EP2178637A1

EP2178637A1 - Catalyst and process for preparing chlorine by gas phase oxidation of hydrogen chloride

Info

Publication number: EP2178637A1
Application number: EP08784582A
Authority: EP
Inventors: Aurel Wolf; Leslaw Mleczko; Oliver Felix Karl SCHLÜTER; Stephan Schubert
Original assignee: Bayer Technology Services GmbH
Current assignee: Bayer Intellectual Property GmbH
Priority date: 2007-07-13
Filing date: 2008-07-01
Publication date: 2010-04-28
Also published as: RU2010104937A; JP2010533058A; WO2009010167A1; US20100202959A1; RU2469790C2; EP2178636A1; CN101743059A; US7985395B2; CN101687178A; JP5269075B2; WO2009010182A1; JP5225377B2; RU2010104936A; JP2010533059A; US20100183498A1; RU2486006C2

Abstract

The present invention relates to a catalyst and to a process for preparing chlorine by catalytic oxidation of hydrogen chloride. The catalyst comprises an active component and a support material, said active component comprising at least uranium or a uranium compound. The catalyst is notable for a high stability and activity at a lower cost compared to the noble metals.

Description

Catalyst and process for producing chlorine by gas phase oxidation of hydrogen chloride

The present invention relates to a catalyst and a process for the production of chlorine by catalytic oxidation of hydrogen chloride. The catalyst comprises an active component and a carrier material, wherein the active component comprises at least uranium or a uranium compound. The catalyst is characterized by a high stability and activity at a lower price compared to the precious metals.

A reaction of great industrial interest is the process of catalytic hydrogen chloride oxidation with oxygen developed by Deacon in 1868:

4 HCl + O ₂ => 2 Cl ₂ + 2 H ₂ O.

Due to the chloralkali electrolysis, the Deacon process has been pushed to the background in the past. Nearly all of chlorine was produced by the electrolysis of aqueous saline [Ulimann Encyclopedia of Industrial Chemistry, Seventh Release, 2006, p 3]. However, the attractiveness of the Deacon process has increased again recently, as the global demand for chlorine is growing faster than the demand for caustic soda. This development is countered by the process for the production of chlorine by oxidation of hydrogen chloride, which is decoupled from the sodium hydroxide production. In addition, hydrogen chloride precipitates in large quantities, for example in phosgenation reactions, such as in isocyanate production, as by-product.

The oxidation of hydrogen chloride to chlorine is an equilibrium reaction. The position of the equilibrium shifts with increasing temperature to the detriment of the desired end product. It is therefore advantageous to use catalysts with the highest possible activity, which allow the reaction to proceed at low temperature.

The first catalysts for the oxidation of hydrogen chloride with the catalytically active component ruthenium were described as early as 1965 in DE 1 567 788, in this case starting from RuCl ₃ .

Further Ru-based catalysts with the active component of ruthenium oxide or ruthenium mixed oxide were described in DE-A 197 48 299. In this case, the content of ruthenium oxide is from 0.1% by weight to 20% by weight and the average particle diameter of ruthenium oxide is from 1.0 nm to 10.0 nm. Other supported on titanium oxide or zirconium Ru catalysts are known from DE-A 197 34 412. For the preparation of the ruthenium chloride catalysts described therein, which contain at least one compound titanium dioxide and zirconium dioxide, a number of Ru starting compounds have been indicated, such as, for example, ruthenium-carbonyl complexes, ruthenium salts of inorganic acids, ruthenium-nitrosyl complexes, ruthenium-amine. Complex, ruthenium complexes of organic amines or ruthenium-acetylacetonate complexes. In a preferred embodiment, titanium dioxide in the form of rutile was used as carrier.

Although the known Ru catalysts already have a fairly high activity, for industrial use in the hydrogen chloride oxidation, a further increase in activity with good long-term stability is desirable. Although the activity of the Ru catalysts could be increased by increasing the reaction temperature, they tend to sinter and thus deactivate at higher temperatures.

