2) United States Patent cher et al. 'US00637592082 US 6,375,920 B2 ‘Apr. 23, 2002 a0) Patent No.: (45) Date of Patent: (54) PROCESS FOR THE MANUFACTURE OF HYDROGEN PEROXIDE, (75) Inventors: Martin Fischer, Ludwigshafen; Gerd Kaibel, Lampertheim; Achim Stammer, Freinsheim; Klemens Flick, Heerxheim; Stefan Quaiser, Limburgerhof, Wolfgang Harder, Weinheim; Klemens Massonnk Westheim, all of (DE) (73) Assignee: BASF Aktiengesellschatt, Ludwigshafen (DE) (*) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 U.S.C. 154(b) by 0 days, (21) Appl. Nox 09/284,247 (22) PCT Filed: Oct. 15, 1997 (86) PCT'No PCT/EP97/05659 §371 Date: Apr. 15, 1999 § 102(¢) Date: Apr. 15, 1999 (87) PCT Pub. No: WO98/16463, PCT Pub, Date: Apr. 23, 1998 (30) Foreign Application Priority Data at. 16, 1996 (DE) 196 42.770 (51) Int. CL? COLB 15/01 (52) US.CL 423/584 (58) Field of Search 3/584 (56) References Cited USS, PATENT DOCUMENTS. 3873409 A HITS Foster eta. 4000'252 A 2/1977 Taumi et al 451914 A 5/1979 Bhat 433389 A 6/1982 Cunningham 4335092 A * 6/1982. Dalton, Jee a 425/584 4336238 A 6/1982. Dalton, Jn et 4336239 A * 6/1982 Dalton, Jn. et a. 423/584 308888 A 121982 Levin 4389.39 A 6/1983. Dalton, Jeet a 4AS024 A 5/1984 Domesle et al SATLOL4 A 9/1984. Hartog et al. (List continued on next page.) POREIGN PATENT DOCUMENTS DE 4113525 10/1992 oB 144133 ALs7s wo wo%208277 3/1992 wo Woo208976 41992 Wo Woo)05138 211996 OTHER PUBLICATIONS Joba R. Kosak, “A Novel Fixed Bed Catalyst for the Direct Combination of H. and O, to H,0,", Catalysis of Organic Reactions, (eds. Searos and Praniet), Marcel Dekker Inc, New York, 1995 pp. 115-124, (No month). Rompp Chemie Lexikon, 9 Edition, pp. 1453-1454, (With English Abstract), (No dat). MT Reetz, etal, Agnew. Chem. Int, Ed. Eng, vol 34, No 23/24, pp. 2728-2730, "A New Ste Catalysis: oath). P. Fauehas, etal, Pare anc! Appl. Chem., vol 66, No. 6, pp. 1247-1258, “Plasma Spraying: Present and Future”, 1994, (No month). egy in Heterogeneous The Design of Cortex Catalysis”, 1995, (No Primary Examiner—Wayoe Langel (74) Attorney, Agent, or Firm—Oblon, Spivak, McClelland, Maier & Neustadt, PC ABSTRACT ess for preparing a hydrogen peroxide solution having 4 hydrogen peroxide content of not less than 25% by weight, which comprises continuously reacting hydrogen and oxygen in an aqueous, alcoholic or aqueous/aleobolic reaction medium in the presence of a catalyst containing palladium, 15 Claims, 1 Drawing SheetUS 6,375,920 B2 mea US. PATENT DOCUMENTS pened cor cece eee ann tee oaraayat eased So 5300334 A 3/1995 Kawakami et al. Renee oer 450809 A 1096 Themen ta Sore A «abe Gor savas S020 Aine Genta Sens a | a Sas § eee Pee el eee SARRD A Tio Canby Seer eeel 3 see A ‘Vien Seale wat Reed eel cea + ete by examineU.S. Patent Apr. 23, 2002 US 6,375,920 B2 FIGUREUS 6,375,920 B2 1 PROCESS FOR THE MANUFACTURE OF HYDROGEN PEROXIDE, DESCRIPTION ‘The present invention relates to a process for preparing a hydrogen peroxide solution having a hydrogen peroxide content of not less than 2.5% by weight by continuous reaction of hydrogen and oxygen over a catalyst comprising palladium as aetive component. Customary industrial processes for preparing hydrogen peroxide are the electrolysis of acidic ammonium sulfate Solutions, the oxidation of isopropyl alcohol and the anthraquinone process. The direct synthesis of hydrogen peroxide from the elements over transition metal catalysts is known, but has not found commercial use to date ‘There are several reasons for this. For instance, hydrogen and oxygen form explosive gas mixtures if the level of hydrogen in the gas mixture is above 5% by volume, On the other hand, the rate of formation of hydrogen peroxide on using hydrogen-oxygen mixtures ouside the explosive range is generally too low to ensure reasonable space-time yields. In addition, an excessively high level of oxygen in ihe reaction gas ean speed up the oxidative degradation of the catalysts, ‘The selectivity of the reaction is a further problem. For instance, the reaction to form the hydrogen peroxide has to ‘compete with that to form water. In addition, the catalysts ‘which are suitable for forming hydrogen peroxide from the ‘clement also catalyze the degradation reaction of hydrogen peroxide in the presence of excess hytlrogen in accordance With the following reaction equation: H,0,4H,—>2H,0. ‘This selectivity problem can be solved by using continuous processes at high flow rates, However, this bas the conse~ ‘quence that, at a low reaction rate, the hydrogen peroxide ‘concentrations obiained in the effluent become too low for ‘commercial use ofthis process. Io addition, excessively high flow rates give rise to catalyst abrasion problems, leading to reduced on-stream times and hence likewise to commercial disadvantages for this process. explosive range, for the formation of hydrogen peroxide from hydrogen and oxygen over palladium catalysts. The reaction is carried out as a batch process and the space-time yields which are obtained are unsatisfactory. WO 92(04277 describes the reaction of hydrogen with ‘oxygen in a tubular reactor packed with an aqueous suspen- sion of catalyst, The gas mixtures used are preferably Tocated within the explosive range. A high flow rate of the reaction medium (+1 misee) is used fo ensure that the reaction gas is completely dispersed in the reaction medium in the form of small bubbles, preventing an explosive reaction of the reaction gas. The hydrogen peroxide con ‘centrations obtained alter a single pass through the reaction zone are below 1% by weight. Higher yields can only be ‘obtained by repeated passes through the reaction zone. The fact that the catalyst is used in the form of a suspension turns ‘out to be a problem because this necessitates elaborate filtration and recycling measures, with inevitable losses of the catalyst. Reaction tubes which are suitable for the required reaction pressure—pressures of above 80 bar are disclosed in the illustrative embodiments—are compara~ Lively costly. The cited process must therefore be considered very costly. A similar process with improved fluidization of the hydrogen and oxygen streams is described in WO 96105138, as os ss 4s ss 6s 2 US. Pat. No. 5,500,202 and EP-A 579 109 describe a continuous process for preparing hydrogen peroxide by reacting H,/O. gas mixtures over a stationary pulverulent catalyst (particle sizes within the range 10 yam to 250 jum) in 4 trickle bed reactor, Ta reduce the risk of explosion due to the large gas volume which is customary for a trickle bed reactor, nitrogen is added as an inert gas fo the reaction gas. However, this entails additional costs. The aqueous hydro- gen peroxide solutions obtained in this way only have ‘concentrations within the range from 3 to 5%, The coaver- sion based on hydrogen is merely within the range of 25.35%. No data are provided about catalyst life. Reactors hhaving & maximum internal diameter of 30 mm are recom- ‘mencled because of the considerable beat production. Indus- trial use would therefore require the installation of several thousands of these tubular reactors, which entails. high capital expenditure costs U.S. Pat. No. 4,336,238 and ULS. Pat. No. 4,336,239 describe the reaction of hydrogen and oxygen to form hhydrogen peroxide over palladium catalysts in orgenie sol- vents or solvent mixtures in the presence or absence of water. The process described makes it possible to reduce the proportion of hydrogen in the reaction gas, but the hydrogen peroxide concentrations of more than 2.4% by weight which are obtained on using reaction gas mixtures comprising less than 5% by volume of hydrogen are to low for commercial application. The use of organic solvents has an advantageous eflect on catalyst life. However, over a run of 285 hours catalyst activity decreases 10 69% of the original value, which is stil too low for industrial application, U.S. Pat. No, 4,389,390 describes a similar process in which the catalyst which has become detached from the support is recovered by activated carbon