CN110290869B - Catalyst material for oxidizing hydrocarbons with antimony doped titanium dioxide - Google Patents

Catalyst material for oxidizing hydrocarbons with antimony doped titanium dioxide Download PDF

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CN110290869B
CN110290869B CN201880011548.2A CN201880011548A CN110290869B CN 110290869 B CN110290869 B CN 110290869B CN 201880011548 A CN201880011548 A CN 201880011548A CN 110290869 B CN110290869 B CN 110290869B
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CN110290869A (en
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O·里希特
G·梅斯特尔
W·皮奇
N·弗罗姆
S·伯克莱因
T·维希特
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Clariant International Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
    • C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B01J23/22—Vanadium
    • 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
    • B01J35/613—10-100 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • 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
    • B01J37/06—Washing
    • 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
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof

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Abstract

The invention relates to a catalyst material for the oxidation of hydrocarbons by gaseous oxygen, containing V and TiO doped with Sb 2 Material, and to TiO doped with Sb 2 Use of a material as a support material in a catalyst material for the oxidation of hydrocarbons by gaseous oxygen. The invention further relates to a method for oxidizing hydrocarbons by means of gaseous oxygen, which method is characterized in that the hydrocarbons to be oxidized and oxygen are brought into contact with the catalyst material according to the invention. The invention also relates to a shaped catalyst body comprising an inert support, on which the catalyst material according to the invention is applied, and to a method for producing the catalyst material according to the invention, comprising the following steps: a) Preparation of TiO 2 And Sb 2 O 3 OfCompound, b) calcination of TiO 2 And Sb 2 O 3 To obtain TiO doped with Sb 2 Material, and c) impregnation of TiO doped with Sb with a V-containing compound 2 A material.

Description

Catalyst material for oxidizing hydrocarbons with antimony doped titanium dioxide
The invention relates to a catalyst material for the oxidation of hydrocarbons with the aid of gaseous oxygen, containing V-and Sb-doped TiO 2 A material. The catalyst material is particularly suitable for use as a catalyst for the oxidation of o-xylene and/or naphthalene to phthalic anhydride.
The industrial production of phthalic anhydride from o-xylene or naphthalene is carried out by selective gas phase oxidation in a shell-and-tube reactor, in which 4 to 5 different catalyst zones are introduced into the reactor one after the other in the axial direction. Each catalyst zone consists of a loose bed of catalyst shaped bodies, which are usually composed of rings of inert carriers coated with a catalytically active composition. The active composition is generally composed of V 2 O 5 、Sb 2 O 3 Anatase modification of TiO 2 And other accelerators. Such systems are described, for example, in WO2006092304A1, WO2008077791A1, EP0985648A1 or WO2011061132 A1.
WO2006092304A1 describes the preparation of phthalic anhydride by gas phase oxidation of o-xylene and/or naphthalene using a catalyst containing at least oneA first catalyst zone located closest to the gas inlet side, a second catalyst zone located closer to the gas outlet side and a third catalyst zone located closer to the gas outlet side or at the gas outlet side, wherein the catalyst zones preferably each comprise a catalyst comprising TiO 2 Characterized in that the catalyst activity of the first catalyst zone is higher than the catalyst activity of the second catalyst zone. The activity of the first catalyst zone can be adjusted by means of all measures familiar to the person skilled in the art such that it is higher than the activity of the subsequent second catalyst zone. In a preferred embodiment, the increased activity in the first catalyst zone can be achieved, for example, by increasing the bulk density in the first catalyst zone, for example, by using a further (ring) geometry of the inert shaped bodies used.
WO2008077791A1 describes a gas phase oxidation process wherein a gaseous stream comprising aromatic hydrocarbons and molecular oxygen is passed through two or more catalyst zones. Furthermore, the first disclosure relates to a catalyst system for gas phase reactions using an initial charge. The product or volume of the diameter and height of the initially charged inert and/or catalyst ring is less than the product or volume of the diameter and height of at least one of the subsequent catalyst zones, or the ratio of the surface area to the volume of the initially charged inert and/or catalyst ring is greater than the ratio of at least one of the subsequent catalyst zones.
EP0985648A1 relates to the gas phase oxidation of hydrocarbons, wherein a gaseous mixture comprising a molecular oxygen-containing gas and a hydrocarbon (which may contain substituents) is passed through a fixed catalyst bed and provides a process for the gas phase oxidation by passing a gaseous mixture of the feedstock through a fixed catalyst bed, wherein the proportion of hollow spaces in the catalyst zone increases in one or more steps in the flow direction along the flow of the gaseous mixture of the feedstock.
