|Title of Invention||
MECHANICALLY STABLE CATALYST BASED ON ALPHA-ALUMINUM OXIDE
|Abstract||A catalyst for gas-phase reactions which has high mechamcal stability and comprises one or more active metals on a support comprising aluminum oxide as support material, wherein the aluminum oxide in the support consists essentially of alpha-aluminum oxide, Ruthenium, copper and/or gold are preferred as active metal. Particularly preferred catalysts according to invention comprise a) from 0.001 to 10% by weight of ruthenium, copper and/or gold, b) from 0 to 5% by weight of one or more alkaline earth metals, c) from 0 to 5% by weight of one or more alkali metals, d) from 0 to 10% by weight of one or more rare earth metals, e) from 0 to 10% by weight of one or more further metals selected from the group consisting of palladium, platinum, osmium, iridium, silver and rhenium, in each case based on the total weight of the catalyst, on the support comprising alpha-A1203. The catalysts are preferably used in the oxidation of hydrogen chloride (Deacon reaction).|
As originally filed
Mechanically stabte catalyst based on alpha-aluminum oxide
The invention relates to a mechanically stable catalyst based on alpha-aluminum oxide as support. The invention farther relates to such a catalyst for the catalytic oxidation of hydrogen chloride by means of oxygen to give chlorine and also a process for the catalytic oxidation of hydrogen chloride using the catalyst
In the process for the catalytic oxidation of hydrogen chloride developed by Deacon in 1868? hydrogen chloride is oxidized by means of oxygen to give chlorine in an exothermic equilibrium reaction. The conversion of hydrogen chloride into chlorine enables chlorine production to be decoupled from sodium hydroxide production by chloralkali electrolysis. Such decoupling is attractive since the worldwide demand for chlorine is growing more strongly than the demand for sodium hydroxide. In addition, hydrogen chloride is obtained in large amounts as coproduct in for example, phosgenation reactions, for instance in isocyanate production.
EP-A 0 743 277 discloses a process for preparing chlorine by catalytic oxidation of hydrogen chloride, in which a ruthenium-comprising supported catalyst is used. Here, ruthenium is applied in the form of ruthenium chloride, ruthenium oxychlorides, chlotoruthenate complexes, mthemum hydroxide, ruthenium-amine complexes or in the form of further ruthenium complexes to the support. The catalyst can comprise palladium, copper, chromium, vanadium, manganese, alkali metals, alkaline earth metals and rare earth metals as further metals,
According to GB 1,046,313, mthenium(in) chloride on aluminum oxide is used as catalyst in a process for the catalytic oxidation of hydrogen chloride.
Gamma-aluminum oxide is usually used as aluminum oxide support.
A disadvantage of the known processes which employ catalysts based on gamma-aluminum oxide is the low mechanical strength of the catalysts- This decreases further during use of the catalyst in the reactor. The low mechanical strength of the catalysts results in high attrition. Attrition and fine dust formation can lead to overloading of cyclones and filters or filter chambers in a fluidized-bed process. It is an object of the present invention to improve the mechanical strength of aluminum
oxide supports. A further object is to provide catalysts having an increased mechanical strength or gas-phase reactions, in particular for the catalytic oxidation of hydrogen chloride.
This object is achieved by a catalyst for gas-phase reactions which has high mechanical stability and comprises one or more active metals on a support comprising aluminum oxide as support material, wherein the aluminum oxide in the support consists essentially of alpha-aluminum oxide.
It has surprisingly been found that in a support comprising gamma-aluminum oxide, a phase transformation of gamma-aluminum oxide into alpha-aluminum oxide occurs in places even at comparatively low temperatures as occur, for example, in the gas-phase oxidation of hydrogen chloride to chlorine (380400*0). The domains of crystalline alpha-aluminum oxide formed in this way significantly reduce the strength of the shaped catalyst body, which is also reflected in the significantly increased attrition values of the used catalyst.
The support used according to the invention can comprise alpha-aluminum oxide in admixture with further support materials, Suitable further support materials are, for example, graphite, silicon dioxide, titanium dioxide and zirconium dioxide, preferably titanium dioxide and zirconium dioxide, for example in amounts of up to 50*% by weight. The support preferably consists essentially of aluminum oxide, for example to an extent of 90% by weight and above, and it particularly preferably comprises at least 96% by weight of aluminum oxide. The aluminum oxide in the support consists essentially of alpha-aluminum oxide, preferably at least 90% by weight, particularly preferably at least 98% by weight, of alpha-aluminum oxide, based on the total aluminum oxide in the support. The phase composition of the support can be determined by XRD (X-ray diffraction).
In general, the catalyst of the invention is used for carrying out gas-phase reactions at a temperature above 200QC preferably above 320°C, particularly preferably above 350°C However, the reaction temperature is generally not mote than 600°Q preferably not more than 500°C.