filters. A further advantage of this process is that removal of the catalyst from the reaction ‘medium reduces the tendeney of the hydrogen peroxide to decompose. However, no hydrogen hydrogen peroxide solu- tions having a concentration of above 2.1% by weight are obiained in continuous operation, ‘The literature proposes various solutions for the problem of catalyst deactivation in the preparation of hydrogen peroxide from the elements. For instance, U.S. Pat. No. 5,352,645 and WO 92/04976 describe special solid supports composed of spray-dried, colloidal silica gel. The use of superacidic oxides as support materials is proposed in U.S. Pat. No. 5,236,692 and EP-A 437 $36. This avoids the customary acid content in the reaction medium. EP-A 627 381 teaches the use of niobium, tantalum, molybxlenum or tungsten oxides as support materials which are characterized by high acid resistance. U.S. Pat. No, 5,292,496 describes the use of cerium-comprising support materials to avoid the use of halogen as a stabilizer in the reaction medium. However, in the references cited, hydrogen peroxide is always prepared by batch or semicontinuous processes which have little to recommend them for industrial use. In addition, the short reaction times do not provide any infor- ‘mation about catalyst life, ‘The use of catalyst monoliths comprising palladium as active component is described by Kosak in Catalysis of Organic Reactions (eds Scaros and Prunier), Maree! Dekker Inc., New York 1995, p. 115 et seq., for the preparation of hhydrogen peroxide from the elements. The reaction is car- ried out batchwise in an aqueous reaction medium at a comparatively high pressure of 144 bar and a molar ratio of OzHq=47, ie. in the explosive range. TLisan object of the present invention to provide a process {or preparing hydrogen peroxide from hydrogen and oxygen to prepare hydrogen peroxide solutions having a hydrogenUS 6,375,920 B2 3 peroxide content of above 2.5% by weight even from hydrogen-oxygen mixtures outside the explosive range (Oz:H.>20:1). The catalysts used shall have long on-stream times. ‘We have found that this object is achieved by a continuous, process comprising the reaction of hydrogen and oxygen in water andior C,-C-alkanols as reaction medium over eata~ lytic structures comprising palladium as active component, “The present invention accordingly provides a process for preparing a bydrogen peroxide solution having a hydrogen peroxide content of not less than 2.5% by weight by con- tinuous reaction of hydrogen and oxygen over a catalyst ‘comprising palladium as active component, which com prises performing the reaction in water and/or a C,-Cy- alkanol as reaction medium over a catalytic structure, Catalytic structures are catalysts in which the catalytically active component is situated on the surface of specifically ‘shaped supports. Such supports can be customary packing ‘elements, such as Raschig rings, saddles, Pall rings, wire spirals of wire mesh rings, consinucted from various mate- rials suitable for coating with the active component (See also Rompp-Chemie-Lexikon, 9th edition, p. 1453 et seq). The packing clements provided with the catalytically active ‘component are dumped into the reactor. Preferred structures have channels with hydraulic radii (definition see VDI-W armeatlas, section LE1) within the range from 1 fo 10 mm. Preference is given to catalytic structures which are installed in the reactor ia the form of arranged packings and which have a large surface area relative to the volume due {o.a multiplicity of flow-through channels. Such structures will hereinafter be referred to as catalyst monoliths, Suitable reactors are described for example in EP-A 068 862, EP-A 201 614 and EP-A 448 884, ‘The catalyst monoliths or, to be more precise, the mono lithie supports are generally constructed from wovens, knits, foils, expanded metals andjor sheets. Monolithic supports ‘can also be prepared by extrusion as described in U.S, Pat. No. 4,364,888 and U.S, Pat, No. 4,333,896. Suitable mono- lithic’supports include structures constructed trom open ccelled foams. These foams can be for example ceramic, ‘melamine resin or polyurethane foams. Preference is given to catalyst monoliths constructed from ‘wovens, since they are particularly well permeated by the liguid reaction medium in the reactor and thus peemit high ‘conversion rates Suitable wovens ate constcucted for example from fibers of oxidic materials, such as Al,0, and/or SiO,, or from polymeric fibers, for example polyamide, polyester, polyvi ny! chloride, polyethylene, polypropylene, polytetraluoro- cibylene fibers, or carbon fibers. Preference is given 10 woven catalyst supports constructed from weavable metal wires, for example composed of iron, spring steel, hastelloy, monel, silver, chrome steel, chrome nickel steel or titanium. Very particular preference is given to woven catalyst sup porls constructed from weavable wires of highly alloyed Stainless steels or metals which protect against further ccortosion through formation of a passivating layer, for ‘example Cr steels, CrNi steels, CrNiTi steels and! CiNiMo ‘Steels or heat-resistant steels having the material numbers 1.4016, 14767, 14401, 24610, 1.4765, 14847, 14301, 1.4742. "The wires and fibers mentioned can be used to produce ‘wovens in different constructions, such as flat constructions, twill constructions, galloon constructions, five-shaft satin ‘constructions and other specialty constructions. These wov- fens are preferably joined together to form multilayered 0 as os ss 4s ss 6s 4 assemblies, Suitable woven monolithic catalyst supports are described in EP-A. 498 435, Particularly suitable catalyst monoliths are constructed from a plurality of layers of corrugated, folded andor flat ‘woven arranged in such a way that adjacent layers form more or less closed channels. The hydraulic diameter ofthe channels is preferably within the ange from I to 10 mm, in particular fom 1.5 to 3 mm (as per definition in. VDI ‘Warmeatls, section LEI). These channels can be straight or curved. Preference is given to multilayered wovens in which Hat and corrugated or folded wovens sltemate. Monoliths in Which the woveas are partly or wholly replaced by metal sheets, knits or expanded! metals, ean likewise be used. Such monoliths are preferably installed in the reactor in Sueh a way that the channels are inclined away from the flow direction of the reaction medium. The woven layers them- selves are preferably installed inthe reactor parallel to the direction of flow. If a plurality of these units are to be arranged in series, they ate preferably installed in such a way that the flow channels are altematingly inclined in opposite directions away from the flow direetion. The units are preferably installed in such a way that the woven layers of| two successive units form an angle of preferably about 90° to each other. Wound moduli of corrugated or folded and optionally aso planar woven layers are likewise suitable. ‘The coating of the catalyst supports with the catalytically active component is effected according to customary coating methods (see below). In the case of monolithic supports constructed from wovens, foils, sheets, knits or expanded metals, coating generaly takes place prior 1 further pro- cessing to the catalyst monolith. However, it ean also take place on the preformed support. If the wovens are to be lamped in use frames and then optionally joined together to form catalyst cell, its advisable to coat the wovens in the unprocessed state. ‘The catalytically active component, as well a palladium as ain substituent, may comprise further metals, preferably noble metas especially platinum, rhodium, iridium, copper, silver andior gold as promoters. The ratio of palladium! promoter meta is preferably within the range from 100:1 t0 1:10 and in particular withia the range from 10:1 to 1:1. The palladium and the optional promoter metals generally account for from 5x10 to 1% by weight and in particular {rom 