WO2011061132A1 relates to a catalyst system for preparing carboxylic acids and/or carboxylic anhydrides having a plurality of catalyst zones arranged one above the other in a reaction tube, wherein vanadium antimonate is introduced into the active composition in at least one of the catalyst zones. The invention also relates to a gas phase oxidation process wherein a gaseous stream comprising at least one hydrocarbon and molecular oxygen is passed through a plurality of catalyst zones and the maximum hot spot temperature is less than 425 ℃.
The active composition also contains a binder which makes it possible to bind the active composition to an inert support and to impart mechanical stability to the shaped catalyst bodies. Such adhesives are described, for example, in DE 198243232A 1.
DE 198243232 A1 relates to a process for preparing supported catalysts for the catalytic gas-phase oxidation of aromatic carboxylic acids and/or carboxylic anhydrides, which catalysts consist of a carrier core and a catalytically active metal oxide applied thereto in shell-like form and are obtained by spraying an aqueous active composition suspension (which contains the active metal oxide) onto a heat carrier material at elevated temperature, the spraying being carried out at a temperature of from 50 to 450 ℃, wherein the aqueous active composition suspension contains from 1 to 10% by weight, based on the solids content of the active composition suspension, of a binder consisting of the following a) and B): a) A polymer obtained by free-radical polymerization and containing from 5 to 100% by weight of monomers (a) in the form of ethylenically unsaturated anhydrides or ethylenically unsaturated dicarboxylic acids whose carboxyl groups can form anhydrides, and from 0 to 95% by weight of monoethylenically unsaturated monomers (B), with the proviso that the monomers (a) and (B) have on average not more than 6 carbon atoms which are not functionalized by oxygen-containing groups, and B) an alkanolamine having at least two OH groups, not more than 2 nitrogen atoms and not more than 8 carbon atoms, wherein a: the weight ratio of B is 1:0.05 to 1:1.
after providing the catalyst zones in the reactor, the catalyst shaped bodies forming the respective zones have to be activated. For the purposes of the present invention, this activation is a heat treatment of the catalyst shaped bodies, in which the organic binder present is decomposed and active vanadium oxide-containing compositions are formed. The activation of the catalyst shaped bodies is carried out in situ, i.e. in the reactor tube, by means of a "start-up". In this case, the mixture of air and the hydrocarbon to be oxidized (feed gas) is ignited, a region having the highest temperature ("hot spot") is formed in the first of the first two catalyst zones, while the temperature decreases continuously in the axial direction of the reactor from the location of the hot spot to the end of the reactor. In order that the catalyst zone may be activated after the hot spot, the flow rate of the feed gas may be temporarily increased in order to move the hot spot into the downstream zone (in the flow direction). However, the disadvantage here is that only relatively low hot-spot temperatures are reached, since the feed gas is partially reacted in the preceding zone. By this start-up method it is possible to only inadequately activate the downstream catalyst zone in situ, since only short times and relatively small temperature increases occur in the catalyst bed. However, insufficient activation of the downstream catalyst zone leads to an increased proportion of undesirable under-oxidized products, which leads to impairment of the product quality of, for example, phthalic anhydride. It was therefore an object of the present invention to develop highly active catalysts which can be activated rapidly and at the same time have a high selectivity.
This object is achieved by a composition comprising V-and Sb-doped TiO 2 A catalyst material of the material is achieved which is used for the oxidation of hydrocarbons by means of gaseous oxygen.
The catalyst material of the invention can, for example, represent an active composition which is applied to an inert support shaped body to form a catalyst shaped body. Preference is given to catalyst shaped bodies for the oxidation of o-xylene and/or naphthalene to phthalic anhydride. The inert support shaped bodies are preferably talc rings.
Sb doped TiO 2 The material is preferably present in powder form and may be present in any variant, but preferably in the anatase variant. For the purposes of the present patent application, the term Sb doping is intended to mean that Sb is at least partially present in the TiO in an integrated manner 2 In the material. Sb may be present here isomorphously in place of the Ti atom or in another manner in the TiO atom 2 In the crystal lattice of the material. Sb does not necessarily have to be uniformly distributed in TiO 2 In the material; for example, it may be in a doped TiO 2 The material surface or in the area close to the surface.