It is known that uranium oxides are used as oxidation catalysts for a number of Komplettbzw. Selective oxidations are suitable. A typical example of the use of uranium-based catalysts is the oxidation of CO to CO ₂ , as described, for example, by Campbell et al in J. Molec. Cat. A: Chem., (2006), 245 (1-2), 62-68. Further known oxidations catalyzed by uranium-containing mixed oxides are, for example, those of isobutene to acrolein (Corberan et al., Ind. Eng. Chem. Prod. Res. Dev., (1984), 24, 546, and 1985, 24, 62) and that of propylene to acrolein and acrylonitrile (US Pat. Nos. 3,308,151 and 3,198,750). Furthermore, the total oxidation of VOC (volatile organic compounds) to UjOg the particular of Hutchings et. al. (Nature, (1996), 384, p341). A suitability of uranium compounds for the catalytic hydrogen chloride oxidation with oxygen, however, is not disclosed in this context.

DE 1 078 100 discloses catalysts comprising salts or oxides of silver, uranium or thorium which are located on inert carriers of kaolin, silica gel, diatomaceous earth or pumice. It is not disclosed that the resulting catalysts are calcined, which results in low stability of the disclosed catalysts. It is always disclosed a composition that the presence of silver and salts or

Oxides of rare earths required. Accordingly, in the absence of further disclosure, it can be assumed that the technical teaching is based on a co-catalytic

The effect is aimed at first enabling a turnover in the interaction of the individual catalytically active constituents.

This is disadvantageous because both the use of silver and the rare earth salts or oxides cause the catalyst to be economically disadvantageous versus alternatives without these ingredients. In particular, the use of silver may be considered particularly disadvantageous in view of the continuously increasing prices of this precious metal.

The object of the present invention was therefore to provide a catalyst which accomplishes the oxidation of hydrogen chloride with high activities with good long-term stability and the lowest possible cost. Another object of the present invention was to provide a process for the catalytic gas phase oxidation of hydrogen chloride with oxygen using such a catalyst.

Surprisingly, it has now been found that uranium-based catalysts have a high activity with good long-term stability for the oxidation of hydrogen chloride to chlorine. At the same time, uranium-based catalysts offer economic advantages since they are cheaper than the materials conventionally used in the prior art.

The present invention therefore provides a catalyst for the catalytic oxidation of hydrogen chloride, characterized in that it comprises at least uranium or a uranium compound and a carrier material as catalytically active components.

Suitable support materials for the catalyst include, for example, silica, alumina (e.g., in α or γ modifications), titania (as rutile, anatase, etc.), tin dioxide, zirconia, ceria, carbon nanotubes, or mixtures thereof.

Suitable uranium compounds are, for example, uranium oxides, uranium chlorides and uranium oxychlorides. Examples of suitable uranium oxides include, but are not limited to, UO ₃ , UO ₂ , UO or the non-stoichiometric phases resulting from the mixtures, such as U ₃ O ₅ , U ₂ O ₅₁ U ₃ O ₇ , U ₃ O ₈ , U ₄ O ₉ and / or Uj ₃ O _34.

Preference is given to uranium oxides or mixtures of uranium oxides having a stoichiometric composition of UO _2i i to UO ₂ , ₉ .

These preferred catalysts comprising uranium oxide or mixtures of uranium oxide as catalysts are particularly advantageous because they surprisingly have an extremely high activity and stability for oxidation reactions.

In a preferred embodiment, as a precursor for the uranium oxides, the chloride compounds or the oxychloride compounds (UO _x Cl _y ) can be used. The uranium or the uranium compound can be used alone or together with other catalytically active components. Suitable further catalytically active components are those selected from the list containing ruthenium, osmium, rhodium, iridium, palladium, platinum, copper, silver, gold, rhenium, bismuth, cobalt, iron, antimony, tin, manganese and chromium. Also suitable are their mixtures or chemical compounds comprising at least one of the above-mentioned elements of the list. In a preferred embodiment, ruthenium, gold, bismuth, cerium or Zr and its compounds are used. In a very preferred embodiment, ruthenium is used in oxidic form or as a chloride compound or as an oxychloride compound.