10° to 0.15% by weight, based on the total catalyst ‘mass (supportéactive component). In the case of catalyst supports having a porous surface, as is the case, for example, with catalyst supports having suriaces of active aluminum oxide or SiO, the active component is generally applied by an impregnating or saturating step, which is generally followed by a drying and activating step. Such techniques are deseribed for example- in DE-A 22 56 195 or in DE-A 23 17 560, incorporated herein in full by reference. Also suitable are catalysts in Which an active aluminum oxide layer and then a coating of| palladium is applied to a metal support. The oxide layer is prepared by dipping the support into dispersion of active aluminum oxide and then heat-ieating at elevated tempera- ture, The noble metal is then applied on top ofthis oxide Jayer by saturating with a palladium salt solution, and activated after drying by reduetion with hydrogen a 500° C This process is disclosed in EP-A 075 124, likewise incor porated herein in full by reference. DE-A 41 13 525 deseribes a process for coating surfaces in complex geo- metrical structures with ooble metals by; ina frst Sep, wetting the structures with a solution comprising the eom- plexes of the metals with organie ligands and then destroy- ing these complexes. by UV irradiation. In this way itisUS 6,375,920 B2 5 possible to provide nets, webs, fibers and bodies having a honeycomb, spongey oF porous structure with stable noble metal coatings, irespectively ofthe chemical constitution of| the surface. This coating process is likewise suitable for preparing the catalyst monoliths of the invention. Coatings Suilable forthe pugposes ofthe invention can be obtained in the manner described in EP-A 374 099 by saturating the catalyst support wit suitable pallacium(0) complexes and subsequent thermolysis of these complexes. Reetz et al ‘Angew. Chem. 1995, 107, 2956-2958) describe the coating ‘of Si0, oF Al,0, suctaces with preformed palladium clus- ters. This produces, even in te case of porous surfaces, very thin layers ofthe active component (eggshell catalysts). This method too can be used to prepare catalyst monoliths Suitable for the purposes of the present invention. ‘The application of metals upon thermally stable catalyst supports can also be effected by the process of flame-spraying (see P. Fauchais et al. in Pure and Appl. Chem., Vol. 66, (1994), 58). The catalytically active component can also be ied by vacuum vapor deposition of metals upon the catalyst support. Suitable vacuum vapor deposition tech- niques include in particular therml vapor deposition, fash ‘vapor depesition, cathode atomization and also sputerin, ‘Thermal vapor deposition can be carried out by direct or indirect electrical heating. Electoon beam vapor deposition is preferably employed for this method. The woven catalyst supports of the invention can be coated continuously or batchwise according to these processes. Reference is made to EP-A 198 435 for further details. The process described in DE-A 41 21 418 for applying Pal or Pt alloys to metal surfaces is likewise suitable for preparing the catalysts ofthe invention Palladium and optionally the promoters are preferably applied to the catalyst support by electrolytic, especially by electrochemical, deposition from corresponding metal salt solutions. Suitable reducing agents are in-particular hydrazine, citric acid, ethanol, salis of hypophosphorous acid e.g. NaHl,PO,, lormaldebyde, formic acid, boranates such as sodium borobyclde, or stabilized borane solutions such as, for example, complexes of borane with diethyl ether, dimethylamine or diethylamine (see also A. Laus in Mater. Sci. Eng. A 146 (1991) 33, 49; se also Dechema- ‘Tagungsbeticht XXIX. Jahrestreffen deutscher Katalytiker, Friedrichroda, Marz 1996, p. 66). Here it is advisable to pretreat the catalyst support to improve the adhesion of the active component 10 the Sup- port's surface, This includes for example removing greases for similar substances. which impair the desired surface aahesion, for example by rinsing with organic solvents such asthe, acvtone o: halogenated bydrocarbons, or ealeining Oxide layers on metalic supports ean also be removed by treatment with mineral acids, for example hydrochlorie acid or sulfuric acid. The resulting graining of the metallic surface improves the cementing of the active component, especially in the case of electrolytic or electrochemical ‘eposition ‘The catalyst systems of support and active component! promoter resulting from the processes described ean then be activated by thermal treatment at from 200 to 900° C., preferably 400 to 700° C. This thermal after treatment can lake place in an oxidizing, inert or reducing atmosphere Especially i the ease of polymetalli systems, activation in a reducing atmosphere is prefereed, ince alloys are formed ‘more readily ‘The finshed catalyst systems are then fitted in the reaction space (sce above). Particular preference is given to tubular reactors equipped with cylindrical catalyst unis, since a 0 as os ss 4s ss 6s 6 uniform flow regime is able to form here, which allows particularly good reaction control The waction is generally carried out with a flooded reactor. The reaction medium used is water andior C,-Cy- alkanols, preferably water andlor methanol. Ifthe reaction medium used is water, up 10 20% by weight ofthe alcohol preferably methanol, ean be added to it. If an aleoholic reaction medium is used it can include up to 40% by weight, preferably up to 20% by weight, particularly preferably up to 5% by weight, of water. Very particular preference is given to water as sole reaction medium, To stabilize the hydrogen peroxide against decomposition, the reaction medium is admixed with acids whose pKa value is prefer ably less than that of acetie acd, especially mineral acids such as sulfuric acid, phosphori acid or hydrochloric acid ‘The acid concentration is generally not less than 10"! rmoliliter, preferably within the range from 10 to 10° molfiter. In addition, in general, traces of bromide ot chloride ae added in concentrations of from | to 148 ppm, picferably 5 to 300 ppm. However, it is also possible 10 use other stabilizers, for example formaldehyde The reaction gs, which, as well as hydrogen and oxygen, ‘may further comprise inert gases such a8 nitrogen or noble gases, generally has OH. ratios within the range from 2:1 to 1000:1. Preference is given to molar ratios withio the range 5:1 to 100:1, particularly preferably within the range from 20:1 to 50:1. The oxygen used inthe reaction gas can also be included ia the reaction gas in the form of aie. Ina preferred embodiment, the reaction gasis recycled. la this case, the molar rato inthe fresh gas mixture i in the vicinity of the stoichiometry of the reaction, preferably Within the range from 15:1 to 05:1. The molae ratio of (OH, in the recycle gas should be within the range from 5: to 1000:1, preferably within the range from 20:1 0 100:1, The reaction can be carried out at atmospheric pressure and also at superatmospheric pressures of up 10 200 bat. The pressure is preferably within the range from 10 to 100 bat, especially within the range from 10 to 80 bar. The reaction temperature ean be within the range from 0 t0 60° C., preferably within the range from 20 to 50° C. ‘The partial pressures of the eaction gases inthe reaction ges mitre in the reactor and also in the reeycle gas are preferably chosen so that, under reaction conditions, the hydrogen eoncentra- tioa is below the lower explosion limit Reaction gas and reaction medium can move cocurrently or countercurrently to each other, preferably cocurretly, ia ‘hich ease the liquid phase forms the continous phase and the reaction gas the discontinuous phase. Inthe ease of the preferred vertical reactor design (upright reactor), reaction 2 and reaction medium are preferably passed in cocurrent upwardly through the reactor. Here, hydrogen can be fed into the reactor via one or more intermediate feed