Doped TiO based on the total mass of the catalyst material of the invention 2 The material preferably comprises 0.01 to 5.0 wt.% Sb, even more preferably 0.1 to 3.0 wt.%.
The catalyst material of the present invention may have any BET surface area, but preferably the BET surface area is from 15 to 25m 2 A/g, more preferably 17 to 23m 2 /g。
The present invention further provides a process for preparing a catalyst material according to the invention, comprising the steps of:
a) Production of TiO 2 And a mixture of a Sb-containing compound,
b) Calcination of TiO 2 And a Sb-containing compound to obtain Sb-doped TiO 2 The material(s) of which is (are),
c) Impregnation of Sb-doped TiO with V-containing compounds 2 A material.
TiO as starting material 2 May be any TiO 2 Preferably in powder form, and may be present in any variant form, but preferably in the anatase variant. The Sb-containing compound used as the starting material is preferably antimony oxide such as Sb 2 O 3 Or Sb 2 O 5 Or antimony nitrate, the degree of hydration of which can vary. The starting materials should be intimately mixed for a solid state reaction, where Sb may be doped with TiO 2 。
Calcination of TiO 2 And the Sb-containing compound (step b)) is preferably carried out in air at a temperature of more than 300 ℃, preferably at a temperature of from 400 ℃ to 700 ℃, more preferably at a temperature of from 450 ℃ to 600 ℃ for 1 to 10 hours, more preferably from 3 to 8 hours.
Treating the TiO from step b) with an acid 2 It may be advantageous to remove excess Sb, such as Sb 2 O 3 Or Sb 2 O 5 Form (b) which is not incorporated into TiO 2 In the material. For this purpose, preference is given to using inexpensive mineral acids such as HCl, H 2 SO 4 Or HNO 3 . After the acid treatment, the doped TiO is preferably washed with water 2 The material is treated to remove acid residues and then dried.
Impregnation of Sb-doped TiO with V-containing Compounds 2 The material is preferably formed by forming a doped TiO containing Sb 2 Material and an aqueous suspension containing a compound of V. The aqueous suspension may also contain other compounds, such as P-containing compounds, sb-, cs-or Na-containing compounds, and may also contain a binder. The aqueous suspension is then preferably applied to an inert support body, for example a ring-shaped inert support body, to form a shaped catalyst body. The application of the suspension to the shaped support body is carried out, for example, using a fluidized-bed apparatus as described in DE19709589 A1. The compound containing V in the aqueous suspension is preferably V 2 O 5 。
The invention additionally provides Sb-doped TiO 2 Use of the material as a support material for a catalyst for the oxidation of hydrocarbons by means of gaseous oxygen. The hydrocarbon is preferably o-xylene or naphthalene, or a mixture of both, and the oxidation product is at least partly (at last paratly) phthalic anhydride.
The invention also provides a process for the oxidation of hydrocarbons by means of gaseous oxygen, characterized in that the hydrocarbon(s) to be oxidized and oxygen are brought into contact with the catalyst according to the invention. The hydrocarbon(s) to be oxidized and oxygen are generally contacted here in a reactor at elevated temperature with the catalyst according to the invention. The reaction temperature in the reactor is preferably above 200 c, more preferably in the range of 350 c to 500 c. The reactor is preferably a tube in a shell-and-tube reactor, the temperature of which is adjusted by means of a salt bath.
The catalyst material is preferably applied to the inert support shaped body and forms the catalyst shaped body. If a number of catalyst shaped bodies are introduced into the reactor tube, they form a catalyst zone, i.e. a loose bed of catalyst shaped bodies in the reactor. A plurality of such catalyst zones comprising different catalyst shaped bodies form a catalyst arrangement in the sense of the present patent application. The reaction gases flow axially through the generally tubular reactor, the feed gases being introduced at the gas inlet side of the reactor and the product gases formed exiting the reactor at the gas outlet side.
According to the invention, the catalyst arrangement comprises a catalyst shaped body which contains the catalyst material according to the invention. Preference is given here to a shaped catalyst body of the catalyst zone which is located closest to the gas outlet side with the catalyst material according to the invention.
In the following description of the experiments, the catalyst shaped bodies prepared are also referred to simply as catalysts.
