyst which achieves an MTBE conversion of 97% at 190 ° C. and 1 bar, the isobutene selectivity being 99.5% and the methanol selectivity being 96.5%.
  • EP1894621 A1 describes an amorphous, with alkali and / or
  • Alkaline earth metal oxides doped aluminosilicate as a catalyst With this catalyst, high isobutene selectivities of> 99.9% and likewise high methanol selectivities of> 97.0% are achieved at a conversion of 85% when the reactor is operated at 250 ° C. and 7 bar overpressure. However, the doping leads to a significant reduction in the activity of the catalyst material. More active catalysts have also been described, for example in patent application DE10201 1005608A1, which is still unpublished on the filing date. These can be operated at lower temperatures of 220 ° C with the same conversion of 85%. However, it is reported that because of its high activity, the catalyst had to be diluted with twice the volume of a catalytically inactive material.
  • a dilution implies an increased reactor volume with the same space-time yield, which leads to higher investment costs and thus the
  • the alkali and alkaline earth metals which, for example, in
  • EP1894621 A1 is described. This doping leads to a neutralization active centers, thus permanently reducing activity. The aging of the catalyst is not affected by this.
  • Solid e.g. described in DE10201 1005608A1.
  • the dilution may be made on the one hand prior to shaping of the catalyst, by mixing the catalyst material and an inert material, which are then subjected to shaping (e.g., by tableting or extrusion) to produce shaped articles having a reduced content of catalytically active centers.
  • shaping e.g., by tableting or extrusion
  • Catalyst are filled together with moldings of an inert material in the reactor. Regardless of the type of dilution, a significant aging of the catalyst is observable and the final activity after aging is permanently lower than that of the undiluted material.
  • WO 201/161045 A1 describes the dilution of the educt stream with an inert component. This can lead to a reduction of
  • WO201 1 161045A1 moreover describes the continuous metering of various catalyst poisons into the educt stream of a reactor for the splitting of alcohols into olefins. These poison some of the active sites during operation.
  • suitable substances ammonia or all kinds of organic nitrogen compounds are proposed.
  • aldehydes ketones and carboxylic acid esters should be suitable.
  • the disadvantage of this method is the need for permanent dosage of Poison component, as well as the separation of these compounds from the
  • the invention is based on the object to provide a method for producing an acidic heterogeneous catalyst, which is characterized in the ATAE cleavage by a reduced initial activity.
  • Catalyst poisons are dosed continuously.
  • Another aspect of the invention is the reduction of by-product formation by dimerization of the product olefins in the ATAE cleavage, as well as a reduction in the loss of activity due to aging of the catalyst.
  • the problem is solved by treating the catalyst with methanol prior to its use in the ATAE cleavage.
  • the subject of this invention is therefore a process for the preparation of a
  • Aluminosilicate-containing catalyst which is intended for use in the cleavage of alkyl tert-alkyl ethers to olefins and alcohols, wherein the
  • Catalyst is treated with methanol before its use.
  • the invention applies to amorphous or crystalline aluminosilicate-containing catalysts, ie those based on aluminum oxide (Al 2 O 3) and silicon dioxide (SiO 2).
  • the invention can be applied to such catalysts, which are amorphous or crystalline aluminosilicates, ie
  • Alumina and silica compounds in which aluminum also occupies silicon lattice sites This also expressly includes those compounds which are predominantly silica and contain 1% or less of alumina.
  • These types of catalysts belong to the category of acid heterogeneous catalysts.
  • composition of the catalyst treated according to the invention can thus be defined as follows: silicon: 50 to 99.9% by mass (calculated as SiO 2 );
  • Aluminum 0.1 to 50% by mass, preferably 0.1 to 20% by mass, particularly preferably 0.5 to 1 1% by mass (calculated as Al 2 O 3);
  • Alkali metal 0 to 15 mass% (calculated as M 2 O, where M is the alkali metal);
  • Alkaline earth metal 0 to 30 mass% (calculated as MO, where M stands for the
  • Alkaline earth metal is standing.
  • the invention focuses on the treatment of such catalysts with methanol.