points downstream of the feed point for the oxygen ot air feed point, The supericial velocity of reaction gas and reaction ‘medium is within the range from 50 to 1000 mh, preferably within the range from 150 10 300 mi. ‘The disclosed process makesit possible to produce hydro- gen peroxide solutions baving hydrogen peroxide contents above 2.5% by weight, preferably within the range from 5 10 25% by weight. The concentration can be preselected as desired by adjusting the mass flows. The selectivity of hhyerogen peroxide formation is always above 65%, preer- ably 75%. Long-term studies have shown that catalyst activity and selectivity decrease litle, if at all, in the course of a 40-day rua. FIG. 1 shows by way of example a reactor system featuring an upright reactor 1, which has bytrogen feedUS 6,375,920 B2 7 points 2 arranged intermediate of a plurality of layers 3 of ‘woven catalyst monolith. A pump 4 supplies. methanol and/or water. A connection line 5 supplies oxygen and a gas-liquid disperser, for example a mixing jet 6, disperses it in the form of bubbles in a circulating liquid 7. The same mixing jet 6—or a separate mixing jt, if desired—supplies ‘stream 8 of hydrogen, Further quantities 2 of hydrogen are supplied under quantity control via dispersing means 9 atthe intermediate feed points 10 between the catalyst layers 3. At the upper end of the reactor, a two-phase reactor effluent IL is removed and separated in a separating vessel 12. The gas phase is reintroduced at the lower end of the reactor via the ‘mixing jet 6 after passing through a compressor 13 or, ifthe reactor isnot very tall, preferably directly. A steam 14 of the «gas is fed via a pressure container 1S into the off-gas line 16 to limit the build-up of inerts. The liguid is cooled with ‘cooling water in a heat exchanger 17 and reintroduced via a pump 18, at the lower end of the reacior. In addition, it is also possible to provide intermediate removal points 19 for the two-phase reactor contents along the reactor, to carry out a phase separation 20 and to reintroduce the 1Wo phases— the liquid phase cooled-—at a lower point 21 of the reactor. ‘The liquid reaction proxiuct 22 is removed from the phase separator 12 at the upper end of the reactor as stream 23, ‘The Examples which follow illustrate the present inven- tion, 1. Preparation of catalyst shapes using supports composed of V4A fabric ‘A.corrugated net and a flat net composed of V4A steel (4371, mesh size 180 um, wire diameter 146 jum) were placed on top of each other and rolled to form a cylindrical ‘monolith 5 em in height and 5 em in diameter. The ends of the nets were fixed by spot welding. The net plane spacing ‘of the fat nets was not less than 1 mm. ‘The monolithic support was treated in succession with acetone and distilled water and then dried, Thereafter the ‘monolith was treated with a solution of 254% by weight of ‘concentrated hydrochloric acid and 75% by weight of dis- tilled water at 60° C. for 30 minutes and rinsed off with distilled water. The monolith thus treated was introduced into 150 ml of distilled water. After the addition of 10 drops ‘of concentrated HNO, and 36 ml of a 1% strength by weight aqueous solution of hypophosphorous acid, 20 ml of a palladium nitrate solution having a palladium concentration ‘of 1% by weight were added, This was followed by heating to 60° C, for 17 minutes and then to 80° C. for one hour. This was followed by cooling, and the catalyst monolith was washed with distilled water and dried at 120° C. for 16 ours. I, Preparation of hydrogen peroxide ‘The reaction vessel used is a 270 mi autoclave equipped with stirrer, thermostating and 50 bar pressure maintenance. In this autoclave, the catalyst monolith prepared in I was installed centrally around the stirrer axis, so that it is uniformly supplied with Tiquid and gas by the stirer. The reactor bottom is equipped with feed lines for oxygen, hydrogen and the reaction medium, The reactor lid is ‘equipped with a take-off ine from which the product/gas mixture is continuously removed. After deduction of the volumes for all internals, the effective reaction volume available was 208 ma EXAMPLE 1 ‘The reaction medium consisted of methanol admixed with (0.4% by weight of sulfuric acid, 0.1% by weight of phos- phorie acid and 6 ppm of bromide (in the form of sodium 0 as os ss 4s ss 6s 8 bromide). ‘The reactor was flooded with the reaction medium. A stream of 72.8 g/h of reaction medium, 48.6 Uh of oxygen and 5.5 Uh of hydrogen (gases based on standard conditions) was then passed through the reactor. The product/gis mixture was continuously removed atthe reac- tor lid. ‘The conversion based on hydrogen was 76% (as per determination of the hydrogen content of the off-g35) coupled witha scletvity of 82%. The concentration of the resulting methanolic hydrogen peroxide solution was 7% by tion with 0.1 N KMa0,). EXAMPLE 2 Example 1 was run for 100 hours. Ia total, 2.9 kg of hhydrogen peroxide were obtained in the form of a methan- olic solution having a concentration of 4% by weight. EXAMPLE 3 Accatalyst monolith was prepared from V4A net with « palladium coating similarly to I. This shape was then hyttro- genated with hydrogen at 70° C, and 50 bar, treated with ethanolic HO, solution at 20° C. and dried with nitrogen. ‘The catalyst shape was then installed in the autoclave of IL ‘The reaction was earried out similarly to Example 1: The flow rate through the reactor at 42.2° C, was 214.5 g/h for the reaction medium, 145.8 lh for oxygen and 16.2 Vh for hydrogen. The conversion based on H, was 84% coupled with a selectivity of 75%. The concentration of the metha- nolic hydrogen peroxide solution was 7% by weight. EXAMPLE 4 ‘The same catalyst as in Example 3 was used. The reaction parameters were as follows: 214.5 gih of reaction medium, 1458 Wh of oxygen, 6.1 1 of hydrogen, T=52° C. The conversion based on H. was 90%, coupled with a selectivity ‘of 68%. The concentration of the resulting hydrogen perox- ide solution was 2.7% by weight EXAMPLE 5 ‘The same catalyst as in Example 3 was used. The reaction ‘medium was water admixed wit 0.4% by weight of sulfuric acid, 0.1% by weight of phosphoric acid and 6 ppm of bromide (in the form of sodium bromide). The reaction parameters were as follows: 268.0 g/h of reaction medium, 291.6 Im of oxygen, 32.4 Ih of hydrogen, T=42" C. The ‘coaversioa based on hydrogen was obtained by determining the bydrogen in the off-gas and was found to be 43% coupled with a selectivity of 70%. The concentration of the resulting hydrogen peroxide solution was 5.6% by weight We claim: 1. A process for preparing a hydrogen peroxide solution having a hydrogen peroxide content of not less than 2.5% by ‘weight by contiauous reaction of hydrogen and oxygen over a calalyst comprising palladium as active component, which comprises performing the reaction in water andjor a Cy-C- alkanol as reaction medium over a eatalytie structure, 2. A process as claimed in claim 1, wherein the catalytic structure is an ordered catalytic packing (monolith. 3. A process as claimed in claim 1 or 2, wherein the catalytic structuee is constructed from a woven 4. A process as claimed in claim 3, wherein the woven is 4 metallic woven, 5. A process as claimed in any of the preceding claims, wherein the active component includes not only palladium but also a further noble metal as promoter,US 6,375,920 B2 9 6. A process as claimed in claim §, wherein the molar ratio Of palladium to promoter metal is within the range from 100:1 t0 1:10. 