Method
The proportion of binder was determined as follows: the coated catalyst molded body was calcined at 450 ℃ for 7 hours, resulting in complete thermal decomposition of the organic binder. After calcination, the proportion of binder is determined according to equation 1:
equation 1:
Figure BDA0002164379580000051
A B proportion of binder
M E = weight of catalyst before calcination
M A = weight of catalyst after calcination
The physicochemical characterization of the active composition (BET, XRF) was carried out by mechanically separating the active composition from the carrier ring by means of a sieve after thermal decomposition of the binder. The remaining part of the active composition still adhering to the carrier rings is completely removed by ultrasonic treatment. Finally, the washed carrier rings were dried in a drying oven at 120 ℃ and weighed. The proportion of the active composition is then determined according to equation 2:
equation 2:
Figure BDA0002164379580000061
A A ratio of active composition
M A = weight of catalyst after calcination
M T = weight of carrier ring after detachment
The specific surface area of the active compositions is determined by the BET method in accordance with DIN 66131; disclosures of the BET method can also be found in j.am.chem.soc,60, 309 (1938). The sample to be tested was vacuum dried (F =50ml (min) for 1.5 hours) at 350 ℃ in a quartz tube. The quartz tube was then cooled to room temperature, evacuated and immersed in a Dewar vessel containing liquid nitrogen. Nitrogen adsorption was performed at 77K using an RXM 100 adsorption system (Advanced Scientific Design, inc.).
To determine the chemical composition by means of X-ray fluorescence analysis (XRF), 14g of the active composition are mixed with 3.5g of a wax (F) (by means of a shaker mill)
Figure BDA0002164379580000062
Wachs C micropowder) was mixed well and then pressed by means of a press (17 t pressure, 1 minute pressing time) to obtain three discs. The briquettes were subsequently analysed on a multi-element X-ray fluorescence spectrometer (S4 Pioneer, bruker) without adherence to standards. Each active composition measurement was averaged (three compacts, each measured individually in triplicate) and the composition of the elements detected totaled 100% of their oxide weight.
For the catalytic characterization of the catalysts, 25g of the catalyst molding were used in each case with 540g of inert material (talc rings,
Figure BDA0002164379580000063
3 mm) and introduced into a tube having an internal diameter of 25mm and a length of 1m, which is cooled by means of a salt bath. For the in-situ calcination, 30Nl/h of air were passed through the catalyst in the tube at a salt bath temperature of 410 ℃ for at least 48 hours in each case. A 3mm temperature sensor with a mounted pull-out element is centrally arranged in the tube for measuring the temperature.
For the catalytic measurement, 330Nl (standard liters)/h of air (loading 60g o-xylene/standard m) was used 3 Air (ortho-xylene purity)>98%) was passed through the tube from the top downwards at a total pressure of about 1200 mbar. In each case, the measurements were carried out at a salt bath temperature of 410 ℃.
To determine the activity constant A of each catalyst * And product selectivity S P After the first metered introduction of the feed stream (run time TOS =0 h), the product stream composition is periodically analyzed by means of a gas chromatograph (GC 6890n, agilent) and a non-dispersive IR analyzer (EL 3020, ABB).
From the conversion U measured in each case according to equation 4, the activity constant A of the catalyst based on the active composition can then be calculated according to equation 3 * ：
Equation 3:
Figure BDA0002164379580000071
here, the symbols have the following meanings:
A * : active composition activity constant [ l/(h G) based on active composition]；
Q: total volume flow under reaction conditions [ l/h ]
m Active composition : amount of active composition [ g ] introduced into the reactor]；
U: conversion of starting material, where U is calculated according to equation 4.
Equation 4:
Figure BDA0002164379580000072
M in : the flow rate [ mol/s ] of the starting material o-xylene supplied to the catalyst bed]
M out : the flow of the starting material o-xylene [ mol/s ] leaving the catalyst bed]
Product selectivity S P Determined from equation 5:
equation 5:
Figure BDA0002164379580000073
M in : the flow of the starting material o-xylene [ mol/s ] supplied to the catalyst bed]
M out : the flow of the starting material o-xylene [ mol/s ] leaving the catalyst bed]
M PA : flow rate [ mol/s ] of product phthalic anhydride leaving the catalyst bed]
M TA : the flow of the product toluic anhydride (toluranhydride) leaving the catalyst bed [ mol/s ]]
M TAc : the flow of product toluic acid [ mol/s ] leaving the catalyst bed]
M PD : flow of product phthalide [ mol/s ] leaving the catalyst bed]
The results of the catalytic characterization of the examples according to the invention (see example 1) and of the comparative examples not according to the invention (see comparative examples 1 to 3) are shown in each case in fig. 1 and 2.
