[0001] The invention refers to a process to obtain a hydrogen peroxide solution by means of a direct reaction of hydrogen and oxygen in the presence of a solvent and of a catalyst comprising, at least, a noble or semi-noble metal supported on a halogen-free acid resin.
[0002] Hydrogen peroxide is a highly important commercial product widely used as a whitening agent in the textile or paper industries, as a disinfectant and as a basic product of the chemical industry, e.g. in the production of peroxide compounds (sodium perborate, sodium percarbonate, metallic peroxides or percarboxylic acids) in oxidation reactions (manufacture of amine oxides), epoxidation and hydroxylation (manufacture of plasticizers and stabilizers). It is further used for cleaning surfaces in the semiconductor industry, chemical polishing of copper, tin and other copper alloy surfaces, etching electronic circuits, etc.
[0003] The industrial method currently most widely used for the production of hydrogen peroxide is the autoxidation of alkylanthrahydroquinones. This process, which is comprised of a series of phases of reduction, oxidation, extraction, purification and concentration, is very complicated which makes the investments and variable costs very high. A very attractive alternative to this process is the production of hydrogen peroxide directly from the reaction between hydrogen and oxygen in the presence of metal catalysts of the platinum group, using explosive hydrogen concentrations (U.S. Pat. Nos. 4,681,751, 4,772,458, 4,832,938, 5,338,531), outside the explosivity limit (WO 99/41190, WO 01/05498, WO 01/05501, U.S. Pat. No. 6,168,775 B1). However, a high concentration of H
[0004] To avoid these inconveniences alternative processes have been proposed without the presence of halogen ions and/or acids in the reaction medium. For example, in the European patent no. EP 492064, a palladium based catalyst supported on a resin functionalized with halogens is proposed. The reaction medium is water with a hydrogen peroxide stabilising agent, but the H
[0005] Thus, there is the necessity to have new catalysts available which permit obtaining hydrogen peroxide by means of a direct reaction with hydrogen and oxygen in the presence of said catalysts, easily preparable and reproducible, and of a solvent, to obtain high concentration non-corrosive hydrogen peroxide solutions with high selectivity.
[0006] An objective of this invention is to provide a process to obtain hydrogen peroxide solutions by means of a direct reaction with hydrogen and oxygen in the presence of a solvent and a catalyst that comprises a supported noble or semi-noble metal, that resolves completely or partly the previously mentioned inconveniences in relation to the state of the art processes.
[0007] The inventors have observed that said objective can be achieved using a catalyst comprising, at least, a noble or semi-noble metal supported on a resin that (i) contains, at least, one functional acid group and (ii) is halogen-free. A process such as that provided for this invention permits obtaining high concentration non-corrosive hydrogen peroxide solutions with high hydrogen selectivity.
[0008] This invention refers to a process to obtain a hydrogen peroxide solution by means of the direct reaction of hydrogen and oxygen in the presence of a solvent and a catalyst comprising, at least, a noble or semi-noble metal supported on an halogen-free acid resin.
[0009] The process in accordance with this invention uses catalysts comprising, at least, a noble or semi-noble metal supported on a halogen-free acid resin, unlike the process described in the patent EP 492064, which describes the use of palladium catalysts supported on resin functionalized with halogens. The inventors, surprisingly, have discovered that using catalysts comprising, at least, a noble or semi-noble metal supported on a halogen-free acid resin and using the reaction conditions described herein can obtain non-corrosive hydrogen peroxide solutions, with high concentration (e.g. equal to or above 1% in weight, preferably equal to or above 3% in weight, more preferably equal to or above 5% in weight) and high hydrogen selectivity (e.g. equal to or above 50%) by direct reaction between hydrogen and oxygen.
[0010] The support employed in the catalysts used in the process of this invention includes a resin functionalized with halogen-free acid groups. The resins used in this invention are formed by the reaction of homopolymerization of monomers or by the copolymerization of two or more monomers. By way of an illustration, said resin includes styrenic, acrylic, metacrylic polymers, or styrene-divinylbenzene copolymers. These resins can be functionalized with different types of acid groups such as sulphonic, carboxylic, dicarboxylic, etc. (Encyclopedia of Chemical Technology Kirk-Othmer 3
[0011] In a specific embodiment, said halogen-free resin is a sulphonated styrene and divinylbenzene copolymer.
[0012] The catalyst is prepared by adding a noble or seminoble metal belonging to groups VII to XI of the periodic table, preferably palladium, platinum, silver, gold, rhodium, iridium, ruthenium, osmium, or a mixture of 2 or more of these metals, to the support (non-halogenated acid resin). Amongst those preferred are palladium or a mixture of palladium with another metal, e.g. platinum. The quantity of metal supported can be between 0.001% and 10% in weight with respect to the support, preferably between 0.1% and 5% in weight with respect to the support. The addition of metal can be performed using any of the known preparation techniques of supported metal catalysts, such as, e.g. impregnation, adsorption, ionic exchange, etc. For the impregnation, one can use any kind of organic or inorganic salt of the metal to be impregnated, that is soluble in the solvent used in the addition of the metal, such as acetate, nitrate, halide or oxalate, etc.