7. A process as claimed in claim 5 or 6, wherein the promoter is selected from platinum, rhodium, iridium, ‘copper, silver and gold. 8. A process as claimed in any of the preceding claims, ‘wherein the oxygen is used in the form of ai 9. A process as claimed in any of the preceding claims, \herein the molar ratio of Og:H in the off-as is above 20:1 10. A process as claimed in any of claims 110 8, wherein the reaction gas is recycled. UL. A process as claimed in claim 10, wherein the molar ratio of OH, in the reeyele gas is within the range from 20:1 to 50:1 0 10 12. A process as claimed in any of the preceding claims, wherein the reaction is carried out at a temperature within the range from 0° C. to 80° C. 13. A process as claimed in any of the preceding claims, wherein the reaction is carried out at a pressure within the range from 10 to 100 bar. 14. A process as claimed in any of the preceding claims, wherein the reaction medium comprises water, methanol or 44 methanol-water mixture. 15. A process as claimed in any of the preceding claims, wherein the reaction medium further comprises an acid having a pKa below that of acetic acid.UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. : 6,375,920 B2 Page 1 of 1 DATED ‘April 23, 2002 INVENTOR(S) : Fischer etal. Itis certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected as shown below. tle page, ‘Add Items [45] and Notice as follows ~- [45] Date of Patent: *Apr. 23, 2002 [*] _ Notice: This patent issued on a continued prosecution application filed under 37 CFR 1.53(d), and is subject to the twenty year patent term provisions of 35 U.S.C 154(a)Q). Subject to any disclaimer, the term of this patent is extended or adjusted under 35 USS.C 154(b) by 0 days, -- Signed and Sealed this First Day of October, 2002 Antes: JAMES E. ROGAN Auesting Officer Director ofthe United States Patent and Trademark OfficUNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 6,375,920 B2 Page | of 6 APPLICATION NO. : 09/284247 DATED April 23, 2002 INVENTOR(S) Fischer et al. It is certified that error appears in the above-identified patent and that said Letters Patent is hereby corrected as shown below: Please Delete Columns J Line through Columns 9 Line 12 and Insert Columns 1 Line I through Columns 10 Line 16 as attached. Signed and Sealed this Third Day of March, 2009 An kl JOHN DOLL Aeting Director ofthe United States Patent and Trademark OfficeUS 6,375; PROCESS FOR THE MANUFACTURE OF HYDROGEN PEROXIDE BACKGROUND OF THE INVENTION s 1. Field ofthe Invention The pretont invention relates to a process for propacing a hydrogen peroxide selution having. a hydrogen peroxide content of not less than 2.5% by weight by continuous reac» 4p tion of hydrogen and oxygen over a catalyst comprising pal- Jadiam as szive component. 2. Description ofthe Background Customary industriel processes for preparing hydrogen peroxide are the eloctrolyss of acidio ammonium sulfate ! Solutions, the oxidation of isopropyl alcohol and the anthaguinane process. The direct symhesis of hydrogen peroxide from the elements over ransiton metal catalysts is Known, buthas not found commercial use dae. “There are several reason for this. For instance, hydrogen and oxygen form explosive gas mixtures if the level of Ihydrogen inthe gas mixture i above 5% by volume, On the other hand, the rte of formation of hydrogen peroxide on using hydrogen-oxygen mixtures outside the explosive range is generally too low to ensute reasonable space-time Yields, In adcition, an excesivly high evel of oxygen inthe reaction ges can Speed up the oxidative degradation of the catalysts. ‘The selectivity ofthe reaction isa further problem. Foe instance, the reaction 1 form the hydrogen peroxide has to compete with that to form water In addition, the etaysts which are suitable foe forming hydrogen peroxie frm the ements sso extalyze the degradation reaction of hydrogen peroxide in the presence of excess hydrogen in accordaoe With the following reaction equation: H,0;+H)2H,0. “This selecvty problem ean be solved by using continuous processes at high Row rates. However, this hab the sonae- ‘quence that, ata low reaction rate, the hydrogen peroxide ‘oncentations obtained inthe eflvent become too low for onmercial use ofthis process. In addition, excessively high flow rates give rset catalyst abrasion problems, leading to reduced op-steam times and hence likewise to commercial ‘isadvantages for this process. US. Pat. No 4,009,252 discloses an optimum rato of O, to H, within the range from 15:1 to 20: he explor sive range, forthe formation of hydrogen peroxide from Inydrogen and oxygen over palladium catalyst, The reaction is caried ut asa batch process and the space-time yields ‘which are obiined are unsatisfactory. WO 9208277 describes the reaction of hydrogen with ‘oxygen ina tabular reactor packed with an aqueous suspen sion of catalyst. The gas mixtures used are preferably Jocated within the explosive rage. A high flow rate of the reaction medium (>| nvsex) i used to ensure thatthe reac- tion gas és completely dispersed in the reaction medium in the frm of small bubbles, preventing an explosive reation of the reaction gas. The Iydrogen peroxide concentrations obtained after 2 single passthrough the reastion zone are below 1% by weight Higher yield can only be obtained by repeated passes through the reaction zane. The ict thatthe ‘alalst is used inthe Foon of a suspension tums out t be 3 problem hecause this necessitates elaborate filtration and recycling. measures, with inevitable tosses of the catalyst. Reaction tubes which ae suitable for the required reaction pressure—pressures of above 80 bar are disclased in the ‘Mustrative embodiments—are comparatively costly. The » 0 « Page 2 of 6 920 B2 2 cited process must therefore be considered very costly. A similar process with improved fiudization of the hydrogen fand oxygen streams is described in WO 96/05138, US. Pat. No. 5,500,202 and EP-A 579 109 describe a continuous process for preparing hydrogen peroxide by reacting H,/O, gas mixtures over a stationary pulveratent catalyst (particle sizes within the range 10m to 250 jm) in & trickle bed reactor. To reduce the risk of explosion due to the lage gas volume which is customary for a trickle bed reactor, nitrogen is dded as an iner gas tothe reaction gas. However, his entails edditional costs. The aqueous hyéro- ‘gen peroxide solutions obsained in this say only have con ‘centrations within the range from 3 t0 5%. The conversion ‘based on hydrogen is merely within the range of 25-35%, No data are provided about catalyst life, Reactors having a ‘maximum internal diameter of 30 mm are recommended because of the considerable heat production. Industrial use would therefore require the installation of several thousands Of these tubular reactors, which entails high capital expendi- sure costs, US. Pat. No. 4,336,238 and U.S. Pat. No. 4,336,239 describe the reaction of hydrogen and oxygen to form hydro- gen peroxide over palladium catalysts in organic solvents oF solvent miatures in the presence or absence of water. The process described makes it possible to reduce the proportion of hydrogen in the reaction gas, but the hydragen peroxide concentrations of more than 2.4% by weight which are obtained on using reaction gas mixtures comprising less than 5% by volume of hydrogen are too tow for commercial ‘pplication, The wse of organic solvents has an advantageous effect on catalyst life. However, over a run of 285 hours catalyst ectvity decreases to 69% of the original value, which is stil 100 fow for industrial application. U.S, Pat. No. 4,389,390 describes a similar process in which the catalyst ‘which hs become detached from the support is recovered by ‘activated carbon filters. A Further advantage ofthis process is that removal of the eatalyst from the reaction medium reduces the tendency of the hydrogen peroxide to decom- pose. However, no hydrogen hydrogen peroxide solutions having » concentration of above 2.1% by weight are objained in continuous operation ‘The literature proposes various solutions forthe problem of eatalyst deactivation in the preparation of hydrogen per- ‘oxide from the elements. For instance, U.S. Pat. No. 5,352, 645 and WO 92/08976 describe special solid supports com posed of spray-dried, colloidal silica gel. The use of superacidic oxides as support materials is proposed in U.S. Pat, No. 5,236,692 and EP-A 437 836, This avoids the cus- tomary acid content in the reaction medium. EP-A 627 