Example 1
194.3g of TiO in the form of the anatase modification 2 (titanium dioxide DT20, cristal Global) with 7.72g of Sb 2 O 3 (antimony trioxide, high purity, merck) was thoroughly mixed by means of a hoop mixer and subsequently calcined in air at 500 ℃ for 6 hours. To dissolve unbound Sb 2 O 3 The powder obtained was slurried in each case with 500ml of 6 mol hydrochloric acid a total of 3 times at room temperature and filtered after 1 hour on a white band filter. The resulting powder was finally washed off with 300ml of deionized water for a total of 4 times, filtered by means of a white band filter and dried in air at 80 ℃ overnight. The antimony content of the obtained antimony doped titania support was 1.5 wt%.
To prepare the shaped catalyst bodies, 131.9g of antimony-doped titanium dioxide, 10.9g of V were prepared 2 O 5 (vanadium pentoxide, purum, treibacher Industrie AG) and 0.779g of Cs 2 SO 4 (cesium sulfate, rockwood Lithium GmbH) in 700ml deionized water. In addition, 121.6g of a binder (vinyl acetate-ethylene copolymer) was added to the suspension. 2500g of talc rings having the following dimensions were used as inert carriers: 6 (height) × 5 (outer diameter) × 4 (inner diameter) mm. The suspension is applied to the ceramic support in a fluidized-bed process at 70 ℃ using a fluidized-bed apparatus as described in DE19709589A 1. The final properties of the prepared catalysts are summarized in table 1.
Comparative example 1
194.3g of TiO in the form of the anatase modification 2 (titanium dioxide DT 20), cristal Global) with 16.47g of V 2 O 5 (vanadium pentoxide, purum, treibacher Industrie AG) was mixed thoroughly by means of a hoop mixer and subsequently calcined in air at 500 ℃ for 6 hours.
To prepare the catalyst shaped bodies, 140.5g of vanadium-doped TiO were prepared 2 2.15g of Sb 2 O 3 (antimony trioxide, highPurity, merck) and 0.779g of Cs 2 SO 4 (cesium sulfate, rockwood Lithium GmbH) in 700ml deionized water. In addition, 121.6g of a binder (vinyl acetate-ethylene copolymer) was added to the suspension. 2500g of talc rings having the following dimensions were used as inert carriers: 6 (height) × 5 (outer diameter) × 4 (inner diameter) mm. The suspension is applied to the ceramic support in a fluidized-bed process at 70 ℃ using a fluidized-bed apparatus as described in DE19709589A 1. The final properties of the prepared catalysts are summarized in table 1.
Comparison 2
For the preparation of the shaped catalyst bodies, 129.1g of TiO in the form of the anatase modification were prepared 2 (titanium dioxide DT20, cristal Global), 10.9g of V 2 O 5 (vanadium pentoxide, purum, treibacher Industrie AG), 2.15g of Sb 2 O 3 (antimony trioxide, high purity, merck) and 0.779g of Cs 2 SO 4 (Cesium sulfate, rockwood Lithium GmbH) in 700ml deionized water. In addition, 121.6g of a binder (vinyl acetate-ethylene copolymer) was added to the suspension. 2500g of talc rings having the following dimensions were used as inert carriers: 6 (height) × 5 (outer diameter) × 4 (inner diameter) mm. The suspension is applied to the ceramic support in a fluidized-bed process at 70 ℃ using a fluidized-bed apparatus as described in DE19709589A 1. The final properties of the prepared catalysts are summarized in table 1.
Comparison No. 3
21.9g of V 2 O 5 (vanadium pentoxide, purum, treibacher Industrie AG) with 4.78g of Sb 2 O 3 (antimony trioxide, high purity, merck) was mixed thoroughly by a barrel and hoop mixer followed by calcination in air at 500 ℃ for 6 hours. The antimony vanadate powder produced in this way is finally homogenized in a mortar.