[0013] Hydrogen peroxide formation is carried out by means of a direct reaction between hydrogen and oxygen within a solvent in the presence of a catalyst and, optionally, with the addition of an inert gas. Nitrogen, carbon dioxide, helium, argon, etc, can be used as inert gases. The working pressure is normally above atmospheric pressure, and preferably between 2 and 30 MPa. The molar relation between hydrogen and oxygen ranges from 1/1 to 1/100. The hydrogen concentration in the gas phase in contact with the reaction medium should preferably be below 4.16% molar, to maintain the operation outside the explosivity limits of the hydrogen and oxygen mixtures.
[0014] The solvents that can be used in this invention are those compounds with an inert character in the operation conditions during the formation of hydrogen peroxide by direct reaction between hydrogen and oxygen. As solvents, in the framework of this invention, one can state water, C
[0015] The reaction of oxygen with hydrogen is performed at temperatures ranging from −10° C. to 100° C., preferably from 10° C. to 75° C.
[0016] The process of this invention can be carried out continuously, semi-continuously or discontinuously, by conventional techniques, e.g. in a stirred tank reactor with suspended catalyst particles, in a basket type stirred tank reactor, etc. Once the reaction has reached the desired conversion levels, the catalyst can be separated by different known procedures, such as, e.g. by filtration if the suspended catalyst is used, which would permit its subsequent reutilization. In this case, the quantity of catalyst used corresponds to that necessary to obtain a 0.01% to 10% concentration in weight with respect to the solvent and preferably between 0.1% and 5% in weight.
[0017] The reaction can be performed, likewise, in a fixed bed reactor, in accordance with known procedures. For this, the solvent and gaseous current of oxygen and hydrogen are made to circulate over the catalyst bed, in the presence of an inert gas (or not) in parallel or in counterflow in the above-mentioned temperature and pressure conditions.
[0018] The reaction to obtain hydrogen peroxide in accordance with this invention can be performed, if desired, in the presence of a promoter to improve the H
[0019] If desired, a hydrogen peroxide stabilising agent can be added to the reaction medium. As hydrogen peroxide stabilising agents, one can quote inorganic acids such as phosphoric acid, sulphuric acid, nitric acid, etc.; organic acids such as aminomethylenephosphoric acid etc.; amino acids such as leucine, etc.; phosphoric acid salts such as sodium pyrophosphate, etc.; chelating agents such as ethylenediaminetetraacetic acid (EDTA), etc.; surfactant agents such as alkylbenzyl sulphonates, etc. These stabilisers can be used individually or in mixtures of two or more of them. The preferred stabilisers in this invention are aminomethylenephosphoric acid, 1-hydroxyethylene-1,1-diphosphoric acid, ethylenediaminotetramethylene-phosphoric acid, the sodium salts of said compounds and sodium pyrophosphate. The stabiliser concentration depends on the type of stabiliser and hydrogen peroxide concentration. However, it is preferable to maintain the stabiliser concentration sufficiently low enough to avoid the catalyst metal from dissolving and/or the corrosion of the reactor used. In general, the quantity of stabiliser added is less than 0.5% in weight with respect to the solvent and preferably below 500 ppm.
[0020] The following examples serve to illustrate the invention and should not be considered as limits of its scope.
[0021] Examples 1 to 3 illustrate the preparation of a catalyst according to the invention, whilst Examples 4 to 8 illustrate obtaining hydrogen peroxide solutions according to the invention.
[0022] A catalyst was prepared from a commercial resin functionalized with sulphonic groups, Lewatit K2621® (Bayer AG) (non-halogenated macroporous resin, with an exchange capacity of 1.4 eq/l, pore diameter 70 nm, porosity 0.6 ml/g and a specific surface area BET 40 m
[0023] A catalyst was prepared from a commercial resin functionalized with sulphonic groups Lewatit K2641® (Bayer AG) (non-halogenated macroporous resin, with an exchange capacity of 4.8 eq/l, pore diameter 70 nm, porosity 0.3 ml/g and a specific surface area BET 35 m
[0024] A catalyst was prepared from a commercial resin functionalized with sulphonic groups Lewatit K2621® (Bayer AG) (non-halogenated macroporous resin, with an exchange capacity of 1.4 eq/l, pore diameter 70 nm, porosity 0.6 ml/g and a specific surface area BET 40 m
[0025] 1.6 g of the catalyst from Example 1 were put inside an autoclave with 150 ml of a methanol:water mixture (96:4) and 24 ppm of HBr, and the mixture was stabilised at 40° C. The system was pressurised with a H
[0026] 0.8 g of the catalyst from Example 1 were put inside an autoclave with 150 ml of a methanol:water mixture (96:4) and 12 ppm of HBr, and the mixture was stabilised at 40° C. The system was pressurised with a H
[0027] 0.8 g of the catalyst from Example 2 were put inside an autoclave with 150 ml of a methanol:water mixture (96:4) and 12 ppm of HBr, and the mixture was stabilised at 40° C. The system was pressurised with a H
[0028] 0.8 g of the catalyst from Example 2 were put inside an autoclave with 150 ml of a isobutanol:water mixture (96:4) and 12 ppm of HBr, and the mixture was stabilised at 40° C. The system was pressurised with a H
[0029] 0.8 g of the catalyst from Example 3 were put inside an autoclave with 150 ml of a methanol:water mixture (96:4) and 6 ppm of HBr, and the mixture was stabilised at 40° C. The system was pressurised with a H