381 teaches the use of niobium, tantalum, molybdenum of tung- sten oxides a6 support materials which are characterized by high acid resistance. U.S. Pat. No. 5,292,496 describes the use of cerium-comprising support materials to avoid the use of halogen usa stabilizer in the reaction medium. However, in the references cited, hydrogen peraxide is always pre- ppared by batch of semicontinuous processes which have Fite to recommend them for industrial use. In addition, the short reaction times do not provide any information about catalyst ie ‘The use of catalyst monoliths comprising palladium as, active component is described by Kosak in Catalysis of ‘Organic Reactions (eds. Scaros and Prunier), Marcel Dekker Ine, New York 1995, p. 118 et seq, forthe preparation of hydrogen peroxide ffom the elements. The reaction is car ‘Fed oat batchwise in an aqueous reaction medium at a com- paratively high pressure of 144 bar and # molar ratio of 0:5 j247, Len the explosive range,Page 3 of 6 US 6,375,920 B2 3 Itisan object ofthe present invention to provide process fox preparing hydrogen peroxide fom hydrogen and oxygen to prepare hydrogen peroxide solutions having a hydrogen peroxide content of above 2.5% by weight even from hydrogen-orygen mixtures outside the exptosive range (G,:H,>20:1), The catalysts used shalt have Tong on-stam times. We have found that his objec is achieved by’a continous process comprising the reaction of hydrogen and oxygen in water andr Cy-Cralkanols as reaction medium over exta- lytic structures comprising palladium as active component. ‘The present invention accordingly provides a process for preparing a hydrogen peroxide salstion having a hydrogen peroxide content of nt less than 2.5% by weight by contin ‘us reaction of hydrogen and oxygen over cxilyst com- prising palladium es active component, which comprises, performing the reaction in water andor & G-Cyalkanol as reaction medium over a catalytic ructre ‘Crealytie structures are catalysts in which the catalytically active component is situted on the surface of specifically shaped supports, Such suppors can be customary packing elements, such as Raschig rings, saddles, Pall rings, wire Spirals or wire mesh rings, constcied from various mater- als suitable for coating withthe active component (sce also Rimpp-Chemi-Lenikon, Sth edition, p. 1453 et seq). The packing elements provided with the catalytically active com- nent are dumped into the reactor. Preferred structures have channels with hydraulic radii (defiaition see VDILW rmeatis, section LEI) within the range from 1 to 10 mm. Preference is given to catalytic structures which are instaled in the reacior inthe form of avanged packings and which have a large surface area relative tothe volume de to multiplicity of fow-through channels. Such structures will hereinafter be referred to as cxtalyst sionoliths. Suitable ‘actors ate described for example in EP-A. O68 862, EP-A 201 614 and EP-A 448 884 The catalyst monoliths or, to be more precise, the mono- lithic supports are gonerally constrcted from wovens, kits, foils, expanded metals and/or sheets. Monolithic supports can ako be by extrusion as described in US. Pat ‘No. 4,364,888 and U.S. Pt. No. 4,333,896, Suitable mono- lithic ‘supports include structres constructed from oper- ‘elled foams. These foams can be for example ceramic, ‘melamine resin or polyurethane foams, Preference is gives to catalyst monoliths constructed from wovens, since they are particularly weil permeated by the liquid reaction medium: in the reactor and thus permit high conversion rates. Suitable wovens are constrcted for example from fbers of oxidic materials, such as Al, andr SiO, oF from poly mere fibers, for example polyane, polyester, polyvinyl chloride, polyethylene, polypropylene, pyteraivarocty ‘ene fibers, oc eatbon fibers. Preference is given to woven «aly supports consiructed fom weavable metal wires, for example composed of iron, spring steel, hastelay, mone, silver, chrome stel, chrome nickel steel of titanium. Very particular preference is given to woven catalyst supports sonstructed from weavable wires of highly elloyed swialess steels of metals which protect against further corrosion through formation of a passivating layer, for example Cr stels, CeNi steals, CANT steels and CrNMo steels or heat resistant steels having the atrial numbers 1 4016, 14767, VAMO1, 2.4610, 14765, 14847, LABOL, 1.4782. ‘The wires and fibers mentioned can be used to produce ~wovens in different constructions. such as at consiuctions, ‘will consructions,galloon constuction, five-shaft satin 0 0 4s 2 ss ® 4 constrctions and other specialty constructions. These wov= ens are preferably joined together 10 form multilayered assemblies, Suteble woven monolithic eaalyst support are ‘described in EP-A 498 435, Panicularly suitable catalyst monoliths are constructed from « plurality of layers of corugated, folded andlor Aat Wovens arranged in such a way that adjacent layers form ‘more or less closed channels. The hydraulic diameter ofthe channels is preferably with the range from { t0 10 mm, in particular ffom 1.5 to 3 mim (as per definition in VDILW ‘ments, section LED), These channels can be straight oF ‘aurved, Preference is given to multilayered wovens in which fat and corrugated ce folded wovens alterate. Monolith i which the wovens are partly or wholly replaced by metal sheets, knits or expanded metals, can likewise be used, Such monoliths are preferably installed in the reactor in such a ‘way thatthe channels are inclined away from the flow diree- tion ofthe reaction medivm. The woven layers themselves are preferably installed inthe reactor parle to the direction of flow. If plurality ofthese units are to be arranged in series, they ae preferably installed in such a way thatthe flow channels are alternating inctned in opposite diec- tions away from the flow direction. The units are preferably installed in such a way thatthe woven layers of two succes sive units form an angle of preferably about 90° 10 each ‘other. Wound moduli of corrugated or folded snd optionally also planar woven layers are likewise suitable, The coating ofthe catlyst supports withthe emaytically sctive component is effected according Yo customary costing ‘methods (see below), Inthe case of monolithic suppars cone structed from wavens, foils, sheets, knits or expanded metal, coating generaly takes place prio o further process- ing tothe catalyst monolith. However, it can also tke place on the preformed support. Ifthe wovens are tobe clamped use frames and then optionally joined together to form cata- lyst cells, itis advisable to coat the wovens in the unpros essed state. ‘The catalytically active component, as well as palladium as main substituent, may comprise furher metals, preferably noble metals especially platinum, rhodium, iridium, copper, silver and/or gold es promoters. The ratio of palladium’ ‘promoter rit is preferably within the range from 100:1 10 1:10 and in particular within the range from 101 to Ft. The palladium and the optional promoter metals generally ‘coun for from $10" to 1% by weight and in particular from 10° to 0.15% by weight, based on the total catalyst mass (supporttactve component). Tathe case of catalyst supports having a porous surface, as the cas, for example, with eaalyst sugpors having su faces of sstive aluminurm oxide or Si0,, the active compo- rent is generally applied by an impregnating of seturating step, which is generally followed by a drying and activating step, Such techniques are described for example in DE-A 22, 56 195 or in DE-A 23 17 560, incorporated herein in full by reference. Aiso suitable ar catalysts in which an active alu rminum oxide layer and then # coating of palladium is applied to x metal suppor. The oxide layer is prepared by dipping the support into a dispersion of active aluminum oxide and then heat-treating at elevated temperature. The rable metal is then applied on top of this oxide layer by saturating with 2 palladium salt soluion, and activated