As active metals, the catalyst of the invention can comprise any active metals and also further metals as promoters. These are usually comprised in the catalyst in amounts of up to 10% by weight, based on the weight of the catalyst.
If the catalyst of the invention is to be used in the catalytic oxidation of hydrogen chloride
(Deacon process), the active metals are selected from among the elements of groups 7-11 of the Periodic Table of the Elements,
Particularly preferred active metals are ruthenium, copper and/or gold.
The supported copper or ruthenium catalysts can be obtained, for example, by impregnation of the support material with aqueous solutions of CuCfe or RuCl3 and, if appropriate, a promoter for doping, preferably in the form of their chlorides. The shaping of the catalyst can be carried out after or preferably before impregnation of the support material.
Gold-comprising catalysts according to the invention can be obtained by application of gold in the form of the aqueous solution of a soluble gold compound and subsequent drying or drying and calcination. Gold is preferably applied as an aqueous solution of AnCls or HAuGU to the support.
The ruthenium-, copper- and/or gold-comprising catalysts of the invention for the catalytic oxidation of hydrogen chloride can additionally comprise compounds of one or more other noble metals selected from among palladium, platinum, osmium, iridium, silver and rhenium. The catalysts can also be doped with one or more further metals. Suitable promoters for doping are alkali metals such as lithium, sodium, potassium, rubidium and cesium, preferably lithium, sodium and potassium, particulariy preferably potassium, alkaline earth metals such as magnesium* calcium, strontium and barium, preferably magnesium and calcium, particulariy preferably magnesium, rare earth metals such as scandium, yttrium, lanthanum, cerium, praseodymium and neodymium, preferably scandium, yttrium, lanthanum and cerium, particularly preferably lanthanum and cerium, or mixtures thereof, also titanium, manganese, molybdenum and tin-Preferred catalysts according to the invention for the oxidation of hydrogen chloride comprise
a) from 0.001 to 10% by weight, preferably from 1 to 3% by weight, of rathenium, copper and/or gold,
b) from 0 to 5% by weight, preferably from 0 to 3% by weight, of one or more alkaline earth metals,
c) from 0 to 5% by weight, preferably from 0 to 3% by weight, of one or more alkali
d) from 0 to 10% by weight, preferably from 0 to 3% by weight, of one or more rare earth metals,
e) from 0 to 10% by weight, preferably from 0 to 1 % by weight, of one or more further metals selected from the group consisting of palladium, platinum, osmium, iridium, silver and rhenium,
in each case based on the total weight of the catalyst The weights indicated are based on the weight of the metal, even though the metals are generally present in oxidic form on the
Ruthenium is very particularly preferred as active metal and is generally comprised in amounts of from 0,001 to 10% by weight, based on the weight of the catalyst, fo a specific embodiment, the catalyst of the invention comprises about 1-3% by weight, for example about 1.6% by weight, of ruthenium on alpha-dumiuum oxide as support and no further active metals and promoter metals, with ruthenium being present as RuO2.
The catalysts of the invention are obtained by impregnation of the support material with aqueous solutions of salts of the metals, The metals apart from gold are usually applied as aqueous solutions of their chlorides, oxychlorides or oxides to the support. Shaping of the catalyst can be carried out after or preferably before impregnation of the support material. The catalysts of the invention are also used as fluidized-bed catalysts in the form of powder having a mean particle size of 10-200 Jim. As fixed-bed catalysts, they are generally used in the form of shaped catalyst bodies.
The shaped bodies or powders can subsequently be dried at temperatures of from 100 to 400°C, preferably from 100 to 300°C, for example under a nitrogen, argon or air atmosphere and, if appropriate, calcined, The shaped bodies or powders are preferably firstly dried at from 100 to 150*C and subsequently calcined at from 200 to 400°C The oxides* for example R11O2 or CuO, ace performed from the chlorides during calcination.
The invention also provides a process for producing catalysts by impregnating alpha-aluminum oxide as support with one or more metal salt solutions comprising the active metal or metals and, if appropriate, one or more promoter metals, and drying and calcining the impregnated support. Shaping to produce shaped catalyst particles can be carried out
before or after impregnation. The catalyst of the invention can also be used in powder form.
Suitable shaped catalyst bodies include all shapes, with preference being given to pellets, rings* cylinders, stars, wagon wheels or spheres, particularly preferably rings, cylinders or star extrodates. The specific surface area of the alpha-aluminum oxide support prior to metal salt deposition is generally in the range from 0.1 to 10 m2/g.
Alpha-aluminum oxide can be prepared by heating gamma-aluminum oxide to temperatures above 1000°C; it is preferably prepared in this way. In general it is calcined for 2-24 hours.