The proportion of the active component is usually in the range from 0.1 to 90% by weight, preferably in the range from 1 to 60% by weight, more preferably in the range from 1 to 50% by weight, based on the total mass of active Component and carrier material.

The active component can be applied to the substrate by various methods. For example, wet and wet impregnation of a support material with suitable solution starting compounds or starting compounds in liquid or collodial form, up and co-impingement methods, as well as ion exchange and gas phase coating (CVD, PVD) can be used. Suitable catalysts can be obtained, for example, by applying uranium or uranium compounds to the support material and then drying or drying and calcining.

A catalyst is preferred in which the active component is applied to the carrier material in the form of an aqueous solution or suspension and the solvent is subsequently removed.

Particularly preferred is a combination of impregnation and subsequent drying / calcining or precipitation with reducing (preferably hydrogen, hydrides or hydrazine compounds) or alkaline substances (preferably NaOH, KOH or ammonia).

In a further embodiment, the active component may be applied to the support material in a non-oxidic form and converted to the oxidized form in the course of the reaction.

Particular preference is given to a catalyst which is characterized in that the catalytically active constituent is in the form of an aqueous solution or suspension of uranium halides, oxides, hydroxides or oxyhalides, uranyl halides, oxides, hydroxides, Oxyhalides, nitrates, acetates or acetylacetonates each alone or in any mixture is applied to the carrier and the solvent is then removed.

The catalyst may contain promoters as further component. Suitable promoters are basic-acting metals (for example alkali, alkaline earth and rare earth metals), preference is given to alkali metals, in particular Na and Cs, and alkaline earth metals, particularly preferably alkaline earth metals, in particular Sr, Ba, and the rare earth metal Ce. The promoters may, but are not limited to, be applied to the catalyst by impregnation and CVD processes; preference is given to impregnation, particularly preferably after application of the main catalytic component.

The catalyst may contain as further component compounds for stabilizing the dispersion of the active component. Suitable dispersion stabilizers are, for example, scandium compounds, manganese oxides and lanthanum oxides. The compounds for stabilizing the dispersion are preferably applied together with the active component by impregnation and / or precipitation.

The catalysts can be dried under normal pressure or preferably under reduced pressure under a nitrogen, argon or air atmosphere at a temperature of 40 to 200 ^° C. The drying time is preferably 10 minutes to 6 hours.

The catalysts can be used uncalcined or calcined. The calcination can be carried out in reducing, oxidizing or inert phase, preferably the calcination in an air or nitrogen stream. The calcination is usually carried out in the absence of oxygen in a temperature range from 150 to 100 ⁰ C, preferably in the range 200 to 1100 ⁰ C. In the presence of oxidizing gases calcination takes place in a temperature range of 150 to 1500 ⁰ C, preferably in the range 200 bis 1100 ⁰ C.

In a preferred further development of this invention, the catalyst comprising a uranium or a uranium compound may be subjected to a pretreatment.

The pretreatment is usually a pretreatment under the process conditions of use of the catalyst. Since the catalysts disclosed herein are preferably used in the oxidation of HCl with oxygen, pretreatment with a stoichiometric mixture of oxygen and HCl is preferred. Particularly preferred is a pretreatment with a stoichiometric mixture of HCl and oxygen at at least 400 ⁰ C, preferably at least 500 ⁰ C. The pretreatment is usually carried out for at least 10 h. Preferably at least for 50 h, more preferably at least for 100 h. The pretreatment can be carried out as long as desired at any temperatures. It has been shown that a longer and hotter pretreatment is better than a shorter and colder one. There are also shorter and colder pretreatments conceivable. It is a question of weighing how much additional work in pretreatment, which is reflected in increased activity, can be compensated for by this gain in activity. Therefore, the temperature ranges and periods just given are to be understood as meaningful recommendations, but not as technical limitations.