For the preparation of the catalyst shaped bodies, 13.3g of antimony vanadate powder, 129.1g of TiO in the form of the anatase modification were prepared 2 (titanium dioxide DT20, cristal Global) and 0.779g of Cs 2 SO 4 (cesium sulfate, rockwood Lithium GmbH) in 700ml deionized water. In addition, 121.6g of a binder (vinyl acetate-ethylene copolymer) were added to the suspensionIn (1). 2500g of talc rings having the following dimensions were used as inert carriers: 6 (height) × 5 (outer diameter) × 4 (inner diameter) mm. The suspension is applied to the ceramic support in a fluidized-bed process at 70 ℃ using a fluidized-bed apparatus as described in DE19709589A 1. The final properties of the prepared catalysts are summarized in table 1.
Table 1: properties of the catalyst molded bodies and the active composition produced
Example 1 Comparative example 1 Comparison 2 Comparison 3
A A [ weight% ]] 2 5.4 5.2 5.2 5.1
A B [ weight% ]] 2 2.3 2.2 2.2 2.2
BET[m 2 /g] 19.6 18.5 18.1 18.7
V 2 O 5 [ weight% ]] 1 7.5 7.3 7.8 7.4
Sb 2 O 3 [ weight% ]] 1 1.7 1.6 2.2 1.8
Cs [ wt. ]] 1 0.4 0.4 0.4 0.4
TiO 2 [ weight% ]] 1 90.4 90.7 92.2 90.4
1) Based on the total weight of the active composition
2) Based on the total weight of the catalyst

Claims (14)

1. Catalyst material for the oxidation of hydrocarbons with the aid of gaseous oxygen, containing V and TiO doped with Sb 2 A material, the catalyst material being obtained by：
a) Production of TiO 2 And a mixture of a Sb-containing compound,
b) Calcination of TiO 2 And containing Sb 2 O 3 To obtain Sb-doped TiO 2 The material(s) of which is (are),
c) Impregnation of Sb-doped TiO with V-containing Compounds 2 A material.
2. The catalyst material of claim 1, wherein the TiO is selected from the group consisting of 2 The material has the anatase modification.
3. Catalyst material according to claim 1 or 2, characterized in that TiO, based on the mass of the catalyst material 2 The material contains 0.01-5.0 wt.% Sb.
4. The catalyst material of claim 1 or 2, wherein the TiO is selected from the group consisting of TiO 2 The material is a support material, V being present in oxidized form on its surface.
5. Catalyst material according to claim 1 or 2, characterized in that it has a BET surface area of 15 to 25m 2 /g。
6.Sb doped TiO 2 Use of the material as a support material in a catalyst material for the oxidation of hydrocarbons by means of gaseous oxygen.
7. Process for the oxidation of hydrocarbons by means of gaseous oxygen, characterized in that the hydrocarbon to be oxidized and the oxygen are brought into contact with a catalyst material according to claim 1.
8. Shaped catalyst body comprising a shaped inert support body onto which the catalyst material according to claim 1 has been applied.
9. Catalyst zone consisting of a catalyst shaped body according to claim 8 in a reactor.
10. Catalyst arrangement for the oxidation of hydrocarbons, comprising a reactor having a gas inlet side for feed gases and a gas outlet side for product gases, and a first catalyst zone consisting of catalyst shaped bodies and at least one second catalyst zone consisting of catalyst shaped bodies, characterized in that one of the catalyst zones has a catalyst material according to claim 1.
11. Catalyst arrangement according to claim 10, characterized in that the catalyst zone located closest to the gas outlet side has catalyst shaped bodies which contain the catalyst material according to claim 1.
12. A method of preparing the catalyst material of any one of claims 1 to 5, comprising the steps of:
a) Production of TiO 2 And Sb 2 O 3 The mixture of (a) and (b),
b) Calcination of TiO 2 And Sb 2 O 3 To obtain Sb-doped TiO 2 The material(s) of the material(s),
c) Impregnation of Sb-doped TiO with V-containing compounds 2 A material.
13. The method according to claim 12, characterized in that the Sb-doped TiO from step b) is treated with an acid 2 A material.
14. The method of claim 12 or 13, wherein the compound containing V is V 2 O 5 。
CN201880011548.2A 2017-02-14 2018-02-12 Catalyst material for oxidizing hydrocarbons with antimony doped titanium dioxide Active CN110290869B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102017202351.1A DE102017202351A1 (en) 2017-02-14 2017-02-14 Catalyst material for the oxidation of hydrocarbons with antimony-doped titanium dioxide
DE102017202351.1 2017-02-14
PCT/EP2018/053456 WO2018149791A1 (en) 2017-02-14 2018-02-12 Catalyst material for oxidizing hydrocarbons with antimony-doped titanium dioxide

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