  • Methanol treatment is the subject of unpublished patent application DE10201 1005608A1 on the filing date.
  • the essential steps in the preparation of the catalyst according to the invention are therefore: a) flame-hydrolytic preparation of a mixed oxide containing silicon and aluminum; b) transferring the mixed oxide into a catalyst precursor; c) treating the catalyst precursor with methanol to obtain the
  • Volatile silicon and aluminum compounds are injected into an oxyhydrogen gas flame of hydrogen and oxygen or air in the so-called “co-fumed process.”
  • the volatile silicon and aluminum compounds are produced by the Hydrogenated water resulting from the oxyhydrogen flame and forms the mixed oxide and the acid of the counterion of the silicon and aluminum compounds.
  • an aerosol is fed into an oxyhydrogen flame in which an oxide, for example silicon oxide, is produced from a volatile compound, eg silicon tetrachloride, by flame hydrolysis, a salt of the element to be doped, eg aluminum, being present in this aerosol and so forms the corresponding mixed oxide.
  • the flame-hydrolytically produced oxides or mixed oxides are distinguished by the following special features: ⁇ high chemical purity,
  • silicon-aluminum mixed oxide powders which are predominantly or completely present in the form of aggregated primary particles and in which
  • the weight ratio of (Al 2 O 3 SiO 2 ) tti in the total primary particle 0.002 to 0.05, preferably 0.003 to 0.015, particularly preferably 0.005 to 0.01,
  • the BET surface area is 50 to 250 m 2 / g, preferably 100 to 200 m 2 / g.
  • Such silicon-aluminum mixed oxide powders are characterized among other things from that the proportion of the aluminum oxide compared to the silicon dioxide is very low and the weight ratio (Al 2 O 3 / SiO 2 ) surface of the primary particles in a near-surface layer is smaller than in the total primary particle. This means that the alumina concentration at the surface is further reduced.
  • the total primary particle includes the proportion of silica and alumina in the near-surface layer.
  • the step a) produced silicon-aluminum mixed oxide powder has a weight ratio of (Al 2 O 3 SiO 2) tti 0005-0015, a ratio (Al 2 O 3 / SiO 2) tti / (Al 2 O 3 / SiO 2) Surface of 1 .3 to 20 and a BET surface area of 100 to 200 m 2 / g.
  • Mixed oxide powder is to be understood as an intimate mixture of the mixed oxide components aluminum oxide and silicon dioxide at the atomic level, in which the primary particles also have Si-O-Al bonds. The surfaces of these primary particles are largely or completely free of pores.
  • Such silicon-aluminum mixed oxide powders are preferably obtained by flame hydrolysis and / or flame oxidation of silicon and aluminum compounds in a flame produced by the reaction of hydrogen and oxygen. These powders are described as “pyrogenic” or “fumed”. In the reaction, firstly highly dispersed primary particles are formed, which in the further course of the reaction grow together to form aggregates and which can further assemble them into agglomerates.
  • the weight ratio on the surface can, for example, by
  • X-ray induced photoelectron spectroscopy XPS analysis
  • TEM-EDX analysis energy dispersive X-radiation
  • the weight ratio in the total primary particle is determined by chemical or physico-chemical methods, e.g. X-ray fluorescence analysis, of the powder determined.
  • the silicon-aluminum mixed oxide powder has a dibutyl phthalate number, in g of dibutyl phthalate (DBP) per 100 g of mixed oxide, of from 300 to 350.
  • the DBP number represents a measure of the structure of aggregates. Low numbers correspond to a low structure, high numbers to a high structure.
  • the preferred range of 300 to 350 corresponds to a high structure.
  • DBP absorption the force absorption, or the torque (in Nm), of the rotating blades of the DBP measuring device is measured when defined amounts of DBP are added, comparable to a titration. This results in a sharp for the powder according to the invention
  • the dibutyl phthalate absorption can be measured, for example, using a device RHEOCORD 90 from Haake, Düsseldorf.