The catalyst obtained as above is characterized by high activity in the hydrogen chloride oxidation at low temperature. Without being bound by theory, it is believed that uranium oxides form "oxygen defect lattice sites" and can thus actively support redox cycles, while uranium oxides have high stability to hydrogen chloride, particularly the most preferred uranium oxides or mixtures of uranium oxides with a stoichiometric Composition of UO _2, i to UO _2.9 .

Another object of the present invention is a process for the production of chlorine by catalytic oxidation of hydrogen chloride in the presence of a catalyst comprising an active component and a carrier material, characterized in that the active component comprises uranium or a uranium compound.

In carrying out the process according to the invention, hydrogen chloride is oxidized to chlorine with oxygen in an exothermic equilibrium reaction in the presence of the catalyst already described above to produce water vapor. The reaction temperature is usually 150 to 750 ⁰ C, the usual reaction pressure is 1 to 25 bar. Since it is an equilibrium reaction, it is expedient to work at the lowest possible temperatures at which the catalyst still has sufficient activity. Furthermore, it is expedient to use oxygen in excess of stoichiometric amounts of hydrogen chloride. For example, a two- to four-fold excess of oxygen is customary. Since no loss of selectivity is to be feared, it may be economically advantageous to work at relatively high pressure and, accordingly, longer residence time than normal pressure.

The catalytic hydrogen chloride oxidation may adiabatically or preferably isothermally or approximately isothermally, discontinuously, but preferably continuously as flow or

Fixed bed process, preferably as a fixed bed process, particularly preferably in tube bundle reactors of heterogeneous catalysts at a reactor temperature of 180 to 750 ⁰ C, preferably 200 to

650 ⁰ C, more preferably 220 to 600 ⁰ C and a pressure of 1 to 25 bar (1000 to 25000 hPa), preferably 1.2 to 20 bar, more preferably 1.5 to 17 bar and in particular 2.0 to 15 bar be performed. Typical reactors in which the catalytic hydrogen chloride oxidation is carried out are fixed bed or fluidized bed reactors. The catalytic hydrogen chloride oxidation can preferably also be carried out in multiple stages.

In the case of the adiabatic, isothermal or approximately isothermal mode of operation, it is also possible to use a plurality of reactors with intermediate cooling, that is to say 2 to 10, preferably 2 to 6, particularly preferably 2 to 5, in particular 2 to 3, connected in series. The hydrogen chloride can be added either completely together with the oxygen before the first reactor or distributed over the various reactors. This series connection of individual reactors can also be combined in one apparatus.

A further preferred embodiment of a device suitable for the method consists in using a structured catalyst bed in which the catalyst activity increases in the flow direction. Such structuring of the catalyst bed can be carried out by different impregnation of the catalyst support with active component or by different dilution of the catalyst with an inert material. As an inert material, for example, rings, cylinders or balls of titanium dioxide, zirconium dioxide or mixtures thereof, alumina, steatite, ceramic, glass, graphite or stainless steel can be used. In the preferred use of Katalysatorforrnkörpern the inert material should preferably have similar outer dimensions.

Suitable shaped catalyst bodies are shaped bodies with arbitrary shapes, preference being given to tablets, rings, cylinders, stars, carriage wheels or spheres, particular preference being given to spheres, rings, cylinders or star strands as molds.

The shaping of the catalyst can take place after or preferably before the impregnation of the support material.

The conversion of hydrogen chloride in a single pass may preferably be limited to 15 to 90%, preferably 40 to 85%, particularly preferably 50 to 70%. After conversion, unreacted hydrogen chloride can be partly or completely recycled to the catalytic hydrogen chloride oxidation. The volume ratio of hydrogen chloride to oxygen at the reactor inlet is preferably between 1: 1 and 20: 1, preferably between 2: 1 and 8: 1, more preferably between 2: 1 and 5: 1.