after ‘tying by reduction with hydrogen at 09° C. This process is disclosed in £P-A 075 124, likewise incorporated herein in full by reference: DE-A 41 13 525 deserbes a process for coating surfaces in complex geometricnl structures with nobie metals by, a a first step, wetting the structures with a solution comprising the complenes of the metals withPage 4 of 6 US 6,375,920 B2 5 onganc ligands and then desiraying these complexes by U} irradiation. In this way its possible to provide nets, webs, fibers and bodies having a honeycomb, spongey or porous structure with stable noble metal coatings, irespectively of the chemical constitution ofthe surface. Thx coat im process is likewise suitable for preparing the catalyst monoliths of the invention. Coatings sintable for the purposes of the invention canbe obtained in the manner described in EP-A 374.099 by saturating the catalyst support with suitable pelladium(®) complexes and subsequent thermolysis of these complezes. Reetz t al. (Angew. Chem. (995, 107, 12956-2958) describe the coating of SiO, or Al,Qy surfuces ‘with preformed ‘palladium clusters. This produces, even in the case of porous surfaces, very thin layers of the active component (eggshell catalysts). This method too canbe used to prepare catalyst monoliths suitable forthe purposes of the present invention. The application of metals upon thermally Stable catalyst suppors can also be effected bythe process of flame-spraying (see P. Fauchais el al. in Pure and Appl. Chem., Val, 66, (1994), 1247-1258). The catalytically active ‘somponent can also be applied by vacuum vapor deposition ‘of metals upon the catalyst support. Suitable vacuum vapor ‘deposition techniques include in paricular therm! vapor ‘deposition, fash vapor deposition, cathode atomization and ‘also sputtering, Thermal vapor deposition can be cared out by direct or indirect eeciricl heating. Electron beam vapor deposition is preferably employed for this method. The ‘woven catalyst supports of the invention can be coated con tinuously or batchwise according to these processes. Refer cence is made 10 EP-A 198 435 for further details. The pro- cess described in DE-A 41 21 418 for applying Pd or Pt Alloys to metal surfaces is Hkewise suitable for preparing the catalysts ofthe invention. Palladium and optionally the promoters are preferably applied to the catalyst support by electrolytic, especially by electrochemical, deposition from corresponding mea! sult solutions. Suitable reducing agents are in particular hydrazine, citi acid, etkanol, sais of hypophosphorous acid, e.g. NeHl,PO,, formaldehyée, forme nid, boranates such as sodium borohydride, oF stabilized borane solutions such as, for example, complexes of borane with diethyl ether, dimethylamine or diethylamine (se also A. Laus in Mater. SciEng. & 146 (1991) 33,49; seo also Dechema- “Tagungsbericht XXIX. Jahrestrelfen deutscher Katalytiker, Priedrchroda, Marz 1996, p. 66). Here itis advisable to pretreat the catalyst support to tmprove the adhesion of the active component fo the su port's surfoee. Ths includes for example removing greases or similar substences which impair the desired surface adhesion, for example by rinsing with organie solvents such as ether, acetone or halogenated hydrocarbons, o calcining, Oxide layers on metallic supports can also be removed by treatment with mineral acids, for example hydrochloric acid ‘sulfuric acid, The resuling graning of the metalic sure face improves the cementing ofthe active component, expe cially in the case of electrolytic or electrochemical deposi- tion. The caitlyst systems of support and active componen promoter resulting from the processes desribed can then be activated by thermal treatrent at From 200 10 900° C., pref ‘stably 400 to 700° C. This thera ofterteaiment can take place in an oxidizing, inert or redveing atmosphere. Espe- ‘ally in the case of polymetallic systems, activation i a reducing atmosphere is prefered, since alloys are formed more rey, The finished catalyst systems are then fitted in the reaction space (see above), Paticular preference i given to tubulee s e as 3 “ Py 6 reactors equipped with cylindrical catalyst units, since a unie form flow regime is able wo frm hore, which allows pancu- larly good reaction control. The reaction is generally carried out witha looed reae- tor. The reection medium used is water andlor C,-Cy- alkanols, preferably water and/or methanol Ifthe reaction medium used is water, up t0 20% by weight ofthe alcohol, preferably methanol, can be added it. Ifan alcabolicreac- tion medium is used, it can include up to 40% by weight, preferably upto 20% by weight, pticuarly preferably upto 5% by weight, of water. Very particular preference is given to waer a8 sole reaction medium. To stabilize the hydrogen peroxide against decomposition, the reaction medium is admixed with ecids whose pKa value i preferably less than that of acctc acid, especially mineral acids such as sulfiric acid, phosphoric acid or hydrochloric acid. The acid concen- tration is generally not less than 10 moter, preferably ‘within the range ftom 10~" to 10"! molite. fn addition, in general, traces of bromide or chloride are added in concer ‘tations of from 1 to 1000 ppra, preferably $ 10 300 ppm. However, itis also possible to use other stabilizers, for example formaldehyde. ‘The reaction gas, which, as wel as hydrogen end oxygen, say further comprise inert gases such as nitrogen or noble gases, generally has O,ifty ratios within the range From 2:1 1 20081, Peto i so cera wn, 1 to 100:1, particularly peefernbly within the range Fromm 201 to 50:1 The oxygen ot in the reac on gas can tls be included inthe reaction gas inthe form ofa Ina prefered embodiment the reaction gas i recycled. In this cate, the molae ratio inthe fssh gas mixture is in the vicinity oF the stoichiometry of the reaction, preferably Within the range ftom 1.5:1 to 05:1, The molar ratio of (Ox:H in the recycle gas should be within the range from $:1 to 1000.1, preferably withia the range from 20:1 to 10st. The reaction can be cared outa stmospherc pressure and also at superatmospheric pressures of up to 200 ber. The pressure is preferably within the range from 10 to 100 bar, especially within the range from 10 to 80 bar. The reaction temperature canbe within the range farm 0 (0 60° C.,prefer- ably within the range from 20 to 50° C. The patel pressures of the reaction gases inthe reaction gas mixture in the reac- tor and also in the recycle gas are prefersbly chosen so that, tnder reaction conditions, the hydrogen concentration is below the lower explosion fit Reaction gas und reaction medium can move cocurently ‘or countercurrently 19 each other, preferably cocurenty, in ‘which ease the liquid phase forms the continuous phase and the reaction gas the discontinuous phase. In the case ofthe prefered vertical reactor design (upright reactor), reaction, 4s and reaction medium are preferably passed in cocurent ‘upwardly through he reactor Here, hydrogen can be fed nto the reactor via one or more intermediate feed points down- stream ofthe feed point for the oxygen or air feed point. The superficial velocity of reaction gas and reaction medium is within the range from $0 to 1000 my, preferably within the range From 150 to 300 mh The disclosed process makes it posible wo produce hydro- en peroride solutions having hydrogen peroxide conten hove 2.5% by weight, preferably within the range from Sto 25% by weight. The concenzation can be preselected as desiced by adjusting the mass flows. The selectivity of hydrogen peroxide formation is always above 65%, prefer- ably 75%. Long-term studies have shown that exalt activ. lty and selectivity decreas litle, fat all inthe course of a Oday run,Page 5 of 6 US 6,375,920 B2 1 FIG. 4 shows by way of example a rector system featur- ing an upright reacie f, which has hydrogen feed points 2 arranged intermediate of a plurality of layers 3 of woven, "alalyat monolith, A pur 4 supplies methanol and/or water ‘A connection line 5 