The present invention also provides a process for the catalytic oxidation of hydrogen chloride by means of oxygen to give chlorine over the catalyst of the invention.
For this purpose, a stream of hydrogen chloride and an oxygen-comprising stream are fed into an oxidation zone and hydrogen chloride is partially oxidized in the presence of the catalyst to give chlorine, so that a product gas stream comprising chlorine, unreacted oxygen, unreacted hydrogen chloride and water vapor is obtained. The hydrogen chloride steam, which can originate from a plant for the preparation of isocyanates, can comprise impurities such as phosgene and carbon monoxide.
The reaction temperatures are usually in the range from ISO to 500CC, and the reaction pressures are usually in the range from 1 to 25 bar, for example 4 bar. The reaction temperature is preferably >300°C, particularly preferably from 350°C to 400°C. Furthermore, it is advantageous to use oxygen in superstoichiometric amounts. A L5- to four-fold, for example, oxygen excess is usual. Since no losses of selectivity have to be feared, it can be economically advantageous to carry out the reaction at relatively high pressures and accordingly at residence times which are longer than under atmospheric pressure.
Usual reaction apparatuses in which the catalytic oxidation according to the invention of hydrogen chloride is carried out are fixed-bed or fluidized-bed reactors- The oxidation of hydrogen chloride can be carried out in one or more stages.
The catalyst bed or fluidized catalyst bed can comprise further suitable catalysts or additional inert material in addition to the catalyst of the invention.
The catalytic oxidation of hydrogen chloride can be carried out adiabatically or preferably
isothermally or approximately isothermally, batchwise or pieferably continuously as a moving-bed or fixed-bed process, preferably as fixed-bed process, particularly preferably in shell-and-tube reactors, at reactor temperatures of from 200 to 500°C, preferably from 300 to 400°C, and a pressure of from 1 to 25 bar, preferably from I to 5 bar.
In isothermal or approximately isothermal operation, it is also possible to use a plurality of reactors, for example from 2 to 10 reactors, preferably from 2 to 6 reactors, particularly preferably from 2 to 5 reactors, in particular 2 or 3 reactors, connected in series with additional intermediate cooling. The oxygen can either all be added together with the hydrogen chloride upstream of the first reactor or distributed over the various reactors. This series arrangement of individual reactors can also be combined in one apparatus, In one embodiment of the fixed-bed process, a structured catalyst bed in which the catalyst activity increases in the direction of flow is used. Such structuring of the catalyst bed can be achieved by different impregnation of the catalyst support with active composition or by different dilution of (he catalyst bed with an inert material. Inert materials which can be used are, for exajonple, rings, cylinders or spheres comprising titanium dioxide, zirconium dioxide or mixtures thereof, aluminum oxide, steatite, ceramic, glass, graphite or stainless steel. The inert material preferably has similar external dimensions to the shaped catalyst bodies.
The conversion of hydrogen chloride in a single pass can be limited to from 15 to 90%, preferably from 40 to 85%, Unreacted hydrogen chloride can, after having been separated off, be recirculated ia part or in its entirety to the catalytic oxidation of hydrogen chloride. The volume ratio of hydrogen chloride to oxygen at the reactor inlet is generally from 1:1 to 20:1, preferably from 1.5:1 to 8:1, particularly preferably from 1.5:1 to 5:1.
The chlorine formed can subsequently be separated off in a customary maimer from the product gas stream obtained in the catalytic oxidation of hydrogen chloride* The separation usually comprises a plurality of stages, namely isolation and, if appropriate, recirculation of unreacted hydrogen chloride from the pioduct gas stream from the catalytic oxidation of hydrogen chloride, drying of the resulting residual gas stream which consists essentially of chlorine and oxygen and separation of chlorine from the dried stream.
The invention is illustrated by the following examples.
Determination of attrition and proportion of fines by the Montecalini method:
The attrition test simulates the mechanical stresses to which a fluidized material (e.g. a catalyst) is subjected in a fluidized gas/solid bed and gives as results an attrition value (AT) and a proportion of fines (PF) which describe the strength behavior.
The attrition apparatus comprises a nozzle plate (nozzle diameter = 0.5 mm) which is connected in a gastight and solids-tight manner to a glass tube, A steel tube having a conical widening is fixed above the glass tube, likewise in a gastight and solids-tight manner. The apparatus is connected to the 4 bar compressed air supply. A reducing valve decreases the pressure to 2 bar absolute upstream.of the apparatus.
60.0 g of catalyst are introduced into the apparatus, The amount of compressed air for carrying out the experiment is 3501/h, The apparatus itself is operated under atmospheric conditions (1 bar, 20*C). Owing to the high gas velocity at the nozzle, the particles are subjected to abrasion or broken up by particle/particle and particle/wall impacts. The solid discharged travels via a tube bend into a filter paper thimble (pore size: 10-15 Jim) and the purified gas flows into the exhaust air system of the laboratory.