The heat of reaction of the catalytic hydrogen chloride oxidation can be used advantageously for the production of high-pressure steam. This can be used to operate a phosgenation reactor and / or distillation columns, in particular of isocyanate distillation columns. The following examples illustrate but do not limit the present invention.

Examples

Example 1: Uranium Oxide Catalyst on Tin (TV) Support

2 g of stannic oxide spheres (Saint-Gobain, BET surface area of 44.6 m ² / g) were mixed with a ca. 10% strength by weight aqueous solution of uranyl acetate dihydrate ( Fa. Riedel-de-Haen) impregnated by spraying and subsequent weighing, so that the result is a load of 2 wt .-% U on the carrier. After a waiting time of 60 minutes, the catalyst was dried in an air stream at 80 ^° C. for 2 hours. The subsequent calcining was carried out for four hours at 800 ⁰ C in the air stream, whereby a uranium oxide catalyst supported on tin (rV) oxide was obtained.

Example 2: Uranium Oxide Catalyst on TiO ₂ Support

2 g of titanium dioxide (BET of 8.8 m ² / g, from Saint Gobain) were analogously mixed with a ca. 10% strength by weight aqueous solution of uranyl acetate dihydrate (Riedel-de-Haen) in a beaker impregnated to Example 1, so that the converted results in a loading of 2 wt .-% U on the support. After a waiting time of 60 minutes, the catalyst was dried in an air stream at 80 ^° C. for 2 hours. The subsequent calcining was carried out for four hours at 800 ⁰ C in the air stream, whereby a uranium oxide catalyst supported on titanium (rV) oxide was obtained.

Example 3: Uranium oxide catalyst on alpha-Al ₂ O _{3 support}

In a beaker were 2 g of alpha-A ^ C ^ (BET of 0.02 m ² / g, Fa. Saint Gobain), with an approximately 10 wt .-% - aqueous solution of uranyl acetate dihydrate (Riedel). de-Haen) are impregnated analogously to Example 1, so that the conversion results in a loading of 2% by weight of U on the support. After a waiting time of 60 minutes, the catalyst was dried in an air stream at 80 ^° C. for 2 hours. The subsequent calcination was carried out for four hours at 800 ⁰ C in the air stream, whereby a uranium oxide catalyst supported on alpha alumina was obtained.

Example 4: Uranium oxide catalyst on gamma-Al ₂ C> _{3 support}

2 g of gamma-Al ₂ O ₃ shaped bodies (BET of 260 m ² / g, from Saint Gobain) were impregnated in a glass beaker with a 10% strength by weight aqueous solution of uranyl acetate dihydrate (Riedel de Haen) analogously to Example 1 , After a contact time of 1 h, the residual water was separated in an air stream at 80 ⁰ C for 2 h. The process was repeated until 12 wt .-% uranium were on the moldings.

The moldings were then calcined for four hours at 800 ⁰ C in an air stream. Example 5: Uranium oxide catalyst on Al ₂ O _{3 support} with calcination at 800 ° C, and analysis

Analogously to Example 4, 40 g of gamma-Al ₂ O ₃ shaped bodies (BET of 200 m ² / g, Saint Gobain) were impregnated with uranium and calcined.

Examination by XRD (theta / theta reflection diffractometer SIEMENS D 5000) showed the presence of gamma Al ₂ O ₃ , as well as U ₃ O ₈ .

Example 6-8: Use of the catalysts from Examples 1-3 in the HCl oxidation at 500 ^° C.

0.2 g of the catalysts obtained according to Example 1-3 were ground and introduced as a mixture with 1 g of silica sand (100-200 microns) in a quartz reaction tube (diameter ~ 10 mm).

The quartz reaction tube was heated to 500 ⁰ C and subsequently operated at this temperature.