  • 12 g of the silicon-aluminum mixed oxide powder to 0.001 g in exactly one
  • the flame-hydrolysis production of the silicon-aluminum mixed oxide is preferably carried out in a process in which a1) a vapor containing one or more silicon compounds selected from
  • Aluminum compound calculated as Al 2 O 3
  • silicon compound calculated as SiO 2 , 0.003 to 0.05
  • the process can also be carried out so that the steam of the
  • Silicon compounds may contain up to 40 wt .-% SiCl 4 . Particularly preferred may be a mixture of 65 to 80 wt .-% CH 3 SiCl 3 and 20 to 35 wt .-% SiCl 4 .
  • Aluminum chloride is preferably aluminum chloride.
  • the fuel gas is preferably selected from the group consisting of hydrogen, methane, ethane, propane and mixtures thereof. Particularly preferred is hydrogen.
  • the introduced into the mixing chamber air is sufficient at least for complete combustion of the fuel gas and the silicon compounds and aluminum compounds. As a rule, an excess of air is used.
  • the steam treatment serves the purpose of removing as much as possible chloride residues adhering to the particles, so that the powder contains not more than 1% by weight of chloride, preferably not more than 0.2% by weight of chloride.
  • the flannnennenhydrolytically produced oxides or mixed oxides are X-ray amorphous.
  • X-ray amorphous is a substance whose range of distances is below the coherence length of the X-ray radiation used and thus does not produce an interference pattern.
  • a catalyst precursor within the meaning of the invention is a substance which catalyzes ATAE cleavage but has not yet undergone methanol treatment to reduce its initial activity.
  • the flame-hydrolytically produced, aluminum and silicon-containing mixed oxide will usually already be catalytically active, so that it can be used in principle immediately without further processing as a catalyst precursor.
  • the mixed oxide produced according to the invention already has the relevant material composition of the catalyst:
  • Silicon 50 to 99.9 mass% (calculated as S1O2);
  • Aluminum 0.1 to 50% by mass, preferably 0.1 to 20% by mass, particularly preferably 0.5 to 1 1% by mass (calculated as Al 2 O 3);
  • Alkali metal 0 to 15 mass% (calculated as M 2 O, where M is the alkali metal);
  • Alkaline earth metal 0 to 30 mass% (calculated as MO, where M stands for the alkaline earth metal).
  • a catalyst precursor to convert it to a catalyst precursor.
  • Alkaline earth metal hydroxide solution or the mixing of the mixed oxide with an alkali metal and / or alkaline earth metal salt has the purpose of alkali and / or
  • Catalyst precursor to make a shape Catalyst precursor to make a shape.
  • a powdery catalyst is useful in ATBE cleavage
  • the industrial scale catalyst should undergo a macroscopic shaping to be more manageable, minimize flow losses in the reactor, and optimize heat transfer.
  • microscopic catalyst powder can be formed into macroscopic tablets, pellets or extrudates.
  • the shaping takes place with the addition of binders or temporary auxiliaries.
  • suitable binders clays, ceramic clays, colloids, for example, amorphous zeolites can be used.
  • the catalyst precursor is preferably free of organic
  • the conversion of the mixed oxide into a catalyst precursor therefore preferably comprises the following chronological steps: b1) macroscopic shaping of the powdery mixed oxide with the optional use of temporary auxiliaries and / or binders; b2) calcining the shaped mixed oxide to obtain the
  • the catalyst precursor is subjected to a methanol treatment to reduce its initial activity. Only in this way is a catalyst which can be used according to the invention obtained.
  • the methanol treatment must be carried out after any calcination, otherwise the methanol would be expelled again by the calcination.
  • the methanol treatment can optionally be carried out remotely from the site of the catalyst (ex situ) or at the site of the catalyst (in situ).
  • the ex situ treatment takes place in the catalyst factory.
  • the catalyst which has been treated with methanol, is transported from there to its place of use in the reactor of an ATAE plant, installed there and can be used immediately.
  • In the in situ treatment only a catalyst precursor untreated with methanol is produced in the catalyst factory.
  • the catalyst precursor is then transported to its place of use in the reactor of an ATAE slitting line and installed there.
  • the methanol treatment is then carried out in the reactor of the ATAE splitter before it is put into splitting operation.