supplics oxygen and a gas-liquid $ ispeser, for example a mixing jet 6, disperses it inthe for of bubbles in a circulating figuid 7. The same mixing jet or a separate mixing je, if desived—-suppliesa stream 8 of hydrogen, Furher quantities 2 of hydrogen are supplied tunder quantiy contol vie dispersing means 9 at the interme ite feed points 10 berween the catalyst layers 3. At the Upper end ofthe reactor, a two-phase reactor effluent 1 is removed and seperated in a separating vessel 12. The gas phase is reintroducod atthe lower end ofthe reactor via the mixing jet 6 afer passing through a compressor 13 or, if the rector isnot very tall preferably directly. steam 14 ofthe 2s is fed vie a pressure container 1 into the off-gas line 16 to limit the build-up of iners. The liquid is cooled with cooling water ina heat exchanger 17 and reintroduced vie pump 18, tthe lower end ofthe reactor. In adition itis also possible to provide intermediate removal points 19 for the two-phase reactor contents along the resto, to cary out & phase separition 20 and to reintroduce the two figuid phase cooled—at e lower pint 21 of the reactor. The liguid reaction product 22 is removed ffom the phase separa- tor 12 atthe upper end of the reactor as steam 23. ‘The Examples which follow iustrate the presen inven- tion 1. Preparation of Catalyst Shapes Using Supports Composed of V8A Fabric ‘A comupated net and a fat net composed of V4A set (LAST, mesh sine 180 jn, wire diameter 146 jim) were placed on top of each other and rolled to form acyindical Tronalith Sem in height and 5 em in dlameter. The ends of the nets were fixed by spot welding, The net plane spacing of °8 the lat nets was got es than Tm “The monolithic support was treated in succession with scetone and distilled water and then dried, Thereafter the monolith was treated with a solution of 25% by weight of Concentrated hydrochloric acd and 75% by weight of dis (ied water a 60° C. for 30 minutes and rinsed off with distilled water, The monolith thus treated was introduced {no 150 ml of distilled waer. After te ation of 10 drops of concenzated HINO, and 36 mf of a 1% strength by weight ‘aqueous solution of hypophosphorous acid, 20 tl ofa pallae dium nite solution having a palladium concentration of 1% by weight were added. This was followed by heating to 60° C for 17 minutes and then to 80° . for one hour Tis svas followed by cooling, and the eatalyst monolith was svashed with ditled water and dried a 120°C. for 16 tours. 1 Preparation of Hydrogen Peroxide “The reaction vesse! used is © 270 mil autoclave equipped with atime, thermostatng and $0 bac pressure maintenance. Te this autoclave, he catalyst monolch prepared in 1 was Insaled cerally around the stirrer xi so that itis uni formly supplied with liquid and gas by the sierer. The reac- tor bottom is equipped with fed lines for oxygen, hydrogen and the rovtion medium. The reactor lid is equipped with a take-of line from which the product’gas mixture i contina- cusly removed, After deduction of the volumes for al intemals, the effective reaction volume available was 208 © s EXAMPLE | ‘The reaction medium coosisted of methanol admixed with 0.4%5by weight of sulfuric acid, 0.1% by weight of phospho~ 8 sic acid and 6 ppm of bromide (in the form of sodium bromide). The reactor was flooded with the reaction medium, A steam of 72.8 gh of reaction medium, 48.6 7h oF exygen and 5.5 lh of bydrogen (gases based om standard conditions) was then passed through the reactor. The produel'gs mixture was continuously removed athe reac~ tor id ‘The conversion based on hydrogen was 76% (asperdetor- mination of the hydrogen content ofthe off-gas) coupled with selectivity of 82%. The concentration of the resulting methanolic hydrogen peroxide solution was 7% by weight (tration with 0.1 N KMNO,) EXAMPLE 2 Example | was run for 100 hours. In total, 2.9 ‘nydrogen peroxide were abteined in the form o li solution having « concentration of 4% by weight. EXAMPLE 3 ‘A catalyst monolith was prepared from V4A net with a pallodium coating similarly to 1. This shape was then hyéro- gensted with hydrogen at 70° C. and $0 bar, treated with ‘methanolic HO, solution st 20° C. and dried with nitrogen. The catalyst shape was then instalied in the autoclave of I. ‘The reaction was earied out similarly to Example 1: The flow rate through the reactor at 422° C. was 214.5 gih for the reaction medium, 145.8 Uh for oxygen and 16.2 Vh for hydrogen. The conversion based on H, was 84% coupled witha selectivity of 5%. The concentration of the methin- lie hydrogen peroxide solution was 7% by weight. BXAMPLE4 ‘The samme catalyst as in Example 3 was used. The reaction parameters were as follows: 214.5 g/h of reaction medium, 145.8 Vn of oxygen, 6.1 | of hydrogen, T=52° C. The conver- sion based on Hy was 90%, coupled with» selectivity of 68%. The concentration ofthe resuting hydrogen peroxide solution was 2.7% by weight. EXAMPLES ‘The sume caialystas in Example 3 was used. The reaction medium was water admixed with 0.4% by weight of sulfuric acid, 0.1% by weight of phosphoric acid and 6 ppm of bro- mide (in the form of sodium bromide). The reaction param- ters were as follows: 268.0 gh of reaction medium, 291.6 Uh of oxygen, 324 Ub of hydrogen, T=42° C. The conver- sion based on hydrogen was obtained by determining the hydrogen in the off-gas and was found to be 43% coupled with a selectivity of 70%, The concentration of the resulting hydrogen peroxide solution was 5.6% by weight. Weeclaim: 1A process for preparing a hydrogen peroxide solution comprising reacting in reactor, hydrogen and oxygen in ¢ reaction medium containing water, @ Cj-Cy alkanol, or mix- ture thereof concurrently over a catalyst comprising pall dium wherein the hydrogen peroxide solution obtained com- prises not less than 2.5% by weight of hydrogen peroxide, nd wherein the catalyst is catalytic structure is the form of an ordered packing materiat which i installed in the reactor, land wherein the catalytically active component of said cala- iyst is situated on the surface of « support, wherein said suppor is selected from the group consisting of Reschig ‘ings, saddles, Pall rings, wire spirals, wire mesh rings and monolithic supports; wherein the superficial velocity of| reaction gas and reaction medium i within the range fromPage 6 of 6 US 6,375,920 B2 9 50 to 1,000 mh, and wherein the pariat pressures of the reaction gases are chosen under the reaction conditions ‘where the hydrogen concentration is below the lower expio- sion lint. 2, The process as claimed in claim 1, wherein hydrogen and onygen ae reacted ia molar tio OH rom 201 to 3. The process of claim 1, wherein the catalytic structure isconsrutted from « woven materi 44"The process of ceim 3, wherein the woven ise metalic the proves of claim 1, when the active componen © proces of claim 1, wherein the active component includes not only palladim fut also a further noble meta as promoter. 6. The process of claim $, wherein the molar ratio of palladium fo promoter metal i within the range from 100:], 10 1:10. 7. The process of ciaim $, wherein the promoter is selected from the group consisting of platinum, rhodium, ictdiu, copper, silver and gold. '8. The process of claim 1, wherein the oxygen is used in ‘the form of ait. % 10 9. The process of claim 1, wherein the snolar ratio of OH inthe offgas is above 20:1 10. The process of claim 1, wherein the reaction gas is rexycled, 11, The process of claim 10, wherein the molar ratio of Oy:Hy in the recycle gas is within the range ffom 20:1 to 100: 12. The process of elaim 1, wherein the reaction is caried ‘out ata temperature within the range from 0° C. to 80° C. 13. The process of claim 1, wherein the reaction is carried ‘out ata pressure within the range from 10 to 100 bar. 14. The process of claim 4, wherein the reaction medium ‘comprises water, methanol or a methanol-water mixture, 18. The process of claim 1, wherein the reaction medium further comprises an acid having a pK, below that of acetic acid