A gas mixture of 80 ml / min HCl and 80 ml / min oxygen was passed through the quartz reaction tube. After 30 minutes, the product gas stream was passed into a 16% by weight potassium iodide solution for 10 minutes, and the resulting iodine was back titrated with a 0.1 N thiosulfate solution to determine the amount of chlorine introduced.

The productivities of the catalysts shown in Table 1 were found to be 500 ^° C.

Example 9: Use of the catalyst from Example 4 in the HCl oxidation at 540 ^° C.

An experiment was carried out analogously to those of Examples 10-12 for the catalyst according to Example 4, wherein now the quartz reaction tube was heated to 540 ⁰ C and subsequently operated at this temperature.

There the productivity of the catalyst shown in Table 2 at 54O ⁰ C. resulted

Examples 10: Use of the catalyst from Example 4 in the HCl oxidation at 600 ⁰ C.

An experiment was carried out analogously to those of Examples 10-12 for the catalyst according to Example 4, wherein now the quartz reaction tube was heated to 600 ⁰ C and subsequently operated at this temperature.

The productivity of the catalyst shown in Table 2 was found to be 600 ^° C. Table 1:

Table 2:

Claims

Patentansprflche

1. Catalyst for the catalytic oxidation of hydrogen chloride, characterized in that it comprises at least uranium or a uranium compound and a carrier material as catalytically active components.

2. Catalyst according to claim 1, characterized in that the support UO ₃ , UO ₂ , UO or the mixtures resulting from mixtures of these species nichtstöchimoetrischen phases such as U ₃ O ₅ , U ₂ O ₅ , U ₃ O ₇ , U ₃ O ₈ , U ₄ O ₉ Uj ₃ O ₃₄ contains.

3. A catalyst according to claim 1 or 2, characterized in that the uranium or uranium compound as uranium oxide or mixture of uranium oxides having a stoichiometric composition of UO _2J to UO _2-9 is present.

4. A catalyst according to any one of claims 1 to 3, characterized in that further as further catalytically active components substances selected from the list containing ruthenium, osmium, rhodium, iridium, palladium, platinum, copper, silver, gold, rhenium, bismuth, cobalt , Iron, antimony, tin, manganese and chromium, or mixtures thereof or chemical compounds comprising at least one of the above elements of the list

5. A catalyst according to any one of claims 1 to 4, characterized in that the carrier material is selected from the list containing silica, alumina, titania, tin dioxide, zirconia, ceria, carbon nanotubes or mixtures thereof.

6. A process for the production of chlorine by catalytic oxidation of hydrogen chloride in the presence of a catalyst comprising an active component and a carrier material, characterized in that the active component comprises uranium or a uranium compound.

7. The method according to claim 6, characterized in that the uranium or

Uranium compound as uranium oxide or mixture of uranium oxides having a stoichiometric composition of U0 _2> i to UO _{2 9} is present.

8. The method according to any one of claims 6 or 7, characterized in that the proportion of the active component in the range of 0.1 to 90 wt .-%, based on the total mass of active component and carrier material, is located.

9. The method according to any one of claims 6 to 8, characterized in that the reaction temperature is 150 to 750 ⁰ C.

10. The method according to any one of claims 6 to 9, characterized in that the reaction pressure is 1 to 25 bar.

11. The method according to any one of claims 6 to 10, characterized in that it is carried out isothermally, or adiabatically, continuously and as a fixed bed process.

12. The method according to any one of claims 6 to 11, characterized in that multi-stage, in 2 to 10, preferably 2 to 6, particularly preferably 2 to 5, in particular 2 to 3, series-connected reactors is carried out with intermediate cooling.

13. The method according to any one of claims 6 to 12, characterized in that the volume ratio of hydrogen chloride to oxygen at the reactor inlet between 1: 1 and 20: 1, preferably between 2: 1 and 8: 1, more preferably between 2: 1 and 5 : 1 is.