  • WO201 / 000695A1 describes the regeneration of an aluminosilicate-containing ATAE cleavage catalyst at its site of use. Regeneration is carried out by rinsing the deactivated catalyst with water. Regeneration is required in some situations to restore the activity of a catalyst deactivated by sustained use. It is therefore an opposite measure to the practiced here methanol treatment, which serves to reduce the initial activity.
  • the methanol treatment takes place in such a way that the catalyst or the catalyst precursor is overflowed with liquid and / or gaseous methanol, or that the catalyst precursor is immersed in liquid and / or gaseous methanol.
  • the temperature and pressure conditions are chosen according to the desired state of matter of the methanol. It should be understood that the treatment may also be with a biphasic mixture of liquid and gaseous methanol.
  • the space load (WHSV kg methanol / kg catalyst / hour) should be between 0.1 and 20 h -1 , preferably between 0.5 and 5 h -1 .
  • the pressure in the treatment with methanol should be between 0.1 and 1 .5 MPa
  • the temperature in the treatment with methanol should be between 50 and 300 ° C; preferably it should be between 100 and 200 ° C, and more preferably the temperature should be between 15 and 190 ° C.
  • Acid heterogeneous catalysts can convert methanol to dimethyl ether.
  • the methanol treatment should be operated so that the conversion of methanol to dimethyl ether is less than 10%, preferably less than 1% and more preferably less than 0.2%.
  • Decisive for the conversion are the reaction conditions. In particular, under conditions which correspond to those of the ATAE cleavage, this goal can be achieved.
  • the catalyst prepared according to the invention is used in the cleavage of ATAE to olefins and alcohol.
  • the invention therefore also provides a process for cleaving an alkyl tert-alkyl ether (ATAE) of the formula II
  • radical R is an alkyl radical having 1 or 2 carbon atoms
  • radical R 1 is H, methyl or ethyl radical
  • radicals R 2 and R 3 are methyl or ethyl radicals, where the radicals R 2 and R 3 may be the same or different, in which the cleavage takes place in the presence of an aluminosilicate-containing, methanol-treated catalyst.
  • the catalyst used in the cleavage process has the following 100% complementary composition:
  • Silicon 50 to 99.9 mass% (calculated as S1O2);
  • Aluminum 0.1 to 50% by mass, preferably 0.1 to 20% by mass, particularly preferably 0.5 to 1 1% by mass (calculated as
  • Alkali metal 0 to 15 mass% (calculated as M 2 O, where M is the alkali metal);
  • Alkaline earth metal 0 to 30 mass% (calculated as MO, where M stands for the alkaline earth metal). If an ex-situ treated catalyst is used, the process according to the invention comprises the following chronological steps: a) charging the methanol-treated catalyst into a reactor; b) performing the cleavage in the reactor.
  • the process according to the invention comprises the following chronological steps: a) introduction of a methanol-untreated catalyst or a catalyst precursor into a reactor; b) treating the untreated catalyst or catalyst precursor with methanol in the reactor; c) performing the cleavage in the reactor.
  • the treatment is carried out with methanol under pressure and temperature conditions which substantially correspond to those of the cleavage reaction, or a catalyst is introduced, which was treated under these conditions.
  • the methanol treatment shows a particularly pronounced effect and the methanol conversion to dimethyl ether during the treatment is in the desired low range.
  • the catalyst also interacts with another Alcohol can be treated in place of methanol while the same effect is achieved.
  • a variant of the invention is therefore to replace the methanol with which the catalyst is treated completely or partially by another alcohol.
  • alcohol especially monohydric alcohols and ethanol in particular into consideration.
  • a complete replacement of the methanol by ethanol is to be understood as treating the catalyst with ethanol instead of methanol.
  • Partial replacement with ethanol is to be understood as treating the catalyst with a mixture of methanol and ethanol.
  • any ATAE can be cleaved by means of the process according to the invention into the corresponding olefins and alcohols.
  • a compound of the formula II in which R is a methyl or ethyl radical is preferably cleaved.
  • Alkyl tert-alkyl ethers which can be used in the cleavage process according to the invention are, for example, methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE) or tert-amyl methyl ether (TAME).