The solid which has been deposited is weighed after one hour (defined as the proportion of fines PF) and after 5 hours (defined as the attrition AT).
A pulverulent gamma-aluminum oxide support from Sasol (Puralox® SCCa 30/170) was firstly converted into alpha-AhO* The support consists of particles having a mean particle diameter of about 50 fim. For this purpose, 2000 g of Puralox® SCCa 30/170 were heated at 1200-1300°C for 5 hours. 1500 g of the support obtained were impregnated with an aqueous RuCU hydrate solution (55.56 g of RuCl3 hydrate corresponding to 41.8% by weight of Ru in 480 g of water). The water uptake of the support was about 0.38 ml/g* After impregnation to 90% of the water uptake, the impregnated support was dried at 120°C for 6 hours and subsequently calcined at 350°C for 2 hours. The catalyst produced in this way comprises about 2% of Ru02 on alpha-AfeOa- The most important properties of the catalyst are summarized in Table 1.
Comparative Example CI:
The gai»ma-aluminum oxide support Puralox*8' SCCa 30/170 was used directly for producing the catalyst without prior heat treatment. About 1434 g of the support were impregnated with, an aqueous RuCI3 hydrate solution (54 J g of RuCl3 hydrate corresponding to 36.5% of Ru in 1045 g of water). The water uptake of the support was about 0.81 ml/g. The support which had been impregnated to 90% of the water uptake was dried at 120°C for 6 hours and calcined at 350°C for 2 hours. The catalyst produced in this way comprises about 2% of Ru02 on gamma-AI2O3. The most important properties of the catalyst are summarized in Table 1.
Example 2 and Comparative Example 2
A Deacon reactor was operated in the fluidlzed-bed mode using the catalysts from Example 1 and Comparative Example CL The Deacon reactor consisted of a tube having a diameter of 4 cm and a length of 1 m and comprised 600 g of the catalyst At 380-400°C and a reactor pressure of 4 bar, 200 standard J/h of HCi and 100 standard I/h of O2 were fed into the reactor; the HCI conversion was 60-80%- After operation of the reactor for 1000 hours, the catalyst was removed. The catalyst properties of the used catalyst are summarized in Table 2.
As can clearly be seen from the values for proportion of fines and attrition, the catalyst according to the invention has a significantly higher mechanical stability compared to the
corresponding catalyst on gamma^aluminum oxide as support, This is the case evea for the freshly produced catalyst, but in particular for the used catalyst
Claims as enclosed to IPRP
1. A fluidized bed catalyst for gas-phase reactions which has high mechanical stability in the form of powder having a mean particle size of from 10 to 200 jxm and comprises one or more active metals on a support consisting essentially of aluminum oxide as support material, wherein the aluminum oxide in the support consists essentially of alpha-almninum oxide.
2. The catalyst according to claim l, wherein the active metal or metals is/are selected from among the ekmeiits of groups 7-11 of the Periodic Table of the Elements-
3. The catalyst according to claim 1 or 2» wherein the active metal is nithenium, copper
4. The catalyst according to any of claims 1 to 3 comprising
a) from 0.001 to 10% by weight of ruthenium, copper and/or gold,
b) from 0 to 5% by weight of one or more alkaline earth metals,
c) from 0 to 5% by weight of one or more alkali metals,
d) from 0 to 10% by weight of one or more rare earth metals,
e) from 0 to 10% by weight of one or more fuerther metals selected from die group consisting of palladium, platinum, osmium, iridium, silver and rhernum,
in each case based on the total weight of the catalyst
5. The catalyst a
7. The process according to claim 6, wherein alpha-aluminum oxide is prepared by heating gamma-aluminum oxide to temperatures above lOOO0C.
8. A process for the catalytic oxidation of hydcogeix chloride by means of oxygen to
give chlorine over a fluidized catalyst bed comprising catalyst panides of the
catalyst according to any of claims 1 to 5,
9. The process according to claim 7 or 8, wherein the catalytic oxidation is carried out
at a reaction temperature of > 3500C
10. The use of the catalyst according to any of claims 1 to 5 for catalyzing gas-phase
reactions at a reaction temperature of > 300°C.
|Indian Patent Application Number||900/CHENP/2008|
|PG Journal Number||18/2012|
|Date of Filing||22-Feb-2008|
|Name of Patentee||BASF SE|
|Applicant Address||67056, LUDWIGSHAFEN|
|PCT International Classification Number||B01J 21/04|
|PCT International Application Number||PCT/EP06/65559|
|PCT International Filing date||2006-08-22|