  • methyl tert-butyl ether is particularly preferably split into isobutene and methanol or ethyl tert-butyl ether into isobutene and ethanol.
  • MTBE is split into isobutene and methanol in the gas phase.
  • ATAE Used in the cleavage process according to the invention ATAE, which can come from a variety of processes. ATAE production is well known in the art and is practiced on a large scale. A procedure for
  • the cleavage according to the invention on the catalyst treated according to the invention is preferably in the gas phase at a temperature of 1 10 to 400 ° C.
  • the cleavage of MTBE to isobutene and methanol is preferably carried out at a temperature of 150 to 350 ° C., particularly preferably from 180 to 300 ° C. Preferably, it is split at a reaction pressure of 1 to 20 bar (absolute).
  • isobutene is a product, it may be advantageous to carry out the cleavage process according to the invention at a pressure of from 2 to 10 bar (absolute), preferably from 5 to 8 bar (absolute). This is particularly advantageous because at these pressures isobutene can be condensed against cooling water.
  • the specific catalyst loading (WHSV, gram educt at room temperature per gram of catalyst per hour) in the cleavage process according to the invention is preferably from 0.1 to 100 h -1 , preferably from 0.5 to 30 h -1
  • the cleavage of MTBE to isobutene and methanol is preferably carried out at a WHSV of 0.1 to 100 h "1 , more preferably from 0.25 to 25 h " 1 .
  • the process according to the invention is preferably carried out such that the conversions of the compound to be cleaved are more than 70%, preferably more than 80% and particularly preferably from 90% to 100%. If the starting materials contain troublesome secondary components, it may be expedient to limit the conversion. contains
  • the feed mixture in addition to the splitting MTBE also 2-methoxybutane
  • the limitation of the conversion can for example by increasing the WHSV and / or lowering the
  • Reaction temperature can be achieved.
  • JP 19912201 describes the continuous addition of water to an alkali or alkaline earth metal-doped aluminosilicate to reduce the formation of
  • the optional addition of water for moderation of the catalyst takes place in such a way that the water content in the reactor inlet is preferably 0 to 5% by mass, particularly preferably 0.2 to 1 .5% by mass.
  • the supplied water used is preferably completely demineralized or distilled water or steam.
  • the cleavage product mixture can be worked up by known technical methods. Unreacted educt may optionally after a
  • the recovered isoolefins can be used in many ways.
  • a product produced according to the inventive method gap isobutene may, in particular for the production of butyl rubber, polyisobutylene, isobutene oligomers, branched C 5 aldehydes, C 5 carboxylic acids, C 5 alcohols, C 5 olefins, tert-butylaromatics and methacrylic acid and esters thereof be used.
  • the resulting in the cleavage of ATAE alcohols can be reused after workup, for example, for the synthesis of ATAE.
  • the resulting methanol can also be used for the methanol treatment of the catalyst according to the invention. It is also possible that for the
  • Methanol treatment used methanol, if necessary after purification, in the synthesis of ATAE use.
  • the vapor of a mixture consisting of 45 kg / h CH3S1CI3 and 15 kg / h SiCl 4 and the vapor 0.6 kg / h of aluminum chloride are transferred separately from each other by means of nitrogen as a carrier gas in a mixing chamber.
  • the vapors are mixed with 14.6 Nm 3 / h of hydrogen and 129 Nm 3 / h of dried air in the mixing chamber of a burner, and fed via a central tube, at the end of the reaction mixture is ignited, a water-cooled flame tube and burned there.
  • the resulting powder is then deposited in a filter and with
  • the powder contains 99% by weight
  • the BET surface area is 173 m 2 / g.
  • the DBP number is 326 g / 100 g of mixed oxide.
  • an XPS analysis is applied to determine the weight ratio (Al 2 O 3 SiO 2 ) surface of the primary particles in a near-surface layer with a thickness of about 5 nm. It provides a weight ratio (Al 2 O 3 SiO 2 ) surface area of 0.0042.
  • the weight ratio (AI 2 O 3 SiO 2 ) tti in the total primary particle is determined by X-ray fluorescence analysis on the powder. It provides a weight ratio (Al 2 O 3 / SiO 2 ) tti. from 0.010. This yields a value for (Al 2 O 3 / SiO 2 ) tt i /
  • Example 0.2 Conversion of the mixed oxide powder into a catalyst product by preparation of catalyst extrudates
  • pyrogenically prepared aluminosilicate (1% by weight of Al, calculated as Al 2 O 3 ), 24 g of a commercial cellulose ether, 21 g of a commercially available nonionic wax dispersion as pressing aid, 3 g of a commercial polysaccharide as plasticizer, 6 g of 30% aqueous NH 3 solution and fully demineralized water are mixed in an intensive mixer with stick vortex. This is followed by pelleting in the intensive mixer, in which uniformly roundish pellets with a diameter of about 1 to 3 mm are obtained within 30-40 minutes.
  • the wet pellets are processed with a commercial extruder into 3 mm extrudates (screw housing 300 mm, screw diameter 80-64 mm, gear rotation speed 160 rpm, extrusion pressure 31 kg / h).
  • the extrudates thus obtained are dried at 120 ° C in a stream of air and calcined at 600 ° C in air.
  • Example 1 Methanol Treatment in the Gas Phase (Inventive)
  • Thermostat was heated. If necessary, the liquid starting material stream can be completely evaporated in an evaporator tube.
  • the filled reactor was sealed, leak tested and purged with nitrogen. After two hours, the reactor jacket was heated to 190 ° C while maintaining the nitrogen flow. The evaporator was heated to 200 ° C. After another two hours, the nitrogen flow was turned off and the
  • Methanol treatment started.
  • 1000 g / h of liquid methanol at 7 bar (absolute) were continuously driven through the experimental plant. This corresponds to a space load WHSV of 4.8 h ⁇ 1 .
  • the methanol was completely evaporated in the evaporator and the methanol vapor flowed over the catalyst to be treated.
  • the composition of the product stream after the reactor was
  • Example 3 Methanol Treatment in the Liquid Phase (Inventive)
  • the reactor which was filled with 210 g of catalyst, was closed tightly and purged with nitrogen. After two hours, the reactor jacket and the evaporator were heated to 1 15 ° C while maintaining the nitrogen flow. After another two hours, the nitrogen flow was turned off and the
  • Methanol treatment started. For this purpose, 1000 g / h of liquid methanol at 7 bar (absolute) were continuously driven through the experimental plant. The methanol was heated in the evaporator but not evaporated and flowed liquid over the
  • the composition of the product stream after the reactor was analyzed by gas chromatography and contained only 200 ppm of dimethyl ether in addition to methanol.
  • the treatment was stopped after 24 hours by stopping the methanol feed and purging the reactor with nitrogen. After purging the reactor with nitrogen and heating to suitable temperatures, the cleavage of ATAE according to the invention in the same reactor
  • Example 4 Cleavage of MTBE with untreated (not according to the invention) or treated catalysts (according to the invention)
  • the cleavage was carried out in a fixed bed reactor with a heating jacket through which a
  • Heat transfer oil (Marlotherm SH from Sasol Olefins & Surfactants GmbH) flowed, carried out.
  • the feed was technical MTBE (DRIVERON® from Evonik
  • the MTBE Before entering the reactor, the MTBE was completely evaporated in an evaporator at 180 to 270 ° C. At a temperature of 180 to 270 ° C (temperature of the Marlotherm in the inlet of the reactor jacket) and a pressure of 7 bar (absolute) were hourly 1500 g MTBE by about 210 g of catalyst, corresponding to a WHSV value of 7.1 h ⁇ 1 , passed through. The gaseous product mixture was analyzed by gas chromatography. To compensate for the ongoing
  • the catalysts used were the catalysts of the invention treated in Examples 1 to 3 and, for comparison, an untreated catalyst of the same type.
  • a technical catalyst was investigated (Specialyst 071 Evonik Industries AG: an amorphous aluminosilicate with magnesium doping to reduce the activity). 340 g of this catalyst were used because it is significantly less active than the pyrogenically produced aluminosilicate of the other experiments.
  • DME selectivity 2 * moles of DME formed to moles of converted MTBE
  • Table 1 shows the test results of a catalyst not treated according to the invention. It becomes clear that the catalyst shows a very high activity at the beginning of the experiment. At a jacket temperature of 190 ° C., a conversion of 94.6% is achieved, with the temperature in the catalyst bed dropping by almost 54 K compared to the jacket temperature. The resulting
  • the catalyst treated according to Example 1 achieves only about 74% MTBE conversion under these conditions. However, this leads to a reduction of
  • Catalyst and the critical temperature difference in the reactor is only 30 or 40 K. Also, the resulting minimum temperatures do not lead to
  • the treated catalysts must be run at higher temperatures due to the reduced initial activity.
  • Column B of Tables 1 to 5 allow the comparison of the catalysts at about 91% conversion. Pressure and load were not changed.
  • the untreated catalyst is still very active (temperature 190 ° C), and shows after 54 h a significantly lower C8 selectivity (0.8%) than immediately after the start (4%).
  • the catalysts treated according to the invention stand out clearly from here again.
  • the C8 selectivities are 0.35 to 0.50% and are thus in some cases only half as large as in the case of the untreated catalyst.
  • the temperature difference in the reactor is still critical for the untreated catalyst (49.5 K).
  • the catalysts treated according to the invention show significantly lower temperature differences with 31 to 36 K. Since at the same time the jacket temperature was raised in these catalysts (for conversion to 91%), the minimum temperature measured in the reactor in all treated catalysts is well above the condensation range of the high boilers.
  • Example 1 treated catalyst is subject to significantly reduced aging and so the temperature must be raised only by 18 K.
  • the catalyst treated according to Example 2 requires an increase of 22K.
  • the catalyst treated according to Example 3 shows a similar aging as the untreated material.
  • Jacket temperature is 230 ° C ⁇ 3%, at 90 to 91% conversion.
  • the DME selectivity of the treated catalysts is slightly higher, while C8 selectivity is up to 40% lower than that of the untreated catalyst.
  • the amorphous aluminosilicate differs here in particular in the activity, which is so much lower that despite much larger catalyst mass, the temperature of 245 ° C is well 15 K above the average of the other catalysts. But the aging is a bit lower.
  • the DME selectivity is extremely high at 2.7%, the C8 selectivity is comparable to the other catalysts.
  • Treatment of these materials with methanol according to this invention is capable of significantly reducing the high initial activity.
  • material aging is significantly reduced during the first 1000 hours of operation.
  • the activities and selectivities after this run-in phase are just as good as those of the untreated catalyst and significantly better than with conventional technical catalysts.
  • the treated catalyst is thus not permanently damaged, so that you can benefit from its high activity and selectivity in stationary operation, without massive problems

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un procédé de production d'un catalyseur contenant de l'aluminosilicate, ledit catalyseur étant destiné à être utilisé pour le craquage d'alkyl-tert-alkyléthers (ATAE) en oléfines et en alcools. L'objectif de la présente invention est de mettre au point un procédé de production d'un catalyseur hétérogène acide caractérisé par une activité de départ réduite lors du craquage ATAE. A cette fin, ledit catalyseur est traité à l'aide de méthanol avant d'être utilisé pour le craquage ATAE.
PCT/EP2013/066919 2012-09-10 2013-08-13 Traitement au méthanol de catalyseurs de craquage atae contenant de l'aluminosilicate WO2014037192A1 (fr)

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DE102012215956.8A DE102012215956A1 (de) 2012-09-10 2012-09-10 Methanolbehandlung von Alumosilicat-haltigen ATAE-Spaltkatalysatoren
DE102012215956.8 2012-09-10

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DE102012217924A1 (de) 2012-10-01 2014-04-03 Evonik Degussa Gmbh Spaltung von Ethern und Alkoholen unter Verwendung von Bor-Zeolithen
DE102012217923A1 (de) 2012-10-01 2014-04-03 Evonik Degussa Gmbh Herstellung von Katalysatoren auf Basis von Bor-Zeolithen

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